PT97573A - Process for the preparation of a non-aqueous liquid detergent composition for an automatic washing machine comprising an organic liquid carrier and an anti-stain agent based on polyacrylate - Google Patents

Abstract

The application is directed to a nonaqueous liquid automatic dishwasher detergent composition with improved anti-filming and anti-spotting properties and to a method of using the detergent composition. The detergent composition comprises a nonaqueous organic carrier liquid, silica, alumina or titanium dioxide anti-filming agent, a water soluble polyacrylate anti-spotting agent, inorganic builder salts, bleach compound and detergent. The compositions provide reduced filming and spotting on dishware, glassware, china and the like, particularly in hard water. The nonaqueous liquid automatic dishwasher detergent compositions are stable in storage and are readily dispersible in water.

Description

REQUESTS ..... AFINS

This Order is related to Mo Series Orders »323.13S deposited on 13 March 1995 Series Ho» 323 = 126 filed March 1®, now US Patent 4,839 6535 Mo Series 323 = 134 filed May 13, 1989, filed March 13, 1989, all of which relate to aqueous automatic dishwashing detergent compositions containing an anti-foaming agent or an anti-foaming agent and anti- stains"

The present invention relates to a process for the preparation of a non-aqueous liquid detergent composition having improved anti-foaming and / or spotting properties. The present invention relates to a process for the preparation of a stable non-aqueous liquid detergent composition containing an anti-foaming agent and / or bleaching for use in an automatic dishwashing machine; destined to wash dishes5 glasses and the like.

More particularly, the present invention relates to a non-aqueous liquid dishwashing detergent composition with improved anti-foil and anti-stain properties, as well as to a method of washing dishes and articles of porcelain and the like with such detergent composition The dishwashing composition contains an anti-foaming agent or an anti-foaming agent and anti-staining agent of polyacrylic acid polymer, or. Inorganic builder salts3 Detergent bleaching compound

The dishwashing detergent composition of the present invention reduces the formation of smear film on dishes, cups, porcelain articles and the like, particularly in hard water at low temperatures.

More specifically, the invention relates to the use of a non-abrasive amount of substantially water-insoluble silica particles, such as an anti-foaming agent and polyacrylic acid polymer, or salt, as antiperspirant, in detergent compositions liquid detergent for washing dishes, to reduce the formation of film and / or

The detergent compositions do not require the aid of a supplemental rinse with water, are stable in storage and are readily dispersible in the wash bath. The present invention relates specifically to non-aqueous automatic dishwashing detergent compositions having improved anti- which are readily dispersible in the washing medium, providing effective cleaning of dishes, cups, porcelain articles, etc.

The present invention also relates to a better non-aqueous liquid composition and to a method of using this composition.

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to a non-aqueous automatic dishwashing detergent composition having improved anti-foaming properties and /

staining, dish washing, cups, porcelain articles and the like * The detergent composition contains as essential ingredient one. non-abrasive amount of particulates substantially insoluble in water of silica, alumina or titanium dioxide as anti-foaming agent. The compositions may additionally contain a polyacrylic acid polymer, or salt, as a stain-forming agent. The present invention relates specifically to non-aqueous liquid detergent compositions for automatic dishwashing, having improved anti-film and / or anti-stain properties for cleaning dishes, glasses, porcelain articles, etc.

The non-aqueous liquid compositions are stable in storage, do not settle, are easily pourable and readily disperse in water.

«05 ....... TéÇNJCA. DA ... ESP-ECIAt.IDftDE

Household dishwashing detergents on the market in the form of foot or liquid have many disadvantages. Commercially available powdered detergents have the following disadvantages; non-uniform composition, costly operations required for its manufacture, tendency to agglutinate in storage at high humidity, resulting in the formation of difficult-to-disperse clumps? dusting, a source of particular irritation for users who suffer from allergies and tendency to swell in the distributor of the machine.

In addition, commercially available powdered detergents often require a separate step of manually wiping cloths and dishes, cups, porcelain articles and the like to prevent the deposition of residues or film. The use of liquid detergent compositions has other problems . The structuring salts settle in store and are not easily redispersed. The compositions also become increasingly thick in the store and are not easily poured.

For effective use, it is recommended that dishwashing detergent, hereinafter also referred to as DL.A. sodium tripolyphosphate (NsTPF) to soften or bind hard water minerals and to emulsify and / or peptize dirt. (2) sodium silicate to provide the alkalinity required for effective detergency and to provide dish protection, namely fine porcelain articles and corrosion protection of the machine, < 3 > sodium carbonate, generally regarded as being optional, to increase alkalinity? C4) a chlorine releasing agent to aid in cleaning C5 > a surfactant? and (6) a foam suppressant to enhance the efficiency of the machine. See, for example, " SDA Detergent in Depth ", E.OlmLations_AgeBCIg ___ of ........... BafiMP.fi ___ QMMMM? Thomas Oberle (1974). The cleaning products which approach the compositions described above are mostly liquids or blades. Generally such compositions omit hypochlorite bleaching agent as it tends to react with other chemically active ingredients, in particular surfactant, thereby impairing their effectiveness. U.S. Patent 3,985,668 describes cleaning products abrasive degreasers of gel-like consistency containing? (1.) suspending agent, preferably esmeetite-like clays and attapulgite? abrasive, e.g. e.g., silica sand or perlite? and 3 > filler consisting of standing polymers; low density, expanded perlite and the like. The perlite has a floating power and therefore a stabilizing effect on the composition, besides serving as a

dilating agent, thereby replacing water otherwise available for formation of an undesirable supernatant layer due to the absence of waterproofing and phase stabilization. The foregoing are the essential ingredients. bleaching based on hypoclarite; surfactant in the presence of the bleaching agent and buffer solution, e.g. The naphthalenesulfonates may be included as other optional ingredients to provide or complete the structuring function not provided by the buffer solution, not exceeding the amount of such a structured - 5% of the total composition, according to the patent. Maintenance of the desired pH levels equal to or greater than 10 is achieved by the drain / buffer solution components. A high pH is taken as minimizing the decomposition of the bleaching agent è. chlorine-based and undesirable reaction between the surfactant and the bleaching agent. When present, NaTPF is limited to an amount of 5% as stated. No disclosure is made as to a foaming suppressor. U.S. Patent 4,511,487 issued April 1, 1985 discloses a low foaming detergent paste for dishwashing machines. The composition is based on a mixture of timidly divided sodium metasilicate hydrate, a active chlorine compound and a thickening agent which is a hectorite type silica. A minor amount of nonionic surfactants and alkali metal hydrides and / or carbonates may be used. Laitem et al., U.S. Patent 4, 753, 748 discloses a non-aqueous liquid detergent composition for washing automatic dishwashing agent consisting of a liquid nonionic surfactant contains a stable or easily redispersible suspension of a

