JPS612799A - Synthetic organic detergent composition for antistatic purpose - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to detergent compositions. More particularly, the present invention relates to detergent compositions comprising an anionic synthetic organic detergent or a mixture of said detergents, a polyacetal carboxylate builder of said detergent and a cationic antistatic detergent. It is also within the scope of the invention to clean soiled and/or contaminated textile materials to remove static electricity [clinching] of such soils and/or contaminated materials.
ging) J is included.

The need to remove dirt and contamination from textile materials is an old one, and numerous compositions have been described for achieving said results. While soap was once a general purpose detergent, today almost all household laundry detergent compositions are based on one or more synthetic organic detergents. Among such detergents, anionic and nonionic detergents are the most effective, and anionic detergents are the most used. Amphoteric and cationic detergents can also be used. Cationic compounds with detersive activity often also have bactericidal activity and act as antistatic agents. Antistatic agents are particularly important because they reduce static build-up on cleaned items of synthetic organic polymer plastics, such as nylon, polyester, and acrylic. Cationic compounds also have fabric softening properties. However, a drawback of cationic detergents is their reactivity with anionic substances, such as anionic detergents, and this property can greatly reduce detergent action.

Recently, cationic detergents, such as quaternary ammonium halides, have been developed to provide antistatic properties to synthetic organic polymers, plastics, washed materials or laundry, without significantly adversely affecting the cleaning activity of the composition. It has been used in detergent compositions to impart mold-neutral properties. Also,
Recently, builders of polyacetal carboxylates have been
It has been used in place of polyphosphate builders because it does not contain phosphorus and therefore is not thought to promote eutrophication of inland waters. Another advantage of such builders is that they can be easily decomposed in normal acidic wastewater.

Although the main components of the detergent compositions of the present invention have been used in other such compositions, the detergent compositions of the present invention are novel, non-obvious, and unexpectedly superior soil and detergent compositions. The detergent compositions of the present invention, particularly the phosphate-incompatible compositions, which are believed to have stain-removal properties, remove various stains and soils from synthetic textile materials and remove such materials during conventional mechanical cleaning. has a greatly improved ability to impart antistatic and flexible properties to
The antistatic properties prevent washed materials from sticking together during automatic laundry drying.

According to the present invention, an antistatic detergent composition, a synthetic machine detergent with a cleaning ratio, a cleaning enhancement (detergency build)
ding) ratio of said detergent or a mixture of said polyacetal carboxylate builder and zeolite builder in an enhancing ratio, and an antistatic cationic component in an antistatic ratio.

Preferred such compositions include about 5-30% sodium linear higher alkylbenzene sulfonate, wherein said higher alkyl has 12-14 carbon atoms; 5-4
0% of a polyacetal carboxylate builder or a mixture of said ruders and zeolite A builder with a calculated weight average molecular weight ranging from 3.500 to 10,000; 2 to 10% of distearyldimethylammonium chloride; 2 to 20% moisture; and the remainder one or more fillers and/or other builders and/or auxiliaries. It is also within the scope of this invention that soiled and contaminated textile materials are
washing in water having a mixed calcium and magnesium hardness in the range of 50 ppm, at a temperature in the range of 10 to 55°C and at a concentration of said detergent composition, said detergent water A method for removing dirt and stains from textile materials is encompassed, characterized in that it contains a synthetic organic detergent in a proportion of a synthetic organic detergent, a polyacetal carboxylate builder of said detergent in a wash-enhancing proportion, and a cationic antistatic agent in an antistatic proportion. .

