EP0110472B1 - Flüssige Detergens-Zusammensetzungen - Google Patents

Flüssige Detergens-Zusammensetzungen Download PDF

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Publication number
EP0110472B1
EP0110472B1 EP83201655A EP83201655A EP0110472B1 EP 0110472 B1 EP0110472 B1 EP 0110472B1 EP 83201655 A EP83201655 A EP 83201655A EP 83201655 A EP83201655 A EP 83201655A EP 0110472 B1 EP0110472 B1 EP 0110472B1
Authority
EP
European Patent Office
Prior art keywords
silica
weight
liquid detergent
corrosion
composition
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
Application number
EP83201655A
Other languages
English (en)
French (fr)
Other versions
EP0110472A3 (en
EP0110472A2 (de
Inventor
Cornelis Bernard Donker
John Raymond Samuel
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.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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 Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to AT83201655T priority Critical patent/ATE35283T1/de
Publication of EP0110472A2 publication Critical patent/EP0110472A2/de
Publication of EP0110472A3 publication Critical patent/EP0110472A3/en
Application granted granted Critical
Publication of EP0110472B1 publication Critical patent/EP0110472B1/de
Expired 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions

Definitions

  • the present invention relates to liquid detergent compositions and in particular to aqueous liquid detergant compositions having improved non-corrosive properties.
  • an anti-corrosion agent in detergent compositions in order to inhibit the corrosive and discolouring influence of the washing liquid on metal or enamel parts of washing machines and to prevent thereby the malfunctioning of the machines or the discolouring of fabrics which come into contact with such corroded parts.
  • Aqueous liquid detergent compositions containing corrosion inhibiting agents are known in the art.
  • soluble silicates such as metasilicate, orthosilicate and sesquisilicate.
  • Such compounds provide the liquid detergent composition with a highly alkaline environment, which is not always a desirable circumstance, especially if in such compositions alkali-sensitive ingredients are used.
  • Further anti-corrosive agents described in the detergent art include sulphites, nitrites, carbonates, borax or organic compounds such as benzoates.
  • the present invention provides aqueous liquid detergent compositions with improved non-corrosive properties, comprising conventional detergent ingredients and an effective amount of silica having a surface area greater than 200 m 2 /g.
  • FR-A-2.300.800 detergent compositions which contain 1-40% by weight of a silica with a particle size of less than 20 microns and a surface area of preferably greater than 200 m 2 /g.
  • This silica is used in a composition comprising orthophosphate for the purpose of catching away the insoluble calcium ortho- and pyrophosphates formed in the wash liquor.
  • These compositions may furthermore comprise water-soluble silicates as corrosion inhibitors.
  • the silica of the present invention must dissolve in the wash liquor in order to achieve the corrosion inhibition properties of the invention.
  • the silica in order to achieve optimal anti-corrosion protection, from 1% to 10% of the silica must be present in a form such that in the wash liquor when dosed at 10 g/I, the silica is in a dissolved form at a concentration of at least 120 ppm by weight and preferably 150 ppm by weight. According to the present invention therefore, in order to provide the required amount of dissolved silica in the wash liquor to ensure adequate anti-corrosion protection, the silica will be incorporated in the liquid detergent composition in an amount which is the equivalent of from about 1% to 10% by weight, preferably from 1.5% to 5% by weight and most preferably from 2% to 4% by weight of the liquid detergent composition which is intended for use at an in-wash product dosage of 10 g/I.
  • liquid detergent composition is formulated having a preferred in-wash product dosage which is different from 10 g/litre, the amount of silica that should be incorporated to achieve adequate anti-corrosion protection must be adjusted accordingly, such that the amount thereof corresponds with the ranges as defined for 10 g/I product dosage.
  • the silica to be used in the present invention should have a surface area which is greater than 200 m 2 per gram and preferably greater than 350 m 2 per gram or even 500 m 2 per gram.
  • the upper limit of the surface area is not a critical factor, but normally surface areas range to about 1200 m 2 per gram.
  • such silicas have elementary particle sizes of less than about 30 nm, in particular less than about 25 nm. Preferably, elementary particle sizes are less than 20 nm or even 10 nm. There is no critical lower limit of the elementary particle size; the lower limit is governed by other factors such as the manner of manufacture etc. In general, commercially available silicas have elementary particle sizes of 1 nm or more.
  • Suitable forms of silica include amorphous silica, such as precipitated silica, pyrogenic silica and silica gels, such as hydrogels, xerogels and aerogels, or the pure crystal forms quartz, tridymite or crystobalite, but the amorphous forms of silica are preferred.
  • amorphous silica such as precipitated silica, pyrogenic silica and silica gels, such as hydrogels, xerogels and aerogels, or the pure crystal forms quartz, tridymite or crystobalite, but the amorphous forms of silica are preferred.
  • Suitable silicas may readily be obtained commercially. They are sold, for instance, under the Registered Trade Marks of Aerosil 380 (ex Degussa Corp., N. J., USA), Cab-O-Sil M5 (ex Cabot Corp., III, USA), Tixosil 38A (ex SI Chimie, France) and Gasil 200 (ex Crosfield, UK).
  • the liquid detergent compositions of the invention further comprise an active detergent material, which may be an alkali metal or alkanolamine soap of C l6 -C 24 fatty acid, including polymerized fatty acids, or an anionic, nonionic, cationic, zwitterionic or amphoteric synthetic detergent material, or a mixture of any of these.
  • active detergent material may be an alkali metal or alkanolamine soap of C l6 -C 24 fatty acid, including polymerized fatty acids, or an anionic, nonionic, cationic, zwitterionic or amphoteric synthetic detergent material, or a mixture of any of these.
