CA1284926C - Bleaching synthetic detergent composition - Google Patents
Bleaching synthetic detergent compositionInfo
- Publication number
- CA1284926C CA1284926C CA000482759A CA482759A CA1284926C CA 1284926 C CA1284926 C CA 1284926C CA 000482759 A CA000482759 A CA 000482759A CA 482759 A CA482759 A CA 482759A CA 1284926 C CA1284926 C CA 1284926C
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- CA
- Canada
- Prior art keywords
- detergent
- sodium
- perborate
- range
- detergent composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- 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
- C11D3/395—Bleaching agents
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- 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
- C11D3/3942—Inorganic per-compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3711—Polyacetal carboxylates
Abstract
BLEACHING SYNTHETIC DETERGENT COMPOSITION
ABSTRACT OF THE DISCLOSURE:
Bleaching detergent compositions which are especially useful to remove particulate and sebum stains from fibrous materials, such as those of polyester, in high temperature washing processes comprise a synthetic organic detergent or a mixture of such detergents, a polyacetal carboxylate builder for such detergent(s) and a perborate. Also described are processes for washing fibrous polyester materials stained with particulate and sebum stains, in hard water and at elevated temperature.
ABSTRACT OF THE DISCLOSURE:
Bleaching detergent compositions which are especially useful to remove particulate and sebum stains from fibrous materials, such as those of polyester, in high temperature washing processes comprise a synthetic organic detergent or a mixture of such detergents, a polyacetal carboxylate builder for such detergent(s) and a perborate. Also described are processes for washing fibrous polyester materials stained with particulate and sebum stains, in hard water and at elevated temperature.
Description
` ~ 2~3~26 This invention relates to detergent compositions.
More particularly, it relates to bleaching detergent compo-sitions comprising a synthetic organic deterg~nt or mixture of such detergents, a polyacetal carboxylate builder for such detergent(s) and a perborate. Also within the invention is a process for washing stained fibrous polyester materials that had been stained with particulate soil and sebum.
The need for removing soils and stains from fibrous materials is age-old and a multitude of compositions has been described for accomplishing that result. One kind of prepara-tion which has been employed to test the detersive and stain removing activity of detergent compositions is a mixed sebum and particulate soil, which severely stains fibrous materials contacted with it, especially those incorporating polyester fibers, such as polyester knits and polyester-cotton blends.
Such soil is often employed to produce an artificial ~collar staining soil". As is well known, "collar soil n is considered to be difficult to remove from shirt collars (and cuffs) 4~3~6 during automatic washing o~erations. It is difficult to remove whetheL washiny is conducted at a relatively low temperature, such as from 10 to 30C. or at higher temperature, as in accor-dance with European practice, such as 50 to 90 or 95C.,or higher.
Whereas once soap was the universal detergent today almost all home laundry detergent compositions are based on one or more synthetic organic detergents. Of such detergents the anionic and nonionic detergents are considered to be most effec-tive, although ampholytic or amphoteric and cationic detergentsmay also be employed. Sodium perborate has long been used in detergent compositions for its bleaching effect. Recently poly-acetal carboxylate builders have been employed in detergent compositions in replacement of polyphosphate builders because they do not contain phosphorus and accordingly have not been thought to promote eutrophication of inland waters. Another plus for such builders is their ready degradability in normally acidic waste waters.
Although the main components of the present deter-gent compositions have been employed in other such compositions,they are considered to be novel and unobvious and to possess unexpectedly beneficial stain removing properties. Particularly important is the greatly improved capacity of the present compo-sitions to remove a combination of sebum and particulate stains from polyester-containing fibrous ~ ~34926 material when such material is washed in hot wash water containing the invented detergent composition. Such effect is even obtained when hard wash water is used.
In accordance with the present invention there is provided a bleaching detergent composition which comprises about 3 to 30% of a synthetic organic detergent or a mixture of such detergents, about 4 to 50% of a polyacetal carboxylate builder for such detergent(s) which is of a molecular weight in the range of 3,500 to 10,000 and 10 to 50% of a perborate.
This composition, in wash water at elevated temperature, is especially effective to remove particulate and sebum stains from polyester fabrics. The invention also provides a process for removing mixed particulate and sebum stains from fibrous polyester materials which comprises washing such stained fibrous materials in wash water at a temperature in the range of 50 to 90C. with a detergent composition of claim 1 at a concentration in the wash water in the range of 0.05 to 1.5% by weight. Preferred such compositions comprise about 4 to 20% of sodium higher alkylbenzene sulfonate wherein the higher alkyl is of 10 to 18 carbon atoms, about 2 to 10% of a nonionic detergent which is a condensation product of ethylene oxide and higher fatty alcohol, wherein the higher fatty alcohol is of 10 to 18 carbon atoms and the nonionic detergent contains 3 to 20 moles of ethylene oxide per mole, about 10 to 30~ of sodium polyacetal carboxylate builder of a calculated weight average molecular weight in the range of 5,000 to 9,000, about 10 to 40% of sodium perborate tetrahydrate, about 3 to 20% of moisture, including hydrate moisture which is removable at 105 C., and the balance of filler(s) and/or other builder(s) and/or other adjuvant(s). Also within the invention is a process for removing mixed particulate and sebum stains from d ~2~4~26 fibrous polyester ma~erials which comprises washing such stained fibrous materials in wash water at a temperature in the range of 50 to 99C. which contains a detergent composition including a detersive proportion of a synthetic organic detergent or a mix-ture of such detergents, a detergency building proportion of a polyacetal carboxylate builder for such detergent(s) and a bleaching proportion of a perborate, at a concentration of such detergent composition in the wash water in the range of 0.05 to 1.5%.
The synthetic organic detergent which is primarily employed for its cleaning characteristics in the present compo-sitions will normally be an anionic detergent. Of the anionic detergents, the sulfated and/or sulfonated lipophilic materials having an alkyl chain of 8 to 20 carbon atoms, preferably 10 to 18 and more preferably 12 to 16, will usually be those of choice. While various water soluble salt-forming cations may be used to form the desired soluble sulfated and sulfonated deter-gents, including ammonium and lower alkanolamime (such as tri-ethanolamine), and magnesium, usually an alkali metal, such as sodium or potassium, is employed, and very preferably such cation will be sodium. Among the various anionic detergents that are useful in the practice of this invention the linear higher alkylbenzene sulfonates of 10 to 18 carbon atoms in the alkyl chain, preferably 12 to 16 and most preferably about 12 or 13, are considered most suitable for ~ - 5 -1 ~34~26 the practice of the invention Also, useful, among others, are the monoglyceride sulfates, higher fatty alcohol sulfates, sulfated polyethoxylated higher alkanols, wherein such alkan-ols may be synthetic or natural, containing from 3 to 20 or 30 ethoxy groups per mole, paraffin sulfonates and olefin sulfonates, in all of which compounds the alkyl group present is of 10 to 18 carbon atoms. Some such alkyl groups may be slightly branched but will still be of a carbon chain length within the described range.
The nonionic detergents, which are often employed to supplement the detersive action of the primary anionic detergents,but in some instances may be the primary detergent(s), are preferably normally solid materials (especially when being incorporated in solid or particulate solid products) and will preferably be condensation products of ethylene oxide and higher fatty alcohol, with the higher fatty alcohol usually being of 10 to 18 carbon atoms, preferably averaging 12 to 15 carbon atoms, e.g., about 12 to 13 carbon atoms, and with the ethylene oxide content being within the range of 3 to 20 moles, preferably 3 to 12 moles and more prefer-ably 5 to 9 moles, e.g., about 6.5 or 7 moles of ethylene oxide, per mole of fatty alcohol. Amo~g other nonionic detergents that are also useful are the ethylene oxide condensation products of alkyl phenols of 5 to 12 carbon atoms in the alkyl groups, such as nonylphenol, in which the ethylene oxide content is from 3 to 30 moles per mole.
Additionally, condensation products of ethylene oxide and propylene oxide, such as those sold under the trademark Pluronic~ may be employed, as may be various others of the well known group of nonionic detergents.
The cationic detergPnts that may be employed, usually in limited proportion, e.g., no more than 10% and preferably less than 5~, are preferably di-higher alkyl, di-lower alkyl ammonium halides, wherein the higher alkyls 10 are of 10 to 18, preferably 16 to 18 carbon atoms, the lower alkyls are of 1 to 3, preferably 1 carbon atom(s) and the halogens are chlorine or bromine. Among such materials there may be mentioned distearyl dimethyl ammonium chloride, di-tallow dimethyl ammonium chloride (wherein the alkyl is obtained from animal fats) and dihydrogenated tallow dimethyl ammonium bromide. However, various other such cationic materials, including N-cetyl-ethyl morpholinium ethosulfate, often classified as antistatic agents tthey also often have deodorant and germicidal properties), may also be employed.
Of the amphoteric materials the Miranols may be mentioned as examples, such as that which has been marketed under the designation Miranol~C2M Conc. Other such detergents, includ-ing anionic, nonionic, amphoteric and cationic detergents, are all described in the various annual publications entitled McCutcheon's Detergents and Emulsifiers, for example, in that issued in 1969.
