DE3518656A1 - BLEACHING DETERGENT - Google Patents

Description

description

The invention relates to detergents, in particular bleaching detergents that contain a surfactant or a mixture of

Surfactants, a polyacetal carboxylate builder for surfactant 5

or which contain surfactants and a perborate, as well as a Method of washing soiled polyester fiber materials that are contaminated with particulate! Dirt and grease are contaminated.

The need for removing dirt and stains from fibrous materials is ancient, and a multitude of ones Compositions to achieve this result are described. A type of preparation that uses to test the cleaning and stain removing activity of laundry detergents is a mixed fat and Particulate dirt that permanently contaminates the fiber materials that come into contact with it, in particular those containing polyester fibers such as polyester knits and hosiery and polyester-cotton blends.

Such soil is often used to create an artificial "collar patch" soil. It is known that "collar patch soils" are considered difficult to remove from shirt collars (and cuffs) in automatic laundering operations. It is difficult to remove, no matter whether the wash at relatively low temperatures, for example at 10 to 30 ⁰ C, or at higher temperatures under European washing practice, for example at up to 90 ° C or 95 ° C or higher, is carried out.

While soap was once the commonly used cleaning agent was, today almost all household detergents are based on one or more surfactants. Of these Surfactants, the anionic and nonionic surfactants are believed to be the most effective, although ampholytic or

amphoteric and cationic surfactants can also be used

can. Sodium perborate has long been used in laundry detergents for its bleaching properties. Lately have been Polyacetal carboxylate builders are used in detergents instead of polyphosphate builders because they do not contain phosphorus and therefore it cannot be assumed that they promote the eutrophication of inland waters. A Another advantage of these builders is their easy degradability in normal acidic sewage.

Although the main components of the present detergents have been used in other such compositions, these are new and not nearby and they have surprisingly good stain removal properties.

The object of the invention is to create a detergent which has a significantly improved ability to remove has a combination of fat and particulate impurities from polyester-containing fiber material, when such material is washed in hot wash water containing such detergent. This effect is intended to be obtained even when hard washing water is used.

The task is solved by a bleaching detergent,

that amount of one containing a cleaning amount of a surfactant or a mixture of surfactants, a builder effect Contains polyacetal carboxylate builders for the surfactant or surfactants and a bleaching amount of a perborate, and that in elevated temperature wash water is particularly effective in removing particulate and greasy contaminants is made of polyester fabrics. Preferred detergents contain about 4 to 20% sodium higher alkyl benzene sulfonate, in which the higher alkyl radical is 10 to 18 carbon atoms, about 2 to 10% of a nonionic surfactant that the condensation product of ethylene oxide and

is a higher fatty alcohol, the higher fatty alcohol having 10 to 18 carbon atoms and the nonionic surfactant containing 3 to 20 moles of ethylene oxide per mole, about 10 to 30% sodium polyacetal carboxylate builder with a weight average molecular weight in the range of 5,000 to 9,000, about 10 to 40% Natriumperborattrihydrat, about 3 to 20% of moisture, including hydrate moisture which is removable at 105 ⁰ C, and the balance of filler (s) and / or other builders and / or other excipient (s). The invention also relates to a method for removing mixed particulate and grease contaminants from polyester fiber materials, in which the soiled fiber materials are washed in washing water at a temperature in the range of 50 to 99 ° C, which is a detergent

contains that a cleaning amount of a surfactant or a Mixture of surfactants, a builder amount of a polyacetal carboxylate builder for the surfactant or contains the surfactants and a bleaching amount of a perborate, the concentration of the detergent in the

Wash water is in the range of 0.05 to 1.5%.

The surfactant that is used in the compositions according to the invention mainly because of its cleaning properties is usually an anionic surfactant. Of the anionic surfactants, the sulfated ones are and / or sulfonated lipophilic materials with an alkyl chain of 8 to 20, preferably 10 to 18 and especially 12 to 16 carbon atoms usually the of choice. While various water-soluble salt-forming

Cations can be used to form the desired soluble sulfated and sulfonated surfactants, including ammonium and lower alkanolamine (such as triethanolamine) and magnesium, usually becomes one Alkali metal such as sodium or potassium is used, and a particularly preferred cation is the sodium ion. Under the

various anionic surfactants according to the invention are useful, the linear higher alkylbenzenesulfonates with 10 to 18, preferably 12 to 16 and am most preferably about 12 or 13 carbon atoms in the Chain considered to be most suitable according to the invention. Among others, the monoglyceride sulfates are also useful, higher fatty alcohol sulfates, sulfated polyethoxylated higher alkanols, in which the alkanols are synthetic or can be natural and have 3 to 20 or 30 ethoxy groups per molecule contain paraffinsulfonates and olefin sulfonates, with the existing in all compounds Alkyl group has 10 to 18 carbon atoms. Some of these alkyl groups can be slightly branched, but they still have a carbon chain length within the range described.

