EP2794833B1 - Isotropes wässriges flüssigwaschmittel mit komplexbildner - Google Patents

Isotropes wässriges flüssigwaschmittel mit komplexbildner Download PDF

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Publication number
EP2794833B1
EP2794833B1 EP12787453.5A EP12787453A EP2794833B1 EP 2794833 B1 EP2794833 B1 EP 2794833B1 EP 12787453 A EP12787453 A EP 12787453A EP 2794833 B1 EP2794833 B1 EP 2794833B1
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Prior art keywords
composition according
composition
amine
mea
hedp
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English (en)
French (fr)
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EP2794833A1 (de
Inventor
Andrew David Green
Alyn James Parry
John Francis Wells
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • 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
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • 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
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/361—Phosphonates, phosphinates or phosphonites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • 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
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • 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
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • 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
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides

Definitions

  • This invention relates to isotropic aqueous liquid laundry detergents that deliver lower than normal levels of surfactants to the wash and have correspondingly higher than normal levels of performance enhancers comprising polymers, enzymes and sequestrants to compensate for the reduced cleaning due to the reduction in surfactant.
  • performance enhancers are more weight efficient than the surfactant they replace and thus facilitate compositions that require very low dosage.
  • WO09153184 suggests that a laundry detergent liquid concentrate may be designed by replacing surfactant with a mixture of more weight efficient ingredients selected from polymers and enzymes.
  • a preferred composition uses a combination of EPEI and a polyester soil release polymer (SRP) to achieve excellent oily soil and particulate detergency at significantly lower in-wash surfactant levels than would normally be delivered from a high performance liquid.
  • the exemplified compositions comprise anionic surfactant comprising linear alkyl benzene sulphonate neutralised with sodium hydroxide and further comprise soap formed by neutralisation of fatty acid by sodium hydroxide.
  • the compositions are alkaline.
  • the SRP used for the examples has a higher level of stability if the concentrated liquid compositions including it are formulated at about pH6.5. There is insufficient space for a conventional bleaching system in such concentrated liquids. However, it is known that bleachable stains may also be removed if relatively high levels of sequestrants are included in the liquid.
  • the sequestrant used was Dequest 2066, a polyphosphonate.
  • Other sequestrants disclosed in WO09153184 are: alkali metal, citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates.
  • Specific examples include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, C 10 -C 22 fatty acids and citric acid.
  • Other examples are DEQUESTTM, organic phosphonate type sequestering agents and alkanehydroxy phosphonates.
  • FR2677370 (NLN SA) teaches to use a sequestering agent for liquid detergent compositions for linen (washing) containing at least 20 percent by weight of water. It consists of a mixed alkaline-earth metal and alkali metal ammonium C2-C8 alkanolamine or C2-C8 alkaneamine salt of 1-hydroxyethane-11-diphosphonic acid (HEDP) or of a mixture of the said mixed salts.
  • Another subject of the invention is the stable liquid detergent compositions containing the said sequestering agent.
  • the HEDP is added to liquid detergents that don't have bleach.
  • Alkanolamine neutralised surfactants may pose a problem for alkali metal salts of HEDP. This precipitation problem is made worse by protease in the liquid.
  • the invention uses either sodium or potassium salts of HEDP premixed with magnesium chloride. TEA / HEDP compositions at pH 7.7 are stable when magnesium chloride is added.
  • HEDP sequestrant 1-Hydroxyethylidene-1, 1-Diphosphonic Acid
  • HEDP sequestrant 1-Hydroxyethylidene-1, 1-Diphosphonic Acid
  • Dequest 2010 gives excellent performance on bleachable stains, even when delivered from the mildly acidic concentrated liquid chosen for soil release polymer stability.
  • HEDP has been found to be much harder to incorporate into isotropic liquids with acceptable physical stability compared with the prior art Dequest 2066, this is especially a problem at the incorporation levels needed for a 20ml dose to European front loading automatic washing machines.
  • the high temperature stability of acid HEDP containing versions of the liquids found in WO09153184 has been found to be poor.
  • WO 99/49009 suggests that the presence of certain EPEI polymers may stabilise HEDP in liquid detergent compositions.
  • EPEI polymers may stabilise HEDP in liquid detergent compositions.
  • Sokalan HP20 which is a nonionic polyethylene imine with a backbone molecular weight of about 600, ethoxylated with an average of 20 moles of ethylene oxide per nitrogen.
  • US2008015135 discloses compact fluid laundry detergent compositions having good economics good cleaning and positive consumer value impression.
  • Amine oxide or betaine may be used.
  • HEDP is one of many possible chelants in the general disclosure.
  • JP2007077362A discloses a liquid detergent composition for clothing which is effective for mud stain and has excellent storage stability.