~ 284~6 The polyacetal carboxylate maybe considered to be that described in U.S. patent 4,144,226 and may be made by the method mentioned therein. A typical such product will be of the formula Rl - (CHO)n - R2 COOM
wherein M is selected from the group consistiny of alkali metal, ammonium, alkyl groups of 1 to 4 carbon atoms, tetraalkylammonium groups and alkanolamine groups, both of 1 to 4 carbon atoms in the alkyls thereof, n averages at least 4, and Rl and R2 are any chemically stable groups which stabilize the polymer against rapid depolymeriation in alkaline solution.
Preferably the polyacetal carboxylate will be one wherein m is alkali metal, e.g., sodium, n is from 20 to 200, Rl is H3C or MOOC
or a mixture thereof, R2 is -CH
and n averages from 20 to 100, more preferably 30 to 80. The calculated weight average molecular weights of the polymers will desirably be within the range of 2,000 to ~ - 8 -~ ~4~26 20,000, preferably 3,500 to 10,000 and more preferably 5,000 to 9,000, such as 7,000 to 9,000, specifically, about 8,000.
Although the preferred polyacetal carboxylates have been described above, it is to be understood that they may be wholly or partially replaced by other such polyacetal carboxylates or related organic builder salts described in various Monsanto Co. patents on such compounds, processes for the manufacture thereof and compositions in which they are employed. Also, the chain terminating groups described in the various patents, especially U.S. 4,144,226, may be utilized, providing that they have the desired stabilizing properties, which allow the mentioned builders to be depo-lymerized in acidic media, facilitating biodegradation thereof in waste streams, but maintain their stability in alkaline media, such as washing solutions.
The perborate utilized is a water soluble perborate which is capable of releasing active bleaching oxygen in aqueous media, such as in wash water at elevated temperature.
Such perborate is preferably an alkali metal or equivalent salt and most preferably is sodium perborate tetrahydrate.
Usually the perborate is hydrated but that is not necessary.
Generally the hydrate is the tetrahydrate but it has been found that the monohydrate is also useful and some perborates with contents of water of hydration less than one mole per 2S mole may be especially useful in certain applications or _ g _ ~ 2~45~
when packaged in vapor tight containers (wherein higher hydrates may tend to liquefy, or cake the detergent compo-sition).
While the ordinary higher fatty acid soaps, usual-ly the sodium soa~s, are detergents, they are not generallyconsidered to bc synthetic organic detergents, and according-ly are not to be taken as within the group of such detergents for the purpose of this invention. The soaps do have deter-sive properties but may be employed for other purposes too, such as for their foam limiting characteristics. Among the soaps that may be utilized in the present compositions, those of alkali metals, such as sodium, of 10 to 18 carbon atoms and preferably highly saturated, will be preferred.
Among such are the sodium hydrogenated tallow soaps, sodium stearate and sodium palmitate, but soaps of tallow and mixtures of tallow with coconut oil may also be employed, e.g., 4:1 tallow:coco soaps, as composition components.
In the compositions of the invention other builders than the polyacetal carboxylate may also be present although such are not necessary. Often it will be desired to avoid the presence of phosphorus in the detergent compositions so the polyphosphates, which have been the builders of choice in the detergent art for many years (especially pentasodium tri-polyphosphate), will preferably be omitted from the present formulations. Still, in some instances, they may be present, 4~X~i at least in relatively small proportions, e.g., up to 5 or 10%. Among builders other than polyphosphates, such as sodium tripolyphosphate and tetrasodium pyrophosphate, those which may be desirably incorporated in the present compositions to supplement the building action of the poly-acetal carboxylate include sodium carbonate, sodium bi-carbonate, sodium sesquicarbonate, sodium silicate, zeolites, e.g., Zeolite A, NTA, sodium citrate, sodium gluconate, borax, other borates, and other builders known in the deter-gent art.
Fillers may be present, such as sodium sulfate andsodium chloride, to add bulk to the product when that is considered to be desirable. In liquid compositions, which should usually be employed soon after making, solvents or extenders may be used, such as water, ethanol and isopropanol.
Among the various adjuvants that may be employed are colorants, such as dyes and pigments, perfumes, enzymes, stabilizers, activators (especially activators for causing active oxygen release from perborates), fluorescent bright-eners, buffers, fungicides, germicides and flow promoting agents. Also included among adjuvants, unless in other classes previously mentioned, are various additional components or impurities present with other ingredients. For example, it is known that sodium carbonate and water are often present 4~
with polyacetal carboxylate in Builder U, the product which is the present source of polyacetal carboxylate.
Moisture will usually be present in the invented compositions, either as free moisture or in one or more hydrates. While moisture is not an essential component of these bleaching detergent compositions it will normally be present due to the use of water in manufacturing, and it may help to solubilize other composition components and bind them.
The proportions of components of the invented compositions given below are those for particulate products, which are usually of particle sizes in the 8 or lO to 100 or 140 sieve (or mesh) range, U.5. Sieve Series. However, such proportions also apply to other olid forms, such as bars or cakes, more fine]y divided or coarser powders, granular lS compositions and agglomerates, and also to liquid prepara-tions, althouqh because of their relatively low stability aqueous liquid preparations should be used relatively soon after manufacture. Also, while the proportions of all the components except water may be about the same in liquid preparations, such products are often much more dilute, 80 that the proportion of water or other solvent or a mixture of solvents present may be much greater. In some aspects of the invention the components may be added directly to the wash water, in which case it may be considered that the detergent composition is the wash water containing the various active and other components.
4~
In the particulate solid and other solid detergent compositions of this invention the total proportion of detergent present will normally be from 5 to 40%, more preferably from 10 to 25% and most preferably about 12%.
Such detergent will desirably include either sulfated or sulfonated anionic detergent or nonionic detergent but pre-ferably will include both such detergents. The proportion of anionic detergent present will usually be from 3 to 30%, preferably 4 to 20% and more preferably 4 to 10%, e.g., about 8%, and the proportion of nonionic detergent will be about 2 to 25%, preferably 2 to 10% and more preferably 2 to 6%. The proportion of polyacetal carboxylate builder will usually be within the range of 4 to 50%, preferably 10 to 30%, and more preferably 10 to 25%, e.g., 18~. The perborate content is normally in the range of 10 to 50%, preferably being 10 to 40% and more preferably 15 to 30%, e.g., 22%, which percentages are on the basis of sodium perborate tetrahydrate and may be modified accordingly when the anhydrous salt or a different hydrate is employed. The proportion of soap, when it is present, will usually be in the range of 1 to 10%, preferably 2 to 6%, and the percentage of moisture will normally be from 3 to 20%, preferably 5 to 15%, e.g., about 10%. Such percentages include moisture in hydrate form that is released during heating for two hours at 105C. (the standard moisture analyzer method). The proportions of ~ 284'326 other components, such as fillers,will normally be limited to no more than 40% and usually will be in the range of 0 to 30% or 5 to 20%. Similarly contents of builders other than the polyacetal carboxylate will be limited, generally being less than 25%, such as 3 to 20% or 5 to 15%, but often no such supplemental builders will be present. The total adjuvar.t content will usually not exceed 10% or 20~, and preferably will be less than 5%, with the contents of individual adjuvants generally not exceeding 3% or 5%, and preferably being less than 1 or 2%. For example, sodium carboxy-methyl cellulose, which is a desirable antiredeposition agent, will usually be present within the range of 0.~ to 3%, preferably 0.5 to 2%, e.g., 1%.
In preferred forms of the invention, particulate solid compositions of particle sizes such as those previous-ly described, it is often preferred to spray dry as much of the formulation as feasible so as to obtain substantially uniformly shaped globular particles. Because the perborate i6 heat-unstable it will normally be post-added to the rest of the composition. Of course, to prevent segregation during shipping and storage of the final product it is desirable that the perborate be of shape and particle sizes like those of the rest of the composition. The polyacetal carboxylate may sometimes be spray dried with the detergent composition providing that care is exercised to prevent it 9~6 from being decomposed by heat. However, it may also be post-added, and again the particle sizes for post-adding are desirably the same as those previously mentioned, to avoid product component segregations. In an alternative method of manufacture the various components, in finely divided form, may be merely mixed together. Also, when the initial particle sizes of the components are less than desired, such as in the 160 to 325 mesh range, particles thereof may be agglomerated to the desired size, sometimes with the aid of agglomerating agents, such as a dilute aqueous solution of sodium silicate, and at other times with only water to assist in agglomeration.
When an anionic detergent is the primary detergent of the desired composition it may be spray dried with fillers, lS such as sodium sulfate, builders, such as sodium carbonate, sodium bicarbonate, borax and sodium silicate, and adjuvants, such as fluorescent brighteners, pigments and dyes, and may be spray dried in the normal manner, utilizing a conventional countercurrent or concurrent spray drying tower with drying 20 air entering at about 200 to 600C. (preferably 150 to 300 or 350C. when polyacetal carboxylate is present). Then the polyacetal carboxylate and perborate may be admixed, in either order or conjointly, or the perborate and polyacetal carboxylate may be pre-blended and then mixed with the spray dried beads. When a relatively small proportion of nonionic detergent is to be present with the anionic detergent it may be spray dried with such anionic detergent, fillers, etc., and stable amphoteric and cationic materials that are to be present can also be incorporated in the crutcher and then spray dried with the anionic detergent. However, when more than about 4 or 5~ ~sometimes more than 2~) of nonionic detergent is present in the formula any additional proportion will usually be post-added, as by spraying onto tumbling particles of detergent beads or base beads. Such base beads may be made from any builders, fillers and stable adjuvants of the final product. Then the polyacetal carboxylate and perborate may be post-added. In some instances the poly-acetal carboxylate may be dispersed and/or dissolved in the nonionic detergent, which is heated so as to be in liquid state (or may be dissolved in a solvent) and the combination oS nonionic detergent and polyacetal carboxylate may be sprayed onto the detergent beads or base beads, followed by addition of perborate. Desirably, the particulate material made will be of particle sizes in the ~ to 120 or 10 to 100 mesh range and the manufacturing process will be designed accoxdingly. ~owever, screening may be employed to remove under- and over-sized particles, which may be reworked, ground, agglomerated or otherwise processed to sizes desired.