The polyphosphate disintegrant and / or citrate salt is an alkylene glycol monoalkyl ether sn-gel agent. Scott's U.S. Patent 4,438 discloses a powder formulation containing a novel nonionic surfactant for detergent compositions for the automatic dishwasher. The nonionic surfactant consists of an alkyl group to which is directly attached a propylene oxide polymer, to which a disordered copolymer of ethylene oxide of propylene oxide is once attached. The nonionic surfactants are described as providing an optimum cleaning performance and good results in the formation of film spots as well as a good suds suppressing power »mmiNssojRE .....

The non-aqueous liquid detergent compositions of the present invention overcome many of the problems of the prior art in combination with liquid and powder detergents. Due to the addition of a small but effective amount of an anti-foaming agent of silica, alumina or titanium or anti-stain agent and palmitic acid polymer, or salt, to the composition, it is not necessary to resort to an additional coating with water, it is also not necessary to pass with a cloth or to dry to obtain dishes, cups, bowls and other utensils clean bright s

Non-aqueous liquid dishwashing liquid detergent compositions of the present invention have the advantages of being stable, non-sedimenting or gelled in the store, and readily soluble in the dishwashing machine. The liquid compositions of the present invention are readily

easy to measure and easy to dishwasher *

Furthermore, since the dishwashing machines as constructed are commercially available having a compartment where the detergent is placed, the concentrated nature of the concentrated liquid detergent composition of the present invention allows the dishwasher to be placed with more liquid detergent acfcivoj p »s >; * Polyunsaturated polyphosphate and other builders for detergents *

The non-aqueous liquid detergent compositions of the present invention, with the composition of the anti-foaming agent, are readily soluble in the washing water of the dishwashing machine.

It is an object of the present invention to provide a non-aqueous automatic dishwashing liquid detergent composition having improved anti-foaming and / or anti-forming properties It is another object of the invention to provide a non-aqueous liquid detergent composition which is stable in storage, does not degrade or decompose, is easily pourable, is readily dispersible and readily soluble in water. Another object of the invention is to provide a washing machine for dishwashing articles, glassware, fine porcelain and in an automatic dishwashing machine, the like method using a washing machine.

a non-aqueous liquid detergent composition without the addition of unnecessary addition of rinsing with additional water, it is a further object of the invention to provide a method for washing dirty articles of porcelain, fine glass and the like in an automatic dishwashing machine using a non-aqueous liquid detergent composition by which dishes, cups, porcelain articles and the like are machine dried, having reduced film formation and / or staining. it is still another object of the invention to provide a better non-aqueous liquid detergent composition, in particular an automatic dishwashing detergent composition, wherein a small but effective amount of the anti-foaming agent is incorporated into the composition silica base or anti-film and anti-stain agents of silica and polymer or polyacrylic acid salt.

These and other objects of the invention which will become more readily apparent from the following specification and preferred embodiments are achieved by incorporating in a non-aqueous liquid detergent composition a small but effective amount of an anti- film-forming based on silica, alumina or titanium dioxide; anti-foaming agent, and polyacrylic acid polymer anti-stain agent, or salt. More particularly, in a preferred and specific embodiment of the invention, there is provided a non-aqueous detergent composition for automated washing machine , wherein about 1% of a silica-based film anti-foaming agent, or anti-foaming agent and about 30% of a soluble anti-foaming polymer or salt of polyacrylic acid in water the film-forming agent based on silica has particles having dimensions of about 0.1 to 1 microns, the polyacrylic acid polymer. or water-soluble salts have a molecular weight of about 1000 to 1 ΘΘ ΘΘ,,

In accordance with the present invention. there is provided a non-aqueous automatic dishwashing liquid detergent composition comprising on a weight basis (a) 20 to 6% organic liquid carrier;

Cb) 2β to 10% organic or inorganic structural salt; (c) 5 to 30% sodium silicate? < d) 3 to 15% bleaching compound è. base of minerals

Ce) at 8% bleach activator? <f), 5 to 1% of silica-based film anti-foaming agent (g) to 30% polyacrylic acid polymer, or salt%

Ch) to 25% of alkali metal carbonate?

Ci) 0.1 to 12% of water dispersible organic detergent active material? The present invention also provides a method for washing dishes, glassware and porcelain and the like in an automatic dishwashing machine with an aqueous washing bath containing an effective amount of the composition Non-aqueous liquid detergent for automatic dishwasher CDLAL) previously described. According to this aspect of the invention, the composition

DLAL is stable in storage, it is easy to measure and pads to be easily poured into the automatic dishwasher. The invention will now be described in more detail through its specific embodiments.

According to the present invention, a better automatic dishwashing detergent composition is prepared by incorporating small amounts of a silica-based anti-foaming agent or silica anti-film agent and salt or acid polymer polyacrylic acid in a dishwashing composition. The present invention is based on the discovery that substantially better film and / or antifilling properties of stains can be obtained by adding to the non-aqueous liquid detergent composition a small but effective amount of a silica-based film anti-foaming agent or silica anti-film agent and anti-foaming agent of polyacrylic acid polymer, or salt

According to an embodiment of the present invention, a non-aqueous liquid detergent composition for automatic dishwashing is prepared by dispersing a polyphosphate builder in an organic liquid carrier. The polyphosphate builder may be substituted totally or partially by an organic designer »

In addition, other ingredients, such as antifouling agents, antifoam agents, optical brighteners, enzymes and perfume, may be added to the composition.

Carriers 1 Liquid Organics

The organic liquid carriers which may be used according to the present invention are liquids, diluents and solvents which are compatible with the ingredients of the composition. Suitable organic liquid carriers are only polyethylene glycol-PM 30®, PM 400 and PM 4β- , propylene glycol, propylene carbonate, polypropylene glycol-MW 200 and PM 3.00 meta-meta-propylene glycol, Carbowax MPEB 350, polyethylene glycol methyl ether of Union CarbideP triethanolamine, &quot; Butyl Carbitol &quot; ", By Dupont Co," Blyme18 (ethylene glycol dimethyl ether), '.