  • the composition comprises (A) a polyoxyethylene alkyl ether containing a 10-20C alkyl group and having the average addition mol number of ethylene oxide of 3-26 (B) 1-hydroxyethane-11-diphosphonic acid and/or its salt (C) monoethanolamine (D) one or more compounds selected from a semi-polar surfactant an amphoteric surfactant a polyoxyethylene addition type ammonium salt and a polyoxyethylene addition type amine. Paragraph 0032 makes clear that the pH should not be acidic. Amine oxides and Betaines are both preferred surfactants in these MEA containing liquids with HEDP.
  • an isotropic liquid laundry detergent comprising:
  • HEDP is 1-hydroxyethane 1,1-diphosphonic acid (HEDP).
  • the composition comprises at least 2 wt%, more preferably at least 2.5 wt%, HEDP
  • the composition contains triethanolamine (TEA) as the buffer amine and monoethanolamine (MEA) as the non buffering amine with pKa at least 2 units higher than the in-bottle pH of the composition.
  • the surfactant system containing an amine oxide together with a linear alkylbenzene sulfonate (LAS), a neutralised fatty acid and an ethoxylated alcohol.
  • the composition comprises at least 0.75 wt%, preferably at least 1.0 wt% amine oxide (a(ii)).
  • the composition also contains two or more enzymes and a polymer system containing ethoxylated polyethyleneimine (EPEI) and a polyethylene terephthalate (PET) polyoxyethylene terephthalate (POET) polyester.
  • EPEI ethoxylated polyethyleneimine
  • PET polyethylene terephthalate
  • POET polyoxyethylene terephthalate
  • Preferred compositions comprise at least 4 wt% EPEI. More preferred compositions comprise at least 3 wt% polyester based soil release polymer.
  • the in-bottle pH of the composition lies in the range 6.0 to less than 7, preferably 6.3 to 6.7.
  • in-bottle we mean in whatever container or pack the liquid is stored. It could be a plastic pack in the form of a bottle, squeezable or rigid, stored upright or inverted, or a unit dose format such as a soluble pouch, or a sachet.
  • the composition comprises at least 1.5 wt% triethanolamine.
  • the composition may comprise at least 10 wt% nonionic surfactant.
  • the composition may comprise as an additional anionic surfactant at least 2 wt% alkyl ether sulphate.
  • the weight ratio of TEA to MEA is preferably from 1:1 to at most 20:1.
  • the weight ratio of LAS acid to the total of MEA and TEA lies in the range 1.1:1 to 2.5:1.
  • a washing process comprising the steps of adding to a front loading automatic washing machine 25 ml or less, preferably 20 ml, of a composition according to the first aspect, diluting it with at least 800 times as much tap water, washing clothes with the wash liquor formed by the dilution step and then rinsing the clothes.
  • HEDP is not stable in concentrated isotropic aqueous laundry liquids as crystallization occurs on storage at low temperature. This instability is due to poor solubility of Na-HEDP.
  • This salt of HEDP is formed when a composition comprising the acid form of HEDP is neutralised using sodium hydroxide.
  • Sodium hydroxide is the normal neutralising system employed with linear alky benzene sulphonate surfactant in liquid detergent compositions. In more dilute liquids the amount of excess water is sufficient to keep even the sodium salt of the HEDP in solution. This becomes more difficult as the amount of water is reduced for a concentrated composition.
  • the stability problem gets even worse when water hungry polymers are included into the composition at high levels as is the case with the liquids proposed in WO09153184 .
  • HEDP HEDP in aqueous detergent liquids
  • the necessary physical stability of HEDP in aqueous detergent liquids was obtained by replacing TEA/NaOH with TEA/MEA for buffering and pH adjustment (while still maintaining pSRP hydrolytic stability).
  • the Empigen BB carbobetaine was also removed.
  • Empigen BB and Dequest 2010 appear to be incompatible.
  • Empigen OB amine oxide was added into the composition.
  • the MEA may be defined as a non buffering material because the pKa of its conjugate acid lies more than 2 units higher than the final, in-bottle pH of the composition provided the composition is formulated as an acidic in bottle composition.
  • TEA must therefore also be used to provide some buffering capacity to the concentrated composition. This ensures that the polyester soil release polymer and other ingredients are maintained at the correct pH for their optimum storage stability.
  • a proviso on the selection of the neutralising system is that the amount of alkali metal salts should not exceed 0.2 wt% in the liquid composition and they are preferably substantially absent to avoid the alkali metal, particularly sodium, forming HEDP salts that come out of solution and render the liquid non isotropic with poor cleaning due to the HEDP being absent from the upper parts of the liquid after storage in-bottle.
  • the TEA buffer could be partial or fully replaced with another material whose conjugate acid has a pKa of about 6.5.
  • amphoteric surfactant could also be replaced with another that has a capacity to buffer to an acidic pH.
  • Pass means a stable and isotropic liquid was maintained for at least 12 weeks storage.
  • Fan means that material had precipitated or the liquid had split into distinct phases.
  • the target level of inclusion of HEDP for stain removal and cleaning is over 2.5 wt% in these liquids.
  • HEDP was added at gradually increasing amounts to the liquid composition given in table 1 and the pH adjusted to 6.5 with sodium hydroxide.
  • the stability is shown in table 2.
  • HEDP crystallizes out of the liquid at levels of NaOH greater than 0.3 when the carbobetaine Empigen BB used. Insufficient HEDP can be included in this acidic modification of the liquids disclosed in WO09153184 .
  • Example 1 using MEA to adjust pH to 6.5

