FI57442B - TVAETTPULVER FOER TYG - Google Patents

Description

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Patent * and National Board of Registration NihtMks. ^ J. Date of issue -, "

Patent and registration authorities' Anttilan utiagd odi utUkrifun public · ™) 30.0¾. 80 (32) (33) (31) Requested curiosity —Begird prlerltet 31.01.73

England-England (GB) 1 + 818/73 Proven-Styrkt (71) Unilever NV, Burgemeester s'Jacobplein 1, Rotterdam, Holland-Holland (NL) (72) Francis Geoffrey Foster, Wirral, Cheshire, England-England (GB) ) (71+) Leitzinger Oy (5¾) Fabric washing powder - Tvättpulver för tyg The present invention relates to a particulate detergent composition suitable for washing fabrics, comprising a detergent active compound, preferably about 5 to 35% by weight, ortho- and / or pyrophosphate as a bulking agent. or as part thereof and a homopolymer of acrylic acid or a substantially completely hydrolysed ester thereof as an additive.

Tripolyphosphates, especially sodium polyphosphates, are commonly used in fabric washing compositions as a detergent builder. Tripolyphosphates have a problem with their heat sensitivity. Thus, if processed into detergent compositions through a spray-drying step, they tend to decompose into orthophosphates and pyrophosphates. We have found that it is common for about 10-30% of the original tripolyphosphate to degrade in this manner. This naturally results in a detergent mixture containing about 10-30% less tripolyphosphate than intended and having about 10-30% by weight of tripolyphosphate as ortho and / or pyrophosphate.

Orthophosphates and pyrophosphates are sometimes also used on their own as a detergent builder.

When pure white fabrics, especially cotton, are washed together with soiled fabrics in detergent compositions containing more than about 2 or 3 ortho-57442 and / or pyrophosphate, a decrease in reflectivity may occur.

Without wishing to be bound by any theory, we believe that the observed decrease in reflectivity is due to the precipitation of calcium phosphates on the fabrics and is not caused by the phosphates themselves but by the dirt entrapped in the phosphates and deposited on the fabrics.

It has now been found that this reduction in reflectivity can be substantially reduced by adding certain polyacrylates to the mixture.

The detergent composition according to the invention is characterized in that the acrylic acid has an average molecular weight of 3,000 to 3,000,000, preferably 3,500 to 27,000, and a concentration in the composition of 0.2 to 5% by weight.

Polyacrylic acid has been proposed as a suitable detergent builder. However, the amount of polyacrylic acid used in the invention is such that it would not be possible to obtain any significant body properties. For example, we have found that very good results can be obtained using 2% polyacrylic acid.

The detergent composition according to the invention contains at least one detergent active compound. The detergent composition content of the detergent composition is generally from about 1 to about 50, most preferably from about 5 to 35, and especially from about 10 to 25 weight percent of the composition. The quality of the detergent compound or compounds in the detergent composition is not an essential feature of the invention: All detergent compounds that are commonly added or proposed to be added to fabric detergent compositions can be used. These detergent active compounds and the various amounts and combinations in which they are preferred for use are known to those skilled in the art of fabric detergent compositions. The detergent active compound or compounds may be anionic, nonionic, amphoteric or zwitterionic in nature.

Water-soluble or water-dispersible salts of various organic acids are typical anionic detergent active compounds. The cations of such salts are usually alkali metals, such as sodium and, less preferably, potassium, but other cations, such as ammonium or substituted ammonium, may also be used if desired. Examples of suitable organic acids are 3,544,442 as follows: alkylbenzenesulfonic acids having alkyl chains containing from about 8 to about 20 carbon atoms, such as p-dodecylbenzenesulfonic acid and linear alkyl (C10-15) benzenesulfonic acid; mixtures of sulfonic acids obtained by reacting straight and branched olefins, especially straight cracked wax or Ziegler alpha-olefins containing from about 8 to about 22 carbon atoms, with sulfur dioxide; alkylsulfonic acids obtained by reacting alkanes containing from about 8 to about 22 carbon atoms with sulfur trioxide / oxygen or sulfur dioxide / chlorine (and in the latter case by subsequent hydrolysis), or by adding bisulphite to olefins, in particular by direct cracking; wax "or" Ziegler "for alpha-olefins containing from about 8 to about 22 carbon atoms; alkyl sulfuric acids obtained by reacting aliphatic alcohols containing from about 8 to about 22 carbon atoms with sulfur dioxide; alkyl ether sulfuric acids obtained by reacting aliphatic alcohols containing from about 6 to about 18 carbon atoms with a mole of about 1 to about 15 moles of ethylene oxide or a suitable mixture of ethylene oxide and propylene oxide and then reacting the alkoxylated alcohol with sulfur trioxide to the desired acid; and natural or synthetic aliphatic carboxylic acids, especially acids derived from natural sources such as tallow, coconut oil, palm oil, palm kernel oil and peanut oil.

