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
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3947—Liquid compositions
• • 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
  • C11D3/12—Water-insoluble compounds
  • C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2
• • 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
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
  • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions

Definitions

• the present invention relates to an automatic dishwasher detergent composition having improved anti-filming and/or anti-spotting properties.
• the present invention is particularly directed to a stable nonaqueous liquid dishwasher detergent composition containing an anti-filming and/or anti-spotting agent for use in an automatic dishwasher to clean dishware, glassware and the like.
• the present invention more particularly relates to a nonaqueous liquid dishwashing detergent composition with improved anti-filming and anti-spotting properties and to a method of using the detergent composition to clean dishware, glassware, china and the like.
• the dishwashing composition contains an anti-filming agent, or an anti-filming agent and polyacrylic acid polymer or salt anti-spotting agent, inorganic builder salts, bleach compound and detergent.
• the detergent dishwashing composition of the present invention reduce filming and/or spotting on dishware, glassware, china and the like, particularly in hard water at low temperature.
• the invention relates to the use of a nonabrasive amount of small substantially water insoluble silica particles, as an anti-filming agent and polyacrylic acid or salt polymer as an anti-spotting agent in nonaqueous liquid dishwashing detergent compositions to reduce filming and/or spotting.
• the detergent compositions do not require an added rinse aid, are stable in storage and are readily dispersible in the wash bath.
• the present invention specifically relates to nonaqueous liquid automatic dishwashing detergent compositions having improved anti-filming properties, which are readily dispersible in the washing medium to provide effective cleaning of dishware, glassware, china and the like.
• the present invention also relates to an improved nonaqueous liquid composition and to a method of using the composition.
• the present invention is directed to a nonaqueous liquid automatic dishwasher detergent composition having improved anti-filming and/or anti-spotting properties for cleaning of dishware, glassware, china and the like.
• the detergent composition contains as an essential ingredient a nonabrasive amount of small substantially water insoluble silica, alumina or titanium dioxide particles as an anti-filming agent.
• the compositions can additionally contain a polyacrylic acid polymer or salt as an anti-spotting agent.
• a still further object of the invention is to provide a method of washing dishware, glassware, china and the like in an automatic washing machine using a nonaqueous liquid detergent composition by which method the dishware, glassware, china and the like are machine dried with reduced film and/or spots.
• a nonionic surfactant that can be used is available from Union Carbide Corporation under the trademark Tergitol MDS-42.
• This nonionic surfactant is a C12-C14 linear alcohol containing 55% by weight random distributed oxyalkyl groups of which 42% are ethoxy and 58% propoxy groups.
• a preferred nonionic surfactant that can be used in accordance with the present invention has the following formula R-O-(PO) x -(EO/PO)H
• R is an alkyl group having 8 carbon atoms
• PO is a propylene oxide polymer attached directly to the oxygen of the alkyl group
• x is 8 to 9
• EO/PO represents a copolymer of ethylene oxide and propylene oxide in which the ethylene oxide and propylene oxide are randomly mixed.
• the molar ratio of Eo/PO is about 2:1 to 5:1, e.g. about 3:1.
• the total number of EO and PO groups in the copolymer are such that the number of EO and PO groups are 5 to 8 and the cloud point of the nonionic surfactant is about 20 to 30°C.
• the anti-filming agent comprises a nonabrasive amount of small substantially water insoluble silica particles.
• anti-filming agents alumina and titanium dioxide particles.
• the anti-filming agent accordingly can be a member selected from the group consisting of silica, alumina and titanium dioxide and mixtures thereof.
• the silica, alumina and titanium dioxide can each be used alone or one or more of them can be used mixed together.
• the weight percent amounts mentioned above are the total for the anti-film agent ingredients used in the mixture.
• the amount of alkali metal silicate added and the amount of alkali metal TPP added can be used to obtain the desired alkalinity in the wash bath.
• the sodium carbonate can be added to act as a buffer to maintain the desired pH level in the wash bath.
• the sodium carbonate can be added in an amount of 0 to 25 wt.%, preferably 5 to 20 wt.% and typically about 5 to 15 wt.% of the detergent composition.
• compositions of the present invention can contain inorganic builder salts such as NaTPP or organic builder salts such as the alkali metal salts of polycarboxylic acids.
• a preferred solid builder salt is an alkali metal polyphosphate such as sodium tripolyphosphate (TPP).
• TPP sodium tripolyphosphate
• Suitable other builder salts are alkali metal borates, phosphates and bicarbonates.
• Such builder are sodium tetraborate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, sodium hexametaphosphate, sodium sesquicarbonate, sodium mono and diorthophosphate, potassium bicarbonate and sodium or potassium zeolites.
• the detergent builders e.g. NaTPP may be employed in the nonaqueous liquid ADD composition in a range of 20 to 60%, preferably about 20 to 55 wt.%, and more preferably about 20 to 45 wt.%.
