EP0171008B1 - Agent de nettoyage pour la vaisselle - Google Patents

Agent de nettoyage pour la vaisselle Download PDF

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Publication number
EP0171008B1
EP0171008B1 EP85109466A EP85109466A EP0171008B1 EP 0171008 B1 EP0171008 B1 EP 0171008B1 EP 85109466 A EP85109466 A EP 85109466A EP 85109466 A EP85109466 A EP 85109466A EP 0171008 B1 EP0171008 B1 EP 0171008B1
Authority
EP
European Patent Office
Prior art keywords
weight
mol
alkali
optionally
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP85109466A
Other languages
German (de)
English (en)
Other versions
EP0171008A3 (en
EP0171008A2 (fr
Inventor
Eric Dr. Sung
Peter Dr. Jeschke
Klaus Dr. Schumann
Theodor Dr. Altenschöpfer
Horst Dr. Rutzen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT85109466T priority Critical patent/ATE61066T1/de
Publication of EP0171008A2 publication Critical patent/EP0171008A2/fr
Publication of EP0171008A3 publication Critical patent/EP0171008A3/de
Application granted granted Critical
Publication of EP0171008B1 publication Critical patent/EP0171008B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38609—Protease or amylase in solid compositions only
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • 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
    • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase

Definitions

  • the invention relates to dishwashing detergents, in particular for the automatic washing of dishes at low temperatures, which are distinguished by a high level of cleaning ability, in particular also in relation to stubborn and normally difficult to remove soiling, such as sebum / grease soiling, and by an extraordinarily low foaming ability.
  • alkaline cleaning agent mixtures are used for the automatic cleaning of dishes, which essentially consist of inorganic salts such as alkali phosphates, alkali silicates and alkali carbonates as well as active chlorine carriers and which, in order to improve the wetting effect, may contain minor additions of a low-foaming nonionic surfactant. These mixtures have a good cleaning ability against all stains at generally normal working temperatures of 55 to 65 ° C.
  • the invention therefore relates to agents for the mechanical cleaning of dishes based on polymeric alkali phosphates and / or their substitutes, alkali silicates, alkali carbonates and, where appropriate, compounds which release active oxygen and low-foaming nonionic surfactants, which are characterized in that they contain enzymes and higher molecular weight terminal or internal epoxyalkanes, which have been reacted with mono- or diethanolamine and optionally alkoxylated.
  • Suitable polymeric alkali metal phosphates are the condensed phosphates which are customarily used in detergent and cleaning agent mixtures and which may be present in the form of their alkaline neutral or acidic sodium or potassium salts. Examples include: tetrasodium pyrophosphate, disodium dihydrogen pyrophosphate, pentasodium triphosphate, sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts.
  • the water-soluble organic complexing agents for calcium are essentially found among the polycarboxylic acids, hydroxycarboxylic acids, aminocarboxylic acids, carboxyalkyl ethers, polyanionic polymeric carboxylic acids and the phosphonic acids, these compounds mostly being used in the form of their water-soluble salts.
  • Specific but not exhaustive examples are citric acid, carboxymethyl tartronic acid, mellitic acid, polyacrylic acid, poly- ⁇ -hydroxy acrylic acid, carboxymethyl malic acid, nitrilotriacetic acid and 1-hydroxy-ethane-1,1-diphosphonic acid.
  • Water-soluble sodium or potassium metasilicates are used as alkali metal silicates. They can be anhydrous, hydrated or contain water of crystallization and contain 5 to 9 moles of water.
  • Water glass is understood to mean water-soluble sodium or potassium silicates in which the ratio of alkali oxide to silicon dioxide is approximately 1: 2 to 1: 4. They can be used as anhydrous solid substances or as liquid, approximately 50% solutions
  • Such enzymes are those of animal and vegetable origin, in particular active substances obtained from digestive ferment, yeast and bacterial strains. They usually represent a complex mixture of various enzymatic active ingredients. Of particular interest are enzymes that break down starches, proteins or fats, such as amylases, proteases and lipases.
  • the enzymes are obtained from a variety of processes from bacterial strains, fungi, yeast or animal organs and are sold under different names. Most of these are enzyme mixtures that have a combined effect on starch, protein and fats have.
  • the enzyme preparations obtained from Bacilius subtilis have the particular advantage for practical use that they are relatively resistant to alkalis. The temperature sensitivity of the enzymes no longer plays a significant role here.
  • the manufacturers set the enzymes to a certain degree of activity, optionally with the addition of blending agents such as sodium sulfate, sodium chloride, alkali phosphates or alkali polyphosphates.
  • blending agents such as sodium sulfate, sodium chloride, alkali phosphates or alkali polyphosphates.
  • LVE / g Löhlein-Volhard units per gram
  • IU international units
  • DE / g Device-g
  • the activity is often stated in LVE / g.
  • the proteolytic enzyme activity should be 100 to 5,000, preferably 200 to 2,000 LVE / g.
  • Amylolytic activity is generally reported in SKB / g (Sandstedt-Kneen-Blish units per gram). It should be about 5 to 1,000, preferably 15 to 250, SKB / g in the detergent mixture. The amount of the enzymes to be used in the dishwashing detergents depends on these values.
