CA1239561A - Built synthetic detergent composition - Google Patents
Built synthetic detergent compositionInfo
- Publication number
- CA1239561A CA1239561A CA000482671A CA482671A CA1239561A CA 1239561 A CA1239561 A CA 1239561A CA 000482671 A CA000482671 A CA 000482671A CA 482671 A CA482671 A CA 482671A CA 1239561 A CA1239561 A CA 1239561A
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- Prior art keywords
- detergent
- higher fatty
- fatty alcohol
- ethylene oxide
- range
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/06—Hydroxides
-
- 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
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
Abstract Of The Disclosure Heavy duty built synthetic organic detergent compositions, which are especially useful for washing laundry in wash water of medium hardness, include either anionic or nonionic synthetic organic detergents or mixtures thereof and a polyacetal carboxylate builder of lower molecular weight, i.e., 3,000 to 6,000. The detergent(s) perferably is/are a sulfated higher fatty alcohol ethoxylate and/or a condensation product of ethylene oxide and a higher fatty alcohol, and the polyacetal carboxylate is a sodium carboxylate. The compositions are especially useful for cold water washing of laundry and in such washing processes they are found to be superior in soil and stain removal to similar compositions wherein the polyacetal carboxylate is of higher molecular weight. They are also superior in such performance to control compositions in which sodium tripolyphosphate is present instead of the polyacetal carboxylate builder. Also within the invention are washing processes in which the described compositions or essential detersive and builder components thereof are employed.
Description
123~6~l This invention relates to a built synthetic organic detergent composition. More particularly, it relates to such a composition containing a building proportion of a lower molecular weight polyacetal carboxylate builder for the synthetic organic detergent. The invention also includes prowesses for washing soiled fibrous materials, in which processes the described compositions or the components thereof are utilized.
Synthetic organic detergent compositions in which anionic and/or non ionic detergents have been employed as the detersive components and organic or inorganic builder salts have been present have long been employed commercially.
Among the synthetic organic detergents those which have generally been preferred in the past have been the anionic detergents but non ionic detergent compositions and mixed anionic-nonionic products have been successfully marketed, too. Various organic and inorganic builder salts have been included in commercial home laundry detergent compositions ~L239~
and of these until very recently sodium tripolyphosphate was almost invariably the most preferred. Such polyphosphate is an excellent builder which is safe to the consumer and is reasonably priced, while yet being extremely effective for its intended building purpose. However, in recent years phosphorus has been blamed for inland water pollution due to eutrophication and for that reason its use in detergent compositions has been controlled, restricted or prohibited in various political jurisdictions. Accordingly, efforts have been made to manufacture detergent compositions that are phosphate-free and which yet are effective heavy duty detergents.
Among non-phosphate compounds that have been suggested for use as builders in detergent compositions are the polyacetal carboxylates. Such compounds have been described in various U.S. and foreign patents. For example, detailed descriptions of them have been given in U.S. patents 4,144,226 and 4,146,495, both assigned to Monsanto Company.
Normally, according to such patents, the molecular weights of such materials will be in the range of 1,000 to 40,000 or more, preferably 1,000 to 20,000 and more preferably 5,000 to 10,000. However, while the anionic and non ionic synthetic organic detergents and the polyacetal carboxylates of this invention have been disclosed in the prior art as detergent composition components, such art has not suggested and does I
not make obvious the employment of a combination of synthetic organic detergent having an ethics group therein with a polyacetal carboxylate, the molecular weight of which is in a comparative narrow low range. Such compositions, it has been found by applicant, exert improved cleaning effects, better removing hard to remove soils and stains from a variety of fibrous substrate materials during cold water washing in medium hardness water, compared to similar compositions including a polyacetal carboxylate of higher molecular weight, and are also superior to control compositions in which the polyacetal carboxylate is replaced by a polyp phosphate builder.
In accordance with the present invention a built synthetic organic detergent composition, especially useful for washing laundry in cold water of a hardness in the range of 50 to 150 ppm. as calcium carbonate, comprises from 5 to 30% of a synthetic organic detergent selected from the group consisting of anionic and non ionic synthetic organic detergents and mixtures thereof, which detergent(s) contain(s) at least one ethics group per molecule, 5 to 95~ of polyacetal carboxylate builder of calculated weight average molecular weight in the range of 3,000 to 6,000, and the balance of such composition, if any, of adjutant and/or filler(s) and/or builder(s) and/or delineate. Preferably, the anionic detergent is a sulfated higher fatty alcohol Lowe ethoxylate and the non ionic detergent is a condensation product of ethylene oxide and a higher fatty alcohol. While particulate detergent compositions are preferred such compost-lions can be of other types too, including bars, cakes, liquids, pastes and powders. When particulate products are made various processes may be employed, such as spray drying, spray cooling, agglomeration, granulation, comminution and compaction.
Also included within the invention are processes for washing soiled fibrous materials by utilizing the described compositions to wash the soiled materials in wash waters of harnesses in the 50 to 150 ppm. range and at temperatures in the range of 10 to 70C., preferably 10 to 30C. Additionally, processes for washing laundry with the synthetic organic detergent and polyacetal carboxylate components of the described compositions are parts of this invention.
Although cat ionic and/or amphoteric detergents may be included in minor proportions in the compositions of the present invention, they will normally be limited to a 10~
total thereof and preferably will be held to less than 5%, if present, The primary detergents employed in accordance with the present invention are anionic and/or non ionic. Of the anionic detergents the sulfated and/or sulfonated lipophilic materials having an alkyd chain of 8 to 20 carbon ~23~56~L
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 detergents, including ammonium and lower alkanolamine (such as triethanolamine), 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 are the linear higher alkylbenzene sulfonates, the monoglyceride sulfates, higher fatty alcohol sulfates, paraffin sulfonates and olefin sulfonates. In all of such compounds the alkyd (or aureole, for the monoglyceride sulfates) group present will be in the range of 10 or 12 to 18 carbon atoms. While some such alkyd groups may include branching they will still be of a carbon chain length within the described range. Although the mentioned anionic detergents are useful in the practice of the invention that which is considered most useful and most effective, in combination with the polyacetal carboxylate builder, is an anionic detergent which includes an ethics group. Among these the most preferred are the sulfated polyethoxylated higher alkanols, wherein such alkanols may be synthetic or natural, and which contain from 3 to 20 or 30 ethics groups per mole.
Preferably, such detergents are alkali metal salts, e.g., sodium salts, the higher fatty alcohols thereof are of 12 1~;?3956~l Jo 18 carbon atoms and the detergents contain from 3 to 12, preferably 3 to 7, e.g., 3 or 5 molar proportions of ethics groups per mole.
The non ionic detergents, which may be employed as the primary detergents in place of the anionic detergents, or may be used with the avionics, are preferably normally solid materials (especially when being incorporated in solid or particulate solid products) and will preferably be condemn-station 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 preferably 5 to 9 moles, e.g., about 6.5 to 7 moles of ethylene oxide per mole of fatty alcohol. Among other non ionic detergents that are also useful are the ethylene oxide condensation products of alkyd phenols of 5 to 12 carbon atoms in the alkyd 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 non ionic detergents in which a lipophilic group, such as higher alkyd, alkylphenyl, polyoxy-lower alkaline, e.g., polyoxypropylene, is joined to a polyoxyethyleneethanol by reaction with ethylene oxide.
356~l.
The polyacetal carboxylate may be considered to be of the type that is 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 Al - (Sheehan R2 COO
wherein M is selected from the group consisting of alkali metal, ammonium, alkyd groups of 1 to 4 carbon atoms, twitter alkylammonium groups and alkanolamine groups, both of 1 to 4 carbon atoms in the alkyds thereof, n averages at least 6, and Al and R2 are any chemically stable groups which stabilize the polymer against rapid depolymerization in alkaline soul-lion. Preferably the polyacetal carboxylate will be one wherein M is alkali metal, e.g., sodium, Al is HO- or H3C-CO-or a mixture thereof, R2 is 0,CH2CH3 -OH
SHEA
and n averages from 15 to 120, more preferably 40 to 70.
The calculated weight average molecular weights of the polymers will normally be within the range of 3,000 to ~.3956~
6,000, preferably 4,000 to 6,000 and more preferably 4,500 to swish as about 5,250.
though the preferred polyacetal carboxylates have been described above, it is to be understood that they may be wholly or partially replaced at least in part 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 compost-tions,if of the same molecular weights. The various chain terminating groups described in the various patents, especially U.S. ~,144,226, may be utilized, providing that they have the desired stabilizing properties, which allow the mentioned builders to be depolymerized in acidic media, facilitating biodegradation thereof in waste streams, but maintain their stability in alkaline media, such as washing solutions.