  • the anionic synthetic detergents are synthetic detergents of the sulphate- and sulphonate- types.
  • salts including sodium, potassium, ammonium and substituted ammonium salts, such as mono-, di- and tri-ethanolamine salts
  • C 9 ⁇ C 20 alkyl benzene sulphonates C a -C 22 primary or secondary alkane sulphonates
  • Cg-C 24 olefin sulphonates Cg-C 24 olefin sulphonates
  • sulphonated polycarboxylic acids prepared by sulphonation of the pyrolized product of alkaline earth metal citrates, e.g. as described in British Patent Specification No.
  • nonionic synthetic detergents are the condensation products of ethylene oxide, propylene oxide and/or butylene oxide with C 8 ⁇ C 18 alkylphenols, C 8 ⁇ C 18 primary or secondary aliphatic alcohols, C 8 ⁇ C 18 fatty acid amides; further examples of nonionics include tertiary amine oxides with one C 6- C l . alkyl chain and two C,-C 3 alkyl chains. The above reference also describes further examples of nonionics.
  • the average number of moles of ethylene oxide and/or propylene oxide present in the above nonionics varies from 1 to 30; mixtures of various nonionics, including mixtures of nonionics with a higher degree of alkoxylation, may also be used.
  • cationic detergents are the quaternary ammonium compounds such as alkyl dimethyl ammonium halogenides.
  • amphoteric or zwitterionic detergents are N-alkylamino acids, sulphobetaines and condensation products of fatty acids with protein hydrolysates, but owing to their relatively high cost they are usually used in combination with an anionic or a nonionic detergent. Mixtures of the various types of active detergents may also be used, and preference is given to mixtures of an anionic and a nonionic detergent-active compound. Soaps (in the form of their sodium, potassium, and substituted ammonium salts, such as of polymerized fatty acids, may also be used, preferably in conjunction with an anionic and/or a nonionic synthetic detergent.
  • the amount of the active detergent material varies from 1 to 60% in general, preferably from 2 to 40% and particularly preferably from 5 to 25% by weight. When a soap is incorporated, the amount thereof is from 1 to 40% by weight.
  • the liquid compositions of the invention preferably also comprise up to 60% of suitable builder materials, such as sodium, potassium and ammonium or substituted ammonium pyro-and tripolyphosphates, -ethylenediamine tetraacetates, -nitrilotriacetates, -ether polycarboxylates, -citrates, -carbonates, -orthophosphates, zeolites, carboxymethyloxysuccinates, etc.
  • suitable builder materials such as sodium, potassium and ammonium or substituted ammonium pyro-and tripolyphosphates, -ethylenediamine tetraacetates, -nitrilotriacetates, -ether polycarboxylates, -citrates, -carbonates, -orthophosphates, zeolites, carboxymethyloxysuccinates, etc.
  • Particularly preferred are the polyphosphate builder salts, nitrilotriacetates, citrate
  • the amount of water present in the detergent compositions of the invention varies from 10 to 70% by weight in general.
  • liquid detergent compositions of the invention for example sequestering agents, such as ethylenediaminetetraphosphonic acid; non-builder electrolytes, such as alkalimetal-chlorides, -bromides, -nitrates and -sulphates; soil-suspending agents, such as sodium carboxymethylcellulose, polyvinylpyrrolidone or the maleic anhydride/vinylmethylether copolymer; hydrotropes; dyes; perfumes; alkaline materials, such as silicates; optical brighteners; germicides; anti-tarnishing agents; suds boosters; suds depressants, such as liquid polysiloxane anti-foam compounds; enzymes, particularly proteolytic enzymes, such as the commercially available subtilisins Maxatase@ (ex Gist-Brocades N.
  • sequestering agents such as ethylenediaminetetraphosphonic acid
  • non-builder electrolytes such as alkalimetal-chlorides, -brom
  • enzyme stabilizing systems such as a mixture of a polyol with boric acid or an alkalimetal borate
  • oxygen liberating bleaches such as sodium perborate or percarbonate, diperisophthalic anhydride with or without bleach precursors, such as tetraacetyl ethylene diamine; or chlorine liberating bleaches, such as dichlorocyanurate
  • anti-oxidants such as sodium sulphites
  • opacifiers such as fabric softening agents
  • stabilizers such as polysaccharide hydrocolloids, e.g. partially acetylated xanthan gum, commercially available as "Kelzan@" (ex Kelco Comp., New Jersey, USA); buffers and the like.
  • compositions of the present invention were tested comparatively under various temperature conditions and degrees of water hardness.
  • Example I By means of the corrosion test described above the composition of Example I was compared with a control composition (i.e. the example composition without the silica) at various degrees of water hardness at a temperature of 85°C.
  • the hardness of the water is expressed in degrees of French hardness (one degree French hardness is equivalent to 10 mg CaC0 3 per litre).
  • Example I By means of the corrosion test described above the composition of Example I was compared with the control composition at various temperatures using demineralized water for the wash liquor.
  • Example II To illustrate the corrosive action as a function of product dosage (and accordingly as a function of silica concentration) the composition of Example II was submitted to the corrosion test and compared with a control composition at different product dosages at a temperature of 85°C, using demineralized water for the wash liquor.
  • Example II The above composition was submitted to an experiment equivalent to the one carried out in Example II. As the above product should be used at a much lower dosage, the investigated range of product dosages is different.
  • Example 2 To illustrate the anti-corrosive action of various types of silica the corrosion test was performed on a set of composition prepared according to the formulation of Example 2 but differing therefrom in the type of silica employed. The amounts of silica incorporated equalled 10% by weight of the composition.
  • composition according to Example II was tested on its effectiveness in protecting enamel from corrosion attack.
  • Example II The silica as specifed in Example II was included in an amount of 2.5% by weight.
  • enamel covered steel plates were used having a surface area of 100 cm 2 and-the testing time was extended to a period of 24 hours.
  • Results indicate a significant anti-corrosive action: .