Examples of suitable nonionic detergent active compounds are as follows: condensation of alkylphenols having from about 6 to about 12 carbon atoms in the alkyl group (derived, for example, from polymerized propylene, diisobutylene, octene, dodene, or nonene) in either a straight-chain or branched configuration is about With 25 moles of ethylene oxide per mole of alkylphenol; condensates containing from about 40% to about 80% by weight of polyoxyethylene and having a molecular weight of from about 5,000 to about 11,000 and derived from the reaction of ethylene oxide with the reaction product of ethylenediamine and excess propylene oxide; condensates of straight or branched chain aliphatic alcohols containing from 8 to 18 carbon atoms with ethylene oxide, for example, coconut alcohol-ethylene oxide condensate containing about 6 to 30 moles of ethylene oxide per mole of coconut alcohol; long chain tertiary amine oxides corresponding to the general formula R 1, R 2, R 8 N 2, "57442 wherein R 1 is an alkyl radical of about 8 to 18 carbon atoms, and R 2 and R 3 are each methyl, ethyl or hydroxyethyl radicals, such as dimethyldodesylamine oxide , dimethyloctylamine oxide, dimethylhexadecylamine oxide and N-bis (hydroxyethyl) dodecylamine oxide, long-chain tertiary phosphine oxides corresponding to the general formula RR'R "? - * 0, in which R is an alkyl, alkenyl or monohydroxyalkyl radical, in which 10 and R. (2-hydroxyethyl) dodecylphosphine oxide, 2-hydroxypropylmethyl itetradesylphosphine oxide, dimethyl oleylphosphine oxide and dimethyl-2-hydroxydodesylphosphine oxide; and dialkyl sulfoxides corresponding to the general formula RR'S- * 0, in which R is an alkyl, alkenyl beta or gamma monohydroxyalkyl radical or an alkyl or beta or gamma monohydroxyalkyl radical having one or two other oxygen atoms in the chain, wherein R- groups having 10 to 18 carbon atoms, and wherein Rf is a methyl, ethyl or alkylol radical such as isylmethylsulfoxide, tetradesylmethylsulfoxide, 3-hydroxytridesylmethylsulfoxide, 2-hydroxydodesylmethylsulfoxide, 3-hydroxy-H-dodecyloxybutylmethyl 3-desyloxypropylmethyl sulfoxide, dodecylethyl sulfoxide, 2-hydroxydodesylethyl sulfoxide and dodecyl-2-hydroxyethyl sulfoxide.

Examples of suitable amphoteric detergent compounds are the following: derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical may be straight chain or branched and in which one of the aliphatic substituents contains about 8-18 carbon atoms and one substituent contains an anionic water-soluble dionyl group such as sodium , sodium 3-dodesylaminopropanesulfonate and sodium N-2-hydroxydodesyl N-methyl taurate.

Examples of suitable zwitterionic detergent compounds are: derivatives of aliphatic quaternary ammonium compounds, sulfonium compounds and phosphonium compounds in which the aliphatic radical may be straight chain or branched and in which one of the aliphatic substituents contains about 8-18 carbon atoms, 3- (N, N-dimethyl-N-hesadesylammonium) propane-1-sulfonate betaine, 3- (N, N-dimethyl-N-hexadesylammonium) -2-hydroxypropane-1-sulfonate betaine, 3- ( dodecylmethylsulfonium) propane-1-sulfonate betaine and 3- (cetylmethylphosphonium) ethanesulfonate betaine.