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 tripolyphosphate), will preferably be omitted from the present formulations. Still, in some instances, they may be present, at least in relatively small proportions, e.g., up to 5 or 10%. Among builders other than polyphosphates such ~2~S6~
as sodium tripolyphosphate and tetrasodium pyrophosphate, those which may be desirably incorporated in the present compositions to supplement the building action of the polyp acutely carboxylate include sodium carbonate, sodium bit carbonate, sodium sesquicarbonate, sodium silicate, zeolites,e.g., Zealot A, NAT, sodium citrate, sodium gluconate, borax, other borate, and other builders known in the deter-gent art. Fillers may be present, such as sodium sulfate and sodium 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, delineates, such as solvents, dispersants, extenders and antifreezes, may be present, as well as adjutants, such as buffers, thickeners and stabilizers. The usual delineates include water, ethanol, lo isopropanoland propylene glycol, and the adjutants include gums, clays, polymers, and salts.
Among the various other adjutants that may be employed in particulate compositions (but some can also be used in liquids) are colorants, such as dyes and pigments, perfumes, enzymes, stabilizers, activators (especially activators for causing active oxygen release from perorate, if present), fluorescent brighteners, fungicides, germicides and flow promoting agents. Also included among adjutants, unless in other classes previously mentioned, are various additional components or impurities that may be present with other ingredients. For example, it is known that sodium carbonate and water are often present with polyacetal carboxylate in Builder U, the product which it the present source of polyacetal carboxylate.
~Z3956~
Moisture will usually be present in the invented solid (including particulate) compositions, either as free moisture or in one or more hydrates. While moisture is not an essential component of these improved detergent compost-lions it will normally be present due to the use of water in manufacturing, and it may help to syllables other compost-lion components and bind them together, as is usually desired.
The proportion of total synthetic organic detergent may be a detersive proportion up to 40% of the present compositions but normally will be within the range of 5 to 30%, preferably 5 to 25% and more preferably 10 to 20%, e.g., about 15%. Such proportions normally will be for either the sodium higher fatty alcohol polyethoxylate sulfate anionic detergent, the non ionic detergent which is a condemn station product of higher fatty alcohol and ethylene oxide or a combination of the two. At times when combinations of such two detergents are employed the proportions thereof will generally be within the range of ratios of 1:5 to 5:1, preferably 1:3 to 3:1 and more preferably 1:2 to 2:1, e.g., 1:1. In such compositions the proportion of higher fatty alcohol polyethoxylate sulfate will usually be in the range of 2.5 to 27.5%, preferably 3 to 12% and more preferably 5 to 10~. The percentages of higher fatty alcohol polyoxy-ethylene condensation product in such compositions will be the complements of the percentages of such anionic detergent, ~;~395~;1 with such non ionic detergent percentages being in the same ranges as given previously for the anionic detergent, with the ratio of the anionic detergent to the non ionic detergent being within the range of ratios mentioned, and with the total of anionic and non ionic detergents being deter-size proportions in the ranges previously given.
The proportion of polyacetal carboxylate builder is a building proportion (or is such a proportion in combine-lion with any other builders that may be present). The polyacetal carboxylate builder may be from 5 to 95% of the composition, preferably being from 10 to 50% thereof, more preferably 15 to 40~, and most preferably about 20 to 30%
thereof, e.g., about 25~. Such concentration is on the basis of the active polymer, which normally constitutes about 80 to 87~ or available sources of the polyacetal carboxylate builders, being 83~ of Lot No. 2547312 of Builder U (obtained from Monsanto Company), which is of a calculated weight average molecular weight of 5,250, and which Cantonese of sodium carbonate, with the balance being mostly water.
The ratio of synthetic organic detergent to polyp acutely carboxylate will normally will be in the range of 1:10 to 2:1, preferably being 1:5 to 1:1, more preferably being 1:3 to 4:5, e.g., 5:8. Such ratios include detergents other than those containing at least one ethics per molecule, ~23~5~
but such, if present, will be only a minor part, preferably less than 1/5 and more preferably less than 1/10 of the total detergent.
The other components of the present compositions, S in addition to the synthetic organic detergent(s) and sodium polyacetal carboxylate(s),will be other builder(s) and/or filler(s) and/or solvent(s) and/or delineate and/or dispel-sent and/or adjutant. While technically, only the detergent and polyacetal carboxylate are required components of the invention in its broadest aspects, normally other materials will also be present for their supplementing properties. Any supplementing builder materials that may be present will normally be limited to 50~, preferably being from 2 or 3 to 40~ and more preferably from 5 to 30%. Among the move preferred of the supplementing builders are sodium carbonate, sodium bicarbonate, Zealot A (but other zealots may also be employed), sodium silicate of Nash ratio in the range of 1:1.6 to 1:3.0, preferably 1:2.0 to 1:2.6, and in some cases (although not preferred), polyphosphates, such as sodium ~ripolyphosphate and tetrasodium pyrophosphate.
The proportions of such individual components will usually be limited to 30% and preferably will be no more than 20%.
The proportion of sodium carbonate which may be employed is more preferably 5 to land the quantity of sodium silicate is more preferably from 3 to 12%. If phosphates are present the proportions thereof will preferably be limited to 10% or less.
~,2395~;1 The content of filler in the present formulations will normally be no more than 70~, preferably being in the range of 10 to 60~, more preferably 10 to 40%. While such filler is usually sodium sulfate, it may also include a minor proportion, less than half thereof, of other filler materials, such as sodium chloride.
Adjutants in the invented compositions wit]. normal-lye total no more than 20% and preferably will not exceed 10%
with the exception that when bleaching material such as sodium perorate, is employ edit can constitute up to about 30~ of the product), and preferably the total adjutant content will be less than Wyeth individual adjuvant.contents generally not exceeding I or 5%, and preferably individually being less than 1 or 2%. Thus, if a sodium soap of a higher fatty acid (10 to I carbon atoms) is present, (for its foam diminishing property) it might be desired to employ 1 to 4% thereof and if sodium carboxymethyl cellulose is utilized (as an anti redeposition agent), the proportion thereof may be in the range of 0.3 to I preferably being about I In liquid preparations highly porous silica products, such as those sold under the trade name Cab-O-Sil~, may be employed in proportions from 0.5 to 5% to help to maintain the polyacetal carboxylate suspended, and from 1 to 5% of hydrotrope(s), such as sodium zillion sulfonate, may be present to promote physical stability and uniformity of the Lowe product. The moisture contents of the invented products will usually be from 3 to 20~, preferably 5 to 15% and more preferably 5 to 12%, for solid or particulate solid products, and for liquids may increase to proportions in the range of 20 to 90~, preferably 25 to 70~ and more preferably 30 to 60%. Part of the water content of liquid (or paste) prepare-lions may be replaced by other solvents, with the percentages of such other solvents (such as ethanol) in the final product normally being in the range of 2 to 30%, preferably 5 to 20%, if present. Such supplementary solvents may help to syllables composition components and can be used to control product viscosity.
he manufacture of the invented compositions may be conducted in any suitable conventional manner, whether solid or liquid products are being made. For liquid products the delineate (solvent or dispersant) may have the various components added thereto, normally preferably with a hydrotrope or other dispersing agent for the polyacetal carboxylate and any other insoluble present, being in the liquid medium when the various components are admixed therewith. Admixing may be sequential or simultaneous with sequential admixing being the usual practice. The order of additions that is followed normally will not matter significantly but usually any colorants and perfumes will be admixed near the end of the procedure. Often too, viscosity adjusting materials will be ~L239~;6~
added after other components. In some instances it may be desirable to withhold some of the solvent for final addition, whereby a final thinning of the mix may be obtained, when desired. Various types of mixers may be employed and in some instances utilization of homogenizing mixers may be preferred. Instead of the liquid form, with viscosities in the readily plowable range, dispensable through a narrow-necked bottle in a practical manner, non-flowing pastes may be produced, which normally will include greater proportions of a thickening agent and often lesser proportions of solvent or delineate.
To make the preferred particulate solid compositions, which will usually be of particle sizes in the 8 to 120 or 10 to 100 sieve (U.S. Sieve Series) range, it will often be preferred to spray dry as much of the formulation as is feasible, so as to obtain substantially uniformly shaped globular particles. because the polyacetal carboxylate of the present compositions can be adversely affected by heat it may be desired to post-add it to other components of the product that have previously been spray dried to form what may be referred to as "base" beads. If the polyacetal carboxylate is to be post-added it will be preferred that it be of essentially the same shapes, particle sizes and approximate density as the rest of the composition so as to inhibit segregations during shipping and storage. However, ~L~3~561 even if more finely divided powdered polyacetal carboxylate is employed, such as that of particle sizes in the lo or 160 to 200 or 325 mesh (or sieve number) range, it has been found that such particles will often adhere to the larger beads, maintain the product in the desired size range and be essentially non-segregating (although, of course, results will not be as good in this respect as when the various components of the composition are all of the same sizes, shapes and bulk density).
lo If the polyacetal carboxylate is spray dried with the detergent composition care will be exercised to prevent its decomposition due to its exposure to high spray tower drying air temperatures. When spray drying is unavailable or when costs are to be minimized the various components of the present compositions may be mixed together, as powders, and may be agglomerated to the desired lo to 100 sieve size, or they may be mixed together as fine powders, usually in the 100, 160 or 200 to 325 mesh range. When a non ionic detergent is to be present in the product in a significant proportion the major proportion thereof may be post-sprayed onto previously spray dried beads or onto particles ox other components of the composition. Normally, no more than about 4% of non ionic detergent, on a final product basis, will be in a spray dried product, unless added after spray drying, due to decomposition of the non ionic detergent that can occur at elevated tower temperatures when more than a relatively small proportion thereof is present in the cxutcher slurry being spray dried. Other temperature sensitive components of the product may also be post-added so as to avoid undesir-able subjections to elevated temperatures. Thus, if bleaching agent, such as sodium perorate, is to be present it the for~ulation,it will ye post-added, as will be enzyme powder, perfume and other heat sensitive components. On the other hand, materials like the inorganic builders, such as sodium carbonate, sodium bicarbonate, sodium silicate and zealots, and fillers, such as sodium sulfate, help to make strong, attractive and free flowing spray dried beads and preferably will be incorporated in crutches slurries to be spray dried for their physical characteristics, as well for their building and filling functions.