The nonionic surfactants that are often used to strengthen the cleaning effect of the primary anionic surfactants, but in some cases also the primary ones

Surfactants are usually preferred solid materials (especially when they are in solid or particulate solid products are incorporated) and they are preferably condensation products of ethylene oxide and a higher fatty alcohol, the higher fatty alcohol usually being 10 to 18, preferably an average 12 to 15, for example about 12 to 13 carbon atoms and the ethylene oxide content in the range of 3 to Moles, preferably 3 to 12 moles and in particular 5 to 9 moles, e.g. about 6.5 or 7 moles of ethylene oxide per mole of fatty alcohol lies. Other nonionic surfactants that are also suitable include the ethylene oxide condensation products of alkylphenols having 5 to 12 carbon atoms in the alkyl groups, such as nonylphenol, in which the Ethylene oxide content is 3 to 30 moles per mole. In addition, condensation products from ethylene oxide and propylene

oxide, such as those sold under the trade name Pluronic,

as well as the various others from the known group of nonionic surfactants.

The cationic surfactants that can be used, 5

usually in limited quantities, e.g. no more than 10% and preferably less than 5%, are preferably di-higher alkyl-di-lower alkylammonium halides, in which the higher alkyl radicals 10 to 18, preferably 16 to 18 Have carbon atoms, the lower alkyl radicals 1 to 3, preferably 1 carbon atom and the halogens are chlorine or bromine. As such materials can be mentioned distearyldimethylammonium chloride, di-tallowdimethylammonium chloride (in which the alkyl radical from animal fats) and di- (hydrotalg) -dime-5

thylammonium bromide. However, different ones can also be used other such cationic materials including N-cetylethylmorpholinium ethosulfate, often called antistatic agents (often they also have deodorant and germicidal properties) are used will. As examples of amphoteric materials, the miranols can be mentioned, such as the one below called Miranoi ^ C2M Cone, was sold. Further such surfactants including anionic, nonionic, amphoteric and cationic surfactants are disclosed in US Pat 25th

various annual publications entitled McCutcheon's Detergents and Emulsifiers, e.g. Edition 1969, described.

As the polyacetal carboxylate, that described in U.S. Patent 4,144,226 can be considered, and it can be through the process described there can be produced. A typical such product has the formula

R ₁ -

COOM

in which M is selected from the group consisting of alkali metal, ammonium, alkyl groups with 1 to 4 carbon atoms, tetraalkylammonium groups and alkanolamine groups, both of which have 1 to 4 carbon atoms in their alkyl radicals, η is at least average and R ₁ and R- any chemically stable Are groups that stabilize the polymer against rapid depolymerization in alkaline solution. A polyacetal carboxylate is preferred in which M is an alkali metal, for example sodium, η 20 to 200, R ₁

CH-, CH ₂ O MOOC I.

HCO- _or H ₃ C-CO-H ₃ C MOOC

or a mixture of these,
25th

OCH ₂ CH ₃

'

-CH

CH ₃

35ί8656

and η on average 20 to 100, preferably 30 to 80 is. It is desirable that the calculated weight average molecular weights be in the range of 2,000 up to 20,000, preferably 3,500 to 10,000, especially 5,000 to 9,000, such as 7,000 to 9,000, especially at about 8,000 lie.

While the preferred polyacetal carboxylates have been described above, it should be understood that they replaced in whole or in part by other such polyacetal carboxylates or related organic builder salts can be found in various Monsanto Co. patents for such compounds, processes for their preparation and compositions in which they are used are described. Also the chain end groups that are in the various patents, notably U.S. Patent 4,144 226 can be used provided they have the desired stabilizing properties Have properties that allow the builders mentioned to be depolymerized in acidic media, whereby the

biodegradation of the same in wastewater is facilitated, but their stability in alkaline media, such as washing solutions, preserved.

The perborate used is a water-soluble perborate, which is capable of active bleaching oxygen in aqueous Media, such as in washing water, to be dispensed at an elevated temperature. Such a perborate is preferably a Alkali metal or equivalent salt, and most preferred is sodium perborate tetrahydrate. Ordinary is

the perborate hydrates, but this is not necessary. Generally the hydrate will be the tetrahydrate, but the monohydrate has been found to be useful as well, and some perborates with lower water hydration contents than 1 mole per mole may be particularly useful for certain. Applications or for packaging in vapor-tight containers

(in which the higher hydrates tend to liquefy or cause the detergent to stick together can).