  • the products used together with the enzymes as cleaning enhancers are prepared in a known manner by reacting higher molecular weight terminal or internal epoxyalkanes with a linear C10-C20 alkyl chain, preferably a C10-C15 alkyl chain with 1 mol of diethanolamine, and then 3 to 20, preferably 5 to 12 moles of ethylene oxide attaches, which is preferably at elevated temperatures of about 50 to 200 ° C under normal pressure or happens under increased pressure.
  • the reaction is generally accelerated by basic or acidic catalysts.
  • the epoxyalkanes used as starting materials for the preparation of the hydroxyamines are obtained in a manner known per se from the corresponding olefins or olefin mixtures.
  • alpha or 1,2-epoxyalkanes are obtained via alpha monoolefins, which are obtained, for example, by polymerizing ethylene with organic aluminum compounds as catalysts or by thermal cracking of paraffin wax.
  • alpha monoolefins those with chain lengths in the range C10-C18 were preferably used.
  • the internal epoxyalkanes are obtained, for example, by producing them from linear aliphatic olefins having 10 to 20 carbon atoms and internal, statistically distributed double bonds by epoxidation using peracids or hydrogen peroxide and lower carboxylic acids forming peracids, or also by epoxidation of olefin mixtures by catalytic dehydrogenation or by chlorination / dehydrochlorination of linear paraffins and selective extraction of the monoolefins.
  • Monoolefins with an internal double bond can also be prepared by isomerizing alpha-olefins.
  • alkali perborates, persulfates and percarbonate which can be activated by activators such as tetraacetylethylenediamine, tetraacetylglycoluril, pentaacetylglucose, but also compounds such as magnesium monoperphthalate, can be used as compounds which release active oxygen, but also compounds such as magnesium monoperphthalate, it being possible to dispense with the addition of activator.
  • activators such as tetraacetylethylenediamine, tetraacetylglycoluril, pentaacetylglucose, but also compounds such as magnesium monoperphthalate, can be used as compounds which release active oxygen, but also compounds such as magnesium monoperphthalate, it being possible to dispense with the addition of activator.
  • Preferred non-ionic low-foaming surfactants are ethylene oxide adducts with higher molecular weight polypropylene glycols with a molecular weight of 900 to 4,000, and ethylene oxide or. Ethylene oxide and propylene oxide adducts with C12-C18 alkanols and nonylphenol into consideration.
  • the preparation is carried out in a known manner by addition of the alkylene oxides in question in the presence of mostly alkaline catalysts, if appropriate under pressure and at elevated temperatures, it being possible to add up to three times the amount by weight of the starting compounds on alkylene oxides.
  • Suitable addition products are the adduct of 10% by weight of ethylene oxide with a polyoxypropylene glycol with a molecular weight of 1750, and the adduct of 9 mol of ethylene oxide and 10 mol of propylene oxide with nonylphenol, and the like.
  • the useful nonionic surfactants also include the surface-active amine oxides, which are mostly derived from tertiary amines with a hydrophobic C10-C20 alkyl group and two shorter alkyl and / or alkylol groups each containing up to 4 C atoms.
  • Typical representatives are, for example, the compounds N-dodecyl-N, N-dimethylamine oxide, N-tetradecyl-N, N-dihydroxyethl-amine oxide and N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) amine oxide.
  • the claimed mixtures may contain further components, in particular inorganic salts such as sodium sulfate, as a blending agent.
  • inorganic salts such as sodium sulfate
  • acidic or alkaline or buffering inorganic or organic compounds can be used to establish a pH value which is advantageous for the enzyme action.
  • preference is given to the organic hydroxycarboxylic acids such as citric acid or tartaric acid, which are also used as complexing agents, and also phosphoric acid or acidic alkali orthophosphates.
  • enzyme-activating additives such as ammonium chloride, sodium chloride, dyes, perfumes and the like can also be added to the mixtures.
  • the claimed agents are generally used as mixtures of granular or powdery individual substances or as granulated, agglomerated or prilled products.
  • the claimed cleaning agent combinations are characterized by a high wetting effect and an extraordinarily good low-temperature cleaning ability, especially in the case of stubborn stains such as grease, protein and starch deposits.
  • the application takes place by adding the powdered, granulated, agglomerated or prilled agents by hand into the dishwashing liquor or preferably by means of automatic dosing devices.
  • the application concentrations in the cleaning liquor should be about 2 to 7 g / l, temperatures of about 40 to 45 ° C. being used.
  • results represent mean values from 4 parallel assessments by 4 test subjects.
  • the test soils consisted of oatmeal porridge and starch in the form of mashed potatoes, which were placed on plates and scraped off. The dishes were then left to stand in the air for 6 hours at room temperature and then placed in the dishwasher.
  • the procedure for soiling beef tallow was as follows: 0.5 to 0.8 g of beef tallow were heated to liquefaction and approx. 2% titanium dioxide was stirred in. Then the still warm mass was spread evenly onto red plastic plates using a brush.
  • a conventional standard cleaning agent (A) was used, which had the following composition:

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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)
  • Washing And Drying Of Tableware (AREA)
  • Bidet-Like Cleaning Device And Other Flush Toilet Accessories (AREA)

Claims (2)

  1. Agents pour le lavage de la vaisselle en machine, à base de phosphates de métaux alcalins polymères et/ou de leurs produits de substitution, de silicates de métaux alcalins, de carbonates de métaux alcalins ainsi que, le cas échéant, de composés libérant de l'oxygène sotif et des tensioactifs non ioniques peu moussants, caractérisés en ce qu'ils renforment des enzymes et des époxyalcanes de poids moléculaire élevé, situés à l'intérieur ou en fin de chaîne, que l'on a fait réagir avec de la mono- ou de la diéthanolamine et qui ont été éventuellement alcoxylés en plus.
  2. Agents nettoyants selon la revendication 1, caractérisés en ce qu'ils sont constitués d'une combinaison de
    0 à 50,    de préférence 10 à 40% en poids d'un phosphate de métal alcalin polymère appartenant au groupe des diphosphates de métaux alcalins et des triphosphates de métaux alcalins,
    0 à 60,    de préférence 5 à 50% en poids de zéolithes insolubles dans l'eau et formant des complexes, du type NaA ou NaX ou de leurs mélanges, ou de complexants pour le calcium, organiques et solubles dans l'eau, au moins un le ces composés ou un des phosphates de métaux alcalins polymères devant être présents,
    10 à 60,    de préférence 20 à 50% en poids de métasilicate de métal alcalin,
    2 à 40,    de préférence 5 à 30 % en poids de carbonate de sodium,
    0 à 20,    de préférence 5 à 20 % en poids d'hydrogénocarbonate de sodium,
    1 à 20   , de préférence 1 à 15 % en poids de silicate de sodium ou de potassium,
    0,1 à 5,    de préférence 0,5 à 3 % en poids d'une enzyme ou d'un mélange d'enzymes faisant partie du groupe des hydrolases, de préférence des amylases, des protéases et des lipases,
    0,1 à 10,    de préférence 0,5 à 5% en poids d'époxyalcanes de poids moléculaire élevé, situés à l'intérieur ou en fin de chaîne, que l'on fait réagir avec 1 mole de mono- ou de diéthanolamine par mole d'alcane et qui peuvent encore éventuellement être alcoxylés avec 1 à 5, de préférence 1 à 4 mole d'oxyde d'éthylène ou de propylène.
    0 à 10,    de préférence 0,5 à 5 % en poids de composés libérant de l'oxygène actif, le cas échéant également d'activateurs pour ceux-ci, et
    0 à 5,    de préférence 0,5 à 2 % en poids d'un tensioactif non ionique peu moussant appartenant au groupe des adduits d'oxyde d'alkylène à des alcanols de C₁₂ à C₁₈, à du nonylphénol ou à des polypropylèneglycols dont le poids moléculaire va de 900 à 4.000.
EP85109466A 1984-08-04 1985-07-27 Agent de nettoyage pour la vaisselle Expired - Lifetime EP0171008B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85109466T ATE61066T1 (de) 1984-08-04 1985-07-27 Geschirreinigungsmittel.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19843428833 DE3428833A1 (de) 1984-08-04 1984-08-04 Geschirreinigungsmittel
DE3428833 1984-08-04