In the practice of the washing process of this invention, wherein soiled (and stained) fibrous materials, such as conventional clothing and "laundry" fabrics, of cotton, polyester-cotton blends, polyesters, acrylics, nylons, acetates, rayons and various blends thereof, are washed in an aqueous washing medium, such medium will contain a suitable detergent, as described, and a polyacetal car boxy-late of the desired calculated weight average molecular weight. Preferably, such components will be parts of a detergent composition but it is within the invention to ~23~3~;6~
charge such materials separately to the wash water. Although improvements in wishing effects are obtainable with the described compositions based on the previously mentioned preferred non ionic detergent at intermediate or medium water harnesses and at higher harnesses too, during both cold water and hot water washing, the most significant improve-mints in such cases are when the wash water is of medium hardness. Also, when the detergent is the preferred anionic detergent the most significant improvement is for cold water washing with water of medium hardness, with cold water washing with water of higher hardness also being improved but not to as great an extent. Thus, preferred conditions for washing with the invented compositions, whether anionic, non ionic or mixed anionic and non ionic detergents are em-plowed, will be in cold water (10 to 30C.) of medium hard-news (50 to 150 ppm., as calcium carbonate). Such prefer-fences also apply when the active components are employed and are separately added to the wash water in an automatic washing machine. Yet, in many cases the wash water may be 20 of a higher hardness, such as 150 or 200 to 300 or 400 ppm., and may be at a higher temperature, often up to 70C.
Preferably the washing will be done with a deter-gent composition of this invention and from 0.05 to 0.5%
thereof will be used, more preferably 0.1 to 0.3~ and most 1239~;61 preferably about 0.15%. Wash waters used will normally contain from 0.0025 to 0.15% of the synthetic organic deter-gent(s) and 0.0025 to 0.475% of the polyacetal carboxylate.
Preferred ranges of such materials will be 0.005 to 0.075~
and 0.01 to 0.15%, respectively and in the 0.15~ concentra-lion of the composition preferred proportions of the deter-gent and polyacetal carboxylate builder will be about 0.0225%
and about 0.0375~, respectively. The water employed will desirably be of a hardness of 50 to 150 ppm. and at a temperature in the range of 10 to 70C., preferably 10 to 30C., e.g., 21C. The water hardness will more preferably be about 100 ppm., as calcium carbonate (usually with the ratio of calcium to magnesium hardness being within the range of 1:1 to 10:1, e.g., 3:2 to 4:1.
Under the conditions described, improved cleanings are obtained using the preferred anionic and/or non ionic detergents of this invention with the described low mole-ular weight polyacetal carboxylate. When, in such compost-lions, the low molecular weight polyacetal carboxylate is replaced by a similar material but of higher molecular weight (8034) the cleaning is significantly less, especially in cold water washing in a medium hardness water. When other detergents than those which have been taught herein to be preferred are employed with the described polyacetal carboxylate of this invention results obtained are notice-ably inferior to those wherein the preferred detergents are 1~3g~6~
utilized with the polyacetal carboxylate. Also, with such other detergents it has been noted that the higher molecular weight polyacetal carboxylate appears to be slightly more effective than the lower molecular weight carboxylate, which is the opposite of the results noted with respect to the invented compositions. Also, when the builder of this invention is replaced by the prior art standard and preferred builder, sodium tripolyphosphate, washing results are notice-ably inferior to those of this invention.
The following examples illustrate but do not limit the invention. Unless otherwise noted all parts are by weight and all temperatures are in C., in these examples, the rest of the specification and the claims.
15 Parts of Noodles, which is the sodium salt of a polyethoxylated (3 ethoxies) higher fatty alcohol (of an average of 12 to 15 carbon atoms) sulfuric acid, obtainable from Shell Chemical Company, 30 parts of Builder U (Lot 2547313, containing 83% of sodium polyacetal car boxy-late of molecular weight of 5,250, 3.9% of sodium carbonate and the balance mostly water) end 55 parts of sodium sulfate, an hydrous, are dissolved at a concentration of 0.15~ in wash water (0.0225~ of the detergent, 0.045% of the builder and 0.0825~ of the filler being in the water) at a temperature of 21C. and of hardness of 100 ppm., as calcium carbonate ~23956~
(with the Cam ratio in the water being about 3:2), and the wash water is used to wash test swatches of various soils and stains on various substrate fabrics in a Tergotomete~laboratory washing machine, employing a ten minute wash cycle. The swatches are dried and their light reflectance are measured and from such reflectance of any remaining soils and stains on the different materials, soil Rand stain) removal indices are computed. The higher the index the whiter the test swatch after washing and the more effective the washing operation. Such test is repeated with a standard control detergent composition formula, in which sodium tripolyphosphate is substituted for the sodium polyacetal carboxylate. A very significant improvement (plus 21) over the control is obtaiIIed. Lyon such test is repeated except for the replacement of the anionic Nudely 25-3S with non ionic Nudely 25-7 (condensation product of seven moles of ethylene oxide with one mole of higher fatty alcohol averaging 12 to 15 carbon atoms, obtainable from Shell Chemical Company), an even greater improvement (plus 2Q 23) is noted. inn sodium linear dodecylbenzene sulfonate is employed as the anionic detergent in place of the Nudely 25-3S a decrease in washing effectiveness, compared to the control, is noted. However, when sodium linear dodecylbenzene sulfonate is only a minor proportion, e.g., 1/10, of the anionic detergent present, with the other such detergent being the Nudely 25-3S, significant improvement over the control in the detergency will be obtained.
395~i1 In the previously described experiments when a higher molecular weight polyacetal carboxylate, Builder U
Lot No. 2538422, of a molecular weight of issue employed instead of the lower molecular weight material previously described improvements over the control are still obtained with both Nudely 25-3S and Nudely 25-7 "formulas". However, the improvements are not as great and it is evident that the washing processes utilizing the lower moo wt. polyacetal carboxylate are significantly more effective than those in which the higher mol. wt. carboxylate is present. Also, when the previous experiment, in which sodium linear dodecylbenzene sulfonate was employed, is repeated but the higher molecular weight Builder U is employed, cleaning is inferior to the control.
In the foregoing experiments, when instead of the components being added separately to the wash water they are first mixed together to form detergent compositions, either by mixing of finely divided powders (particle sizes in the 20 range of 100 to 200 mesh) or by spray drying the anionic detergent and filler from suitable aqueous crutches mixes to particle sizes in the 10 to 100 mesh range, followed by mixing with the polyacetal carboxylate of the same particle size sand non ionic detergent, when used), or by agglomera-lion of finely divided powders of components to particles in the 10 to 100 sieve range, cleaning results by the described tests are the same. Similarly, when the compositions are 12~C~61 made into liquid products, such as those wherein water is substituted for the sodium sulfate filler, and when such are employed at the same concentration in the wash water Tao%) the same results are obtained.
Instead of employing "bare" formulas previously given, aesthetically,functionally and commercially more acceptable products may also be made in manners previously described in the specification. Thus, a composition comprise in 15~ of Nudely 25-7, 30% of Builder U (Lot 2547312), 10%
of sodium carbonate, 10~ of sodium silicate (Nash =
1:2.4), 1% of sodium carboxymethyl cellulose, 0.5% of perfume, 10% of moisture and the balance of sodium sulfate is made by spray drying base beads of all the materials except the non ionic detergent and Builder U, spraying melted non ionic detergent onto the base beads and mixing with the product the powdered Builder U, to produce particles in the 10 to 100 sieve size range. Such product will also show signify-cant cleaning superiority against a control of the type previously mentioned, and against similar products wherein the higher molecular weight (8034) Builder U lot is employed instead of the lower molecular weight (5250) material.
Similarly, when liquid compositions are made wherein some of the water is replaced by 10% of ethanol, I of sodium zillion sulfonate (hydrotrope) and 0.5% of perfume, leaving 41.5% of water (preferably deionized), all figures being on - I -~23~56~
a composition basis, the same results are obtainable.
When the experiments with Nudely 25 7 of Example 1 are repeated, with the only change being that the wash water temperature is 49C., even greater improvement in washing power compared to the control results. When the lower molecular weight polyacetal carboxylate of this experiment is replaced by the higher molecular weight material (Lot No.