To manufacture the present products into bar, cake or briquette form the compositions may be extruded, pressed ~ ~84~26 or molded to shape in known manners. To convert them to liquid preparations the components may be dissolved and/or dispersed in liquid media, such as water and/or suitable solvent(s).
To practice the stain removing process of the invention the described composition may be added to "wash water" or the vari-ous components may be so added. ~ormally the concentration of the compositions employed will be in the range of 0.05 or 0.1 to 1.0 or 1.5~, preferably 0~1 to 1.3%, and more preferably 0.15 to 1.1 or 1.2%. Higher concentrations, as from 1.0 to 1.5% or more, are often employed in machine washing according to European practice, which utilizes high temperature wash water, in which the perborate releases active bleaching oxygen.
Usually the washing temperature in America will be in the range of 10 to 55C., often being from 10 to 30C., compared to 60 to - 99, often 70 to 90 or 95C.,in Europe. In American practice lower concentrations, such as from 0.05 to 0.2~, often prefer-ably about 0.07 to 0.15~, of the composition are employed.
Following American practice perborate oxygen is not released to the same extent because the washing temperature is lower. Con-sequently any bleaching effect is not as great as when higher wash temperature are used, unless an activator is also present to assist in the release of active oxygen from the perborate.
Various such activators are known for this purpose and may be employed to adapt the process invention to American practice.
Among such activators are those known as TAED (tetraacetylethy-lene diamine, acyloxybenzene, sulfonates, such as described in U.S. Patent 4,412,934, and TAGU.
~ X~34~326 In the washing or stain removing operation convention-al washing machines will be employed, such as GE automatic washers (top loading), following the American practice, and Miele machines, following European practice. While it is con-sidered that the present compositions operate better than con-trols utilizing sodium tripolyphosphate in place of polyacetal carboxylate, whether washing is at high or low temperatures, providing that equivalent proportions of active oxygen are released from the perborate, it is often preferred to follow the European practice, which does not require the presence of an accelerator to promote the release of active oxygen from the perborate. Various hardnesses of water may be utilized and while it might be expected that the softer the water the better the stain removal, unexpectedly it has been found that even under hard water conditions the present compositions and stain removing processes are superior to controls wherein pentasodium tripolyphosphate is employed instead of the polyacetal carboxy-late. This improved stain removing capacity is most pronounced at elevated temperatures (60 to 90C.) when the stain is a very critical stain, usually found in normal laundry, a combination of particulate and sebum stains, such as may be found on shirt collars and cuffs. The good effect in removing such stains is obtained even when hard water is used, such as that of hard-nesses that are quite high, such as in the 250 - 350 p.p.m.
range, as Xl - 18 -~ ~4~
CaCO3. In addition to better removal of such stains, which is even more evident at 90C. than at 60C., it is found that the invented compositions and processes result in significant improvements with respect to removals of various other typical stains too. Surprisingly then, the present compositions, incorporating a builder which is stable during washing and stain treatment but is degradable in normally acidic waste waters, and omitting one of the best previously known builders, sodium tripolyphosphate, in~combination with synthetic organic detergent (especially a mixture of anionic and nonionic detergents) and perborate bleach, give superior stain removal, which is apparently attributable to the particular unique combination of components employed.
Such effect is obtained even in very hard water, which is unexpected in view of the excellent sequestering activity of the sodium tripolyphosphate builder and its known stability and widespread utility in washing and stain removal opera-tions.
The following examples illustrate but do not limit the invention. Unless it is otherwise indicated, all parts are by weight and all temperatures are in C. in these examples, elsewhere in the specification, and in the claims.
128~926 Component Percent * Sodium linear tridecylbenzene sulfonate 8.0 ~ * Nonionic detergent lNeodol 25-7, a condensation 4.0 product of hiqher fatty alcohols averaging 12 to 15 carbon atoms, and 7 moles of ethylene oxide per mole of fatty alcohol, obtainable from Shell Chemical Co.) * Sodium hydrogenated tallow soap 4.0 * Sodium carboxymethyl cellulose 1.0 Sodium perborate tetrahydrate 22.0 Builder U (79.7% of sodium polyacetal carboxylate, of 22.0 calculated weight average molecular weight of about 8,000, obtained from Monsanto Co.) * Filler (sodium sulfate, anhydrous) 29.0 Moisture 10.0 100. 0 * in spray dried beads A stain removing detergent composition of the above formula is made by spray drying a crutcher mix, contain-ing about 55% of solids and 45% of water (city water of hardness of about 100 p.p.m., as calcium carbonate) and at a temperature of about 50C., into a countercurrent spray drying tower, wherein it is dried to a moisture content of about 10%. The tower inlet air is at about 450C. and at the outlet from the tower such air temperature has been reduced to about 150C. The spray dried beads resulting are ~ rr~dt ~1ar~
~.~849~6 62301-1318 of particle sizes in the range of No's. 10 to 100, U.S. Sieve Series. With such beads there are admixed in an inclined tumb-ling drum the sodium perborate tetrahydrate and Builder U, also of particLe sizes in the 10 to 100 sieve range. When the compo-nent materials are supplied as finer powders and none is spray dried they are (or may be) agglomerated to the desired sizes, alone or together. Such polyacetal carboxylate - perborate agglomerates may be of pro- portions in the range of 1:5 to 5:1 and may contain from 0.1 to 5% of sodium silicate (Na2O:SiO2 =
1:1.6 to 1:3), as a binder.
The product obtained is tested for stain removing action, utilizing a Miele*/multi-stain light reflecting procedure wherein delta Rd's are measured for washed experimental and control swatches. In such procedure the experimental composition and control detergent composition (containing trisodium polyphosphate instead of Builder U) are separately charged to a Miele washing machine at a concentration of about 1.1~ (225 grams per 20 liters of wash water) at 60C., with water over 200 p.p.m. (300 p.p.m) hardness as calcium carbonate, and having a hardness of a 4:1 ratio of calcium ion to magnesium ion. The test specimens employed are of different materials and have been stained with different stains. A
plurality of test cloths is employed for each combination of cloth and stain and average reflectance readings from the cloths are taken after normal washings and *Trade-mark ~ - 21 -~Z84~26 dryings with the experimental composition of this example and are compared to those for the control detergent composi-tion, wherein 22~ of sodium tripolyphosphate is present instead of the Builder U. Such procedures are repeated at 90~C. with the exception that the washing procedure is modified so that half of the detergent composition and half of the control are employed in pre-wash steps and the other halves are employed in the main washings.
By the test method described, which is considered to be a standard for testing stain removal properties of detergent compositions, it is found that the invented compo-sition of this example and use of the washing process of this example result in significant improvements with respect to removals of various typical stains found on items to be laundered, including Spangler sebum/particulate stain on Dacro~ double knit material, liquid makeup on cotton percale, on Qiana jersey and on Dacron double knit materials, Bico9 black pen ink on Dacron-cotton blend material and French dressing on a Dacron double knit, at 60C., and Spangler sebum/particulate stain on Dacron double knit material, liquid makeup on cotton percale, on Dacron-cotton blend and on Qiana jersey, and colored shortening on Dacron double knit,at 90C. The invented compositions and processes were found to be inferior in stain removal to tripolyphosphate-containing controls only for brewed tea stain on polyester/cotton blend and for barbeque sauce on Dacron double knit fJ D~ R 1~, 4~2~;
(both at 60C.), and for liquid makeup on Dacron double knit and for French dressing on Dacron double knit (both at 90C. ) .
Results like those described above are also obtain-able when the experimental formula is varied by increasing the alkylbenzene sulfonate content to 16%, omitting the nonionic detergent and soap, and replacing the 29~ of sodium sulfate with a third each of sodium bicarbonate, sodium carbonate and sodium silicate of Na20:5iO2 ratio of about 1:2.4. Similarly, such second formula may be varied by utilizing a mixture of equal parts of the alkylbenzene sulfonate and sodium lauryl sulfate (totalling 16%) or by omitting the alkylbenzene sulfonate and replacing it with ~ post-sprayed nonionic detergent (Neodol 25-7 or Neodol 23-6.5), after which the sodium perborate and Builder U are admixed with the base beads containing nonionic detergent.
In such instances the improved stain removing property, attributable to the combination of polyacetal carboxylate and perborate in the present formulations, will also be obtained. Instead of the mentioned nonionic detergents other such detergents may be substituted, including the condensation products of ethylene oxide and nonylphenol, as previously described, Pluronics, e.g., F-68, and Neodol 45-11, and mixtures thereof containing two to four components.