Publications (3)

Publication Number Publication Date
EP0171008A2 EP0171008A2 (fr) 1986-02-12
EP0171008A3 EP0171008A3 (en) 1989-05-03
EP0171008B1 true EP0171008B1 (fr) 1991-02-27

Family

ID=6242386

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85109466A Expired - Lifetime EP0171008B1 (fr) 1984-08-04 1985-07-27 Agent de nettoyage pour la vaisselle

Country Status (4)

Country Link
EP (1) EP0171008B1 (fr)
JP (1) JPS6142596A (fr)
AT (1) ATE61066T1 (fr)
DE (2) DE3428833A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3569235D1 (en) * 1984-06-02 1989-05-11 Hoechst Ag Process for the isomerisation of mono- or dichlorotoluene
GB8629538D0 (en) † 1986-12-10 1987-01-21 Unilever Plc Enzymatic dishwashing & rinsing composition
GB8727659D0 (en) * 1987-11-26 1987-12-31 Unilever Plc Machine dishwashing compositions
JP2638866B2 (ja) * 1988-01-14 1997-08-06 ブラザー工業株式会社 ミシンにおける加工布用スタッカー
SE462583B (sv) * 1988-11-25 1990-07-23 Corroventa Ab Saett och anordning foer avfuktning av luft
WO1997016408A1 (fr) * 1995-10-27 1997-05-09 Basf Aktiengesellschaft Derives d'acides gras et leur utilisation comme agents tensio-actifs dans des produits de lavage et de nettoyage

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1767567A1 (de) * 1968-05-24 1971-09-09 Henkel & Cie Gmbh Geschirrspuelmittel
DE2062465B2 (de) * 1970-12-18 1976-11-25 Henkel & Cie GmbH, 4000 Düsseldorf Geschirrspuelmittel
US4101457A (en) * 1975-11-28 1978-07-18 The Procter & Gamble Company Enzyme-containing automatic dishwashing composition
CH651314A5 (fr) * 1981-12-23 1985-09-13 Colgate Palmolive Co Composition detergente pour lave-vaisselle.
SE450835B (sv) * 1983-05-03 1987-08-03 Eka Nobel Ab Maskindiskmedelskomposition
GB8321923D0 (en) * 1983-08-15 1983-09-14 Unilever Plc Machine-dishwashing compositions

Also Published As

Publication number Publication date
DE3428833A1 (de) 1986-02-13
EP0171008A3 (en) 1989-05-03
JPS6142596A (ja) 1986-03-01
EP0171008A2 (fr) 1986-02-12
ATE61066T1 (de) 1991-03-15
DE3581857D1 (de) 1991-04-04

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