2538422) it is found that the lower molecular weight polyp acutely carboxylate washing process is significantly Beatrice shown by the fact that its SRI (soil land stain] removal index) is significantly higher. Such is also the case when compositions of the invention, whether in particulate, solid, paste or liquid form, are made and tested in the same manner.
When the experiments of Examples 1 and 2 are repeated, utilizing water temperatures in the 10 to 30C.
range, e.g., 15 and 25C., and water harnesses in the 50 20 to 150 ppm. range, e.g., Andy 125 ppm., for the export-mints of Example 1, and using temperatures in the 40 to 60C. range, e.g., 45 and 55C., and water harnesses in the 50 to 150 ppm. range, e.g., 75 and 125 ppm., for the experiments of Example 2, the same significant improvements in washing power against the control will be obtained and 1~3~356~
the same improvements in washing effects when the lower molecular weight polyacetal carboxylates are utilized instead of the higher polymers will be noted.
A wash water containing 100 ppm. of hardness, as calcium carbonate, and which is at a temperature of Casey made containing 0.0113% of Nudely 25-7 and 0.0113% of Nudely 25-3S, 0.045% of Builder U (mow.= 5250) and 0.0825%
of sodium sulfate. When various soiled fabrics are washed in such wash water in the manner described in Example 1, they are very satisfactorily cleaned and the Skis there-of art hither than for a control composition in which the Builder U is replaced by sodium tripolyphosphate. Also, such indexes are higher than for similar wash waters in which the Builder employed is of a molecular weight of 8034.
Similar results are obtainable when the Nudely 25-7 is replaced by either Nudely 23-6.5 (condensation product of one mole of higher fatty alcohol of 12 to 15 carbon atoms and Ç.5 moles of ethylene oxide), Pluronics (condensation products of ethylene oxide and propylene oxide), and condemn-station products of nonyl phenol and polyoxyethylene ethanol, and when 30% of the sodium sulfate is replaced by 10% of sodium carbonate, 10% of sodium silicate and 10~ of moisture.
~239~6~
When, in the experiments of the preceding examples the proportions of components are varied ~10% and +25% and when the concentrations in the wash water of such components are varied +10% or ~25%, while still keeping within the proportion ranges and percentages recited in the specification, the detergent compositions and the wash waters so made will have satisfactory washing properties, will be superior to similar wash waters and compositions in which sodium Tripoli-phosphate is employed instead of the lower molecular weightpolyacetal carboxylate, and will be superior to those combo-sessions in which higher molecular weight polyacetal car boxy-late is substituted for the lower molecular weight material.
Such is also the case when various other builders, including sodium bicarbonate, Zealot PA, sodium sesquisilicate and sodium citrate, are employed in a total building proportion, and when adjutants, such as fluorescent brighteners, enzymes, bleaches, clays, flow improving agents and fabric softeners, are also present in functional proportions.
The invention has been described with respect to various illustrations and examples thereof but is not to be limited to these because it is evident that one of skill in the art, with the present specification before him or her, will be able to utilize substitutes and equivalents without departing from the invention.
Synthetic organic detergent compositions in which anionic and/or non ionic detergents have been employed as the detersive components and organic or inorganic builder salts have been present have long been employed commercially.
Among the synthetic organic detergents those which have generally been preferred in the past have been the anionic detergents but non ionic detergent compositions and mixed anionic-nonionic products have been successfully marketed, too. Various organic and inorganic builder salts have been included in commercial home laundry detergent compositions ~L239~
and of these until very recently sodium tripolyphosphate was almost invariably the most preferred. Such polyphosphate is an excellent builder which is safe to the consumer and is reasonably priced, while yet being extremely effective for its intended building purpose. However, in recent years phosphorus has been blamed for inland water pollution due to eutrophication and for that reason its use in detergent compositions has been controlled, restricted or prohibited in various political jurisdictions. Accordingly, efforts have been made to manufacture detergent compositions that are phosphate-free and which yet are effective heavy duty detergents.
Among non-phosphate compounds that have been suggested for use as builders in detergent compositions are the polyacetal carboxylates. Such compounds have been described in various U.S. and foreign patents. For example, detailed descriptions of them have been given in U.S. patents 4,144,226 and 4,146,495, both assigned to Monsanto Company.
Normally, according to such patents, the molecular weights of such materials will be in the range of 1,000 to 40,000 or more, preferably 1,000 to 20,000 and more preferably 5,000 to 10,000. However, while the anionic and non ionic synthetic organic detergents and the polyacetal carboxylates of this invention have been disclosed in the prior art as detergent composition components, such art has not suggested and does I
not make obvious the employment of a combination of synthetic organic detergent having an ethics group therein with a polyacetal carboxylate, the molecular weight of which is in a comparative narrow low range. Such compositions, it has been found by applicant, exert improved cleaning effects, better removing hard to remove soils and stains from a variety of fibrous substrate materials during cold water washing in medium hardness water, compared to similar compositions including a polyacetal carboxylate of higher molecular weight, and are also superior to control compositions in which the polyacetal carboxylate is replaced by a polyp phosphate builder.
In accordance with the present invention a built synthetic organic detergent composition, especially useful for washing laundry in cold water of a hardness in the range of 50 to 150 ppm. as calcium carbonate, comprises from 5 to 30% of a synthetic organic detergent selected from the group consisting of anionic and non ionic synthetic organic detergents and mixtures thereof, which detergent(s) contain(s) at least one ethics group per molecule, 5 to 95~ of polyacetal carboxylate builder of calculated weight average molecular weight in the range of 3,000 to 6,000, and the balance of such composition, if any, of adjutant and/or filler(s) and/or builder(s) and/or delineate. Preferably, the anionic detergent is a sulfated higher fatty alcohol Lowe ethoxylate and the non ionic detergent is a condensation product of ethylene oxide and a higher fatty alcohol. While particulate detergent compositions are preferred such compost-lions can be of other types too, including bars, cakes, liquids, pastes and powders. When particulate products are made various processes may be employed, such as spray drying, spray cooling, agglomeration, granulation, comminution and compaction.
Also included within the invention are processes for washing soiled fibrous materials by utilizing the described compositions to wash the soiled materials in wash waters of harnesses in the 50 to 150 ppm. range and at temperatures in the range of 10 to 70C., preferably 10 to 30C. Additionally, processes for washing laundry with the synthetic organic detergent and polyacetal carboxylate components of the described compositions are parts of this invention.
Although cat ionic and/or amphoteric detergents may be included in minor proportions in the compositions of the present invention, they will normally be limited to a 10~
total thereof and preferably will be held to less than 5%, if present, The primary detergents employed in accordance with the present invention are anionic and/or non ionic. Of the anionic detergents the sulfated and/or sulfonated lipophilic materials having an alkyd chain of 8 to 20 carbon ~23~56~L
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 detergents, including ammonium and lower alkanolamine (such as triethanolamine), 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 are the linear higher alkylbenzene sulfonates, the monoglyceride sulfates, higher fatty alcohol sulfates, paraffin sulfonates and olefin sulfonates. In all of such compounds the alkyd (or aureole, for the monoglyceride sulfates) group present will be in the range of 10 or 12 to 18 carbon atoms. While some such alkyd groups may include branching they will still be of a carbon chain length within the described range. Although the mentioned anionic detergents are useful in the practice of the invention that which is considered most useful and most effective, in combination with the polyacetal carboxylate builder, is an anionic detergent which includes an ethics group. Among these the most preferred are the sulfated polyethoxylated higher alkanols, wherein such alkanols may be synthetic or natural, and which contain from 3 to 20 or 30 ethics groups per mole.
Preferably, such detergents are alkali metal salts, e.g., sodium salts, the higher fatty alcohols thereof are of 12 1~;?3956~l Jo 18 carbon atoms and the detergents contain from 3 to 12, preferably 3 to 7, e.g., 3 or 5 molar proportions of ethics groups per mole.
The non ionic detergents, which may be employed as the primary detergents in place of the anionic detergents, or may be used with the avionics, are preferably normally solid materials (especially when being incorporated in solid or particulate solid products) and will preferably be condemn-station 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 preferably 5 to 9 moles, e.g., about 6.5 to 7 moles of ethylene oxide per mole of fatty alcohol. Among other non ionic detergents that are also useful are the ethylene oxide condensation products of alkyd phenols of 5 to 12 carbon atoms in the alkyd 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 non ionic detergents in which a lipophilic group, such as higher alkyd, alkylphenyl, polyoxy-lower alkaline, e.g., polyoxypropylene, is joined to a polyoxyethyleneethanol by reaction with ethylene oxide.
356~l.
The polyacetal carboxylate may be considered to be of the type that is 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 Al - (Sheehan R2 COO
wherein M is selected from the group consisting of alkali metal, ammonium, alkyd groups of 1 to 4 carbon atoms, twitter alkylammonium groups and alkanolamine groups, both of 1 to 4 carbon atoms in the alkyds thereof, n averages at least 6, and Al and R2 are any chemically stable groups which stabilize the polymer against rapid depolymerization in alkaline soul-lion. Preferably the polyacetal carboxylate will be one wherein M is alkali metal, e.g., sodium, Al is HO- or H3C-CO-or a mixture thereof, R2 is 0,CH2CH3 -OH
SHEA
and n averages from 15 to 120, more preferably 40 to 70.