While the common higher fatty acid soaps, usually the sodium soaps, are detergents, but they are are generally not regarded as surfactants, and accordingly they do not belong to the group of the invention suitable surfactants. The soaps have cleaning properties, but they can also be used for other purposes be used, for example because of their foam-limiting properties. Of the soaps that are used in the invention Compositions that can be used are those of the alkali metals, such as sodium, which have 10 to 18 carbon atoms and are preferably highly saturated, preferred. These include the sodium hydrotalgum soaps, Sodium stearate and sodium palmitate, but also soaps Tallow and mixtures of tallow with coconut oil can be used as components of the compositions, e.g.

4: 1 tallow: coconut soaps.
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In the compositions according to the invention can also builders other than the polyacetal carboxylate may be present, although this is not necessary. It is often desirable to avoid the presence of phosphorus in detergents, so that the phosphates that during many years the pictures of choice for detergents (especially pentanate tripolyphosphate), preferably from those according to the invention Formulations are omitted. In some cases, they may still be there, at least in relative terms small amounts, e.g. up to 5 or 10%. To the from the Polyphosphates, such as sodium tripolyphosphate and tetrasodium pyrophosphate, various builders that are desirable the compositions of the invention can be incorporated to the builder effect of the Polyacetal carboxylates include sodium

carbonate, sodium bicarbonate, sodium sesqux carbonate, Sodium silicate, zeolites, e.g. zeolite A, nitrilotriacetic acid (NTA), sodium citrate, sodium gluconate, borax, others Borates and other builders known to those skilled in the art.

Fillers such as sodium sulfate and sodium chloride can be present to add bulk to the product if this is considered desirable. For liquid compositions that should be commonly used soon after preparation, solvent, or such as water, ethanol and isopropanol, ^ ⁰ extenders.

About the various auxiliary materials that are used can include colorants, such as dyes and pigments, perfumes, enzymes, stabilizers, activators (in particular Activators that cause the release of active oxygen from perborates), fluorescent brighteners, buffers, Fungicides, germicides and flow promoters. To the Auxiliary materials also belong to various other classes, if they were not mentioned in other classes beforehand Components or impurities present in the remaining components. For example, it is known that sodium carbonate and water are often present together with polyacetal carboxylate in the builder U, the Product that is the source of polyacetal carboxylate of the present invention is.

Common is in the compositions of the invention Moisture present, either as free moisture

^ O or in one or more hydrates. While moisture It is not an essential part of this bleaching detergent, but it is usually due to the fact that it is Use water present in the manufacture and it can help with the other detergent ingredients too

^ ⁵ solubilize and bind them.

The following are the amounts of the ingredients of the inventive compositions for particulate Products usually have particle sizes in the range of 2.5 or 2.00 to 0.149 or 0.105 mm mesh size (Sieve sizes 8 or 10 to 100 or 140 of the üS sieve series). However, these amounts are also up other solid forms can be used, such as rods or pieces, finely comminuted or coarser powders, granular compositions and agglomerates, and also to liquid preparations; however, should because of their relatively low

^ ⁰ Stability the liquid preparations can be used relatively soon after manufacture. Although the amounts of all components except water can be about the same in liquid preparations, these products are often much more dilute so that the amount of water or another solvent or mixture of solvents present can be much greater. According to the invention, the ingredients can also be added directly to the wash water; this case can be viewed as such that the detergent is the wash water which contains the various active and other ingredients.

In the particulate solid and other solid laundry detergents of the present invention, the total amount of surfactant is usually 5 to 40%, especially 10 to 25%, and most preferably about 12%. It is desirable that that Surfactant comprises either a sulfated or sulfonated anionic surfactant or a nonionic surfactant, but preferably it comprises the two such surfactants. The amount of anionic surfactant present is ordinary 3 to 30%, preferably 4 to 20% and especially 4 to 10%, e.g. about 8%, and the amount of nonionic surfactant is about 2 to 25%, preferably 2 to 10% and especially 2 to 6%. The amount of polyacetal carboxylate builder is usually in the range of 4 to 50%, preferably up to 30% and especially 10 to 25%, e.g. 18%. Of the

Perborate content is usually in the range of 10 to 50%, preferably 10 to 40% and especially 15 to 30%, e.g. at 22%, these percentages being based on sodium perborate tetrahydrate refer and changed accordingly

if the anhydrous salt or another 5

Hydrate is used. The amount of soap that is present is usually in the range of 1 to 10%, preferably 2 to 6%, and the percentage of moisture is usually 3 to 20%, preferably 5 to 15%, e.g. about 10%. These percentages include moisture in hydrate form, which is given off when heated to 105 ^° C. for two hours (standard moisture analysis method). The amounts of the other ingredients, such as fillers, are usually limited to no more than 40%, and are usually in the range of 0 to 30% or 5 to 20%.