Other variations in this example may be made, as ~ -r R ~ D~
~ 3~ ~
by utilizing other builders and fillers than those employed, including small proportions, e.g., 1 to 10 or 2 to 5% of amphoteric and/or cationic detergents (the cationic detergents may be employed as antistatic agents) in the formulas, and/or by varying the proportions of the indicated constituents +10 and +25%, while maintaining them within their respective ranges. Also, the conditions of manufacturing may be varied, as by spray drying essentially all the components (usually except perborate, perfume and enzymes) together, using mild conditions lto prevent degradation of the Builder U).
The formulas of the product of Example 1 are modified by use of a Builder U of calculated weight average molecular weight of about 5,250, which is 83~ of sodium polyacetal carboxylate polymer. Such formulations, when made by the methods described in Example 1, are of improved stain removing properties, compared to controls containing sodium tripoly-phosphate instead of the Builder U polymer, and the experi-mental products exhibit stain removing capabilities like those of the formulations of Example 1. Such is also the case when an equivalent proportion of perborate monohydrate is employed instead of the tetrahydrate,with the difference being made up by inert builder (Na2SO4). The described products are also producible in paste, liquid and bar or 2S cake forms by conventional means, as mentioned previously.
J ~34~2~i In the primary formula of Example 1 the sodium linear tridecylbenzene sulfonate is replaced by sodium dodecylbenzene sulfonate, sodium paraffin sulfonate, sodium olefin sulfonate (averaging about 16 carbon atoms), sodium lauryl sulfate and sodium monoglyceride sulfate, respectively.
When tested by the method described in Example 1 such products are also significantly superior for the removal of stains from laundry, compared to various controls, utilizing other builders instead of the sodium polyacetal carboxylate, among which builders is included pentasodium tripolyphosphate.
In variations of such formulas the composition is modified to include an activating proportion, e.g., about 1%, of TAED (with the sodium sulfate content being correspondingly diminished), with such activator being post-added to the composition. Upon testing in the manner described in Example 1 for use at 60C., but lowering the temperature of the wash water to 30~C., in accordance with American practice, and using a G.E. top-loading washing machine, improved stain removing results are obtained, compared to a control containing sodium tripolyphosphate instead of Builder U. Such is the case with polyacetal carboxylate active polymers of molecular weights of about-5,000 and about 8,00g. However, it is considered that best stain removals are obtained by the primary method of Example 1, which may be modified to have present other polyacetal carboxylates of calculated weight * Monsanto Lot No. 2547312 (M.W. = 5,250) ~* Monsanto Lot No. 2538422 (M.W. = 8,034) ~ ~34~i~6 average molecular weights in the given ranges.
In a modification of this example (Examples l and 2 may also be so modified) a liquid product or slurry is made by replacing the sodium sulfate or other fillers and/or builders (except polyacetal carboxylate) in the various formulas with water. Such products, when made at the same active ingredient concentrations as those of these examples, are also effective stain removers. In still another varia-tion of the invention, the various components of the compo-sition may be separately added to the wash water to obtainthe desired results. Of course, for final commercial products adjuvants will also be present, for example, 0.5%
of perfume, 1% of proteolytic enzyme, 2% of fluorescent brightener composition, 0.2% of colorant, such as Polar Brilliant Blue dye and/or Ultramarine Blue pigment for making a blue product, and 3~ of flow improving agent, such as magnesium silicate hydrate, if thought to be desirable.
It is not considered that employment of any such adjuvants will significantly adversely affect the desirable properties of the invented compositions, or the operations of the invented processes.
From the foregoing description and the examples of compositions and processes within the present invention it is apparent that the combination of polyacetal carboxylate and perborate in the present compositions leads to surpris-ingly improved stain removing products and methods, especially ~284926 with respect to hard to remove combination sebum and partic-ulate stains on polyesters, even when the washing medium is a hard water. It is especially surprising that such results ehould be obtained, considering that sodium tripolyphosphate has been the most effective detergent builder employed in the past, and also considering that the proportion of active polyacetal carboxylate polymer employed is less than the proportion of polyphosphate in the control compositions.
Thus, it is thought that that a significant advance in the stain removing and cleaning arts has been made by the pre-sent invention.
The invention has been described with respect to various illustrations and embodiments thereof but it is not to be limited to these because it will be evident that one of skill in the art, with the present specification before him or her, will be able to utilize equivalents and substitutes without departing from the invention.
More particularly, it relates to bleaching detergent compo-sitions comprising a synthetic organic deterg~nt or mixture of such detergents, a polyacetal carboxylate builder for such detergent(s) and a perborate. Also within the invention is a process for washing stained fibrous polyester materials that had been stained with particulate soil and sebum.
The need for removing soils and stains from fibrous materials is age-old and a multitude of compositions has been described for accomplishing that result. One kind of prepara-tion which has been employed to test the detersive and stain removing activity of detergent compositions is a mixed sebum and particulate soil, which severely stains fibrous materials contacted with it, especially those incorporating polyester fibers, such as polyester knits and polyester-cotton blends.
Such soil is often employed to produce an artificial ~collar staining soil". As is well known, "collar soil n is considered to be difficult to remove from shirt collars (and cuffs) 4~3~6 during automatic washing o~erations. It is difficult to remove whetheL washiny is conducted at a relatively low temperature, such as from 10 to 30C. or at higher temperature, as in accor-dance with European practice, such as 50 to 90 or 95C.,or higher.
Whereas once soap was the universal detergent today almost all home laundry detergent compositions are based on one or more synthetic organic detergents. Of such detergents the anionic and nonionic detergents are considered to be most effec-tive, although ampholytic or amphoteric and cationic detergentsmay also be employed. Sodium perborate has long been used in detergent compositions for its bleaching effect. Recently poly-acetal carboxylate builders have been employed in detergent compositions in replacement of polyphosphate builders because they do not contain phosphorus and accordingly have not been thought to promote eutrophication of inland waters. Another plus for such builders is their ready degradability in normally acidic waste waters.
Although the main components of the present deter-gent compositions have been employed in other such compositions,they are considered to be novel and unobvious and to possess unexpectedly beneficial stain removing properties. Particularly important is the greatly improved capacity of the present compo-sitions to remove a combination of sebum and particulate stains from polyester-containing fibrous ~ ~34926 material when such material is washed in hot wash water containing the invented detergent composition. Such effect is even obtained when hard wash water is used.
In accordance with the present invention there is provided a bleaching detergent composition which comprises about 3 to 30% of a synthetic organic detergent or a mixture of such detergents, about 4 to 50% of a polyacetal carboxylate builder for such detergent(s) which is of a molecular weight in the range of 3,500 to 10,000 and 10 to 50% of a perborate.
This composition, in wash water at elevated temperature, is especially effective to remove particulate and sebum stains from polyester fabrics. The invention also provides a process for removing mixed particulate and sebum stains from fibrous polyester materials which comprises washing such stained fibrous materials in wash water at a temperature in the range of 50 to 90C. with a detergent composition of claim 1 at a concentration in the wash water in the range of 0.05 to 1.5% by weight. Preferred such compositions comprise about 4 to 20% of sodium higher alkylbenzene sulfonate wherein the higher alkyl is of 10 to 18 carbon atoms, about 2 to 10% of a nonionic detergent which is a condensation product of ethylene oxide and higher fatty alcohol, wherein the higher fatty alcohol is of 10 to 18 carbon atoms and the nonionic detergent contains 3 to 20 moles of ethylene oxide per mole, about 10 to 30~ of sodium polyacetal carboxylate builder of a calculated weight average molecular weight in the range of 5,000 to 9,000, about 10 to 40% of sodium perborate tetrahydrate, about 3 to 20% of moisture, including hydrate moisture which is removable at 105 C., and the balance of filler(s) and/or other builder(s) and/or other adjuvant(s). Also within the invention is a process for removing mixed particulate and sebum stains from d ~2~4~26 fibrous polyester ma~erials which comprises washing such stained fibrous materials in wash water at a temperature in the range of 50 to 99C. which contains a detergent composition including a detersive proportion of a synthetic organic detergent or a mix-ture of such detergents, a detergency building proportion of a polyacetal carboxylate builder for such detergent(s) and a bleaching proportion of a perborate, at a concentration of such detergent composition in the wash water in the range of 0.05 to 1.5%.
The synthetic organic detergent which is primarily employed for its cleaning characteristics in the present compo-sitions will normally be an anionic detergent. Of the anionic detergents, the sulfated and/or sulfonated lipophilic materials having an alkyl chain of 8 to 20 carbon atoms, preferably 10 to 18 and more preferably 12 to 16, will usually be those of choice. While various water soluble salt-forming cations may be used to form the desired soluble sulfated and sulfonated deter-gents, including ammonium and lower alkanolamime (such as tri-ethanolamine), and magnesium, usually an alkali metal, such as sodium or potassium, is employed, and very preferably such cation will be sodium. Among the various anionic detergents that are useful in the practice of this invention the linear higher alkylbenzene sulfonates of 10 to 18 carbon atoms in the alkyl chain, preferably 12 to 16 and most preferably about 12 or 13, are considered most suitable for ~ - 5 -1 ~34~26 the practice of the invention Also, useful, among others, are the monoglyceride sulfates, higher fatty alcohol sulfates, sulfated polyethoxylated higher alkanols, wherein such alkan-ols may be synthetic or natural, containing from 3 to 20 or 30 ethoxy groups per mole, paraffin sulfonates and olefin sulfonates, in all of which compounds the alkyl group present is of 10 to 18 carbon atoms. Some such alkyl groups may be slightly branched but will still be of a carbon chain length within the described range.