The calculated weight average molecular weights of the polymers will normally be within the range of 3,000 to ~.3956~
6,000, preferably 4,000 to 6,000 and more preferably 4,500 to swish as about 5,250.
though the preferred polyacetal carboxylates have been described above, it is to be understood that they may be wholly or partially replaced at least in part 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 compost-tions,if of the same molecular weights. The various chain terminating groups described in the various patents, especially U.S. ~,144,226, may be utilized, providing that they have the desired stabilizing properties, which allow the mentioned builders to be depolymerized in acidic media, facilitating biodegradation thereof in waste streams, but maintain their stability in alkaline media, such as washing solutions.
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 tripolyphosphate), will preferably be omitted from the present formulations. Still, in some instances, they may be present, at least in relatively small proportions, e.g., up to 5 or 10%. Among builders other than polyphosphates such ~2~S6~
as sodium tripolyphosphate and tetrasodium pyrophosphate, those which may be desirably incorporated in the present compositions to supplement the building action of the polyp acutely carboxylate include sodium carbonate, sodium bit carbonate, sodium sesquicarbonate, sodium silicate, zeolites,e.g., Zealot A, NAT, sodium citrate, sodium gluconate, borax, other borate, and other builders known in the deter-gent art. Fillers may be present, such as sodium sulfate and sodium 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, delineates, such as solvents, dispersants, extenders and antifreezes, may be present, as well as adjutants, such as buffers, thickeners and stabilizers. The usual delineates include water, ethanol, lo isopropanoland propylene glycol, and the adjutants include gums, clays, polymers, and salts.
Among the various other adjutants that may be employed in particulate compositions (but some can also be used in liquids) are colorants, such as dyes and pigments, perfumes, enzymes, stabilizers, activators (especially activators for causing active oxygen release from perorate, if present), fluorescent brighteners, fungicides, germicides and flow promoting agents. Also included among adjutants, unless in other classes previously mentioned, are various additional components or impurities that may be present with other ingredients. For example, it is known that sodium carbonate and water are often present with polyacetal carboxylate in Builder U, the product which it the present source of polyacetal carboxylate.
~Z3956~
Moisture will usually be present in the invented solid (including particulate) compositions, either as free moisture or in one or more hydrates. While moisture is not an essential component of these improved detergent compost-lions it will normally be present due to the use of water in manufacturing, and it may help to syllables other compost-lion components and bind them together, as is usually desired.
The proportion of total synthetic organic detergent may be a detersive proportion up to 40% of the present compositions but normally will be within the range of 5 to 30%, preferably 5 to 25% and more preferably 10 to 20%, e.g., about 15%. Such proportions normally will be for either the sodium higher fatty alcohol polyethoxylate sulfate anionic detergent, the non ionic detergent which is a condemn station product of higher fatty alcohol and ethylene oxide or a combination of the two. At times when combinations of such two detergents are employed the proportions thereof will generally be within the range of ratios of 1:5 to 5:1, preferably 1:3 to 3:1 and more preferably 1:2 to 2:1, e.g., 1:1. In such compositions the proportion of higher fatty alcohol polyethoxylate sulfate will usually be in the range of 2.5 to 27.5%, preferably 3 to 12% and more preferably 5 to 10~. The percentages of higher fatty alcohol polyoxy-ethylene condensation product in such compositions will be the complements of the percentages of such anionic detergent, ~;~395~;1 with such non ionic detergent percentages being in the same ranges as given previously for the anionic detergent, with the ratio of the anionic detergent to the non ionic detergent being within the range of ratios mentioned, and with the total of anionic and non ionic detergents being deter-size proportions in the ranges previously given.
The proportion of polyacetal carboxylate builder is a building proportion (or is such a proportion in combine-lion with any other builders that may be present). The polyacetal carboxylate builder may be from 5 to 95% of the composition, preferably being from 10 to 50% thereof, more preferably 15 to 40~, and most preferably about 20 to 30%
thereof, e.g., about 25~. Such concentration is on the basis of the active polymer, which normally constitutes about 80 to 87~ or available sources of the polyacetal carboxylate builders, being 83~ of Lot No. 2547312 of Builder U (obtained from Monsanto Company), which is of a calculated weight average molecular weight of 5,250, and which Cantonese of sodium carbonate, with the balance being mostly water.
The ratio of synthetic organic detergent to polyp acutely carboxylate will normally will be in the range of 1:10 to 2:1, preferably being 1:5 to 1:1, more preferably being 1:3 to 4:5, e.g., 5:8. Such ratios include detergents other than those containing at least one ethics per molecule, ~23~5~
but such, if present, will be only a minor part, preferably less than 1/5 and more preferably less than 1/10 of the total detergent.
The other components of the present compositions, S in addition to the synthetic organic detergent(s) and sodium polyacetal carboxylate(s),will be other builder(s) and/or filler(s) and/or solvent(s) and/or delineate and/or dispel-sent and/or adjutant. While technically, only the detergent and polyacetal carboxylate are required components of the invention in its broadest aspects, normally other materials will also be present for their supplementing properties. Any supplementing builder materials that may be present will normally be limited to 50~, preferably being from 2 or 3 to 40~ and more preferably from 5 to 30%. Among the move preferred of the supplementing builders are sodium carbonate, sodium bicarbonate, Zealot A (but other zealots may also be employed), sodium silicate of Nash ratio in the range of 1:1.6 to 1:3.0, preferably 1:2.0 to 1:2.6, and in some cases (although not preferred), polyphosphates, such as sodium ~ripolyphosphate and tetrasodium pyrophosphate.
The proportions of such individual components will usually be limited to 30% and preferably will be no more than 20%.
The proportion of sodium carbonate which may be employed is more preferably 5 to land the quantity of sodium silicate is more preferably from 3 to 12%. If phosphates are present the proportions thereof will preferably be limited to 10% or less.
~,2395~;1 The content of filler in the present formulations will normally be no more than 70~, preferably being in the range of 10 to 60~, more preferably 10 to 40%. While such filler is usually sodium sulfate, it may also include a minor proportion, less than half thereof, of other filler materials, such as sodium chloride.
Adjutants in the invented compositions wit]. normal-lye total no more than 20% and preferably will not exceed 10%
with the exception that when bleaching material such as sodium perorate, is employ edit can constitute up to about 30~ of the product), and preferably the total adjutant content will be less than Wyeth individual adjuvant.contents generally not exceeding I or 5%, and preferably individually being less than 1 or 2%. Thus, if a sodium soap of a higher fatty acid (10 to I carbon atoms) is present, (for its foam diminishing property) it might be desired to employ 1 to 4% thereof and if sodium carboxymethyl cellulose is utilized (as an anti redeposition agent), the proportion thereof may be in the range of 0.3 to I preferably being about I In liquid preparations highly porous silica products, such as those sold under the trade name Cab-O-Sil~, may be employed in proportions from 0.5 to 5% to help to maintain the polyacetal carboxylate suspended, and from 1 to 5% of hydrotrope(s), such as sodium zillion sulfonate, may be present to promote physical stability and uniformity of the Lowe product. The moisture contents of the invented products will usually be from 3 to 20~, preferably 5 to 15% and more preferably 5 to 12%, for solid or particulate solid products, and for liquids may increase to proportions in the range of 20 to 90~, preferably 25 to 70~ and more preferably 30 to 60%. Part of the water content of liquid (or paste) prepare-lions may be replaced by other solvents, with the percentages of such other solvents (such as ethanol) in the final product normally being in the range of 2 to 30%, preferably 5 to 20%, if present. Such supplementary solvents may help to syllables composition components and can be used to control product viscosity.
he manufacture of the invented compositions may be conducted in any suitable conventional manner, whether solid or liquid products are being made. For liquid products the delineate (solvent or dispersant) may have the various components added thereto, normally preferably with a hydrotrope or other dispersing agent for the polyacetal carboxylate and any other insoluble present, being in the liquid medium when the various components are admixed therewith. Admixing may be sequential or simultaneous with sequential admixing being the usual practice. The order of additions that is followed normally will not matter significantly but usually any colorants and perfumes will be admixed near the end of the procedure. Often too, viscosity adjusting materials will be ~L239~;6~
added after other components. In some instances it may be desirable to withhold some of the solvent for final addition, whereby a final thinning of the mix may be obtained, when desired. Various types of mixers may be employed and in some instances utilization of homogenizing mixers may be preferred. Instead of the liquid form, with viscosities in the readily plowable range, dispensable through a narrow-necked bottle in a practical manner, non-flowing pastes may be produced, which normally will include greater proportions of a thickening agent and often lesser proportions of solvent or delineate.