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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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (5)

1. Wäßrige, flüssige Detergens-Zusammensetzung mit herkömmlichen Detergens-Bestandteilen und 1 bis 10 Gew.-% Kieselsäure mit einer Oberfläche größer als 200 m2/g, dadurch gekennzeichnet, daß die Kieselsäure in einer solchen Menge enthalten ist, daß bei Dosierung in eine Waschflüssigkeit in einer Menge von 10 g/I mindestens 120 ppm bezogen auf das Gewicht, Kieselsäure gelöst werden.
2. Detergens-Zusammensetzung gemäß Anspruch 1, dadurch gekennzeichnet, daß die Kieselsäure eine Oberfläche von oberhalb 500 m2/g besitzt.
3. Detergens-Zusammensetzung gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Kieselsäure in einer Menge von 2 bis 4 Gew.-%, bezogen auf die gesamte Zusammensetzung enthalten ist.
4. Detergens-Zusammensetzung gemäß einem der vorgehenden Ansprüche, dadurch gekennzeichnet, daß die Kieselsäure eine elementare Teilchengröße von weniger als 10 nm besitzt.
5. Verfahren zur Verhinderung der Korrosion von Maschinenteilen während des Waschens, dadurch gekennzeichnet, daß eine Zusammensetzung gemäß einem der vorgehenden Ansprüche in dem Waschverfahren eingesetzt wird.
EP83201655A 1982-11-26 1983-11-21 Flüssige Detergens-Zusammensetzungen Expired EP0110472B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83201655T ATE35283T1 (de) 1982-11-26 1983-11-21 Fluessige detergens-zusammensetzungen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8233752 1982-11-26
GB8233752 1982-11-26