In the same way, the contents of the builders other than the polyacetal carboxylate are limited, im generally to less than 25%, such as 3 to 20% or 5 to 15%, but often there are no additional builders. The total excipient content usually exceeds not 10% or 20%, and is preferably less than 5%, the contents of the individual auxiliaries in the generally not exceed 3% or 5% and preferably be less than 1% or 2%. For example that is Sodium carboxymethyl cellulose, which is a desirable anti-redeposition agent, usually in the range of 0.3 to 3%, preferably 0.5 to 2%, e.g. 1% present.

In the preferred forms of the invention, the particulate solid compositions having the above-described

For example, when the particle sizes are low, it is often preferred to spray dry as much of the formulation as possible in order to substantially uniformly shaped spherical particles. Because the perborate is not heat stable, it will usually after the remainder of the composition

given. To a segregation during transport and the

To prevent storage of the final product, it is of course desirable that the perborate be in shape and particle size is similar to the rest of the composition. The polyacetal carboxylate can sometimes be spray dried with the detergent provided that care is taken to prevent its decomposition by heat. It however, it can also be added subsequently, and again it is desirable that the particle sizes for the subsequent addition match the above in order to separate the product components impede. In an alternative manufacturing process, the various ingredients can be finely ground Shape can easily be mixed together. Even if the initial particle sizes of the ingredients less than desired, approximately in the range of 0.075 to 0.044 mm clear mesh size (160 to 325 mesh), the particles thereof can be agglomerated to the desired size, sometimes with the aid of an agglomerating agent, like a dilute aqueous solution of sodium silicate, and in other cases only with water

to support agglomeration.

If an anionic surfactant is the primary surfactant of the desired composition, then it can be spray dried with the fillers such as sodium sulfate, builders such as sodium carbonate, sodium bicarbonate, borax and sodium silicate, and auxiliaries such as fluorescent whiteners, pigments and dyes, and it can be added to the normal as occurs using a conventional countercurrent or Mitstromtrocknungsturms with drying air at about 200 to 600 ⁰ C (preferably 150 to 350 ⁰ C, or when polyacetal carboxylate is present), are spray dried. The polyacetal carboxylate and the perborate can then be mixed in in any order or together, or the perborate and the polyacetal carboxylate can be premixed and then mixed with

mixed with the spray-dried beads. When a relatively small amount of nonionic surfactant besides If the anionic surfactant is to be present, then it can be spray dried with the anionic surfactant, fillers, etc. and stable amphoteric and cationic materials that should be present can also be the Crutch mix incorporated and then with the anionic Surfactant can be spray-dried. However, if more than about or 5% (sometimes more than 2%) of anionic surfactant in are present in the formulation, then the additional amount is usually added afterwards, such as by Spray onto falling particles of detergent pellets or base beads. Such base beads can consist of all builders, fillers and stable auxiliaries of the End product can be made. Then the polyacetal

carboxylate and the perborate added later. In In some cases the polyacetal carboxylate can be present in the nonionic surfactant which is liquid heated (or dissolved in a solvent) dispersed and / or dissolved, and the combination

of nonionic surfactant and polyacetal carboxylate can be sprayed onto the surfactant beads or base beads followed by the addition of the perborate. It is desirable that the particulate material produced Particle sizes from approx. 2.5 to 0.125 or 2.00 to 0.149 mm clear mesh size (8 to 120 or 10 to 100 mesh) and the manufacturing process is designed accordingly. However, it can be sieved to To remove undersized or oversized particles that have been reprocessed, ground, or agglomerated can otherwise be processed to the desired sizes.

To the products according to the invention to rod, piece or To process briquette form, the compositions can be extruded, pressed or molded in a known manner will. In order to convert them into liquid preparations, the ingredients can be in liquid media, such as water and / or suitable solvents, dissolved and / or dispersed.