To make the preferred particulate solid compositions, which will usually be of particle sizes in the 8 to 120 or 10 to 100 sieve (U.S. Sieve Series) range, it will often be preferred to spray dry as much of the formulation as is feasible, so as to obtain substantially uniformly shaped globular particles. because the polyacetal carboxylate of the present compositions can be adversely affected by heat it may be desired to post-add it to other components of the product that have previously been spray dried to form what may be referred to as "base" beads. If the polyacetal carboxylate is to be post-added it will be preferred that it be of essentially the same shapes, particle sizes and approximate density as the rest of the composition so as to inhibit segregations during shipping and storage. However, ~L~3~561 even if more finely divided powdered polyacetal carboxylate is employed, such as that of particle sizes in the lo or 160 to 200 or 325 mesh (or sieve number) range, it has been found that such particles will often adhere to the larger beads, maintain the product in the desired size range and be essentially non-segregating (although, of course, results will not be as good in this respect as when the various components of the composition are all of the same sizes, shapes and bulk density).
lo If the polyacetal carboxylate is spray dried with the detergent composition care will be exercised to prevent its decomposition due to its exposure to high spray tower drying air temperatures. When spray drying is unavailable or when costs are to be minimized the various components of the present compositions may be mixed together, as powders, and may be agglomerated to the desired lo to 100 sieve size, or they may be mixed together as fine powders, usually in the 100, 160 or 200 to 325 mesh range. When a non ionic detergent is to be present in the product in a significant proportion the major proportion thereof may be post-sprayed onto previously spray dried beads or onto particles ox other components of the composition. Normally, no more than about 4% of non ionic detergent, on a final product basis, will be in a spray dried product, unless added after spray drying, due to decomposition of the non ionic detergent that can occur at elevated tower temperatures when more than a relatively small proportion thereof is present in the cxutcher slurry being spray dried. Other temperature sensitive components of the product may also be post-added so as to avoid undesir-able subjections to elevated temperatures. Thus, if bleaching agent, such as sodium perorate, is to be present it the for~ulation,it will ye post-added, as will be enzyme powder, perfume and other heat sensitive components. On the other hand, materials like the inorganic builders, such as sodium carbonate, sodium bicarbonate, sodium silicate and zealots, and fillers, such as sodium sulfate, help to make strong, attractive and free flowing spray dried beads and preferably will be incorporated in crutches slurries to be spray dried for their physical characteristics, as well for their building and filling functions.
In the practice of the washing process of this invention, wherein soiled (and stained) fibrous materials, such as conventional clothing and "laundry" fabrics, of cotton, polyester-cotton blends, polyesters, acrylics, nylons, acetates, rayons and various blends thereof, are washed in an aqueous washing medium, such medium will contain a suitable detergent, as described, and a polyacetal car boxy-late of the desired calculated weight average molecular weight. Preferably, such components will be parts of a detergent composition but it is within the invention to ~23~3~;6~
charge such materials separately to the wash water. Although improvements in wishing effects are obtainable with the described compositions based on the previously mentioned preferred non ionic detergent at intermediate or medium water harnesses and at higher harnesses too, during both cold water and hot water washing, the most significant improve-mints in such cases are when the wash water is of medium hardness. Also, when the detergent is the preferred anionic detergent the most significant improvement is for cold water washing with water of medium hardness, with cold water washing with water of higher hardness also being improved but not to as great an extent. Thus, preferred conditions for washing with the invented compositions, whether anionic, non ionic or mixed anionic and non ionic detergents are em-plowed, will be in cold water (10 to 30C.) of medium hard-news (50 to 150 ppm., as calcium carbonate). Such prefer-fences also apply when the active components are employed and are separately added to the wash water in an automatic washing machine. Yet, in many cases the wash water may be 20 of a higher hardness, such as 150 or 200 to 300 or 400 ppm., and may be at a higher temperature, often up to 70C.
Preferably the washing will be done with a deter-gent composition of this invention and from 0.05 to 0.5%
thereof will be used, more preferably 0.1 to 0.3~ and most 1239~;61 preferably about 0.15%. Wash waters used will normally contain from 0.0025 to 0.15% of the synthetic organic deter-gent(s) and 0.0025 to 0.475% of the polyacetal carboxylate.
Preferred ranges of such materials will be 0.005 to 0.075~
and 0.01 to 0.15%, respectively and in the 0.15~ concentra-lion of the composition preferred proportions of the deter-gent and polyacetal carboxylate builder will be about 0.0225%
and about 0.0375~, respectively. The water employed will desirably be of a hardness of 50 to 150 ppm. and at a temperature in the range of 10 to 70C., preferably 10 to 30C., e.g., 21C. The water hardness will more preferably be about 100 ppm., as calcium carbonate (usually with the ratio of calcium to magnesium hardness being within the range of 1:1 to 10:1, e.g., 3:2 to 4:1.
Under the conditions described, improved cleanings are obtained using the preferred anionic and/or non ionic detergents of this invention with the described low mole-ular weight polyacetal carboxylate. When, in such compost-lions, the low molecular weight polyacetal carboxylate is replaced by a similar material but of higher molecular weight (8034) the cleaning is significantly less, especially in cold water washing in a medium hardness water. When other detergents than those which have been taught herein to be preferred are employed with the described polyacetal carboxylate of this invention results obtained are notice-ably inferior to those wherein the preferred detergents are 1~3g~6~
utilized with the polyacetal carboxylate. Also, with such other detergents it has been noted that the higher molecular weight polyacetal carboxylate appears to be slightly more effective than the lower molecular weight carboxylate, which is the opposite of the results noted with respect to the invented compositions. Also, when the builder of this invention is replaced by the prior art standard and preferred builder, sodium tripolyphosphate, washing results are notice-ably inferior to those of this invention.
The following examples illustrate but do not limit the invention. Unless otherwise noted all parts are by weight and all temperatures are in C., in these examples, the rest of the specification and the claims.
15 Parts of Noodles, which is the sodium salt of a polyethoxylated (3 ethoxies) higher fatty alcohol (of an average of 12 to 15 carbon atoms) sulfuric acid, obtainable from Shell Chemical Company, 30 parts of Builder U (Lot 2547313, containing 83% of sodium polyacetal car boxy-late of molecular weight of 5,250, 3.9% of sodium carbonate and the balance mostly water) end 55 parts of sodium sulfate, an hydrous, are dissolved at a concentration of 0.15~ in wash water (0.0225~ of the detergent, 0.045% of the builder and 0.0825~ of the filler being in the water) at a temperature of 21C. and of hardness of 100 ppm., as calcium carbonate ~23956~
(with the Cam ratio in the water being about 3:2), and the wash water is used to wash test swatches of various soils and stains on various substrate fabrics in a Tergotomete~laboratory washing machine, employing a ten minute wash cycle. The swatches are dried and their light reflectance are measured and from such reflectance of any remaining soils and stains on the different materials, soil Rand stain) removal indices are computed. The higher the index the whiter the test swatch after washing and the more effective the washing operation. Such test is repeated with a standard control detergent composition formula, in which sodium tripolyphosphate is substituted for the sodium polyacetal carboxylate. A very significant improvement (plus 21) over the control is obtaiIIed. Lyon such test is repeated except for the replacement of the anionic Nudely 25-3S with non ionic Nudely 25-7 (condensation product of seven moles of ethylene oxide with one mole of higher fatty alcohol averaging 12 to 15 carbon atoms, obtainable from Shell Chemical Company), an even greater improvement (plus 2Q 23) is noted. inn sodium linear dodecylbenzene sulfonate is employed as the anionic detergent in place of the Nudely 25-3S a decrease in washing effectiveness, compared to the control, is noted. However, when sodium linear dodecylbenzene sulfonate is only a minor proportion, e.g., 1/10, of the anionic detergent present, with the other such detergent being the Nudely 25-3S, significant improvement over the control in the detergency will be obtained.
395~i1 In the previously described experiments when a higher molecular weight polyacetal carboxylate, Builder U
Lot No. 2538422, of a molecular weight of issue employed instead of the lower molecular weight material previously described improvements over the control are still obtained with both Nudely 25-3S and Nudely 25-7 "formulas". However, the improvements are not as great and it is evident that the washing processes utilizing the lower moo wt. polyacetal carboxylate are significantly more effective than those in which the higher mol. wt. carboxylate is present. Also, when the previous experiment, in which sodium linear dodecylbenzene sulfonate was employed, is repeated but the higher molecular weight Builder U is employed, cleaning is inferior to the control.
In the foregoing experiments, when instead of the components being added separately to the wash water they are first mixed together to form detergent compositions, either by mixing of finely divided powders (particle sizes in the 20 range of 100 to 200 mesh) or by spray drying the anionic detergent and filler from suitable aqueous crutches mixes to particle sizes in the 10 to 100 mesh range, followed by mixing with the polyacetal carboxylate of the same particle size sand non ionic detergent, when used), or by agglomera-lion of finely divided powders of components to particles in the 10 to 100 sieve range, cleaning results by the described tests are the same. Similarly, when the compositions are 12~C~61 made into liquid products, such as those wherein water is substituted for the sodium sulfate filler, and when such are employed at the same concentration in the wash water Tao%) the same results are obtained.