The nonionic detergents, which are often employed to supplement the detersive action of the primary anionic detergents,but in some instances may be the primary detergent(s), are preferably normally solid materials (especially when being incorporated in solid or particulate solid products) and will preferably be condensation products of ethylene oxide and higher fatty alcohol, with the higher fatty alcohol usually being of 10 to 18 carbon atoms, preferably averaging 12 to 15 carbon atoms, e.g., about 12 to 13 carbon atoms, and with the ethylene oxide content being within the range of 3 to 20 moles, preferably 3 to 12 moles and more prefer-ably 5 to 9 moles, e.g., about 6.5 or 7 moles of ethylene oxide, per mole of fatty alcohol. Amo~g other nonionic detergents that are also useful are the ethylene oxide condensation products of alkyl phenols of 5 to 12 carbon atoms in the alkyl groups, such as nonylphenol, in which the ethylene oxide content is from 3 to 30 moles per mole.
Additionally, condensation products of ethylene oxide and propylene oxide, such as those sold under the trademark Pluronic~ may be employed, as may be various others of the well known group of nonionic detergents.
The cationic detergPnts that may be employed, usually in limited proportion, e.g., no more than 10% and preferably less than 5~, are preferably di-higher alkyl, di-lower alkyl ammonium halides, wherein the higher alkyls 10 are of 10 to 18, preferably 16 to 18 carbon atoms, the lower alkyls are of 1 to 3, preferably 1 carbon atom(s) and the halogens are chlorine or bromine. Among such materials there may be mentioned distearyl dimethyl ammonium chloride, di-tallow dimethyl ammonium chloride (wherein the alkyl is obtained from animal fats) and dihydrogenated tallow dimethyl ammonium bromide. However, various other such cationic materials, including N-cetyl-ethyl morpholinium ethosulfate, often classified as antistatic agents tthey also often have deodorant and germicidal properties), may also be employed.
Of the amphoteric materials the Miranols may be mentioned as examples, such as that which has been marketed under the designation Miranol~C2M Conc. Other such detergents, includ-ing anionic, nonionic, amphoteric and cationic detergents, are all described in the various annual publications entitled McCutcheon's Detergents and Emulsifiers, for example, in that issued in 1969.
~ 284~6 The polyacetal carboxylate maybe considered to be that described in U.S. patent 4,144,226 and may be made by the method mentioned therein. A typical such product will be of the formula Rl - (CHO)n - R2 COOM
wherein M is selected from the group consistiny of alkali metal, ammonium, alkyl groups of 1 to 4 carbon atoms, tetraalkylammonium groups and alkanolamine groups, both of 1 to 4 carbon atoms in the alkyls thereof, n averages at least 4, and Rl and R2 are any chemically stable groups which stabilize the polymer against rapid depolymeriation in alkaline solution.
Preferably the polyacetal carboxylate will be one wherein m is alkali metal, e.g., sodium, n is from 20 to 200, Rl is H3C or MOOC
or a mixture thereof, R2 is -CH
and n averages from 20 to 100, more preferably 30 to 80. The calculated weight average molecular weights of the polymers will desirably be within the range of 2,000 to ~ - 8 -~ ~4~26 20,000, preferably 3,500 to 10,000 and more preferably 5,000 to 9,000, such as 7,000 to 9,000, specifically, about 8,000.
Although the preferred polyacetal carboxylates have been described above, it is to be understood that they may be wholly or partially replaced by other such polyacetal carboxylates or related organic builder salts described in various Monsanto Co. patents on such compounds, processes for the manufacture thereof and compositions in which they are employed. Also, the chain terminating groups described in the various patents, especially U.S. 4,144,226, may be utilized, providing that they have the desired stabilizing properties, which allow the mentioned builders to be depo-lymerized in acidic media, facilitating biodegradation thereof in waste streams, but maintain their stability in alkaline media, such as washing solutions.
The perborate utilized is a water soluble perborate which is capable of releasing active bleaching oxygen in aqueous media, such as in wash water at elevated temperature.
Such perborate is preferably an alkali metal or equivalent salt and most preferably is sodium perborate tetrahydrate.
Usually the perborate is hydrated but that is not necessary.
Generally the hydrate is the tetrahydrate but it has been found that the monohydrate is also useful and some perborates with contents of water of hydration less than one mole per 2S mole may be especially useful in certain applications or _ g _ ~ 2~45~
when packaged in vapor tight containers (wherein higher hydrates may tend to liquefy, or cake the detergent compo-sition).
While the ordinary higher fatty acid soaps, usual-ly the sodium soa~s, are detergents, they are not generallyconsidered to bc synthetic organic detergents, and according-ly are not to be taken as within the group of such detergents for the purpose of this invention. The soaps do have deter-sive properties but may be employed for other purposes too, such as for their foam limiting characteristics. Among the soaps that may be utilized in the present compositions, those of alkali metals, such as sodium, of 10 to 18 carbon atoms and preferably highly saturated, will be preferred.
Among such are the sodium hydrogenated tallow soaps, sodium stearate and sodium palmitate, but soaps of tallow and mixtures of tallow with coconut oil may also be employed, e.g., 4:1 tallow:coco soaps, as composition components.
In the compositions of the invention other builders than the polyacetal carboxylate may also be present although such are not necessary. Often it will be desired to avoid the presence of phosphorus in the detergent compositions so the polyphosphates, which have been the builders of choice in the detergent art for many years (especially pentasodium tri-polyphosphate), will preferably be omitted from the present formulations. Still, in some instances, they may be present, 4~X~i at least in relatively small proportions, e.g., up to 5 or 10%. Among builders other than polyphosphates, such as sodium tripolyphosphate and tetrasodium pyrophosphate, those which may be desirably incorporated in the present compositions to supplement the building action of the poly-acetal carboxylate include sodium carbonate, sodium bi-carbonate, sodium sesquicarbonate, sodium silicate, zeolites, e.g., Zeolite A, NTA, sodium citrate, sodium gluconate, borax, other borates, and other builders known in the deter-gent art.
Fillers may be present, such as sodium sulfate andsodium chloride, to add bulk to the product when that is considered to be desirable. In liquid compositions, which should usually be employed soon after making, solvents or extenders may be used, such as water, ethanol and isopropanol.
Among the various adjuvants that may be employed are colorants, such as dyes and pigments, perfumes, enzymes, stabilizers, activators (especially activators for causing active oxygen release from perborates), fluorescent bright-eners, buffers, fungicides, germicides and flow promoting agents. Also included among adjuvants, unless in other classes previously mentioned, are various additional components or impurities present with other ingredients. For example, it is known that sodium carbonate and water are often present 4~
with polyacetal carboxylate in Builder U, the product which is the present source of polyacetal carboxylate.
Moisture will usually be present in the invented compositions, either as free moisture or in one or more hydrates. While moisture is not an essential component of these bleaching detergent compositions it will normally be present due to the use of water in manufacturing, and it may help to solubilize other composition components and bind them.
The proportions of components of the invented compositions given below are those for particulate products, which are usually of particle sizes in the 8 or lO to 100 or 140 sieve (or mesh) range, U.5. Sieve Series. However, such proportions also apply to other olid forms, such as bars or cakes, more fine]y divided or coarser powders, granular lS compositions and agglomerates, and also to liquid prepara-tions, althouqh because of their relatively low stability aqueous liquid preparations should be used relatively soon after manufacture. Also, while the proportions of all the components except water may be about the same in liquid preparations, such products are often much more dilute, 80 that the proportion of water or other solvent or a mixture of solvents present may be much greater. In some aspects of the invention the components may be added directly to the wash water, in which case it may be considered that the detergent composition is the wash water containing the various active and other components.
4~
In the particulate solid and other solid detergent compositions of this invention the total proportion of detergent present will normally be from 5 to 40%, more preferably from 10 to 25% and most preferably about 12%.
Such detergent will desirably include either sulfated or sulfonated anionic detergent or nonionic detergent but pre-ferably will include both such detergents. The proportion of anionic detergent present will usually be from 3 to 30%, preferably 4 to 20% and more preferably 4 to 10%, e.g., about 8%, and the proportion of nonionic detergent will be about 2 to 25%, preferably 2 to 10% and more preferably 2 to 6%. The proportion of polyacetal carboxylate builder will usually be within the range of 4 to 50%, preferably 10 to 30%, and more preferably 10 to 25%, e.g., 18~. The perborate content is normally in the range of 10 to 50%, preferably being 10 to 40% and more preferably 15 to 30%, e.g., 22%, which percentages are on the basis of sodium perborate tetrahydrate and may be modified accordingly when the anhydrous salt or a different hydrate is employed. The proportion of soap, when it is present, will usually be in the range of 1 to 10%, preferably 2 to 6%, and the percentage of moisture will normally be from 3 to 20%, preferably 5 to 15%, e.g., about 10%. Such percentages include moisture in hydrate form that is released during heating for two hours at 105C. (the standard moisture analyzer method). The proportions of ~ 284'326 other components, such as fillers,will normally be limited to no more than 40% and usually will be in the range of 0 to 30% or 5 to 20%. Similarly contents of builders other than the polyacetal carboxylate will be limited, generally being less than 25%, such as 3 to 20% or 5 to 15%, but often no such supplemental builders will be present. The total adjuvar.t content will usually not exceed 10% or 20~, and preferably will be less than 5%, with the contents of individual adjuvants generally not exceeding 3% or 5%, and preferably being less than 1 or 2%. For example, sodium carboxy-methyl cellulose, which is a desirable antiredeposition agent, will usually be present within the range of 0.~ to 3%, preferably 0.5 to 2%, e.g., 1%.