The compounds of formula (I) may also be prepared by reacting a compound of formula (I) with a compound of formula (I). . ere s inonoa 1 "QUÍ l Ci Ci s al al al al al al gl gl gl gl gl. _ C Dffí p ost rtc. ani &gt; 1 i. CGS of bei K O O s m al cular, in ρ artic - 5 Ί U ã. Ã Ã Uns Uns Uns Uns Uns Uns Uns Uns Uns Uns Uns Uns Uns Uns Uns Uns 13. 13. 13. 13. 13. 13. 13. 13. 13. 13. 13. 13. 13. 13. 13. 13. 13. 13. 13. 13. 13. 13. 13. 13. 13. 13. 13. 13. 13. 13. 13. 13. 13. 13. 13. 13. 13. (a) and (b) of the compounds of formula (I). ethylene glycol, ethylene glycol, and the like. Z ether. Xylene glycol C 1 H 2 O (CH 2) 2 -CH

CO CJS d x p rο ρ x 1 eno g 1 x c o 1 wH- ,. -CH (CHO)

I ru

The foregoing organic liquid carriers may be used alone or. in the mixture, so as to obtain a desired viscosity and stability of the liquid product 'remain stable and

The compositions of the present invention have good viscosity and stability characteristics at low temperatures.

Detergents Surfactants ... nlo ... Ionic. X. £ guMps

Liquid nonionic surfactant detergents which may be used in the practice of the present invention are preferably polyalkoxy lower lipophilic sides of reduced foam formation,

Useful nonionics are represented by the low foaming &quot; Piursíac &quot; series of the BASF Chemical Company which are the reaction product of a higher linear alcohol and a mixture of ethylene and propylene oxides containing a mixed oxide of ethylene and propylene oxide, terminated by a hydroxyl group. Examples include a fatty alcohol condensed with 6 mol of ethylene oxide and 3 mol of propylene oxide, a fatty alcohol condensed with 7 mol of propylene oxide and 4 mol of ethylene oxide, Fat condensed with 5 mol of propylene oxide and 10 mol of ethylene oxide,

Other useful surfactants are "Nsodal 25-7" and "Meado! Which are products made by Shell Chemical Company, Inc. The first is a condensation product of a mixture of higher fatty alcohols having on average about 12 to 15 carbon atoms with about 7 mol of ethylene oxide are according to a corresponding mixture in which the carbon content of the higher fatty alcohol is 12 to 13, the number of ethylene oxide groups present is, on average, 6.5 g higher alcohols are primary alkanols. Other examples of such detergents include &quot; Tergitol 15-S-7 &quot; and "Tergitol 15-S-9" (trade marks), which are both secondary linear alcohol ethoxylates made by Union Carbide Corp. G is a mixed secondary linear alkanol ethoxylate of 11 to 15 carbon atoms with

seven milligrams of stilish oxide and the second is a similar product but the reaction is carried out with nine moles of ethylene oxide

A nonionic surfactant which may be used is sold by Union Carbide Corporation under the trademark "Tergitoi MDS-42". This nonionic surfactant is a linear C álcool álcool alcohol containing 55% by weight of randomly distributed oxyalkyl groups, of which 42% are ethoxy groups and 5% are propoxyl groups. &gt;

A preferred nonionic surfactant which may be used according to the present invention will have the following formula

R-O-COP), - C OE / OP &gt; H is an alkyl group having 8 carbon atoms, OP is a polymer of propylene oxide directly bonded to the oxygen of the alkyl group, x is 8 to 8, EO / OP represents a copolymer of ethylene oxide and propylene oxide, but the ethylene oxide and propylene oxide are randomly mixed. The OE / OP molar ratio is from about 2: 1 to 5: 1, for example about 3: 1 → 0

total number of OE and OP groups in the copolymer is such that the number of OE and OP groups is 5a If the cloud point of the nonionic surfactant is about 2Â ° to 3Â ° C

One method for the manufacture of the nonionic surfactant is a complete description of the nonionic surfactant disclosed in U.S. Patent 4,438,834 to Scoti, which is incorporated herein by reference in its entirety.

Other useful nonionic surfactants are the S-Poly-Tergent S-LF surfactants available from the Company. These surfactants are linear, biodegradable fatty alcohols of

* The " names with foam &gt; poly-Tergent S-LF 18% &quot; Polysiloxane &quot; and &quot; Polysulfone &quot;. CS &quot;

Tergetst

Mixtures of two or more of the liquid nonionic surfactants may be used, in some instances, the use of such mixtures may be advantageous.

In addition to the aforementioned nonionic surfactants, anionic surfactants may also be used.

The anionic surfactants that may be used are mono and / or di- &lt; 1 &gt; CRP &lt; / RTI &gt; linear or branched-diphenyl-oxide mono and / or alkali metal disulfonates. for example, &quot; DQWFAX &quot; (Req. Tag) I! 3E-2H and DQWFAX 2A-1 &quot;,

Other suitable surfactants include the preferred alkylsulfonates: 1-methyl-1-methyl-1-pyrrolidin-1-one,

Examples of such compounds include the compounds of formula (I) or the pharmaceutically acceptable acid addition salts thereof. Examples include 1-hydroxy-1-naphthyl ester, (1), (1) and (2) and (b) thereof. The compounds of formula (I) are prepared as described above. · 3. f '12 -18: orres ρon d in t is non-sw. sodium ionates. Potassium potassium salts *

Their prior art are well known in the art and are described, for example, in U.S. Pat. 1 Ξ Ξ Ξ Ξ j j j j j j j j j j j j j 4 4 4 4 4 4 4 4. which are incorporated herein by reference.

The anionic and anionic surfactants are used in amounts of from 1% to 12% S, preferably 0.5 to 16.0%, and more preferably about 1% to 2%. to 3%, for example 2 to 7% (film). The film-forming anti-foaming agent consists of a non-abrasive amount of small silica particles substantially insoluble in water. The film anti-foaming agent may accordingly be a member selected from the group consisting of silica, alumina and titanium dioxide and mixtures thereof. ;

The materials that may be used for the silica-based anti-foaming agent are fumed or precipitated natural or synthetic silica. The silica may be amorphous or crystalline. The silica material used may contain up to about 6.1 to 5% alumina, usually up to about 5% to 3% and more usual

about 1% alumina, based on the weight of silica.