Instead of employing "bare" formulas previously given, aesthetically,functionally and commercially more acceptable products may also be made in manners previously described in the specification. Thus, a composition comprise in 15~ of Nudely 25-7, 30% of Builder U (Lot 2547312), 10%
of sodium carbonate, 10~ of sodium silicate (Nash =
1:2.4), 1% of sodium carboxymethyl cellulose, 0.5% of perfume, 10% of moisture and the balance of sodium sulfate is made by spray drying base beads of all the materials except the non ionic detergent and Builder U, spraying melted non ionic detergent onto the base beads and mixing with the product the powdered Builder U, to produce particles in the 10 to 100 sieve size range. Such product will also show signify-cant cleaning superiority against a control of the type previously mentioned, and against similar products wherein the higher molecular weight (8034) Builder U lot is employed instead of the lower molecular weight (5250) material.
Similarly, when liquid compositions are made wherein some of the water is replaced by 10% of ethanol, I of sodium zillion sulfonate (hydrotrope) and 0.5% of perfume, leaving 41.5% of water (preferably deionized), all figures being on - I -~23~56~
a composition basis, the same results are obtainable.
When the experiments with Nudely 25 7 of Example 1 are repeated, with the only change being that the wash water temperature is 49C., even greater improvement in washing power compared to the control results. When the lower molecular weight polyacetal carboxylate of this experiment is replaced by the higher molecular weight material (Lot No.
2538422) it is found that the lower molecular weight polyp acutely carboxylate washing process is significantly Beatrice shown by the fact that its SRI (soil land stain] removal index) is significantly higher. Such is also the case when compositions of the invention, whether in particulate, solid, paste or liquid form, are made and tested in the same manner.
When the experiments of Examples 1 and 2 are repeated, utilizing water temperatures in the 10 to 30C.
range, e.g., 15 and 25C., and water harnesses in the 50 20 to 150 ppm. range, e.g., Andy 125 ppm., for the export-mints of Example 1, and using temperatures in the 40 to 60C. range, e.g., 45 and 55C., and water harnesses in the 50 to 150 ppm. range, e.g., 75 and 125 ppm., for the experiments of Example 2, the same significant improvements in washing power against the control will be obtained and 1~3~356~
the same improvements in washing effects when the lower molecular weight polyacetal carboxylates are utilized instead of the higher polymers will be noted.
A wash water containing 100 ppm. of hardness, as calcium carbonate, and which is at a temperature of Casey made containing 0.0113% of Nudely 25-7 and 0.0113% of Nudely 25-3S, 0.045% of Builder U (mow.= 5250) and 0.0825%
of sodium sulfate. When various soiled fabrics are washed in such wash water in the manner described in Example 1, they are very satisfactorily cleaned and the Skis there-of art hither than for a control composition in which the Builder U is replaced by sodium tripolyphosphate. Also, such indexes are higher than for similar wash waters in which the Builder employed is of a molecular weight of 8034.
Similar results are obtainable when the Nudely 25-7 is replaced by either Nudely 23-6.5 (condensation product of one mole of higher fatty alcohol of 12 to 15 carbon atoms and Ç.5 moles of ethylene oxide), Pluronics (condensation products of ethylene oxide and propylene oxide), and condemn-station products of nonyl phenol and polyoxyethylene ethanol, and when 30% of the sodium sulfate is replaced by 10% of sodium carbonate, 10% of sodium silicate and 10~ of moisture.
~239~6~
When, in the experiments of the preceding examples the proportions of components are varied ~10% and +25% and when the concentrations in the wash water of such components are varied +10% or ~25%, while still keeping within the proportion ranges and percentages recited in the specification, the detergent compositions and the wash waters so made will have satisfactory washing properties, will be superior to similar wash waters and compositions in which sodium Tripoli-phosphate is employed instead of the lower molecular weightpolyacetal carboxylate, and will be superior to those combo-sessions in which higher molecular weight polyacetal car boxy-late is substituted for the lower molecular weight material.
Such is also the case when various other builders, including sodium bicarbonate, Zealot PA, sodium sesquisilicate and sodium citrate, are employed in a total building proportion, and when adjutants, such as fluorescent brighteners, enzymes, bleaches, clays, flow improving agents and fabric softeners, are also present in functional proportions.
The invention has been described with respect to various illustrations and examples thereof but is not to be limited to these because it is evident that one of skill in the art, with the present specification before him or her, will be able to utilize substitutes and equivalents without departing from the invention.
Claims (17)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A built synthetic organic detergent composition, useful for washing laundry in cold water of a hardness in the range of 50 to 150 p.p.m. as calcium carbonate, which comprises from 5 to 30% of a synthetic organic detergent selected from the group consisting of anionic and nonionic synthetic organic detergents and mixtures thereof, which detergent(s) contain(s) at least one ethoxy group per molecule, 5 to 95% of polyacetal carboxylate builder of calculated weight average molecular weight in the range of 3,000 to 6,000, and the balance of such composition, if any, of a substance selected from the group consisting of an adjuvant, filler, builder and diluent.
2. A detergent composition according to claim 1 wherein the synthetic anionic organic detergent is a sulfated higher fatty alcohol ethoxylate and the synthetic nonionic organic detergent is a condensation product of ethylene oxide and a lipophilic group donating compound selected from the group consisting of higher fatty alchols, alkylphenols and polyoxypropylenes.
3. A phosphate-free particulate detergent composi-tion according to claim 1 wherein the anionic detergent is an alkali metal salt of a higher fatty alcohol polyethoxy sulfuric acid, in which the higher fatty alcohol is of 10 to 18 carbon atoms, and which contains from 1 to 30 moles of ethylene oxide per mole, and wherein the nonionic detergent is a condensation product of 3 to 20 moles of ethylene oxide with a mole of higher fatty alcohol of 10 to 18 carbon atoms and/or with a mole of alkylphenol of 6 to 12 carbon atoms in the alkyl group.
4. A detergent composition according to claim 3 which comprises from 5 to 25% of higher fatty alcohol poly-ethoxylate sulfate and/or condensation product of ethylene oxide and higher fatty alcohol, and 10 to 50% of polyaceta carboxylate builder.
5. A detergent composition according to claim 4 which comprises from 10 to 20% of sodium higher fatty alcohol polyethoxylate sulfate which contains from 1 to 5 moles of ethylene oxide per mole and in which the higher fatty alcohol is of an average of 12 to 15 carbon atoms, and/or a condensa-tion product of 5 to 9 moles of ethylene oxide per mole of higher fatty alcohol of an average of 12 to 15 carbon atoms, and 15 to 40% of polyacetal carboxylate of molecular weight in the range of 4,500 to 5,500.
6. A detergent composition according to claim 5 which comprises about 15% of sodium higher fatty alcohol polyethoxylate sulfate which contains about 3 moles of ethylene oxide per mole, and about 25% of polyacetal carboxylate of molecular weight of about 5,250.
7. A detergent composition according to claim 5 which comprises about 15% of condensation product of ethylene oxide and higher fatty alcohol which contains about 7 moles of ethylene oxide per mole, and about 25% of polyacetal carboxylate of molecular weight of about 5,250.
8. A detergent composition according to claim 5 which comprises sodium higher fatty alcohol polyethoxylate sulfate and condensation product of ethylene oxide and higher fatty alcohol in a proportion in the range of 1:3 to 3:1.
9. A detergent composition according to claim 8 which comprises about 5 to 10% of sodium higher fatty alcohol polyethoxylate sulfate which contains about 3 moles of ethylene oxide per mole, about 5 to 10% of condensation product of about 7 moles of ethylene oxide and a mole of higher fatty alcohol, and about 25% of polyacetal carboxylate of molecular weight of about 5,250.
10. A process for washing soiled fibrous material to remove soils therefrom which comprises washing such soiled fibrous material in wash water of a hardness of 50 to 150 p.p.m., as calcium carbonate, at a temperature in the range of 10 to 70°C. with a built detergent composition comprising from 5 to 30% of synthetic organic detergent selected from the group consisting of anionic and nonionic synthetic organic detergents and mixtures thereof, which detergent(s) contain(s) at least one ethoxy group per molecule, 5 to 95% of a polyacetal carboxylate builder of calculated weight average molecular weight in the range of 3,000 to 6,000, with the balance of such composition, if any, of a substance selected from the group consisting of an adjuvant, filler, builder and diluent, at a concentration of such detergent composition in the wash water in the range of 0.05 to 0.5%.
11. A process according to claim 10 wherein the detergent composition comprises from 5 to 25% of higher fatty alcohol polyethoxylate sulfate and/or condensation product of ethylene oxide and higher fatty alcohol, and 10 to 50% of polyacetal carboxylate builder, the concentration of the detergent in the wash water is in the range of 0.1 to 0.3%, and the wash water temperature is in the range of 10 to 30°C.
12. A process according to claim 11 in which the detergent is sodium higher fatty alcohol polyethoxylate sulfate of a higher fatty alcohol of 10 to 18 carbon atoms and about 3 moles of ethylene oxide per mole, the proportion of such detergent in the detergent composition is about 15%, the polyacetal carboxylate is of a molecular weight of about 5,250, the proportion thereof in the detergent composition is about 25%, the wash water temperature is about 21°C., the concentration of detergent composition in the wash water is about 0.15% and the wash water is of a hardness of about 100 p.p.m., as calcium carbonate.