The anionic synthetic organic detergents of the present invention are typically sulfated and/or sulfonated, having from 8 to 20 carbon atoms, preferably from 10 to 18 carbon atoms, more preferably from 12 to 16 carbon atoms. It may be a lipophilic material. Although various water-soluble salt-forming cations can be used to form the desired soluble sulfated and sulfonated detergents, such as ammonium and lower alkanolamines (e.g., triethanolamine), alkali metals,
For example, sodium or potassium is used, and very preferably such cation is sodium. Among the various anionic detergents useful in the practice of this invention, those containing 10 to 18 carbon atoms, preferably 12 to 16 carbon atoms, and most preferably 12 or 13 carbon atoms in the alkyl chain. It is believed that linear higher alkylbenzene sulfonates having the same structure as sulfuric acid are also suitable in the practice of this invention. Also, monoglyceride sulfates, higher aliphatic alcohol sulfates, sulfated polyethoxylated alkanols, where the alkanols can be synthetic or natural, and 3 to
Mention may be made of paraffin sulfonates and olefin sulfonates containing 20 or 30 ethoxy groups per mole, in all of which compounds the alkyl groups present have from 10 to 18 carbon atoms.

Some of the alkyl groups may be slightly branched and still have carbon chain lengths within the desired range.

Cationic detergents which can usually be used in limited proportions, for example less than 10%, preferably less than 5%, are preferably di-higher alkyl, di-lower alkyl ammonium halides, where higher alkyl is 10- It has 18 carbon atoms, preferably 16 to 18 carbon atoms, lower alkyl has 1 to 3 carbon atoms, preferably 1 carbon atom, and halogen is chlorine or bromine. Among these substances, mention may be made of distearyldimethylammonium chloride, tallow dimethylammonium chloride (where the alkyl is obtained from animal fat) and tallowdimethylammonium dihydrogen bromide. However, various other such cationic substances, such as N-cetyl-ethylmorpholinium ethosulfate, often classified as antistatic agents (they also often have deodorizing and bactericidal properties), are used. You can also do that. A variety of suitable anionic and cationic detergents include McCutcheon's Detergents and Emulsifiers.
Detergents and Emulsifi
Annual publications of the species// entitled ers), e.g. 19
It is listed in the book published in 1969. Additionally, such cationic substances form a well-known class,
and additional non-ionic detergents and amphoteric detergents, which are described in detail in said literature (as well as anionic detergents), and therefore it will not be necessary to explain them further here. Detergents are also described in said document and are present together with anionic and cationic detergents in a proportion smaller than the proportion of anionic detergents and smaller than the proportion of cationic detergents normally present. can do.

Polyacetal carboxylates are disclosed in U.S. Patent No. 4.1.
No. 44.226 can be considered and can be produced by the methods described therein. A typical such product would have the formula: R1(CHO)n-R2 000M where M is an alkali metal, ammonium, an alkyl group of 1 to 4 carbon atoms, tetraalkyl ammonium group and alkanolamine group (both have 1 in the alkyl moiety)
~4 carbon atoms), n is on average at least 4, and R1 and R2 are any chemically stable compounds that stabilize the polymer against rapid depolymerization in alkaline solution. It is the basis. Preferably, the polyacetal carboxylate is 1M alkali metal, such as sodium, n is 20-200, Ro or a mixture thereof, and R2 is 0CR2CH.

The calculated weight average molecular weight of this polymer ranges preferably from 2.000 to 80, preferably from 20 to 100, more preferably from 30 to 80.
20,000, preferably 3,500 to 10,000,
More preferably 5°000 to 9.000, for example 7.
000-9.000, in particular about 8.000.

Although preferred polyacetal carboxylates have been described above, they may include other such polyacetal carboxylates or related organic builder salts as described in various patents of Monsanto Co., Ltd. for such compounds. The preparation and use of said compounds are described in those patents. Also, the various patents mentioned above, especially U.S. Pat.
Chain termination techniques described in US Pat. Although promoting biodegradation, alkaline media, e.g.
Their stability must be maintained in the washing solution.

The zeolite component usually has the formula (Na20)x・(Al2O
2"!・(Sin2)z*wH20, where X is l, y is 0°8 to 1.2, preferably about 1, and 2 is 1.5 to 3 .5, preferably 2-3
or about 2, and w is 0 to 9, preferably 2.
It is 5-6. Such zeolites are cation exchangeable and have an exchange capacity for calcium ions of about 200-400 milliquivalents per Ig or more. Preferably they are hydrated to a moisture content of 5-30%, preferably 10-25%, such as about 20% moisture. Zeolite A is preferred (X and Y are also useful) and among such zeolites:
Type 4A zeolites are most preferred; the particle size of the zeolites is usually between 100 and 400 mesh (or sieve number), preferably between 140 and 350 mesh, but their ultimate size will be less than 1 micron. 1 Literature Zeolite fist molecular sieve (Zeoli)
te MolecularSieves), Donald W.