To carry out the stain removal method according to the invention, the detergent described can be added to the washing water, or the various components are added. Usually the concentration of the compositions used is in the range of 0.05 or 0.1 to 1.0 or 1.5%, preferably 0.1 to 1.3% and especially 0.15 to 1.1 or 1.2% . Higher concentrations, such as 1.0 to 1.5% or more, are often used in machine washing according to European practice, using high temperature wash water in which the perborate gives off active bleaching oxygen. In America, the washing temperature is usually in the range of 10 to 55 ° C, often 10 to 30 ⁰ C, compared to 60 to 99 ° C, often 70 to 90 or 95 ° C in Europe. According to American practice, lower concentrations such as 0.05 to 0.2%, often preferably about 0.07 to 0.15% of the composition are used. In American practice, the perborate oxygen is not given off to the same extent because the washing temperature is lower. Consequently, the possible bleaching effect is not as great as when a higher washing temperature is used, unless an activator is also present to support the release of the active oxygen from the perborate. Various such activators are known for this purpose and can be used to adapt the process of the invention to American practice

adapt. These activators include those known as TAED (Tetraacety! Ethylenediamine) known, acyloxybenzyl sulfonate, as described in U.S. Patent 4,412,934 and TAGU.

In the washing or stain removal process, conventional washing machines are used, such as automatic GE washing machines (loading from above) according to American practice and Miele machines according to European practice. Although the compositions according to the invention work better than comparative compositions in which sodium tripolyphosphate is used instead of polyacetal carboxylate, regardless of whether washing is carried out at high or low temperatures, provided that equivalent amounts of active oxygen are given off by the perborate, it is often preferred to use the European To follow practice that does not require the presence of an accelerator to promote the release of the active oxygen from the perborate. Various water hardnesses can be used and while the softer the water is expected to be the better the stain removal, it has surprisingly been found that, even under hard water conditions, the compositions of the present invention and the stain removal methods are superior to the comparative compositions and methods , ° in which pentasodium tripolyphosphate is used instead of the polyacetal caboxylate. This improved stain removal ability is most pronounced at elevated temperatures (60 to 90 ^° C.) when the soil is a particularly critical soil such as is usually found in normal laundry, namely a combination of particulate! and greasy dirt such as those found on shirt collars and cuffs. The good effect of removing these stains is obtained even when hard water is used, such as that of quite high hardnesses in the range of 250 to

300 ppm as CaCO ₃ . In addition to the better removal of these contaminants that is more evident than 6O ⁰ C at 90 ⁰ C, it was found that the inventive compositions and methods of removing various other typical stains lead regard also to sustainable improvements. Surprisingly, the compositions according to the invention, which incorporate a builder which is stable during washing and stain treatment, but which is degradable in normal acidic sewage, and from which one of the best builders known to date, namely sodium tripolyphosphate, is omitted, in combination with a surfactant (especially a mixture of anionic and nonionic surfactants) and perborate bleach

Spot removal, which is obviously the special 15

a unique combination of the components used. This effect will be itself in a great deal hard water, given the excellent sequestering properties of sodium tripolyphosphate builder and its known stability and widespread use in laundry and stain removal processes is unexpected.

In the following the invention is illustrated by means of examples

" ₌ Explained in more detail, but not limited. If not otherwise 25

indicated, in these examples, elsewhere in the description and in the claims, all parts refer to the Weight and all temperatures on C.

- 21 Example 1

Component percent

* Sodium linear tridecylbenzenesulfonate 8.0

* Non-ionic surfactant (Neodol 25-7, 4.0 a condensation product of higher fatty alcohols with an average of 4-Θ * to 15 Carbon atoms and 7 moles of ethylene oxide per mole of fatty alcohol available from Shell Chemical Co.)

* Sodium hydrotalgum soap 4.0

* Sodium carboxymethyl cellulose 1/0 sodium perborate tetrahydrate 22.0 Builder U (79.7% sodium ^{polyacetal carboxy-:} 22.0 lat with a calculated weight average molecular weight of about 8,000, available from Monsanto Co.) * Filler (sodium sulfate, anhydrous) 29 , 0

* Moisture 10.0

100.0

* as spray-dried beads

A stain removing detergent of the above formulation was made by using a crutch mix that is about 55% solids and about 45% water (city water a hardness of about 100 ppm as calcium carbonate)

contained, at a temperature of about 50 ⁰ C in a 30

Countercurrent spray drying tower spray dried where it was dried to a moisture content of about 10%. The air let into the tower was about 450 ^° C

warm and at the outlet from the tower, the air was cooled to about 150 ⁰ C. The resulting spray-dried

Beads had particle sizes in the range of 2.00 to 0.149 mm internal mesh size (sieve numbers 10 to 100 of the US sieve series). The sodium perborate tetrahydrate and the builder U, which also had particle sizes in the range from 2.00 to 0.149 mm clear mesh size, were then mixed with these spheres in a sloping falling drum; if the constituent materials are supplied as finer powders and none are spray dried, then they are agglomerated to the desired sizes, either individually or together. Such polyacetal carboxylate perborate agglomerates can have ratios in the range from 1: 5 to 5: 1 and _{contain 0.1 to 5% sodium silicate (Na 2} O: SiO ₂ = 1: 1.6 to 1: 3) as builder.