Publications (3)

Publication Number Publication Date
EP0110472A2 EP0110472A2 (de) 1984-06-13
EP0110472A3 EP0110472A3 (en) 1985-04-10
EP0110472B1 true EP0110472B1 (de) 1988-06-22

Family

ID=10534545

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83201655A Expired EP0110472B1 (de) 1982-11-26 1983-11-21 Flüssige Detergens-Zusammensetzungen

Country Status (9)

Country Link
EP (1) EP0110472B1 (de)
JP (1) JPS59140300A (de)
AT (1) ATE35283T1 (de)
AU (1) AU550913B2 (de)
BR (1) BR8306514A (de)
CA (1) CA1221293A (de)
DE (1) DE3377140D1 (de)
NZ (1) NZ206355A (de)
ZA (1) ZA838713B (de)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8616615D0 (en) * 1986-07-08 1986-08-13 Unilever Plc Rinse aid
GB2204319A (en) * 1987-05-08 1988-11-09 Unilever Plc Liquid dishwashing composition for aluminium pans
GB8818144D0 (en) * 1988-07-29 1988-09-01 Unilever Plc Liquid detergent compositions
DE69509531T2 (de) * 1994-07-04 1999-09-09 Unilever Nv Verfahren zum waschen und zusammensetzung
DE19904512A1 (de) 1999-02-04 2000-08-17 Henkel Ecolab Gmbh & Co Ohg Verfahren zur Reinigung von Mehrwegflaschen
PL399250A1 (pl) 2012-05-21 2013-11-25 Zaklad Mechaniczny Marpo Spólka Jawna M. Przygodzki I Wspólnicy Sposób i urzadzenie do prowadzenia recyklingu odpadów organicznych, a szczególnie zuzytych opon, przy wykorzystaniu techniki mikrofalowej

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2977260A (en) * 1958-10-09 1961-03-28 Ca Atomic Energy Ltd Inhibition of corrosion of aluminum alloys
GB1531432A (en) * 1975-02-14 1978-11-08 Procter & Gamble Ltd Detergent compositions
JPS5346303A (en) * 1976-10-08 1978-04-25 Sanpooru Kk Liquid cleanser
JPS6026155B2 (ja) * 1976-11-15 1985-06-21 株式会社トクヤマ 防蝕性皮膜の形成方法
JPS5496503A (en) * 1978-01-13 1979-07-31 Inoue Kagaku Kougiyou Kk Cleaner for automobile window glass
US4199467A (en) * 1978-05-04 1980-04-22 The Procter & Gamble Company Alkaline dishwasher detergent
JPS54147141A (en) * 1978-05-11 1979-11-17 Nippon Shii Bii Kemikaru Kk Metal surface treatment chemicals and treatment using same
JPS557840A (en) * 1978-07-01 1980-01-21 Shinkiyoku Kogyo Kk Glass cleaning solution
DE2851988C3 (de) * 1978-12-01 1981-09-17 Helmut 3167 Burgdorf Haberer Wasch- und Poliermittel für lackierte Flächen, insbesondere für Kraftfahrzeugkarosserien
DE3066202D1 (en) * 1979-11-03 1984-02-23 Procter & Gamble Granular laundry compositions
DE3277729D1 (en) * 1981-09-25 1988-01-07 Procter & Gamble Laundry additive products containing amino-silanes

Also Published As

Publication number Publication date
EP0110472A3 (en) 1985-04-10
BR8306514A (pt) 1984-07-03
AU2162683A (en) 1984-05-31
JPS59140300A (ja) 1984-08-11
CA1221293A (en) 1987-05-05
ATE35283T1 (de) 1988-07-15
EP0110472A2 (de) 1984-06-13
NZ206355A (en) 1986-04-11
DE3377140D1 (en) 1988-07-28
JPS6119678B2 (de) 1986-05-19
ZA838713B (en) 1985-07-31
AU550913B2 (en) 1986-04-10

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