A preferred 244% silica material which is amorphous silica has a particle size of 4 microns and is supplied by W.R. Srace Ca. Another suitable silica material is &quot; SíIok 15 &quot;, also of ul.R. Grace Co =, which has a particle size of about 4 miarons.

Another preferred silica material is Huber Zeo 49 &quot; which is amorphous silica and is supplied by J. Huber Corporation and contains about 1% alumina.

The particle size of the silica material is an important parameter for obtaining the desired film forming properties.

The silica particles that are used are finely divided and may have a dimension of θ â? ¤ 10 to 1 microns, preferably 0.5 to 8 microns, and more preferably about 16 to 59 microns. amount used herein are not abrasive. &gt;

The finely divided particles of the silica material in the dishwashing bath will coagulate the particulate proteinaceous soils and suspend them to prevent them from depositing in the washed cups or dishes, forming a film. The suitable materials are sold under the tradenames &quot; Alumina Oxide C &quot; and &quot; Alumina Oxide &quot; and &quot; Alumina Oxide C &quot; by Degussa Company, and &quot; Catapal D &quot; by Vista Corp. Preferred alumina materials are fumed alumina and precipitated alumina. The titanium dioxide material which can be used as an anti-foaming agent is water insoluble and has the formula TiOâ, ". Suitable materials are sold under the trade names Titanium Dioxide P25 by Degussa Preferred tifanium dioxide materials are fumed titanium dioxide and precipitated titanium dioxide. The particle size of the alumina material is titanium dioxide is an important factor for obtaining the desired anti-film forming properties.

The alumina or titanium dioxide particles which are used are finely divided and may have a dimension of Θ, ΘΙ to 10 microns, preferably Θ to ΘΙ B microns, and most preferably about Θ .020 to 4.0 microns For example, a suitable particle size is about 5 to 10 microns. The alumina and titanium dioxide particles of this size and in the amount used herein are non-abrasive, finely divided particles of the alumina material or titanium dioxide in the dishwashing bath have a coagulant action of the particulate proteinaceous soils and keep them in. suspension to prevent deposits of washed dishes in the dishes »

Without wishing to limit the invention in any way, there is the theory that the anti-foaming agents based on alumina and titanium dioxide operate in the following ways The surface of the glassy articles contains negative charge points through Si- the oxygen atoms carry these loams "it is assumed that these negatively charged ions attract positively charged particles, thereby forming a layer of" artificial soiling "This protective mono-layer will then repel normal food soiling and increase the anti-property -deposition of automatic dishwashing detergent. "The alumina particles and titanium dioxide-Kido, respectively, will generate positively charged particles that will attach to the surface of the glassware, forming a layer of artificial dirt that will prevent the formation of film »

The amount of film-forming agent based on silica, alumina or titanium dioxide which will be used to achieve the desired improvement in film formation will depend on the hardness of the water, detergent active compound, inorganic salts and other ingredients DLA * Anti-foaming agents based on silica, alumina or titanium dioxide are particularly effective in hard water of, for example, 30% hardness or more. s &gt; ) The amount of each film-based anti-drug agent based on silica, alumina or titanium dioxide which is used may be about 0.5% to 1%, preferably about 1 to 8%, and most preferably about 1% , 5 to 6% by weight, based on the weight of the total composition. Silica, alumina and titanium dioxide may be used alone or one or more of them may be used in admixture. When anti-foaming agents are used The percentages by weight mentioned above represent the total ingredients of the anti-pellicle agent used in the mixture, &gt;

MlSJgMmCgD. SE ..... SPOTS

EsIijjSfm-already ^ acycloPlac and its Salts

Anti-film forming agents based on polyacrylic acid polymers and salts thereof which may be used are generally commercially available and are briefly described below.

Polyacrylic acid polymers and salts thereof which may be used comprise water-soluble low molecular weight polymers having the formula

wherein R1, R2, R3, may be the same or different and may be hydrogen, C1 -C4 lower alkyl, or combinations thereof. The value of n is 5 to 1, preferably. 1 to 5% and more preferably 20 to 10%. M represents hydrogen, or an alkali metal, namely sodium or potassium. The preferred substituent for Li is sodium.

Preferred R.sup.- and .sup.-FU groups are hydrogen, methyl, ethyl, propyl, the preferred acrylic acid monomer is one in which R1, are hydrogen, e.g. Acrylic acid, or wherein R1 and R2 are hydrazine and FU is methyl, e.g. and monomer of e. &Quot; methyl acrylic acid, the degree of polymerisation, i.e., the value of n, is determined by the limit compatible with the solubility of the polymer in the water. The end or end groups of the polymer are non-critical and may be H, OH, CH 3, or a low molecular weight hydrocarbon.

Polyacrylic acid polymers and their salts may have a molecular weight of from 5 to 1.0% to 100% by weight, preferably from 1.5% to 10% by weight.

Specific polyacrylic acid polymers which may be used include the acrylic acid polymers &quot; Fritsol LMU &quot; of Rohm and Haas, namely &quot; Acrysol LMUJ-45-M &quot;, a neutralized sodium salt having a molecular weight of about of 4.50% and &quot; Acrysol LMW-2 &quot;, a neutralizing sodium salt, having a weight

molecular weight ratio of about 2% = 0% Other polymers of polyacrylic acid or salts thereof which can be used are &quot; Alcosperse 149 &quot;, molecular weight 2,000,000. Alcosperse 124 ", molecular weight 200" and "Alcosperse" 0.02M% molecular weight 450 ", all of which are commercially available from Alco Chemical Corp. The polymers of low molecular weight acrylic acid may, for example, have a molecular weight of about 1.0 to 1%. Another polyacrylic acid polymer which may be used as &quot; Alcosperse 110 &quot; (from AIco), which is a sodium salt of an organic polycarboxylate and which has a molecular weight of about Ο Ο ΚΘΘ * *

The above polyacrylic acid polymers and salts thereof may be made by methods known in the art (see, for example, U.S. Pat. No. 4,193 = 858). The amount of polyacrylic acid polymer, or salt, which may be used to achieve the desired improvement in the antimicrobial properties of the antimicrobials will depend on the hardness of the water, detergent active compound, inorganic salts and other ingredients DLA = the anti-staining agent of polyacrylic acid or its salts 1 is particularly effective in reducing spotting in hard water, for example hardness of 3.0 ppm or more.