In preferred forms of the invention, particulate solid compositions of particle sizes such as those previous-ly described, it is often preferred to spray dry as much of the formulation as feasible so as to obtain substantially uniformly shaped globular particles. Because the perborate i6 heat-unstable it will normally be post-added to the rest of the composition. Of course, to prevent segregation during shipping and storage of the final product it is desirable that the perborate be of shape and particle sizes like those of the rest of the composition. The polyacetal carboxylate may sometimes be spray dried with the detergent composition providing that care is exercised to prevent it 9~6 from being decomposed by heat. However, it may also be post-added, and again the particle sizes for post-adding are desirably the same as those previously mentioned, to avoid product component segregations. In an alternative method of manufacture the various components, in finely divided form, may be merely mixed together. Also, when the initial particle sizes of the components are less than desired, such as in the 160 to 325 mesh range, particles thereof may be agglomerated to the desired size, sometimes with the aid of agglomerating agents, such as a dilute aqueous solution of sodium silicate, and at other times with only water to assist in agglomeration.
When an anionic detergent is the primary detergent of the desired composition it may be spray dried with fillers, lS such as sodium sulfate, builders, such as sodium carbonate, sodium bicarbonate, borax and sodium silicate, and adjuvants, such as fluorescent brighteners, pigments and dyes, and may be spray dried in the normal manner, utilizing a conventional countercurrent or concurrent spray drying tower with drying 20 air entering at about 200 to 600C. (preferably 150 to 300 or 350C. when polyacetal carboxylate is present). Then the polyacetal carboxylate and perborate may be admixed, in either order or conjointly, or the perborate and polyacetal carboxylate may be pre-blended and then mixed with the spray dried beads. When a relatively small proportion of nonionic detergent is to be present with the anionic detergent it may be spray dried with such anionic detergent, fillers, etc., and stable amphoteric and cationic materials that are to be present can also be incorporated in the crutcher and then spray dried with the anionic detergent. However, when more than about 4 or 5~ ~sometimes more than 2~) of nonionic detergent is present in the formula any additional proportion will usually be post-added, as by spraying onto tumbling particles of detergent beads or base beads. Such base beads may be made from any builders, fillers and stable adjuvants of the final product. Then the polyacetal carboxylate and perborate may be post-added. In some instances the poly-acetal carboxylate may be dispersed and/or dissolved in the nonionic detergent, which is heated so as to be in liquid state (or may be dissolved in a solvent) and the combination oS nonionic detergent and polyacetal carboxylate may be sprayed onto the detergent beads or base beads, followed by addition of perborate. Desirably, the particulate material made will be of particle sizes in the ~ to 120 or 10 to 100 mesh range and the manufacturing process will be designed accoxdingly. ~owever, screening may be employed to remove under- and over-sized particles, which may be reworked, ground, agglomerated or otherwise processed to sizes desired.
To manufacture the present products into bar, cake or briquette form the compositions may be extruded, pressed ~ ~84~26 or molded to shape in known manners. To convert them to liquid preparations the components may be dissolved and/or dispersed in liquid media, such as water and/or suitable solvent(s).
To practice the stain removing process of the invention the described composition may be added to "wash water" or the vari-ous components may be so added. ~ormally the concentration of the compositions employed will be in the range of 0.05 or 0.1 to 1.0 or 1.5~, preferably 0~1 to 1.3%, and more preferably 0.15 to 1.1 or 1.2%. Higher concentrations, as from 1.0 to 1.5% or more, are often employed in machine washing according to European practice, which utilizes high temperature wash water, in which the perborate releases active bleaching oxygen.
Usually the washing temperature in America will be in the range of 10 to 55C., often being from 10 to 30C., compared to 60 to - 99, often 70 to 90 or 95C.,in Europe. In American practice lower concentrations, such as from 0.05 to 0.2~, often prefer-ably about 0.07 to 0.15~, of the composition are employed.
Following American practice perborate oxygen is not released to the same extent because the washing temperature is lower. Con-sequently any bleaching effect is not as great as when higher wash temperature are used, unless an activator is also present to assist in the release of active oxygen from the perborate.
Various such activators are known for this purpose and may be employed to adapt the process invention to American practice.
Among such activators are those known as TAED (tetraacetylethy-lene diamine, acyloxybenzene, sulfonates, such as described in U.S. Patent 4,412,934, and TAGU.
~ X~34~326 In the washing or stain removing operation convention-al washing machines will be employed, such as GE automatic washers (top loading), following the American practice, and Miele machines, following European practice. While it is con-sidered that the present compositions operate better than con-trols utilizing sodium tripolyphosphate in place of polyacetal carboxylate, whether washing is at high or low temperatures, providing that equivalent proportions of active oxygen are released from the perborate, it is often preferred to follow the European practice, which does not require the presence of an accelerator to promote the release of active oxygen from the perborate. Various hardnesses of water may be utilized and while it might be expected that the softer the water the better the stain removal, unexpectedly it has been found that even under hard water conditions the present compositions and stain removing processes are superior to controls wherein pentasodium tripolyphosphate is employed instead of the polyacetal carboxy-late. This improved stain removing capacity is most pronounced at elevated temperatures (60 to 90C.) when the stain is a very critical stain, usually found in normal laundry, a combination of particulate and sebum stains, such as may be found on shirt collars and cuffs. The good effect in removing such stains is obtained even when hard water is used, such as that of hard-nesses that are quite high, such as in the 250 - 350 p.p.m.
range, as Xl - 18 -~ ~4~
CaCO3. In addition to better removal of such stains, which is even more evident at 90C. than at 60C., it is found that the invented compositions and processes result in significant improvements with respect to removals of various other typical stains too. Surprisingly then, the present compositions, incorporating a builder which is stable during washing and stain treatment but is degradable in normally acidic waste waters, and omitting one of the best previously known builders, sodium tripolyphosphate, in~combination with synthetic organic detergent (especially a mixture of anionic and nonionic detergents) and perborate bleach, give superior stain removal, which is apparently attributable to the particular unique combination of components employed.
Such effect is obtained even in very hard water, which is unexpected in view of the excellent sequestering activity of the sodium tripolyphosphate builder and its known stability and widespread utility in washing and stain removal opera-tions.
The following examples illustrate but do not limit the invention. Unless it is otherwise indicated, all parts are by weight and all temperatures are in C. in these examples, elsewhere in the specification, and in the claims.
128~926 Component Percent * Sodium linear tridecylbenzene sulfonate 8.0 ~ * Nonionic detergent lNeodol 25-7, a condensation 4.0 product of hiqher fatty alcohols averaging 12 to 15 carbon atoms, and 7 moles of ethylene oxide per mole of fatty alcohol, obtainable from Shell Chemical Co.) * Sodium hydrogenated tallow soap 4.0 * Sodium carboxymethyl cellulose 1.0 Sodium perborate tetrahydrate 22.0 Builder U (79.7% of sodium polyacetal carboxylate, of 22.0 calculated weight average molecular weight of about 8,000, obtained from Monsanto Co.) * Filler (sodium sulfate, anhydrous) 29.0 Moisture 10.0 100. 0 * in spray dried beads A stain removing detergent composition of the above formula is made by spray drying a crutcher mix, contain-ing about 55% of solids and 45% of water (city water of hardness of about 100 p.p.m., as calcium carbonate) and at a temperature of about 50C., into a countercurrent spray drying tower, wherein it is dried to a moisture content of about 10%. The tower inlet air is at about 450C. and at the outlet from the tower such air temperature has been reduced to about 150C. The spray dried beads resulting are ~ rr~dt ~1ar~
~.~849~6 62301-1318 of particle sizes in the range of No's. 10 to 100, U.S. Sieve Series. With such beads there are admixed in an inclined tumb-ling drum the sodium perborate tetrahydrate and Builder U, also of particLe sizes in the 10 to 100 sieve range. When the compo-nent materials are supplied as finer powders and none is spray dried they are (or may be) agglomerated to the desired sizes, alone or together. Such polyacetal carboxylate - perborate agglomerates may be of pro- portions in the range of 1:5 to 5:1 and may contain from 0.1 to 5% of sodium silicate (Na2O:SiO2 =
1:1.6 to 1:3), as a binder.
The product obtained is tested for stain removing action, utilizing a Miele*/multi-stain light reflecting procedure wherein delta Rd's are measured for washed experimental and control swatches. In such procedure the experimental composition and control detergent composition (containing trisodium polyphosphate instead of Builder U) are separately charged to a Miele washing machine at a concentration of about 1.1~ (225 grams per 20 liters of wash water) at 60C., with water over 200 p.p.m. (300 p.p.m) hardness as calcium carbonate, and having a hardness of a 4:1 ratio of calcium ion to magnesium ion. The test specimens employed are of different materials and have been stained with different stains. A
plurality of test cloths is employed for each combination of cloth and stain and average reflectance readings from the cloths are taken after normal washings and *Trade-mark ~ - 21 -~Z84~26 dryings with the experimental composition of this example and are compared to those for the control detergent composi-tion, wherein 22~ of sodium tripolyphosphate is present instead of the Builder U. Such procedures are repeated at 90~C. with the exception that the washing procedure is modified so that half of the detergent composition and half of the control are employed in pre-wash steps and the other halves are employed in the main washings.
