EP0652940B1 - Detergent compositions - Google Patents

Detergent compositions Download PDF

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Publication number
EP0652940B1
EP0652940B1 EP93917976A EP93917976A EP0652940B1 EP 0652940 B1 EP0652940 B1 EP 0652940B1 EP 93917976 A EP93917976 A EP 93917976A EP 93917976 A EP93917976 A EP 93917976A EP 0652940 B1 EP0652940 B1 EP 0652940B1
Authority
EP
European Patent Office
Prior art keywords
composition
weight
condensed phosphate
amount
phosphate builder
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
EP93917976A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0652940A1 (en
Inventor
James 4 Orchard Road Swales
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.)
Imperial Chemical Industries Ltd
Original Assignee
Imperial Chemical Industries Ltd
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 Imperial Chemical Industries Ltd filed Critical Imperial Chemical Industries Ltd
Publication of EP0652940A1 publication Critical patent/EP0652940A1/en
Application granted granted Critical
Publication of EP0652940B1 publication Critical patent/EP0652940B1/en
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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
    • 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
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates

Definitions

  • This invention relates to detergent compositions and in particular to non-aqueous laundry liquid detergent compositions.
  • Detergent compositions which comprise a suspension of a builder and optionally other solids in an organic liquid which comprises a surfactant.
  • Non-aqueous compositions of this type are described in European Patent Specifications Nos EP 0030096 B and EP 0120659 B.
  • Such compositions may contain phosphate builders, for example alkali metal condensed phosphates, for example sodium tripolyphosphate.
  • detergents are placed in containers which are introduced into the washing zone. If the container has restricted access solid deposits may be left in it especially if it was not dry when detergent was placed in it.
  • This invention accordingly provides a substantially non-aqueous liquid laundry detergent composition which comprises a surfactant, a condensed phosphate builder and a water soluble salt of a hydroxycarboxylic acid containing 1 to 6 -COOH groups and 1 to 5 -OH groups in an amount to give a weight ratio of the condensed phosphate builder to the hydroxy carboxylic acid of 60:1 to 5:1.
  • substantially non-aqueous we mean that the amount of water in the composition is sufficiently small that the tendency of the condensed phosphate builder to hydrolyse and thus to cause the viscosity of the detergent formulation to increase or the formulation to gel during storage prior to use is overcome.
  • it is free water i.e. water that is not chemically bound as in water of crystallisation, in the formulation that is problematical and the amount of free water will usually be kept to less than 2%, and very desirably less than 1%, by weight of the composition.
  • Small quantities of free water are typically present in various components of the formulation e.g. non-ionic surfactants and polyethylene glycol, and it is the concentration of water from such sources that should be kept suitably low. Water of crystallisation in materials such as the hydroxycarboxylic acid salt(s), as in sodium citrate dihydrate, is not usually a problem.
  • the hydroxycarboxylic acid salt is desirably a salt of an acid which contains a total of at least 3 hydroxyl and carboxyl groups. Salts of tartaric and citric acids are particularly useful materials. Mixtures of salts of these acids can be used if desired. The use of salts of either or both of these acids forms a particularly advantageous feature of this invention.
  • the salt cation is desirably an ammonium, substituted ammonium or alkali metal, particularly sodium, salt.
  • the salt is present in an amount to give a weight ratio of the condensed phosphate builder to the hydroxycarboxylic acid salt of 60:1 to 5:1, particularly 30:1 to 7:1, especially about 20:1.
  • the amount of hydroxycarboxylic acid salt used in compositions of this invention is relatively small. At relatively high concentrations, hydroxycarboxylic acid salts can act as builders in detergent formulations. In this invention, the amount used is typically sufficiently small that the hydroxycarboxylic acid salt does not provide significant effect as a builder over and above that provided by the condensed phosphate builder.
  • the composition is preferably alkaline in reaction i.e. when added to water, as in use, the laundry water is rendered alkaline. It is preferred that normally acidic substances when present in the composition are in a form neutralised with alkali, particularly containing one or more of ammonium, substituted ammonium or, and preferably, alkali metal ions. Specific additives can be included to control the alkalinity of the laundry water in use, such as sodium disilicate or, especially if somewhat less alkaline conditions are desired, sodium bicarbonate.