• the NaTPP may be anhydrous or hydrated, including the stable hexahydrate with a degree of hydration of 6 corresponding to about 18% by weight of water or more.
• anhydrous NaTPP is preferred.
• the NaTPP may be replaced in whole or in part by organic builder salts. Since the compositions of this invention are generally highly concentrated, and, therefore, may be used at relatively low dosages, it is desirable to supplement any phosphate builder (such as sodium tripolyphosphate) with an auxiliary builder such as an alkali metal polycarboxylic acid.
• Suitable alkali metal polycarboxylic acids are alkali metal salts of citric and tartaric acid, e.g. monosodium and disodium citrate (anhydrous). The sodium salts of citric and tartaric acids are preferred.
• alkyl phosphonic acid esters of the formula available, for example, from BASF-Wyandotte (PCUK-PAE), and especially the alkyl acid phosphate esters of the formula available, for example, from Hooker (SAP) and Knapsack (LPKN-158), in which one or both R groups in each type of ester may represent independently a C12 ⁇ 20 alkyl group.
• SAP Hooker
• LNKN-158 Knapsack
• R groups in each type of ester may represent independently a C12 ⁇ 20 alkyl group.
• Mixtures of the two types or mixtures of mono- and di-esters of the same type may be employed.
• a mixture of mono- and di-C16 ⁇ 18 alkyl acid phosphate esters such as monostearyl/distearyl acid phosphates 1.2/1 (Knapsack).
• the peroxygen bleach compounds are preferrably used in the compositions of the present invention.
• the oxygen bleaches are well known and are represented by percompounds which liberate hydrogen peroxide in solution. Preferred examples include sodium and potassium perborates, percarbonates, and perphosphates, and potassium monopersulfate.
• the perborates, particularly sodium perborate monohydrate, are preferred.
• the peroxygen compounds can be used in an amount of 3 to 15, preferably 4 to 12 and more preferably 4 to 8% by weight.
• acetylsalicyclic acid derivatives include, for example, acetylsalicyclic acid derivatives, ethylidene benzoate acetate and its salts, ethylidene carboxylate acetate and its salts, alkyl and alkenyl succinic anhydride, tetraacetylglycouril (TAGU), and the derivatives of these.
• acetylsalicyclic acid derivatives ethylidene benzoate acetate and its salts
• ethylidene carboxylate acetate and its salts include alkyl and alkenyl succinic anhydride, tetraacetylglycouril (TAGU), and the derivatives of these.
• TAGU tetraacetylglycouril
• the conventionally used dishwasher detergent composition chlorine bleach compounds such as dichloro-isocyanurate, alkali metal, e.g. potassium and sodium, hypochlorite should not be used because they are unstable in the organic carrier liquids used in the compositions of the present invention. That is compounds that contain hypochlorite or that generate hypochlorite in the product liquid should not be used. Compounds that are stable in the product liquid, but that develop hypochlorite ion in the dishwasher water can however be used. For example, a combination of sodium chloride and Oxone (TM for potassium monopersulfate) which develop hypochlorite ion in the dishwasher water can be used.
• TM sodium chloride and Oxone
• the detergent active materials used in the present invention can be either the nonionic or anionic detergents.
• the nonionic detergents are, however, preferred.
• the composition may also include conventional organic or inorganic thickening agents in amounts sufficient to obtain a product consistency of a cream or a paste.
• the thickening agents i.e. thickeners or suspending agents which provide thickening properties
• the thickening agents may be organic or inorganic, water soluble or insoluble, dispersible or colloid-forming, and monomeric or polymeric, and should of course be stable in these compositions, e.g. stable to alkalinity.
• the preferred thickeners generally comprise the inorganic, colloid-forming clays of smectite and/or attapulgite types. These materials are generally used in amounts of about 1.5 to 10, preferably 2 to 5 wt.%, to confer the desired thickening properties to the formulation.
• Smectite clays include montmorillonite (bentonite), hectorite, attapulgite, smectite, saponite, and the like. Montmorillonite clays are preferred and are available under tradenames such as Thixogel (Registered Trademark) No. 1 and Gelwhite (Registered Trademark) GP, H, ect., from Georgia Kaolin Company; and ECCAGUM (Registered Trademark) GP, H, ect., from Luthern Clay Products.
• Attapulgite clays include the materials commercially available under the tradename Attagel (Registered Trademark), i.e.
• Attagel 40, Attagel 50 and Attagel 150 from Engelhard Minerals and Chemicals Corporation. Bentonite 27 and Betone 38 from NL Chemicals can also be used. Mixtures of smectite and attapulgite types in weight ratios of 4:1 to 1:5 are also useful. Thickening or suspending agents of the foregoing types are well known in the art, being described, for example, in USP 3,985,668, which is incorporated herein by reference thereto.