The product obtained was said to have a stain removing effect

tested using a Miele multi-spot light reflection method, in which differential measurements were made on washed experiment or comparison cloths. In this process, the experimental detergent and the comparative detergent

(which contained trisodium polyphosphate instead of Builder U) separately in a Miele washing machine at a concentration of about 1.1% (225 g per 20 1 washing water) at 60 ^° C. in washing water above 200 ppm (300 ppm) hardness as calcium carbonate and with given a hardness of the ratio 4: 1 of calcium ions to magnesium ions. The test pieces used were made of different materials and they were stained with different stains. Several test rags were used for each combination of rag and soil and measurements were made of the average reflectance on the rags after normal washing and drying with the experimental composition of this example and compared to the values for the comparative detergent in which 22% sodium tripolyphosphate was substituted from Builder U were present. This procedure was carried out at 90 C with the

Difference repeats that the washing procedure was modified so that half of the detergent composition and half of the comparative detergent were used in a prewash stage and the other half in the main washes.
5

In the test procedure described, which is used as a standard procedure for testing detergent stain removal properties, it has been found that the inventive detergents of this example and the use of the washing method of this example to one sustained improvement in terms of the removal of various typical soiling that leads to Items of laundry are found, including spangler's

Fatty milk dirt on double-knitted Dacron material, liquid make-up on cotton percale, on Qiana Jersey and on double-knitted dacron materials, black filler ink (bic) on dacron-cotton blend and French dressing on double-knitted Dacron at 60 °, and Spangler fat particle dirt on double knitted dacron material, liquid make-up on cotton percale, on dacron-cotton blend fabric and on Qiana Jersey, and dyed shortening on double-knitted dacron at 90 C. The compositions according to the invention and methods were found in stain removal versus tripolyphosphate-containing comparative compositions only for tea stains on polyester-cotton blend fabrics and for barbecue sauce on double-knitted fabrics Dacron (both at 60 ° C) and for liquid make-up on double-knitted Dacron and for French dressing Double knitted Dacron (both at 90 C) underneath.

Results such as those described above are obtained even if the experimental formulation is modified by increasing the alkylbenzenesulfonate content to 16%, omitting the nonionic surfactant and the soap,

and replaced the 29% sodium sulfate with 1/3 each of sodium bicarbonate, sodium carbonate and sodium silicate with a Na ₂ O: SiO ₂ ratio of about 1: 2.4. In the same way, this second formulation can be modified by using a mixture of equal parts of alkylbenzenesulfonate and sodium laurylsulfate (16% in total) or by omitting the alkylbenzenesulfonate and replacing it with a nonionic surfactant (Neodol 25-7 or Neodol 23- 6.5), whereupon the sodium perborate and the builder ü are mixed with the base beads containing the nonionic surfactant. In these cases, too, the improved stain removal ability is obtained, which is attributable to the combination of polyacetal carboxylate and perborate in the formulations according to the invention. Instead of the nonionic surfactants mentioned, other surfactants can be used as substitutes, including the condensation products of ethylene oxide and nonylphenol, as described above, Pluronics, eg F-68, and Neodol 45-11 and mixtures thereof which contain two to four components.

Other modifications to this example can be made by adding other builders and in the formulations Fillers are used, including small amounts, e.g.

up to 10 or 2 to 5% amphoteric and / or more cationic Surfactants (the cationic surfactants can be used as antistatic agents) and / or by modification of the Quantities of the specified components by + 10 and + 25%, keeping them within their respective ranges. The manufacturing conditions can also be modified by mixing essentially all of the ingredients (usually with the exception of perborate, perfume and the enzymes) together using milder conditions