  • the condensed phosphate builder may be an alkali metal, preferably a potassium or sodium salt of a condensed phosphate.
  • Linear condensed phosphates are better builders than cyclic materials and are thus preferred.
  • the condensed phosphate will be a di-phosphate (pyrophosphate) for example sodium pyrophosphate Na 4 P 2 O 7 , or tri-phosphate (tripolyphosphate), for example potassium tripolyphosphate, or, and particularly desirably, sodium tripolyphosphate.
  • the total builder content of the composition (including the condensed phosphate builder) will generally be from 25 to 60% by weight.
  • Other builders e.g. sodium carbonate and sodium bicarbonate, can be included if desired, but the amounts of such builders, when present, are usually relatively small for example from 1 to 10% by weight of the composition.
  • the composition can include a bleach such as a perborate or percarbonate e.g. as an alkali metal, particularly sodium, salt.
  • a bleach such as a perborate or percarbonate e.g. as an alkali metal, particularly sodium, salt.
  • the amount of the bleach will typically be from 1 to 25%, particularly 2 to 20%, more particularly 5 to 20%, and especially about 10 to about 15%, by weight of the composition.
  • a bleach activator such as tetra-acetyl ethylene diamine, can also be included in the composition.
  • the surfactant will typically include at least one non-ionic surfactant.
  • Suitable non-ionic surfactants include alkylene oxide derivatives, particularly where the alkylene oxide is ethylene and/or propylene oxide, especially ethylene oxide.
  • Particularly suitably materials include reaction products of an amine, alkyl phenol or alkanol with ethylene and/or propylene oxide, especially ethylene oxide.
  • the amine will usually be an alkyl amine in which the alkyl group can be straight or branched chain and can contain from 6 to 20, particularly 10 to 16, carbon atoms.
  • alkyl phenol reaction products are used, the alkyl group can be straight or branched chain and can contain from 6 to 20, particularly 6 to 12, carbon atoms.
  • the alkanol is preferably a primary or secondary alkanol having a linear or mono branched alkyl chain and the alkanol can contain 6 to 20, preferably 10 to 16, carbon atoms.
  • the (poly)oxyalkylene chain in the non-ionic surfactant has from 1 to 10, preferably 3 to 8, alkylene oxide residues.
  • the number of alkylene oxide residues given is an average value.
  • the amount of non-ionic surfactant is typically from 5 to 25%, particularly 7 to 20%, by weight of the composition.
  • non-ionic surfactants are generally the preferred surfactants in this invention
  • the surfactant may alternatively be or include one or more anionic or cationic surfactants.
  • anionic or cationic surfactants may be of known type for example the anionic detergents may be soaps, alkylbenzene or olefin sulphonates, alcohol sulphates or alcohol alkoxylate sulphates; the cationic surfactants are suitably di-C 10-22 and preferably di-C 16-18 alkyl, di-lower alkyl ammonium salts or hydroxides for example chlorides or sulphates or for example fabric softeners of the C 10-16 alkyl, di-lower alkyl (for example methyl), substituted ethyl ammonium salts.
  • the substituent on the ethyl group may be an -OOCR group where R is a C 13-22 alkyl group, and the anion of the salt may be a RSO 4 - group where R is lower alkyl for example methyl.
  • the lower alkyl groups are suitably methyl groups.
  • the composition desirably also includes a polyalkylene glycol, for example a polyethylene/polypropylene glycol or and particularly advantageously a polyethylene glycol.
  • a polyalkylene glycol for example a polyethylene/polypropylene glycol or and particularly advantageously a polyethylene glycol.
  • the polyalkylene glycol desirably has a molecular weight of 100 to 1500 D, especially 100 to 500, and for example 150 to 400 D.
  • Polyalkylene glycols, particularly polyethylene glycols, of average molecular weight 100 to 400 and preferably 150 to 300 are especially useful as they can act to reduce the pour point of the liquid laundry detergent compositions thus making them more easily usable in a cold environment.
  • the polyalkylene glycol, particularly polyethylene glycol is typically present as 5 to 55%, particularly 10 to 50% and especially 25 to 45%, by weight of the composition.
  • the composition may also contain additives conventionally found in detergent compositions, for example fabric conditioners, anti-redeposition aids such as carboxymethyl cellulose (see below), pH adjusters (see above), anti-corrosion additives e.g. sodium disilicate (which also acts as a pH adjuster), optical brighteners, sequestrants e.g. ethylene diamine tetra-acetic acid, dyes, perfumes and/or enzymes.