Generally, the amounts of the polyacrylic acid polymer anti-stain agent, or salt, which may be used range from about 1% to> to 30%, preferably from about 2.0 to 25%, most preferably about 4 to 20%

STRUCTURE-ORES SAFETY Is the efficacy of DLA qerally associated with (a) levels of oxygen bleaching agent? (ta) alkalinity? It is preferred here that the pH of the aqueous washing bath, after addition of the liquid DLA composition, is at least about 9.5, more preferably about 16.5 to 13.5 and most preferably all of at least about 11.5 The amount of alkali metal silicate added to the amount of added alkali metal TPF may be used to provide the desired alkalinity in the The sodium carbonate may be added to act as a buffer solution to maintain the desired pH level in the wash bath. Sodium carbonate may be added in an amount of 6 to 25% by weight, preferably 5 to 10% by weight. 26% by weight, and typically about 5 to 15% by weight of the detergent composition.

The compositions of the present invention may contain inorganic crosslinking salts such as NaTPF or organic builder salts, such as alkali metal salts of polycarboxylic acids

A preferred solid builder salt is an alkali metal polyphosphate, such as sodium tripolyphosphate (TPF). Instead of all or part of the alkali metal polyphosphate, one or more other builder salts for detergents may be used. Other suitable builder salts are borates, phosphates and bicarbonates of alkali metals. Specific examples of such builders are sodium tetraborate, sodium pyrophosphate, potassium pyrophosphate.

sodium bicarbonate, sodium hexastaphosphate, sodium sesquicarbonate, sodium mono-diortophosphate, potassium bicarbonate and sodium and potassium zeolites,

Detergent builders, for example, NaTPF may be used in the non-aqueous liquid DLA composition in the range of 20 to 66%, preferably about 20 to 55% by weight, and most preferably about 2% to 45%, in NaTPF may be anhydrous or hydrated, the stable hexahydrate having a degree of hydration of β corresponding to about 18% by weight of water or more. However, anhydrous NaTPF is preferred. be fully or partially replaced by organic struffing salts. Since the compositions of this invention are very concentrated and therefore can be used in relatively small dosages, it is desirable to supplement any phosphate based cleaner with sodium tripolyphosphate) with an auxiliary dehydrator such as alkali metal polycarboxylic acid. Preferred alkali metal polycarboxylic acids are alkali metal salts of citric and tartaric acid, eg Preferred are the sodium salts of citric acid and tartaric acid.

Foam inhibitors Foam inhibition is important to increase the effectiveness of the dishwashing machine and to minimize the destabilizing effects that could occur due to the presence of an excess of foam inside the machine during operation. The foam may be sufficiently reduced by appropriate sorting of the type and / or quantity of detergent working material, the principal

companion foam generator. 0 degree. of foam is also somewhat dependent on the hardness of the water. in the machine, a suitable adjustment of the proportions of MaTPF, which has a softening effect on the water, can contribute to achieving the desired degree of foam inhibition. However * it is generally preferred to include a foam suppressor or inhibitor Particularly effective are the phosphonic acid alkyl esters of formula

0 H

HO-P- R

for example, BASF-Wyandotte (PCUK-PAE), and in particular the acid phosphate alkyl esters of the formula 0

H

HO-P-DR L, sold, for example, by Hooker (SAP) s Knapsack CLPKIm-158) in which one or both R groups in each type of ester may independently represent an alkyl group Mixtures of two types or mixtures of monosodiates of the same type, a mixture of acid phosphate mono- and di-esters, especially monostearyl / distearyl acid phosphates 1.2 / 1 ("Knapsack &quot; ) When the foam suppressant is used in the composition, proportions of from 1 to 6% by weight, preferably from 5% to 5% by weight, especially from 0.5 to 4.5% by weight, by weight, the weight ratio of detergent detergent active ingredient in the range of about 1 to 1% and preferably about 4 to 1% by weight.

for example, the known silicones, namely &quot; Doh Corning 406: 5%, which are polysiloxanes mixed with dispersed silica.

Whitening Agents

The peroxygen bleaching compounds are preferably used in the compositions of the present invention. Oxygen-based bleaching agents are well known and are represented by percompounds which release hydrogen peroxide in solution. Preferred examples include sodium and potassium perborates, percarhonates and perphosphates, and potassium monopersulfate. Preferred are the perborates, in particular the monohydrate of sodium perborate. Peroxygen compounds may be used in an amount of 3 to 15%, preferably 4 to 12 and more preferably 4 to 8% by weight. The peroxygen compound is preferably used in admixture with an activator for such purposes. Suitable activators are used which can reduce the effective operating temperature of the bleaching agent based on oxygen. &gt;

Preferred modifiers are polyacylated compounds among these. Compounds such as tetraacetyl-ethylenediamine (tetra) and pentaacetyl glucose are particularly preferred. Bleach activators may be useful in an amount of from 8 to 8, preferably from 8 to 8, more preferably from 2 to 6%. by weight, for example 2 to 4% by weight.

The bleach activators react with the peroxygen compounds to form a peroxyacid bleaching agent in the wash water.

Other useful actives include, for example, acetylsalicylic acid derivatives, ethylidene benzoyl acetate and its salts, ethylidene carboxylate acetate and salts thereof, alkyl anhydride and dialkyl succinic anhydride, tetraacetyl glycoryl derivatives thereof.

The chlorine bleaching compounds conventionally used in the automatic dishwashing detergent composition, such as dichloroisocyanurate, alkali metal hypochlorite, potassium, sodium, and potassium should not be used because they are unstable in vehicles organic liquids used in the compositions of the present invention. That is, compounds containing hypochlorite or hypochlorite in the liquid of the product should not be used. However, compounds which are stable in the liquid of the product but which do not develop hypochlorite ion in water of the washing machine. For example, a combination of sodium chloride and &quot; Οκοπε8 CMR for potassium monopersulfate), which develop hypochlorite ion in dishwashing water may be used.