Spray dry (to prevent Builder U from degrading). 35

Example 2

The formulations of the product from Example 1 were modified by adding a Builder U with a weight by weight calculated average molecular weight of

about 5,250 which used an 83% sodium polyacetal carboxylate polymer was. If these formulations were prepared according to the procedures described in Example 1, they exhibited improved stain removal properties compared to controls containing sodium tripolyphosphate in place of the Builder U polymer and the experimental products showed similar stain removal capabilities like the formulations from example 1. This was also the case when an equivalent amount Perborate monohydrate was used instead of the tetrahydrate, the difference being an inert builder (Na-SO.) Was balanced. The products described can be done with the conventional means previously were called to paste, liquid and chopsticks or

Process piece forms.
20th

Example 3

In the main formulation from Example 1, the sodium linear tridecylbenzenesulfonate was replaced by sodium dodec-

cylbenzenesulfonate, sodium paraffin sulfonate, sodium olefin sulfonate (with an average of about 16 carbon atoms), sodium lauryl sulfate or sodium monoglyceride sulfate replaced. When tested according to the method described in Example 1, these products were also found to be compared

with various comparative compositions using other builders in place of the sodium polyacetal carboxylate were used, including pentasodium polyphosphate among these builders, than for the

Clearly superior to removing stains from laundry. 35

In modifications of these formulations, the composition was modified in such a way that an activating amount, for example about 1% TAED, the sodium sulfate content being correspondingly reduced, was added, the activator being added to the composition afterwards. When tested in the manner described in Example 1 for use at 60 ^° C., but in which

the temperature of the washing water was lowered to 30 C in accordance with American practice and a G.E. to be filled from above Washing machine was used, improved stain removal results were obtained compared to a comparative composition containing sodium tripolyphosphate instead of Builder U. This was also the case with active polyacetal carboxylate polymers with molecular weights of about 5,000 (Monsanto Lot No. 2547312; Molecular weight 5,250) and about 8,000 (Monsanto Lot No. 2538422; molecular weight 8,034). the however, best stain removals were obtained by the main procedure of Example 1, which is can be modified that other polyacetal carboxylates with weight calculated average molecular weights are present in the specified areas.

If this example is modified (example 1 and 2

can also be modified in this way) a liquid 25

Product or slurry made by adding the sodium sulfate or other fillers and / or builders (with With the exception of the polyacetal carboxylate) in the various formulations was replaced by water. If these products prepared with the same concentrations of active ingredients as those of these examples are also they are effective stain removers. With a further modification of the invention, the various ingredients of the composition were added separately to the wash water in order to obtain the

to get the desired results. Of course, in the 35

commercial end products also have auxiliary materials,

e.g. 0.5% perfume, 1% proteolytic enzyme, 2% fluorescent brightener composition, 0.2% colorant, such as Polar Brilliant blue dye and / or ultramarine blue pigment for the production of a blue product and 3% flow promoter, such as magnesium silicate hydrate when deemed desirable. It is not to be assumed that the Use of such auxiliaries the desired properties of the compositions according to the invention or the measures of the method according to the invention in an essential manner adversely affected.

From the preceding description and the examples of It is apparent to compositions and methods of the present invention that the combination of polyacetal carboxylate and perborate in the compositions according to the invention to surprisingly improved

Stain removal products and processes leads, in particular

especially with regard to the difficult to remove '

Combination of grease and particulate dirt on polyesters, even if the washing medium is hard water. It is particularly surprising that these results are obtained when one takes into account that the sodium tripolyphosphate is the most effective detergency builder used in the past, and if one also takes into account, that the amount of active polyacetal carboxylate used is less than the amount of polyphosphate in the comparative compositions. That is, through the present Invention a significant advance in the field of stain removal and cleaning is achieved.

The invention was based on examples and embodiments explained, but it is not limited to these because it is obvious to those skilled in the art that he based on the present description can use equivalents and substitutes without departing from the invention to deviate.

Claims (10)