Other examples of suitable detergent compounds commonly used in the art are given in Schwartz and Perry's "Surface Active Agents, Volume I" (Interscience 1949) and in Schwartz's, Perry and Berch's "Surface Active Agents, Volume II" "(Interscience 1958), the details of which are incorporated herein by reference.

After all, the total detergent content of the detergent composition of the detergent composition of the invention is from about 20% to about 70%, and preferably from about 25% to about 60% by weight of the detergent composition.

As mentioned above, part of this detergent builder may consist of ortho and / or pyrophosphate. The orthophosphate or pyrophosphate may be derived from the decomposition of sodium tripolyphosphate. Thus, the invention includes detergent compositions which are intended to contain up to 70% by weight of sodium tripolyphosphate and which have been spray-dried or otherwise treated in such a way as to cause some or all of the sodium tripolyphosphate to decompose into orthophosphate and / or pyrophosphate.

Examples of other detergent builders that can be used in the compositions of this invention in conjunction with the phosphate builder described above include sodium carbonate; sodium silicate; sodium citrate; natriumoksidiasetaatti; natriumnitrilotriasetaatti; natriumetyleeni-tetraacetate; sodium salts of long chain dicarboxylic acids, for example straight chain C 1-4 succinic acids and malonic acids; sodium carboxymethyl and sodium salts of alpha-sulfonated long chain monocarboxylic acids and modified starches, such as starches oxidized, for example, using sodium hypochlorite, in which some of the anhydroglucose units have been opened to dicarboxyl units.

The detergent composition of the invention may further comprise all conventional ingredients of fabric detergent compositions in all amounts in which such conventional ingredients are commonly used. Examples of these other ingredients include foaming enhancers such as coconut monoethanolamide and palm kernel monoethanolamide; antifoaming agents; inorganic salts such as sodium sulfate and magnesium sulfate; chlorine-releasing bleaches such as trichloroisocyanuric acid and sodium and potassium dichloroisocyanurates; sodium carboxymethylcellulose; and usually only small amounts of perfumes, dyes, fluorescents, corrosion inhibitors, germicides and enzymes.

The detergent composition of the invention may be prepared using any of the conventional manufacturing techniques commonly used or proposed for use in fabric detergent compositions. Such is the case, for example, with the preparation of a slurry, after which sensitive ingredients which could not be added before the drying step can be spray-dried or spray-cooled and subsequently dry-dosed. If necessary, other conventional methods of preparation can be used, such as, for example, nudation, granulation and mixing in a fluidized bed by fluidization. Such methods of preparation are well known to those skilled in the art of fabric detergent compositions.

Using such conventional manufacturing techniques, the detergent composition of the invention can be prepared in any of the usual physical forms associated with fabric detergent compositions, such as powders, flakes, granules, and yarns.

The invention is illustrated by the following examples in which all parts and percentages are by weight.

Example 1

Two phosphate-structured particulate fabric detergent compositions A and B were prepared from the following essential ingredients by conventional slurry preparation, spray-drying and dry-dosing techniques: 7 57442

Ingredient A B

Weight percent Weight percent

Sodium alkyl benzene sulphonate (sulphonated DOB 055, producer

Shell Chemicals Ltd) 11.2 11.3

Sodium soap (80/20 tallow / coconut oil) 3.2 3.2

Tallow fatty amide 11 E0 - 1.6

Non-ionic detergent active compound (sold under the registered trademark "Tergitol 15-S-12") 1.6

Sodium tripolyphosphate1 36.0 36.0

Sodium perborate 23.0 23.0

Sodium carboxymethylcellulose

Sodium silicate - 6.0

Sodium sulphate, water to 100.0 100, Ora 1 After the spray-drying step, the phosphate content of the mixtures was analyzed and the sodium tripolyphosphate was found to decompose as follows:

Component Percentage by weight of original sodium tripolyphosphate_

Sodium tripolyphosphate 76.4

Sodium orthophosphate 2.7

Sodium pyrophosphate 20.9

Test mixtures were prepared by adding 2% by weight of various polyacrylates to powders A and B. These were as follows: 8 57442 No. Polyacrylate Powder 1 Versicol E5, water-soluble polyacrylic acid,

having an average molecular weight of about 3500 Å

2 Versicol E5, water-soluble polyacrylic acid,

having an average molecular weight of about 3500 B.