  • fabric conditioners such as carboxymethyl cellulose (see below), pH adjusters (see above), anti-corrosion additives e.g. sodium disilicate (which also acts as a pH adjuster), optical brighteners, sequestrants e.g. ethylene diamine tetra-acetic acid, dyes, perfumes and/or enzymes.
  • anti-redeposition aids such as carboxymethyl cellulose (see below), pH adjusters (see above), anti-corrosion additives e.g. sodium disilicate (which also acts as a pH adjuster), optical brighteners
  • the liquid composition will generally take the form of a dispersion of solid particles in a liquid medium.
  • the solids will include the condensed phosphate builder, other inorganic builders, when present, the hydroxycarboxylic acid salt(s), the bleach, when present, and other solid minor components not soluble in the liquid medium.
  • the laundry liquid composition will comprise 25 to 70Z and particularly 30 to 65%, for example 40 to 65%, by weight of total solids.
  • the solids will be finely divided solids and in particularly the solids have an average particle size of at most 10 ⁇ m and very particularly from 1.2 to 8 ⁇ m.
  • the proportion of relatively large particles will usually be kept small and, thus, it is very desirable that at least 90% of the solid particles have a size of less than 10 ⁇ m.
  • Stated particle sizes are the diameters of particles of equal volume. Desirably, he particle size distribution is relatively narrow so that average particle sizes expressed as number average or weight average sizes are similar. Particle sizes can be measured, for example, using Coulter counters or laser particle size measuring equipment such as that sold under the Malvern name.
  • the liquid medium will include the liquid surfactant such as non-ionic surfactant(s), when present, the polyoxyalkylene glycol, when present, other minor liquid components and solid components soluble in the liquid medium.
  • the liquid medium will comprise 75 to 30% and particularly 70 to 35%, for example 60 to 35%, by weight of the composition.
  • Cationic and anionic surfactants when present will, depending on their properties either form part of the solids or will be wholly or partly liquid or dissolved in the liquid medium.
  • the formulation can include anti-redeposition aids. These include polycarboxylic acids having at least 10, usually at least 100, particularly 150 to 2000 and especially 200 to 1000, COOH groups. Carboxymethyl cellulose is a suitable anti-redeposition aid.
  • the composition suitably has a pour point (ASTM D 97-66, 1971) of less than 10°C and particularly less than 5°C.
  • the pour point may be adjusted by varying the liquid phase composition, for example, by including surfactants and/or polyethylene glycol of low pour point.
  • compositions according to the invention the dispersion of the solids in the non-ionic surfactant is remarkably stable especially if the particle size of the solids is at most 10 ⁇ m. If the solids separate at all then the resulting phase is usually loosely flocculated and is readily redispersible while if the relative amounts of the solids, polyethylene glycol and surfactant in the composition are correctly chosen there is little phase separation as the liquid fills the space between the loosely packed solid particles.
  • An especially useful substantially non-aqueous liquid laundry detergent composition which forms a particular feature of the invention is one which comprises:
  • compositions according to the invention may suitably be made by a process which comprises milling ingredients together for example by bead milling.
  • Liquid formulations A - H (Control sample C1 - formulation A and Examples 1 to 7 - formulations B - H) were produced by mixing together the components in the amounts given in Table 1 below in a homogeniser and then bead milling the mixtures until the solids had an average particle size of 3 ⁇ m.
  • each formulation was assessed by weighing 60g of the laundry liquid into a commercially available rectangular plastic dosing device measuring ca. 6.5 x 5 x 3.5 cm which was placed in the drum of a Philips 036 washing machine on top of 3.5 kg of laundry (laboratory coats and towels). The machine was started on programme No 5 which has a 27 minute wash cycle with cold water fill, taking 10 minutes to reach the 40°C wash temperature. 10 minutes after the drum had started to roll the machine was stopped, drained and the dosing device removed. The amount of any residues left in the dosing device was recorded. This procedure was carried out at least 3 times for each formulation. The test results are set out in Table 2 below. TABLE 2 Residues (g) after 10 mins Mean Std.