By the test method described, which is considered to be a standard for testing stain removal properties of detergent compositions, it is found that the invented compo-sition of this example and use of the washing process of this example result in significant improvements with respect to removals of various typical stains found on items to be laundered, including Spangler sebum/particulate stain on Dacro~ double knit material, liquid makeup on cotton percale, on Qiana jersey and on Dacron double knit materials, Bico9 black pen ink on Dacron-cotton blend material and French dressing on a Dacron double knit, at 60C., and Spangler sebum/particulate stain on Dacron double knit material, liquid makeup on cotton percale, on Dacron-cotton blend and on Qiana jersey, and colored shortening on Dacron double knit,at 90C. The invented compositions and processes were found to be inferior in stain removal to tripolyphosphate-containing controls only for brewed tea stain on polyester/cotton blend and for barbeque sauce on Dacron double knit fJ D~ R 1~, 4~2~;
(both at 60C.), and for liquid makeup on Dacron double knit and for French dressing on Dacron double knit (both at 90C. ) .
Results like those described above are also obtain-able when the experimental formula is varied by increasing the alkylbenzene sulfonate content to 16%, omitting the nonionic detergent and soap, and replacing the 29~ of sodium sulfate with a third each of sodium bicarbonate, sodium carbonate and sodium silicate of Na20:5iO2 ratio of about 1:2.4. Similarly, such second formula may be varied by utilizing a mixture of equal parts of the alkylbenzene sulfonate and sodium lauryl sulfate (totalling 16%) or by omitting the alkylbenzene sulfonate and replacing it with ~ post-sprayed nonionic detergent (Neodol 25-7 or Neodol 23-6.5), after which the sodium perborate and Builder U are admixed with the base beads containing nonionic detergent.
In such instances the improved stain removing property, attributable to the combination of polyacetal carboxylate and perborate in the present formulations, will also be obtained. Instead of the mentioned nonionic detergents other such detergents may be substituted, including the condensation products of ethylene oxide and nonylphenol, as previously described, Pluronics, e.g., F-68, and Neodol 45-11, and mixtures thereof containing two to four components.
Other variations in this example may be made, as ~ -r R ~ D~
~ 3~ ~
by utilizing other builders and fillers than those employed, including small proportions, e.g., 1 to 10 or 2 to 5% of amphoteric and/or cationic detergents (the cationic detergents may be employed as antistatic agents) in the formulas, and/or by varying the proportions of the indicated constituents +10 and +25%, while maintaining them within their respective ranges. Also, the conditions of manufacturing may be varied, as by spray drying essentially all the components (usually except perborate, perfume and enzymes) together, using mild conditions lto prevent degradation of the Builder U).
The formulas of the product of Example 1 are modified by use of a Builder U of calculated weight average molecular weight of about 5,250, which is 83~ of sodium polyacetal carboxylate polymer. Such formulations, when made by the methods described in Example 1, are of improved stain removing properties, compared to controls containing sodium tripoly-phosphate instead of the Builder U polymer, and the experi-mental products exhibit stain removing capabilities like those of the formulations of Example 1. Such is also the case when an equivalent proportion of perborate monohydrate is employed instead of the tetrahydrate,with the difference being made up by inert builder (Na2SO4). The described products are also producible in paste, liquid and bar or 2S cake forms by conventional means, as mentioned previously.
J ~34~2~i In the primary formula of Example 1 the sodium linear tridecylbenzene sulfonate is replaced by sodium dodecylbenzene sulfonate, sodium paraffin sulfonate, sodium olefin sulfonate (averaging about 16 carbon atoms), sodium lauryl sulfate and sodium monoglyceride sulfate, respectively.
When tested by the method described in Example 1 such products are also significantly superior for the removal of stains from laundry, compared to various controls, utilizing other builders instead of the sodium polyacetal carboxylate, among which builders is included pentasodium tripolyphosphate.
In variations of such formulas the composition is modified to include an activating proportion, e.g., about 1%, of TAED (with the sodium sulfate content being correspondingly diminished), with such activator being post-added to the composition. Upon testing in the manner described in Example 1 for use at 60C., but lowering the temperature of the wash water to 30~C., in accordance with American practice, and using a G.E. top-loading washing machine, improved stain removing results are obtained, compared to a control containing sodium tripolyphosphate instead of Builder U. Such is the case with polyacetal carboxylate active polymers of molecular weights of about-5,000 and about 8,00g. However, it is considered that best stain removals are obtained by the primary method of Example 1, which may be modified to have present other polyacetal carboxylates of calculated weight * Monsanto Lot No. 2547312 (M.W. = 5,250) ~* Monsanto Lot No. 2538422 (M.W. = 8,034) ~ ~34~i~6 average molecular weights in the given ranges.
In a modification of this example (Examples l and 2 may also be so modified) a liquid product or slurry is made by replacing the sodium sulfate or other fillers and/or builders (except polyacetal carboxylate) in the various formulas with water. Such products, when made at the same active ingredient concentrations as those of these examples, are also effective stain removers. In still another varia-tion of the invention, the various components of the compo-sition may be separately added to the wash water to obtainthe desired results. Of course, for final commercial products adjuvants will also be present, for example, 0.5%
of perfume, 1% of proteolytic enzyme, 2% of fluorescent brightener composition, 0.2% of colorant, such as Polar Brilliant Blue dye and/or Ultramarine Blue pigment for making a blue product, and 3~ of flow improving agent, such as magnesium silicate hydrate, if thought to be desirable.
It is not considered that employment of any such adjuvants will significantly adversely affect the desirable properties of the invented compositions, or the operations of the invented processes.
From the foregoing description and the examples of compositions and processes within the present invention it is apparent that the combination of polyacetal carboxylate and perborate in the present compositions leads to surpris-ingly improved stain removing products and methods, especially ~284926 with respect to hard to remove combination sebum and partic-ulate stains on polyesters, even when the washing medium is a hard water. It is especially surprising that such results ehould be obtained, considering that sodium tripolyphosphate has been the most effective detergent builder employed in the past, and also considering that the proportion of active polyacetal carboxylate polymer employed is less than the proportion of polyphosphate in the control compositions.
Thus, it is thought that that a significant advance in the stain removing and cleaning arts has been made by the pre-sent invention.
The invention has been described with respect to various illustrations and embodiments thereof but it is not to be limited to these because it will be evident that one of skill in the art, with the present specification before him or her, will be able to utilize equivalents and substitutes without departing from the invention.
Claims (10)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A bleaching detergent composition which comprises about 3 to 30% of a synthetic organic detergent or a mixture of such detergents, about 4 to 50% of a polyacetal carboxylate builder for such detergent(s) which is of a molecular weight in the range of 3,500 to 10,000, and 10 to 50% of a perborate.
2. A composition according to claim 1 which is particulate and substantially free of phosphate and wherein the synthetic organic detergent is selected from the group consisting of anionic, nonionic and mixed anionic and nonionic detergents and the perborate is an alkali metal perborate selected from the group consisting of anhydrous sodium perborate and sodium perborate hydrate having a content of water of hydration up to four moles per mole.
3. A detergent composition according to claim 2 which is phosphate-free and wherein the detergent is a mixture of anionic detergent and nonionic detergent, the polyacetal carboxylate is of a calculated weight average molecular weight in the range of 5,000 to 9,000 and the alkali metal perborate is a sodium perborate.
4. A detergent composition according to claim 3 which comprises about 3 to 30% of sulfated or sulfonated anionic detergent having a lipophilic moiety that includes an alkyl chain of 3 to 20 carbon atoms, and about 2 to 25% of nonionic detergent which is a condensation product of ethylene oxide and a lipophilic group donating compound capable of forming the nonionic detergent with the ethylene oxide, 4 to 50% of polyacetal carboxylate builder and 10 to 50% of a hydrated sodium perborate.
5. A detergent composition according to claim 4 which comprises about 4 to 20% of higher alkylbenzene sulfonate wherein the higher alkyl is of 10 to 18 carbon atoms, about 2 to 10% of a nonionic detergent which is a condensation product of ethylene oxide and higher fatty alcohol, wherein the higher fatty alcohol is of 10 to 18 carbon atoms and the nonionic detergent contains from 3 to 20 moles of ethylene oxide per mole, about 10 to 30% of polyacetal carboxylate builder wherein the carboxylate is sodium carboxylate, about 10 to 40% of sodium perborate tetrahydrate, about 3 to 20% of moisture, including hydrate moisture which is removable at 105°C., and the balance of filler(s) and/or other builder(s) and/or adjuvant(s).
6. A detergent composition according to claim 5 which comprises 4 to 10% of sodium linear tridecylbenzene sulfonate, 2 to 6% of higher fatty alcohol polyethoxy ethanol wherein from 5 to 9 moles of ethylene oxide are condensed with a mole of higher fatty alcohol of an average of 12 to 15 carbon atoms, 10 to 25% of polyacetal carboxylate builder of calculated weight average molecular weight in the range of 7,000 to 9,000, 15 to 30% of sodium perborate tetrahydrate, 2 to 6% of sodium higher fatty acid soap wherein the higher fatty acid is of 10 to 18 carbon atoms, 0.3 to 3% of sodium carboxymethyl cellulose, and 5 to 15% or moisture.