• an automatic dishwashing detergent concentrate composition is formulated using the below named ingredients.
• the nonaqueous liquid dishwasher detergent compositions of the present invention can contain conventional dishwashing detergent composition additives.
• the formulations can be prepared with commercially available detergent builders, peroxygen bleach compounds and bleach activators and surfactant compounds.
• the formulations can be prepared using the conventional blending and mixing procedures used for the preparation of liquid detergent compositions as briefly described below.
• compositions of the present invention can be prepared in two stages.
• silica, alumina or titanium dioxide anti-film agent, powdered silicate and low molecular weight polyacrylate powder (when used) are premilled using a ceramic ball mill.
• the premilled materials are then mixed using a standard rotary mixer. This mixed material is then transferred to an attritor and milled for 30 minutes at 500 rpm using 1/4 inch stealite grinding media.
• the organic carrier liquid and Neodol 25-6.5 are mixed, and the defoamer and phosphate builder salts are added.
• the premilled anti-film agent and polyacrylate are then added to the organic carrier liquid and nonionic surfactant mixture followed by the addition of sodium carbonate, oxygen bleach and bleach activator and the remaining ingredients. After mixing the liquids solids mixture is vigorously stirred to obtain a stable dispersion of the solids in the organic carrier liquid.
• One or more of the ingredients can be omitted or additional ingredients such as perfumes and anti-foam agents can be added to the composition.
• nonaqueous liquid compositions as used herein is intended to include compositions containing 0-8% water, typically 2-6% and more typically 1-2% water.
• the water can be present in the form of hydrated compounds, i.e. bound water, for example, sodium tripolyphosphate hexahydrate, hydrated sodium carbonate, hydrated sodium sulfate, sodium perborate monohydrate and/or in the form of moisture, i.e. unbound water. It is preferred, however, that the composition contain less than 1% moisture as unbound water.
• an aqueous liquid automatic dishwasher detergent composition was formulated using the below named ingredients in the amounts indicated and is compared with a prior art commercial powder detergent.
• the commercial powder gave more film than the invention nonaqueous liquid ADD composition. There was- no difference in the spot scores.
• nonaqueous liquid automatic dishwasher detergent compositions were formulated using the below named ingredients in the amounts indicated.
• Test I 100 ppm hardness, 120°F data show that the polyacrylate in the formulations B and C provides substantially improved spot performance as compared to the comparison formulation A without polyacrylate.
• the film performance for the formulations A, B and C were similar.
• Test II 300 ppm hardness, 120°F show that the addition of silica anti-film agent to invention formulation D, which also contains polyacrylate, improves the spot and film performance as compared to the formulation C which contains only the polyacrylate.
• a nonaqueous liquid automatic dishwashing detergent composition is formulated from the following ingredients in the amounts specified.
• the formulation is tested by washing glassware at 130°F in hard water (300 ppm hardness) in a Kenmore automatic dishwasher to clean glass tumblers using the procedure described in ASTMD 3566-79, except that only four cleaning cycles are used.
• the spotting and filming are evaluated as in Example 1.
• the clean tumblers are found to have reduced film as compared to commercial powder formulations not containing alumina anti-film agent.
• Example 3 is repeated with the difference that 2.00 wt.% titanium dioxide is substituted for the alumina anti-filming agent.
• the formulation is tested by washing glassware at 130°F in hard water (300 ppm hardness) as before. The clean tumblers are found to have reduced film as compared to commercial powder formulations not containing titanium dioxide anti-film agent.
• the nonaqueous liquid automatic dishwasher detergent compositions of the present invention provide improved film and/or improved spot properties on glassware and dishware.

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• 1991
  • 1991-05-03 AU AU76364/91A patent/AU637902B2/en not_active Ceased
  • 1991-05-03 NZ NZ238047A patent/NZ238047A/en unknown
  • 1991-05-06 NO NO91911762A patent/NO911762L/no unknown
  • 1991-05-06 CA CA002041902A patent/CA2041902A1/en not_active Abandoned
  • 1991-05-06 BR BR919101818A patent/BR9101818A/pt not_active Application Discontinuation
  • 1991-05-06 PT PT97573A patent/PT97573A/pt not_active Application Discontinuation
  • 1991-05-07 EP EP91304072A patent/EP0460810B1/de not_active Expired - Lifetime
  • 1991-05-07 AT AT91304072T patent/ATE103323T1/de not_active IP Right Cessation
  • 1991-05-07 PL PL29014791A patent/PL290147A1/xx unknown
  • 1991-05-07 DE DE69101467T patent/DE69101467T2/de not_active Expired - Fee Related
  • 1991-05-07 IE IE154491A patent/IE911544A1/en unknown
  • 1991-05-07 MX MX025698A patent/MX172418B/es unknown

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