Landscapes

  • 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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
EP93917976A 1992-08-03 1993-08-03 Detergent compositions Expired - Lifetime EP0652940B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB929216454A GB9216454D0 (en) 1992-08-03 1992-08-03 Detergent compositions
GB9216454 1992-08-03
PCT/GB1993/001636 WO1994003580A1 (en) 1992-08-03 1993-08-03 Detergent compositions

Publications (2)

Publication Number Publication Date
EP0652940A1 EP0652940A1 (en) 1995-05-17
EP0652940B1 true EP0652940B1 (en) 1997-03-12

Family

ID=10719741

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93917976A Expired - Lifetime EP0652940B1 (en) 1992-08-03 1993-08-03 Detergent compositions

Country Status (12)

Country Link
EP (1) EP0652940B1 (es)
JP (1) JPH07509520A (es)
AT (1) ATE150082T1 (es)
AU (1) AU678378B2 (es)
CA (1) CA2141452A1 (es)
DE (1) DE69308856T2 (es)
DK (1) DK0652940T3 (es)
ES (1) ES2098767T3 (es)
GB (1) GB9216454D0 (es)
NZ (1) NZ254900A (es)
WO (1) WO1994003580A1 (es)
ZA (1) ZA935578B (es)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0752466A1 (en) * 1995-07-05 1997-01-08 The Procter & Gamble Company Nonaqueous detergent compositions comprising effervescent systems
EP0816247B1 (en) * 1996-06-26 2001-08-16 The Procter & Gamble Company Venting container containing a liquid product with particulate solids
US6548134B1 (en) 1996-06-26 2003-04-15 The Procter & Gamble Company Vented container containing a liquid product with particulate solids
EP0907707A2 (en) * 1996-06-28 1999-04-14 The Procter & Gamble Company Nonaqueous detergent compositions containing bleach precursors
JP5394635B2 (ja) * 2007-12-07 2014-01-22 正一 中村 洗浄添加剤及びその製造方法
US8871807B2 (en) 2008-03-28 2014-10-28 Ecolab Usa Inc. Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids
AU2009230713C1 (en) 2008-03-28 2018-08-02 Ecolab Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US8809392B2 (en) 2008-03-28 2014-08-19 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US9321664B2 (en) 2011-12-20 2016-04-26 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
CN104254496B (zh) 2012-03-30 2016-10-26 艺康美国股份有限公司 过乙酸/过氧化氢和过氧化物还原剂用于处理钻井液、压裂液、回流水和排放水的用途
US10165774B2 (en) 2013-03-05 2019-01-01 Ecolab Usa Inc. Defoamer useful in a peracid composition with anionic surfactants
US8822719B1 (en) 2013-03-05 2014-09-02 Ecolab Usa Inc. Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring
US20140256811A1 (en) 2013-03-05 2014-09-11 Ecolab Usa Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
US12096768B2 (en) 2019-08-07 2024-09-24 Ecolab Usa Inc. Polymeric and solid-supported chelators for stabilization of peracid-containing compositions

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE381672B (sv) * 1971-07-15 1975-12-15 Mo Och Domsjoe Ab Flytande tvettmedelskomposition
DE3065199D1 (en) * 1979-12-04 1983-11-10 Ici Plc Detergent composition
GB8308508D0 (en) * 1983-03-28 1983-05-05 Ici Plc Detergent compositions
US4767558A (en) * 1985-08-05 1988-08-30 Colgate-Palmolive Company Low phosphate or phosphate free nonaqueous liquid nonionic laundry detergent composition and method of use
IT1200285B (it) * 1986-08-12 1989-01-12 Mira Lanza Spa Detersivo liquido non acquoso e procedimento per la sua fabbricazione
AU602362B2 (en) * 1986-10-29 1990-10-11 Colgate-Palmolive Company, The Built nonaqueous liquid nonionic laundry detergent composition containing hexylene glycol and method of use
US4830782A (en) * 1987-08-31 1989-05-16 Colgate-Palmolive Company Hot water wash cycle built nonaqueous liquid nonionic laundry detergent composition containing amphoteric surfactant and method of use
EP0339999A3 (en) * 1988-04-29 1991-07-17 Unilever Plc Liquid cleaning products
AU624634B2 (en) * 1989-08-18 1992-06-18 Colgate-Palmolive Company, The Non-aqueous, nonionic heavy duty laundry detergent
AU635774B2 (en) * 1989-10-10 1993-04-01 Colgate-Palmolive Company, The Nonaqueous liquid automatic dishwasher detergent composition containing a dual bleach system
GB9025624D0 (en) * 1990-11-26 1991-01-09 S B Chemicals Limited Liquid built detergent concentrates
BR9206050A (pt) * 1991-05-24 1994-12-27 Ici Plc Composições de detergente

Also Published As

Publication number Publication date
CA2141452A1 (en) 1994-02-17
AU678378B2 (en) 1997-05-29
ZA935578B (en) 1994-03-14
GB9216454D0 (en) 1992-09-16
WO1994003580A1 (en) 1994-02-17
EP0652940A1 (en) 1995-05-17
JPH07509520A (ja) 1995-10-19
AU4720493A (en) 1994-03-03
DK0652940T3 (da) 1997-09-01
ATE150082T1 (de) 1997-03-15
DE69308856D1 (de) 1997-04-17
DE69308856T2 (de) 1997-07-10
ES2098767T3 (es) 1997-05-01
NZ254900A (en) 1997-02-24

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