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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)
  • Enzymes And Modification Thereof (AREA)

Claims (13)

  1. Isotropes Flüssigwaschmittel, umfassend:
    a) mindestens 10 Gew.-% eines Tensidsystems, wobei das Tensidsystem Folgendes umfasst:
    a(i) mindestens 5 Gew.-% nicht-ionisches Tensid auf der Basis von ethoxyliertem Alkohol,
    a(ii) gegebenenfalls ein amphoteres Tensid auf der Basis von Aminoxid,
    a(iii) mindestens 5 Gew.-% lineares Alkylbenzolsulfonat, das durch Neutralisation von LAS-Säure mit einem Amin, das den pH-Wert der Zusammensetzung puffert, und einem zweiten Amin, das keine Pufferwirkung ausübt, da sein pKa-Wert mindestens 2 Einheiten höher als der in der Flasche vorliegende pH-Wert der Zusammensetzung liegt, gebildet worden ist,
    a(iv) Seife, die durch Neutralisation der Fettsäure mit dem ersten und zweiten Amin gebildet worden ist, und
    a(v) gegebenenfalls Alkylethersulfat;
    b) mindestens 1,5 Gew.-% HEDP (Hydroxyethyliden-1,1-diphosphonsäure),
    c) mindestens 5 Gew.-% eines Polymersystems, das nicht-ionisches EPEI (ethoxyliertes Polyethylenimin) und nicht-ionisches PET-POET (Polyethylenterephthalat-polyoxylethylenterephthalat)-Polyester-Schmutzlösungspolymer umfasst, und
    d) mindestens 2 Enzyme;
    wobei der in der Flasche vorliegende pH-Wert der Zusammensetzung im Bereich von 6,0 bis weniger als 7 und vorzugsweise im Bereich 6,3 bis 6,7 liegt.
  2. Zusammensetzung nach Anspruch 1, umfassend mindestens 0,75 Gew.-% und vorzugsweise mindestens 1,0 Gew.-% Aminoxid (a(ii)).
  3. Zusammensetzung nach einem der vorstehenden Ansprüche, wobei es sich beim puffernden Amin um Triethanolamin (TEA) handelt.
  4. Zusammensetzung nach einem der vorstehenden Ansprüche, wobei es sich beim nichtpuffernden Amin mit einem pKa-Wert von mindestens 2 Einheiten über dem in der Zusammensetzung in der Flasche vorherrschenden pH-Wert um Monoethanolamin (MEA) handelt.
  5. Zusammensetzung nach einem der vorstehenden Ansprüche, umfassend mindestens 1,5 Gew.-% Triethanolamin.
  6. Zusammensetzung nach einem der vorstehenden Ansprüche, umfassend mindestens 4 Gew.-% EPEI.
  7. Zusammensetzung nach einem der vorstehenden Ansprüche, umfassend mindestens 3 Gew.-% Schmutzlösungspolymer auf Polyesterbasis.
  8. Zusammensetzung nach einem der vorstehenden Ansprüche, umfassend mindestens 2 Gew.-% und vorzugsweise mindestens 2,5 Gew.-% HEDP.
  9. Zusammensetzung nach einem der vorstehenden Ansprüche, umfassend mindestens 10 Gew.-% nicht-ionisches Tensid.
  10. Zusammensetzung nach einem der vorstehenden Ansprüche, umfassend als zusätzliches anionisches Tensid mindestens 2 Gew.-% Alkylethersulfat.
  11. Zusammensetzung nach einem der vorstehenden Ansprüche, umfassend MEA und TEA, wobei das Verhältnis von TEA zu MEA mindestens 1:1 und vorzugsweise mindestens 20:1 beträgt.
  12. Zusammensetzung nach Anspruch 11, wobei das Verhältnis von LAS-Säure zu MEA und TEA im Bereich von 1,1:1 bis 2,5:1 liegt.
  13. Waschverfahren, umfassend die folgenden Stufen:
    Zugeben von 25 ml oder weniger und vorzugsweise von 20 ml einer Zusammensetzung gemäß einem der vorstehenden Ansprüche in eine Frontlader-Waschmaschine, Verdünnen mit mindestens dem 800-fachen an Leitungswasser, Waschen der Textilien mit der durch die Verdünnungsstufe gebildeten Waschflüssigkeit und anschließend Spülen der Textilien.
EP12787453.5A 2011-12-20 2012-11-19 Isotropes wässriges flüssigwaschmittel mit komplexbildner Active EP2794833B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP12787453.5A EP2794833B1 (de) 2011-12-20 2012-11-19 Isotropes wässriges flüssigwaschmittel mit komplexbildner