3 Versicol E7, water-soluble polyacrylic acid,

having an average molecular weight of about 27,000 Å

4 Versicol E9, water-soluble polyacrylic acid,

having an average molecular weight of about 76,000 Å

5 Antiprex A, water-soluble polyacrylic acid,

having an average molecular weight of about 3500 Å

6 Dispex C40, a water-soluble polyacrylic acid with an average molecular weight of approximately 4000-

5000 B

7 R968, water-soluble polyacrylic acid with an average molecular weight between 4000

and 5000 (narrow verse) A

8 Versicol 2000, water-soluble polyacrylic acid,

having an average molecular weight of about 2000 Å

9 Versicol E15, water-soluble polyacrylic acid,

with an average molecular weight of 2.63 x 10 'B

All of the above polyacrylic acids were produced by Allied Colloid Manufacturing Co Ltd., Bradford, Yorkshire, England, ‘Versicol’, Antiprex and ‘Dispex’ are trademarks.

The above powders were used to wash white cotton towel pieces. Each piece of towel was washed 5, and in some cases 10, in a commercially available drum washing machine in the presence of soiled garments in households. Two types of washing conditions were used, which were as follows:

Low temperature wash cycles

Powder concentration: 0.22%

Water: Hardness 24 ° H

Washing temperature: Heating to 60 ° C in 30 minutes, kept at 60 ° C for another 6 minutes

Shelf life: 36 minutes Filling: 1.8 kg

Volume of washing solution: 27.3 1

Stir: 10 seconds per minute during heating, continuously for the last 6 minutes of washing.

9 57442

High temperature wash cycles

Powder concentration: 0.25% in prewash 0.31% in main wash

Water: Hardness 24 ° H

Washing temperature: Heating to 45 ° C (prewash) and then to 88 ° C (main wash)

Duration: Prewash 15 minutes Main wash 40 minutes Filling: 3.6 kg

Washing solution volume: 15.9 1 (prewash) plus 12.3 1 (main wash)

Mix: Prewash, 10 seconds per minute Main wash, 10 seconds per minute 32 minutes and continuously for the last 8 minutes.

To determine the performance of the mixtures, two experiments were performed on the washed towels. The first experiment compared the decrease in reflectivity of each towel when washed 5 or 10 times with a mixture containing polyacrylate to the decrease that occurred when washing the towel with the above base powder. The decreases in resistance are shown in the table.

In the second experiment, the washed towels are heated in an oven to 650 ° C to burn off all the organic matter, and the amount of ash remaining is weighed. The amount of ash can be correlated with the amount of calcium and magnesium phosphate deposited on the towel during washing. The table shows the amounts of ash formed as a percentage of the weight of the washed and dried garment.

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The percentage reduction in elasticity is the percentage difference between the reflectivity of an unwashed garment and that of various washed garments.

The results of the decrease in reflectivity show that by adding the described polyacrylates to the washing mixture, substantial reductions can be achieved. They also show how critical it is to select the correct molecular weight range for the polyacrylate. Thus, washing with a reference mixture 8 using a polyacrylate having a molecular weight of significantly less than 3000 results in a greater reduction in reflectivity.

The ash results show that the amount of phosphate ash deposited on the fabrics in the wash can be substantially reduced by adding the polyacrylates described to the wash mixture.

The result obtained for reference mixture 8, in which the amount of ash increased rather than decreased, shows how important it is to select the correct molecular weight range of the polyacrylate. The best polyacrylic acids, such as Versicol E5, give good results in both combustion and reflection tests, while acids outside the scope of the application give poor results in one or both tests.

Example 2

Another detergent composition according to the invention has the following formulation:

Ingredient Weight percent

Sodium alkyl benzene sulfonate 1 * +, 0

Coconut monoethanolamide 2.0

Sodium toluene sulphonate 1.0

Sodium tripolyphosphate 50.0

Sodium silicate 6.0

Sodium sulphate 9.7

Enzyme spots (14% enzyme) 6.7

Ethylenediaminetetraacetic acid

Sodium carboxymethylcellulose 0.5

Versicol E5 2, 0

Fluorescent substances)

Perfume to 100.0.

Moisture