Sodium Silicate

Sodium silicate, which provides alkalinity and protection to hard surfaces, in particular fine porcelain, is used in an amount ranging from about 5 to 382 by weight, preferably 7 to 26% by weight, and more preferably about 8 to 24% by weight in the composition. For example, the composition may contain 8 to 15% sodium silicate. The sodium silicate also protects the machine against corrosion. The sodium silicate may have

a ratio of 1.6 to 1% sodium silicate may be added as a dry powder or as a non-aqueous dispersion, preferably having a ratio of Na ^ OsSiO--? ae 1/1

The preferred alkali metal silicates are sodium disilicate and anhydrous sodium stannilicate. The preferred alkali metal silicates are sodium disilicate and anhydrous sodium silicate. Most of the other components of the composition, for example? can be added in the form of sscds blades or non-aqueous solutions or dispersions.

The detergent active materials used in the present invention may be nonionic or anionic detergents. Nonionic detergents, however, are preferred.

In such compositions there may be included various conventional ingredients in small amounts, generally less than about 4% by weight, eg 0.5 to 4%, such as perfume, hydrotropic agents such as benzene, toluene, xylene and quinine sodium sulphonates, preservatives, dyes and pigments to the like. Particularly preferred as dyes are the chlorinated phthalocyanates and aluminosilicate polysulfides which provide, respectively, pleasant shades of green and blue

The non-aqueous liquid DLA compositions of this invention are readily utilized in known manner to wash dishes, cups, cups and other utensils in an aqueous washing bath in an automatic dishwashing machine containing an effective amount of the composition. conventional organic and inorganic thickeners, in sufficient quantities to obtain a product having a creamy or pasty consistency '

Thickening agents, i.e. suspending agents and thickeners which provide thickening properties, are known in the art and may be organic or inorganic, soluble or water-insoluble, dispersible or otherwise forming, monomeric or polymeric, and should obviously be stable in such compositions, for example stable. Preferred thickeners generally consist of the inorganic, epoxy forming clays of the smectite and / or alkaline types. These materials are generally used in amounts of about 1.5 to 1, preferably 2 to 5, %, by weight, to give the. the desired thickening properties

Asthmatic clays include montmorillonite (bentoniite), hectorite, attapulite, smectite, saponite-like. Montmorillonite clays are preferred and are marketed under trade names as &quot; Thixogel &quot; (Registered Trade Mark) No.1 and "SelNhite55 (Trade Mark) SP, H, etc." by Beorgia Kaolin Company? and &quot; ECCABUM &quot; (Trademark) SP, H, etc., by Luthern Clay Products. Atapulgite clays include materials marketed under the names "Atfcagel" (Trade Mark), namely "ftttagel 4" &quot; , "Attagel 15", &quot; Attagel 15 &quot; by Engelhard Minerals and Chemicals Corporation Bentone 27SI's &quot; Bentone 38 &quot; of NL Chemicals may also be used. Blends of the smectite and atapulgifc types, in weight ratio of 4-1-1% are also useful. Suspension and suspending agents of the foregoing types are well known in the art, and are described, for example, in U.S. Patent 3,985,668, which is hereby incorporated by reference.

The non-aqueous liquid DLA compositions of this invention are readily utilized, in known manner, to wash dishes, cups, bowls and other cooking utensils and the like in a

dishwasher equipped with a suitable detergent dispenser in an aqueous wash bath containing an effective amount of the composition.

In a preferred form of the invention, a concentrated detergent composition for automatic dishwashing is formulated using the following ingredients. &gt;

Component

by weight preferred weight 20-60 3Φ-43 20 "'60 2Θ-45 0-255-15. 1-12 3-8 5-3Θ 1Θ-24 1-10 1.5-6 1-30 4-2Θ 4-12 4-8 1-8 2-6 Θ, 4 to 3, 0,1 0.1 to &amp; , 50 to 3 Θ 0.1 to 0.5

Organic Liquid Carrier Sodium Tripolyphosphate Sodium Carbonate Detergent Surfactant Sodium Silicate Film Finish Agent Sodium Polyacrylate Oxygen-based Bleaching Agent Bleach Activator Coating Agent Moisture Non-aqueous liquid detergent compositions for the dishwasher The present invention may contain the present preferred conventional additives. The formulations may be prepared with builders for detergents, bleach-based bleach compounds and bleach activators and commercially available surfactant compounds.

The formulations may be prepared by following the standard homogenization and blending procedures used for the preparation of liquid detergent compositions. as hereinafter described in the following Examples. Method ......... to ......, a,

The compositions of the present invention may be prepared in two steps. the anti-silica agent? alumina or titanium dioxide? pulverized silicate and low molecular weight polyacrylate powder (when used) are previously milled in a ceramic ball mill. The pre-milled materials are then mixed in a standard rotary mixer. This mixed material is then transferred to a friction device and ground for 3 minutes at 5ΘΘ rpm? using a 0-63 cm-thick steaite crusher membrane. / 4 p or 1 eg a d).

In a second phase? the organic liquid carrier is mixed with Nsodol 25-6 55 (nonionic surfactant) and the foam suppressant and the phosphate base structure salts are added. The anti-film agent and the polyacrylate (when used) are milled then added to the carrier liquid mixture and non-ionic surfactant? followed by the addition of sodium carbonate? bleaching activator and the remaining ingredients. After mixing the solids and liquids the mixture is vigorously stirred to provide a stable dispersion of the solids in the organic liquid carrier.

You can omit one or both. most of the ingredients either. other ingredients such as perfumes and antifoaming agents may be added. The term &quot; non-aqueous liquid compositions &quot; as used herein, is intended to encompass compositions containing 8% water, typically 2 to 6% and more typically 1 to 2% water. Water may be present in. For example, sodium tripolyphosphate hexahydrate, sodium carbonate hydrate, sodium sulfate hydrate, sodium perborate monohydrate and / or in the form of moisture, i.e. However, it is preferred that the composition contains less than 1% moisture in the form of unbound water.