Claims 1. Bleaching detergent, characterized in that it a cleaning amount of a surfactant or a mixture of surfactants, a builder-producing amount of one Contains polyacetal carboxylate builders for the surfactant or surfactants and a bleaching amount of perborate, and particularly effective in the removal of particulate and particulate matter in wash water at elevated temperature Is grease contamination from polyester fabrics. 2. Detergent according to claim 1, characterized in that it is particulate and essentially free of phosphate and that the surfactant is selected from the group consisting of anionic, nonionic and mixed anionic and nonionic surfactants, the polyacetal carboxylate builder is a weight calculated average molecular weight in the range of about 3 500 to 10 000 and the perborate is an alkali metal perborate selected from the group consisting of anhydrous sodium perborate and sodium perborate hydride with a content of water of hydration up to 4 moles per mole. 3. Detergent according to claim 2, characterized in that it is phosphate-free and that the surfactant is a mixture of an anionic surfactant and a nonionic surfactant, the polyacetal carboxylate is a weight has calculated average molecular weight in the range of 5,000 to 9,000 and the alkali metal perborate Is sodium perborate. 4. Detergent according to claim 3, characterized in that it is about 3 to 30% sulfated or sulfonated anionic surfactant with a lipophilic moiety that is a Comprises an alkyl chain of 8 to 20 carbon atoms, and about 2 to 25% nonionic surfactant which is the Is condensation product of ethylene oxide and a compound that provides a lipophilic group and is capable of is to form the nonionic surfactant with ethylene oxide, 4 to 50% polyacetal carboxylate builder and 10 to 50% Contains hydrated sodium perborate. 5. Detergent according to claim 4, characterized in that it is about 4 to 20% higher alkylbenzenesulfonate, in which the alkyl group has 10 to 18 carbon atoms, about 2 to 10% of a nonionic surfactant which is a condensation product of ethylene oxide and a higher fatty alcohol, wherein the higher fatty alcohol has 10 to carbon atoms and the nonionic surfactant contains 3 to 20 moles of ethylene oxide per mole, about 10 to 30% polyacetal carboxylate builder, where the carboxylate is sodium carboxylate, about 10 to 40% sodium perborate tetrahydrate, about 3 to 20% moisture inclusive the hydrate moisture which is removable at 105 ⁰ C, and the balance being filler (s) and / or other builders and / or excipient (s). 6. Detergent according to claim 5, characterized in that it 4 to 10% sodium linear tridecylbenzenesulfonate, 2 to 6% higher fatty alcohol polyethoxyethanol, in which 5 to 9 Mole of ethylene oxide with one mole of the higher fatty alcohol with an average of 12 to 15 carbon atoms condensed, 10-25% polyacetal carboxylate builder having a weight average molecular weight ranging from 7,000 to 9,000, 15 to 30% sodium perborate tetrahydrate, 2 to 6% sodium soap of a higher fatty acid in which the higher fatty acid is 10 has up to 18 carbon atoms, 0.3 to 3% sodium carboxymethyl cellulose and contains 5 to 15% moisture. 7. Detergent according to claim 6, characterized in that it contains about 8% sodium linear tridecylbenzenesulfonate, about 4% higher fatty alcohol polyethoxyethanol, in which about 7 moles of ethylene oxide with one mole of a higher fatty alcohol with condenses an average of 12 to 15 carbon atoms are about 18% polyacetal carboxylate builder having a weight calculated average molecular weight of about 8,000, about 22% sodium perborate tetrahydrate, about 4% sodium tallow soap, about 1% sodium carboxymethyl cellulose and contains about 10% moisture. 8. Processes for removing mixed particulate and fatty contaminants from fibrous polyester materials; characterized in that the contaminated fibrous materials in washing water washes at a temperature in the range of 50 to 99 ° C with a builder-containing detergent which has a detergent amount of a surfactant or a mixture of surfactants, a builder effect amount of one Polyacetal carboxylate builder for the surfactant (s) and a bleaching amount of a perborate contains, wherein the concentration of the detergent in the wash water is in the range of 0.05 to 1.5%. 9. The method according to claim 8, characterized in that a detergent is used which is essentially free of phosphate and in which the polyacetal carboxylate builder is a weight calculated average Molecular weight in the range from about 3,500 to about 10,000 and the perborate sodium perborate with up to to 4 moles of water of hydration per mole, and that a wash water is used which has a hardness above 200 ppm as Has calcium carbonate. 10. The method according to claim 9, characterized in that a detergent is used which contains about 4 to 20% higher alkylbenzenesulfonate, in which the higher alkyl radical has 10 to 18 carbon atoms, about 2 to 10% of a condensation product of ethylene oxide and a higher fatty alcohol, in which the higher fatty alcohol has 10 to 18 carbon atoms and the nonionic surfactant contains up to 20 moles of ethylene oxide per mole, about 10 to 30% polyacetal carboxylate binders having a molecular weight in the range from 7,000 to 9,000, in which the carboxylate is sodium carboxylate, about 3 to contains 20% of moisture, including hydrate moisture which is removable at 105 ⁰ C, and the balance of filler (s) and / or other builders and / or other excipient (s), and in that the washing at a temperature in the range of 60 to 90 ⁰ C in wash water with a hardness in the range from 250 to 350 ppm as calcium carbonate and at a detergent concentration in the wash water in the range from 1.0 to 1.5% carried out in an automatic washing machine.