Breck, John Willie and Φ
Published by Sands, pages 747-749.

Although other builders other than polyacetal carboxylates may be present in the compositions of the invention,
Since this is not necessary and it is often desirable to avoid the presence of phosphorus in detergent compositions, polyphosphates (particularly pentansodium tripolyphosphate), which have been the builders of choice in the detergent field for many years, are used in the present invention. However, in some cases they may be present at least in a relatively small proportion, for example up to 5% or 10%. Among builders other than polyphosphates, such as sodium tripolyphosphate and tetrasodium pyrophosphate, the building effect of polyacetal carboxylates is
Builders that may be desirable to incorporate into the compositions of the present invention to assist in the oxidation of the compound include sodium carbonate, sodium bicarbonate, sodium sesquicarbonate, sodium silicate, zeolites such as zeolite A, NTA, citric acid. Including sodium, sodium gluconate, borax, other borates, and other builders known in the detergent art. Fillers, e.g.

Sodium sulfate and sodium chloride can optionally be present to bulk up the product. Among the builders, zeolites, as previously indicated, are believed to be particularly effective in these compositions, and the preferred filler will usually be sodium sulfate.

Among the various auxiliaries that can be used are colorants, e.g.
dyes and pigments, fragrances, enzymes, stabilizers.

Activators (particularly activators that cause the release of active oxygen from perborate), optical brighteners, buffers, fungicides and painting side (
fungicide), bactericide (germicide)
and a glidant is present. The adjuvants also include, in addition to the other classes mentioned above, various additional ingredients or impurities that are present with other ingredients. is known to be often present in polyacetal carboxylates (which is a source of polyacetal carboxylates).

Moisture will normally be present in the compositions of the invention as free moisture or in the form of one or more hydrates. Moisture is not an essential component of the detergent composition of the present invention.
It is normally present due to the use of water during manufacture and may solubilize and facilitate binding of the other components of the composition.

The proportions of the components of the compositions of the invention described below are for granular products, which typically have particle sizes ranging from No. 8 or IO to 100 sieves (or meshes) of the American sieve series. However, such ratios also apply to other solid forms, such as bars or cakes, finer or coarser powders, granular compositions and agglomerates. They can also be applied in liquid preparations. However, since they have relatively low stability (due to interactions between anionic and cationic components), aqueous liquid preparations should be used immediately after preparation. Also, although the proportions of all components excluding water are approximately the same as in liquid preparations, such products are often very dilute so that water or other solvents or mixtures of solvents present are It can be very large. In some aspects of the invention, the ingredients can be added directly to the wash water, in which case the detergent composition can be considered a wash water containing various active ingredients and other ingredients.