All the amounts and proportions referred to herein are percent by weight of the composition, unless otherwise indicated. The invention may be practiced in a number of ways and some specific embodiments will be described to illustrate the invention with reference to the examples which accompany them "&gt;

Esemolus

According to the present invention, an automatic liquid dishwashing liquid detergent composition was formulated using the following ingredients in the above amounts and compared with a commercial detergent powder from the previous special technique «AI Liquid Commercial Powder from ATE Ingredient Jnventp iPartes) Powders &lt; Parts) Organic Liquid Carrier 39.1 - Sodium Tripolyphosphate 22.8 35.3 Sodium Carbonate 9.5 26.0 Sodium Sulfate - 18.0 Surfactant Non- 2.8 3.5 Sodium Bilicate &lt; is2.4) 7.6 10.0 Silica Anti-Silicate Agent 4.8 - Sodium Perborate H4 Hydrate 4.8 4.8 ' 2.4 2.4. /) Sodium polyacrylate &quot; or, 2 - Moisture <1 13.0 99.5 101.6

Cl) &quot; Tergitai MDS-42 &quot;, from Union Carbide Corporation. (2) Tetra-acetyl-ethylene diamine (CTAED). of Alco Chemicals (3) &quot; A solution of 3β-

The two previous formulations (A &gt; s) were tested and compared for film formation and staining. The formulations were tested on an automatic dishwasher Kenmare &quot; using the procedure described in &quot; ASTHD 3566-79% with the exception of using only four wash cycles. The film and stain formation was evaluated according to the following value scale

Film Rating Scale &gt; Optimal, no apparent film 2. Slight film formation, becoming apparent 3 »Visible film to increase 4. Continuous and significant increase of film 5» Formation of film making Excessive 6, Excessive formation of film 7, Continuous increase of excessive film formation:

LeCala_de. _Qsifigation ...... of ..... Mane has

The optimum - lack of spots B "Very few visible spots C" Visible spots B. Significant coverage, approximately 5%.

The foregoing compositions were tested in the cleaning of glass cups.

The method &quot; ABlll D3556-79 &quot; for deposition on glass articles during mechanical dishwashing 'for evaluation of the formation of film spots on glass articles. 42 grams of the non-aqueous liquid detergent composition of the invention (A) and 5% of the composition were used in each test

(commercially available) and / or flickr 587.1: 45, 228 (2 SF SF) and powdered BK T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T. The temperature of the wash water was that of water having a hardness of 3ΘΘ ppm.

The results are as follows:

It was -mui acSo Mane h; F "and" F "and" Many "in the Invention <A) • T-1 Trade Agreement! The commercial powder has shown that the non-aqueous liquid DLA composition of the invention is different from the ones used in the present invention.

NMR

Following the instructions of the present invention, the formulations of the non-aqueous automatic dishwashing detergent compositions were prepared from 1 to 5 using the following ingredients in the industrial amounts. uas, ia. . .............. Na 2 SO 4, Na 2 SO 4, Na 2 SO 4, Na 2 SO 4, Na 2 SO 4, Na 2 SO 4, - - 10, Θ Θ Si Si Si Si Si Si Si Si Si Si Si Si Si Θ Θ Θ Θ. 13.7 12.9 6.0 7.6 H W r? /? 3.0. The anti-film component of the film is 1 - 4,8. &lt; 4) Sodium Polysaccharide - SC The w H .C ~ 6.5 w q ju. bleaching agent 4.3 4,3 4 5,0 4,8 Bleaching agent 1 2 31 i7i 2,4 100.0 100.0 100.0 100.0 C1 ) (2) Tergitol HDS, which is a nonionic surfactant of Union C · arbiq® (/ â ζ) W CK. (4) &quot; Alcosperse 130D &quot; of AIca. (5) Sodium perborate monohydrate (Interloc.) (6) Tetra-acetyl-ethylenediamine

The above formulations A, B, C and D were tested according to the test procedure of the evaluation of Example 1. The tests were carried out at 4552 ° C (<20 ° F) with water hardness of 1 x 5 ppm or at 453 ° C (120 ° F) with water of hardness of 3ΘΘ ppin *

Ten glass cups were drawn in each test and the mean values were recorded, The following table shows the results obtained with respect to the yield profile.

r V

Rendimento Profile &gt;

I. &quot; ASTM &quot; water of 1 ppm hardness. 45.2 ° C (120 ° F) Cycle M. A P? Lj ϊϊ | P> T> P. 1 CD 2 - 2 B 2 BC 2 OF 2 AB 2 - AND OF AB - ¾ A '- A A D D 2 AB II. east &quot; ASTM &quot; water of θθθ ftpm, "45.295 CÍ205F)

B

Cycle Μ. 1 P. Μ »P * M" P. M, f * r Λ B 4 AB V X η. w - - 4 5 5 AB * - &gt; - - - - - - - - - -

Test I Π.ΘΘ ppm duresa values, 45% = 2 ° C = 12 ° F) show that the polyacrylate in formulations B is 0 provides a substantially better anti-stain performance than comparison formulation A, which has no polyacrylate. The anti-film yield for formulations A.8 and C was similar.

Test values ϊΐ ΦΘ ΦΘ ppm from durssa, 452SC-12Θ9Ρ) show that the addition of silica-based anti-film agent to the formulation of the invention D, which contains polyacrylate, improves anti-mannability and anti-film yield in comparison with formulation C, which sing only polyacrylate.

Test I values show that addition of polyacrylate to the formulation improves anti-mannan performance, and Test II values show that supplemental silica improves anti-mannan and anti-film yield. εκβιηβ1ο_3

Is the formulation of a non-aqueous liquid detergent composition suitable for automatic dishwashers? using the following ingredients in the indicated amounts *

Formulation of the Invention

Ag.Anti-relic

Alumina QSfflSSnMlte lo.gu.