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP11194458 2011-12-20
PCT/EP2012/072971 WO2013092049A1 (en) 2011-12-20 2012-11-19 Isotropic aqueous liquid laundry detergent comprising sequestrant
EP12787453.5A EP2794833B1 (de) 2011-12-20 2012-11-19 Isotropes wässriges flüssigwaschmittel mit komplexbildner

Publications (2)

Publication Number Publication Date
EP2794833A1 EP2794833A1 (de) 2014-10-29
EP2794833B1 true EP2794833B1 (de) 2016-02-03

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EP (1) EP2794833B1 (de)
CN (1) CN103998591B (de)
BR (1) BR112014013948B1 (de)
ES (1) ES2564700T3 (de)
WO (1) WO2013092049A1 (de)
ZA (1) ZA201403701B (de)

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EP3101103B1 (de) * 2015-06-05 2019-04-24 The Procter and Gamble Company Kompaktierte flüssigwaschmittelzusammensetzung
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WO2017202922A1 (en) * 2016-05-27 2017-11-30 Unilever Plc Laundry composition
EP3472290B1 (de) * 2016-06-16 2023-05-03 Henkel AG & Co. KGaA Konzentrierte isotrope flüssigwaschmittel enthaltend polymere
WO2017216212A1 (de) * 2016-06-16 2017-12-21 Henkel Ag & Co. Kgaa Konzentrierte isotrope flüssigwaschmittel enthaltend polymere
US11447720B2 (en) 2017-05-30 2022-09-20 Conopeo, Inc. Liquid detergent composition
CA3144561A1 (en) * 2019-07-24 2021-01-28 Basf Se Collector composition
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ZA201403701B (en) 2015-08-26
BR112014013948B1 (pt) 2021-04-06
WO2013092049A1 (en) 2013-06-27
ES2564700T3 (es) 2016-03-28
BR112014013948A2 (pt) 2017-06-13
CN103998591B (zh) 2017-04-05
CN103998591A (zh) 2014-08-20
EP2794833A1 (de) 2014-10-29

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