7. A detergent composition according to claim 6 which comprises about 8% of sodium linear tridecylbenzene sulfonate, about 4% of higher fatty alcohol polyethoxy ethanol wherein about 7 moles of ethylene oxide are condensed with a mole of higher fatty alcohol of an average of 12 to 15 carbon atoms, about 18% of polyacetal carboxylate builder of calculated weight average molecular weight of about 8,000, about 22% of sodium perborate tetrahydrate, about 4% of sodium tallow soap, about 1% of sodium carboxymethyl cellulose and about 10% of moisture.
8. A process for removing mixed particulate and sebum stains from fibrous polyester materials which comprises washing such stained fibrous materials in wash water at a temperature in the range of 50 to 90°C. with a detergent composition of claim 1 at a concentration in the wash water in the range of 0.05 to 1.5% by weight.
9. A process according to claim 8 wherein the detergent composition is substantially free of phosphate and the perborate is a sodium perborate having up to 4 moles of water of hydration per mole, and the wash water is of a hardness over 200 p.p.m., as calcium carbonate.
10. A process according to claim 9 wherein the detergent composition comprises about 4 to 20% of higher alkylbenzene sulfonate wherein the higher alkyl is of 10 to 18 carbon atoms, about 2 to 10% of a condensation product of ethylene oxide and higher fatty alcohol, wherein the higher fatty alcohol is of 10 to 18 carbon atoms and the nonionic detergent contains from 3 to 20 moles of ethylene oxide per mole, about 10 to 30% of polyacetal carboxylate builder of molecular weight in the range of 7,000 to 9,000, wherein the carboxylate is sodium carboxylate, about 3 to 20% of moisture, including hydrate moisture which is removable at 105°C., and the balance of filler(s) and/or other builder(s) and/or adjuvant(s), and the washing is at a temperature in the range of 60 to 90°C. in wash water of a hardness in the range of 250 to 350 p.p.m., as calcium carbonate, and at a concentration of detergent composition in the wash water in the range of 1.0 to 1.5% and is conducted in an automatic washing machine.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US61646384A | 1984-06-01 | 1984-06-01 | |
| US616,463 | 1984-06-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1284926C true CA1284926C (en) | 1991-06-18 |
Family
ID=24469575
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000482759A Expired - Lifetime CA1284926C (en) | 1984-06-01 | 1985-05-30 | Bleaching synthetic detergent composition |
Country Status (23)
| Country | Link |
|---|---|
| JP (1) | JPS612800A (en) |
| KR (1) | KR920006028B1 (en) |
| AT (1) | AT394383B (en) |
| AU (1) | AU573832B2 (en) |
| BE (1) | BE902552A (en) |
| CA (1) | CA1284926C (en) |
| DE (1) | DE3518656A1 (en) |
| DK (1) | DK237685A (en) |
| ES (1) | ES8609447A1 (en) |
| FI (1) | FI852194L (en) |
| FR (1) | FR2565245B1 (en) |
| GB (1) | GB2160217B (en) |
| GR (1) | GR851340B (en) |
| IT (1) | IT1182249B (en) |
| LU (1) | LU85930A1 (en) |
| MX (1) | MX162747A (en) |
| NL (1) | NL8501573A (en) |
| NO (1) | NO852162L (en) |
| NZ (1) | NZ212082A (en) |
| PH (1) | PH21670A (en) |
| PT (1) | PT80558B (en) |
| SE (1) | SE8502353L (en) |
| ZA (1) | ZA853573B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA851897B (en) * | 1984-04-02 | 1986-10-29 | Colgate Palmolive Co | Non-caking bleaching detergent composition containing a lower hydrate of sodium perborate |
| US4720399A (en) * | 1984-06-01 | 1988-01-19 | Colgate-Palmolive Company | Process for manufacture of particulate built nonionic synthetic organic detergent composition comprising polyacetal carboxylate and carbonate and bicarbonate builders |
| SE8502149L (en) * | 1984-06-01 | 1985-12-02 | Colgate Palmolive Co | ENHANCED SYNTHETIC DETERGENT COMPOSITION |
| GB8519046D0 (en) * | 1985-07-29 | 1985-09-04 | Unilever Plc | Detergent compositions |
| GB8713756D0 (en) * | 1987-06-12 | 1987-07-15 | Procter & Gamble | Liquid detergent |
| KR100459858B1 (en) * | 2002-03-08 | 2004-12-04 | 위니아만도 주식회사 | A method of charging a precocious meat |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4088615A (en) * | 1975-12-30 | 1978-05-09 | Union Carbide Corporation | Method of improving the diecuttability of polyester urethane foam and the improved diecuttable polyester urethane foams themselves |
| US4144226A (en) * | 1977-08-22 | 1979-03-13 | Monsanto Company | Polymeric acetal carboxylates |
| US4315092A (en) * | 1977-08-22 | 1982-02-09 | Monsanto Company | Polyacetal carboxylates |
| EP0015024A1 (en) * | 1979-02-16 | 1980-09-03 | THE PROCTER & GAMBLE COMPANY | Detergent compositions containing binary builder system |
| US4455249A (en) * | 1982-10-21 | 1984-06-19 | Colgate-Palmolive Company | Stabilized bleach and laundering composition |
| GR79172B (en) * | 1983-01-28 | 1984-10-02 | Procter & Gamble | |
| ZA851897B (en) * | 1984-04-02 | 1986-10-29 | Colgate Palmolive Co | Non-caking bleaching detergent composition containing a lower hydrate of sodium perborate |
| GB8412537D0 (en) * | 1984-05-17 | 1984-06-20 | Unilever Plc | Detergent powder compositions |
-
1985
- 1985-05-10 ZA ZA853573A patent/ZA853573B/en unknown
- 1985-05-13 SE SE8502353A patent/SE8502353L/en not_active Application Discontinuation
- 1985-05-14 NZ NZ212082A patent/NZ212082A/en unknown
- 1985-05-23 AU AU42791/85A patent/AU573832B2/en not_active Ceased
- 1985-05-24 DE DE19853518656 patent/DE3518656A1/en not_active Withdrawn
- 1985-05-28 DK DK237685A patent/DK237685A/en not_active Application Discontinuation
- 1985-05-29 PH PH32330A patent/PH21670A/en unknown
- 1985-05-29 KR KR1019850003725A patent/KR920006028B1/en not_active IP Right Cessation
- 1985-05-29 MX MX205446A patent/MX162747A/en unknown
- 1985-05-29 AT AT0161285A patent/AT394383B/en not_active IP Right Cessation
- 1985-05-30 FR FR8508158A patent/FR2565245B1/en not_active Expired
- 1985-05-30 GR GR851340A patent/GR851340B/el unknown
- 1985-05-30 PT PT80558A patent/PT80558B/en unknown
- 1985-05-30 CA CA000482759A patent/CA1284926C/en not_active Expired - Lifetime
- 1985-05-30 ES ES543669A patent/ES8609447A1/en not_active Expired
- 1985-05-30 NO NO852162A patent/NO852162L/en unknown
- 1985-05-31 BE BE0/215106A patent/BE902552A/en not_active IP Right Cessation
- 1985-05-31 NL NL8501573A patent/NL8501573A/en not_active Application Discontinuation
- 1985-05-31 FI FI852194A patent/FI852194L/en not_active Application Discontinuation
- 1985-05-31 LU LU85930A patent/LU85930A1/en unknown
- 1985-05-31 IT IT48152/85A patent/IT1182249B/en active
- 1985-06-01 JP JP60119656A patent/JPS612800A/en active Pending
- 1985-06-03 GB GB08513936A patent/GB2160217B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| SE8502353L (en) | 1985-12-02 |
| MX162747A (en) | 1991-06-24 |
| PT80558A (en) | 1985-06-01 |
| NL8501573A (en) | 1986-01-02 |
| SE8502353D0 (en) | 1985-05-13 |
| DK237685A (en) | 1985-12-02 |
| PT80558B (en) | 1986-12-15 |
| GR851340B (en) | 1985-11-25 |
| JPS612800A (en) | 1986-01-08 |
| ZA853573B (en) | 1986-12-30 |
| NO852162L (en) | 1985-12-02 |
| DE3518656A1 (en) | 1985-12-05 |
| IT1182249B (en) | 1987-09-30 |
| FR2565245A1 (en) | 1985-12-06 |
| FR2565245B1 (en) | 1987-01-16 |
| BE902552A (en) | 1985-12-02 |
| ATA161285A (en) | 1991-09-15 |
| AU4279185A (en) | 1985-12-05 |
| ES8609447A1 (en) | 1986-08-16 |
| GB2160217A (en) | 1985-12-18 |
| FI852194A0 (en) | 1985-05-31 |
| DK237685D0 (en) | 1985-05-28 |
| AU573832B2 (en) | 1988-06-23 |
| GB2160217B (en) | 1987-12-02 |
| NZ212082A (en) | 1988-01-08 |
| ES543669A0 (en) | 1986-08-16 |
| IT8548152A0 (en) | 1985-05-31 |
| LU85930A1 (en) | 1986-02-18 |
| KR920006028B1 (en) | 1992-07-27 |
| PH21670A (en) | 1988-01-13 |
| KR860000364A (en) | 1986-01-28 |
| FI852194L (en) | 1985-12-02 |
| GB8513936D0 (en) | 1985-07-03 |
| AT394383B (en) | 1992-03-25 |
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