Organic Liquid Carrier '&quot; 38.ΘΘ

NaTFF 27.84

Saturated Carbonate (Anhydrous) 1β-Θ0

Sodium Sodium &lt; l / 2y35 - 43.5%) 12 * 80! IPoly Tergent SLF-18 (s) (2)

Alumina Anti-Film Agent "- &quot; 2

Sodium Perborate Monohydrate, 4.04

Bleach Activator 2.4

Foam suppressor &quot; Knapsack LPKN-lB &quot; (i) The organic liquid carrier is &quot; Polyethylene Slicol 305 &quot; (Union

Carbide) (2) Propylated ethoxylated fatty alcohol (Dlin Chemical) &lt; 3) Aluminum oxide C, having a particle size of Θ, Θ 2 microns and sold by Dequssa Co. TAEDn (4) The formulation is tested for how much washing articles of the glass at 49Â ° C (130Â ° F) in hard water (300Âμs hardness) in an automatic dishwasher using glass beakers and the procedure described in "ASTHD-3566 79 &quot; * with the exception that only four wash cycles have been used. The evaluation of film formation and blemishes was done as in Example 1. The washed glass glasses were found to have reduced film formation compared to commercial powder formulations which did not contain anti-foil-based film-forming agent. ee.gamaio-ji

Example 3 was repeated? with the difference that the anti-film forming agent based on alumina is replaced by weight? of titanium dioxide. The formulation was tested for washing glass articles at 49Â ° C C130Â ° F in hard water at 30Â ° ppm hardness) as before. The washed glass cups were found to have reduced film formation compared to standing commercial formulations which did not contain anti-titan dioxide based film-forming agent.

The automatic dishwashing liquid detergent compositions of the present invention have improved anti-foil and / or anti-staining properties in glassware and other dishes. The invention is not limited by the foregoing description to examples which are given only as illustrations. The invention is to be interpreted in accordance with the appended claims.

Claims (2)

40 i CLAIMS a. the preparation of the urn. A non-aqueous automatic dishwashing detergent composition having a better anti-peeling performance characterized in that the aqueous liquid carrier is present in the composition and at least one ingredient selected from the group consisting of organic detergent, builder for detergents, foam inhibitor and mixtures thereof and a member selected from the group consisting of a non-abrasive amount of from 5 to 10% substantially water insoluble silica particles, alumina or titanium dioxide or mixtures thereof, as the active agent anti-film formation. 2a. - Process for erythrocytosis by inclusion in the hrasiva of 1.0 to 8% of the film age. ! The process according to claim 1, wherein the compound of formula (I) in said composition 1 to 4: t: r. - A process for the preparation of a non-aqueous liquid detergent composition for automatic dishwashing machines, characterized in that it is included in the composition of the present invention. (b) 2 to 60% of inorganic or organic builder for less than 5% (c) 5 to 3% of sodium silicate (d) To 25% of alkali metal carbonate (e), to 12% of water-dispersible organic detergent active material? &lt; f &gt; Θ to 6% foam suppressor (p) 3a to 15% peroxygen bleach compound? Ch &gt; At 8% bleach activator? A non-abrasive amount of θ 5 to 10% of an anti-foaming agent, which is a member selected from the group consisting of silica, alumina, titanium dioxide and mixtures thereof, having a size of particles of microns' 51. A process as claimed in claim 4, wherein the peroxygen bleach compound is a member selected from the group consisting of sodium perborate, potassium monopersulfate, sodium percarbonate and monoperoxy phthalate. A process according to claim 4, characterized in that in addition to said composition is added 25 to 25% of a water-soluble salt or polyacrylic acid polymer. 71. A process for the preparation of an automatic non-aqueous liquid detergent composition for washing machine The composition according to any one of the preceding claims, characterized in that the composition comprises, by weight, in approximate values. (ia) 25 to 55% of organic liquid carrier; Ch &gt; 20 to 55% of the alkali metal tripolyphosphate? ic &gt; 7a 26% sodium silicate? Cd &gt; 5 to 20% alkali metal carbonate? &lt; t &gt; 0.5 to 1.0% of non-ionic, organic detergent active material dispersed in water? (?) 0 = 1 to 5% d-e foam suppressor? Cg) 4 to 12% bleach peroxy compound? th) 2 to 3% bleach activator? and Ci &gt; a non-abrasive amount of from 1 to 8% of an anti-foaming agent which is a stabilized member of the group consisting of silica, alumina, titanium dioxide and mixtures thereof having a particle size from 0.1 to 8 microns. 8ã. The process according to claim 7, further characterized in that in said composition 2 there is further included 25% of a polyacrylic acid salt or polymer stain which has the formulas n wherein R 1, R 2, and R 2. may be the same or different and may be hydrogen, C -C-C alquilo-lower alkyl, S representa is hydrogen, or an alkali metal, n = 5 to 1% to the polymer has a molecular weight of 1ΘΘ a to ΙΦΦΦΦΦΦΦΦ. 9. A process as claimed in claim 7, wherein the bleach activator is tetraacetyl-ethylenediamine. The process of claim 7, wherein the active agent anti-film formation is silica. 7. A process as claimed in claim 7, wherein the anti-foaming agent is alumina. 12. A process as claimed in claim 7, wherein the anti-foaming agent is (a) 30 to 45% of the liquid carrier, characterized in that the liquid detergent composition comprises a liquid detergent composition, organic (b) 20 to 45% alkali metal tripolyphosphate; (c) 1 to 24% sodium silicate; (d) 5 to 15% of the alkali metal carbonate; Ca) 0.5 to 4.5% of the foam suppressant; &lt; f &gt; The dispersible organic nonionic detergent S1! in water; Cg) 4a 12% peroxidized bleaching compound; (h) a non-abrasive amount of 0.5 to 6% of a film forming agent, which is a member selected from the group consisting of silica, alumina, titanium dioxide and mixtures thereof, having a particle size of 0.01 to S microns; s &lt; i &gt; The water soluble polyacrylic acid salt or polymer of claim 4, characterized in that the water-soluble polyacrylic acid salt or polyacrylic acid polymer has formulas C-C R 2 is hydrogen or methyl, H is hydrogen, sodium or potassium, n = 5 to 50, and the polymer has a molecular weight of 1 = 500 to 50 = 000 = I I 15a. - Process as outlined in Example 3. 5. V ΧΠ01.1. . e. 1, which is synthesized by the acid salt or polymer of acrylic acid, is prepared by reacting a compound of the formula: ## STR1 ## 16a. Process according to claim 13; csracts ρ .i. characterized in that the polyacrylic acid salt or polymer has a P85D (W / O) of about 4% by weight of the compound of claim 13, antimicrobial resistance of silica having about 0.1 æg / ml and alumina 5 based on the weight of the silica &lt; 10S s-Proc 5 * 1% * 1 1 according to the claim characterized by α The reaction was stirred at room temperature for 1 hour, after which time the reaction mixture was allowed to warm to room temperature. J, PEREIRA DA CRUZ Official Property Agent Industriei RUA VICTOR COROON, 10-A 3. &quot; 1200 LISBOA