13. A process according to claim 10 wherein the synthetic organic detergent is a condensation product of 5 to 9 moles of ethylene oxide and a mole of higher fatty alcohol of an average of 12 to 15 carbon atoms.
14. A process according to claim 13 wherein the nonionic synthetic organic detergent is of about 7 moles of ethylene oxide per mole, the proportion of such detergent in the detergent composition is about 15%, the polyacetal carboxylate is of a molecular weight of about 5,250 and the proportion thereof in the detergent composition is about 25%, the concentration of detergent composition in the wash water is in the range of 0.1 to 0.3% and the wash water is of a hardness in the range of about 100 p.p.m. to about 300 p.p.m., as calcium carbonate.
15. A process for washing soiled fibrous materials to remove soils therefrom which comprises washing such soiled fibrous material in wash water of a hardness of 50 to 150 p.p.m., as calcium carbonate, at a temperature in the range of 10 to 70°C. with synthetic organic detergent selected from the group consisting of anionic and nonionic synthetic organic detergents and mixtures thereof, which detergent(s) contain(s) at least one ethoxy group per molecule, and a polyacetal carboxylate builder of calculated weight average molecular weight in the range of 3,000 to 6,000, at concen-trations of such components in the wash water in the range of 0.0025 to 0.15% of the synthetic organic detergent(s) and 0.0025 to 0.475% of the polyacetal carboxylate.
16. A process according to claim 15 wherein the wash water temperature is in the range of 10 to 30°C., the anionic detergent is a higher fatty alcohol polyethoxylate sulfate, the nonionic detergent is a condensation product of ethylene oxide and higher fatty alcohol and the proportions of synthetic organic detergent(s) and polyacetal carboxylate are in the ranges of 0.005 to 0.075% and 0.01 to 0.15%, respectively, in the wash water.
17. A process according to claim 16 wherein the synthetic organic detergent is a nonionic synthetic organic detergent which is a condensation product of a higher fatty alcohol of an average of 12 to 15 carbon atoms with about 7 moles of ethylene oxide per mole, the polyacetal carboxylate is of a molecular weight of about 5,250, and the concentra-tions of such components in the wash water are about 0.0225%
and about 0.0375%, respectively.
and about 0.0375%, respectively.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US61646684A | 1984-06-01 | 1984-06-01 | |
| US616,466 | 1984-06-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1239561A true CA1239561A (en) | 1988-07-26 |
Family
ID=24469588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000482671A Expired CA1239561A (en) | 1984-06-01 | 1985-05-29 | Built synthetic detergent composition |
Country Status (22)
| Country | Link |
|---|---|
| JP (1) | JPS612798A (en) |
| KR (1) | KR860000369A (en) |
| AU (1) | AU573840B2 (en) |
| BE (1) | BE902553A (en) |
| CA (1) | CA1239561A (en) |
| DE (1) | DE3518295A1 (en) |
| DK (1) | DK245785A (en) |
| ES (1) | ES8706201A1 (en) |
| FI (1) | FI852195L (en) |
| FR (1) | FR2565240B1 (en) |
| GB (1) | GB2159529B (en) |
| GR (1) | GR851341B (en) |
| IT (1) | IT1182726B (en) |
| LU (1) | LU85926A1 (en) |
| MX (1) | MX161832A (en) |
| NL (1) | NL8501574A (en) |
| NO (1) | NO852163L (en) |
| NZ (1) | NZ212081A (en) |
| PH (1) | PH22278A (en) |
| PT (1) | PT80557B (en) |
| SE (1) | SE8502149L (en) |
| ZA (1) | ZA853355B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4847005A (en) * | 1987-10-22 | 1989-07-11 | Monsanto Company | Solutions of hydrolytically stable polymeric acetal carboxylate salts and stable liquid detergent compositions containing such salts |
| KR20020016342A (en) * | 2000-08-25 | 2002-03-04 | 이지영 | Improvised boiled rice manufacturing method |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4146495A (en) * | 1977-08-22 | 1979-03-27 | Monsanto Company | Detergent compositions comprising polyacetal carboxylates |
| ES472603A1 (en) * | 1977-08-22 | 1979-10-16 | Monsanto Co | Polymeric acetal carboxylates, a method for their preparation and their use in a detergent composition. |
| US4315092A (en) * | 1977-08-22 | 1982-02-09 | Monsanto Company | Polyacetal carboxylates |
| US4144226A (en) * | 1977-08-22 | 1979-03-13 | Monsanto Company | Polymeric acetal carboxylates |
| US4201858A (en) * | 1977-11-21 | 1980-05-06 | Monsanto Company | Method of preparing polyacetal carboxylates |
| EP0015024A1 (en) * | 1979-02-16 | 1980-09-03 | THE PROCTER & GAMBLE COMPANY | Detergent compositions containing binary builder system |
| GR79172B (en) * | 1983-01-28 | 1984-10-02 | Procter & Gamble | |
| US4605506A (en) * | 1984-06-01 | 1986-08-12 | Colgate-Palmolive Company | Fabric softening built detergent composition |
| ZA853573B (en) * | 1984-06-01 | 1986-12-30 | Colgate Palmolive Co | Bleaching synthetic detergent composition |
| SE8502146L (en) * | 1984-06-01 | 1985-12-02 | Colgate Palmolive Co | PARTICULAR REINFORCED NONJONIC SYNTHETIC ORGANIC DETERGENT COMPOSITION |
-
1985
- 1985-05-03 SE SE8502149A patent/SE8502149L/en not_active Application Discontinuation
- 1985-05-03 ZA ZA853355A patent/ZA853355B/en unknown
- 1985-05-14 NZ NZ212081A patent/NZ212081A/en unknown
- 1985-05-22 DE DE19853518295 patent/DE3518295A1/en not_active Withdrawn
- 1985-05-22 KR KR1019850003494A patent/KR860000369A/en not_active Application Discontinuation
- 1985-05-23 FR FR8507791A patent/FR2565240B1/en not_active Expired
- 1985-05-29 CA CA000482671A patent/CA1239561A/en not_active Expired
- 1985-05-29 MX MX205447A patent/MX161832A/en unknown
- 1985-05-30 GR GR851341A patent/GR851341B/el unknown
- 1985-05-30 PH PH32340A patent/PH22278A/en unknown
- 1985-05-30 PT PT80557A patent/PT80557B/en unknown
- 1985-05-30 NO NO852163A patent/NO852163L/en unknown
- 1985-05-31 LU LU85926A patent/LU85926A1/en unknown
- 1985-05-31 FI FI852195A patent/FI852195L/en not_active Application Discontinuation
- 1985-05-31 IT IT48153/85A patent/IT1182726B/en active
- 1985-05-31 ES ES543724A patent/ES8706201A1/en not_active Expired
- 1985-05-31 NL NL8501574A patent/NL8501574A/en not_active Application Discontinuation
- 1985-05-31 BE BE0/215107A patent/BE902553A/en not_active IP Right Cessation
- 1985-05-31 DK DK245785A patent/DK245785A/en unknown
- 1985-06-01 JP JP60119655A patent/JPS612798A/en active Pending
- 1985-06-03 GB GB08513930A patent/GB2159529B/en not_active Expired
- 1985-06-03 AU AU43230/85A patent/AU573840B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| NZ212081A (en) | 1989-01-27 |
| ES8706201A1 (en) | 1987-06-01 |
| GB2159529B (en) | 1988-05-18 |
| FR2565240A1 (en) | 1985-12-06 |
| ES543724A0 (en) | 1987-06-01 |
| FI852195L (en) | 1985-12-02 |
| PT80557A (en) | 1985-06-01 |
| AU573840B2 (en) | 1988-06-23 |
| DE3518295A1 (en) | 1985-12-05 |
| KR860000369A (en) | 1986-01-28 |
| DK245785A (en) | 1985-12-02 |
| PH22278A (en) | 1988-07-14 |
| LU85926A1 (en) | 1986-02-18 |
| AU4323085A (en) | 1985-12-05 |
| GB2159529A (en) | 1985-12-04 |
| PT80557B (en) | 1986-12-15 |
| FI852195A0 (en) | 1985-05-31 |
| IT8548153A0 (en) | 1985-05-31 |
| GB8513930D0 (en) | 1985-07-03 |
| ZA853355B (en) | 1986-12-30 |
| NL8501574A (en) | 1986-01-02 |
| SE8502149L (en) | 1985-12-02 |
| IT1182726B (en) | 1987-10-05 |
| MX161832A (en) | 1990-12-28 |
| NO852163L (en) | 1985-12-02 |
| BE902553A (en) | 1985-12-02 |
| GR851341B (en) | 1985-11-25 |
| FR2565240B1 (en) | 1987-01-30 |
| SE8502149D0 (en) | 1985-05-03 |
| DK245785D0 (en) | 1985-05-31 |
| JPS612798A (en) | 1986-01-08 |
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