In the granular solid and other solid detergent compositions of the present invention, the total proportion of detergent present is usually from 5 to 40%, more preferably from 10 to 25%, most preferably from about 13 to 23%.
%, for example about 19%. Such detergents are usually anionic detergents, and among these alkylbenzene sulfonates, such as linear sodium tridecylbenzene sulfonate, are preferred. However, such detergents may be present together with other anionic detergents or may be completely or partially replaced by one or more such other anionic detergents. I can do it. The proportion of polyacetal carboxylate builder is usually between 5 and 50%, preferably 5% when it is the only builder present or when other builders other than zeolite are also present up to 50%.
When zeolite is present, the sum of polyacetal carboxylates and zeolides will be in the range of ~40%, more preferably 15-30%, most preferably 17-23%, e.g. about 19%. The polyacetal carboxylate will be present at least 5% of the detergent composition in the proportions described above for carboxylate alone and if zeolite is present, and the ratio of polyacetal carboxylate to zeolite will be from 1:3 to 3:1, preferably 2:3 to 2:1, more preferably about 3:4 to 7:4, for example l:1 to 3:
The cationic compound that functions as an antistatic agent (and also has fabric softening properties), which may range from , there will be. Although the detergent compositions of the present invention have been found to be particularly effective in reducing electrical charging (and ultimately electrostatic adhesion) on acetate materials, they may also be used on other synthetic fabrics, e.g. Effective on acrylic and polyester. The proportion of cationic antistatic agent will normally range from 2 to 10%, preferably from 3 to 8%, more preferably from 4 to 6%, for example about 4 or 5%. The moisture ratio is usually 2-20%,
Preferably it will be in the range 3-15%, more preferably 5-12%, such as about 6 or 8%, such percentage will be the hydrate released during heating at 105° C. for 2 hours. (standard moisture analysis method)
, the proportion of other components, such as fillers, will usually be limited to no more than 50% and will often range from 5 to 35%.
Similarly, the content of non-phosphate builders other than polyacetal carboxylates is limited and is generally 40%
%, for example 3-30% or 5-25%, however the presence of other builders and fillers is often desirable; thus, the sodium carbonate
Like sodium silicate, it is a preferred non-phosphate builder. A preferred silicate is Na2O:Si
O2 ratio is 1:1, 6-1.3.0, preferably 1
:2.0-1:2°6, for example, a sodium salt in the range of 1:2.4. The ratio of carbonate and silicate, if present, is from 3 to 25% each, - preferably 5
~10%, more preferably 6-9%. The proportion of fillers, when present, usually ranges from 5 to 35%,
Preferably 20-35%1, more preferably 22-30%
%Will.

The total adjuvant content usually does not exceed 10% or 20%, preferably less than 5%, and the individual adjuvant content usually does not exceed 3% or 5%, preferably less than 1 or 2%. For example, sodium carboxymethyl cellulose, a desirable anti-redeposition agent, may include:
Usually it will be present in the range of 0.5-2%, for example 1%, 0.3-3% of the composition.

In a preferred form of the invention, preferably spray drying as much of the formulation as possible in a particulate solid composition having a particle size as described above to obtain small spherical particles of substantially uniform shape, the cationically charged Anti-1F agent is anionic material 1
For example, since it can react with anionic detergents, it will usually be added later to the rest of the composition. In order to prevent segregation during transportation and storage of the final product, when using ingredients such as cationic compounds, polyacetal carboxylates and enzymes, they should be combined with the remaining ingredients of the composition in shape, particle size and It is desirable that the bulk densities be similar, but even when this is not the case and the post-added material is finely divided, e.g.
Particle size in the 325 mesh range and high bulk density.

They can be post-added to the spray-dried beads or other particles of the base detergent composition that are of larger particle size and often adhere to such particles to a size of 10-10
The polyacetal carboxylate will yield the desired product in the range of 0 mesh (or sieve size).
Sometimes it can be spray dried with the detergent composition, but care must be taken to prevent it from being degraded by heat. In another method of manufacture, the various components can simply be mixed together in micronized form. Also, when the initial mildness of the component is less than desired, e.g. 140-325 mesh,
Particles can be agglomerated to the desired size, sometimes with the aid of a flocculant, such as a dilute solution of sodium silicate, and in other cases water alone can be used to promote agglomeration. can.

The anionic detergent or mixture of detergents that is the predominant detergent of the desired composition may contain fillers such as sodium sulfate,
It can be spray dried with builders such as sodium carbonate, sodium bicarbonate, borax and sodium silicate, and auxiliary agents such as optical brighteners, pigments and dyes, and in the conventional manner Using a flow-type or co-current type spray drying tower, the temperature is about 200-600°C (when polyacetal carboxylate is present).

Spray drying can be carried out using dry air entering at preferably 150-300 or 350<0>C. The polyacetal carboxylate and antistatic agent can then be mixed sequentially or simultaneously, or the antistatic agent and polyacetal carboxylate can be pre-blended and then mixed with the spray dried beads.

When a relatively small proportion of nonionic detergent is present together with anionic detergent, it can be spray dried together with said anionic detergent, filler, etc., and stable amphoteric materials to be present. and the cationic material can be incorporated into a crutcher and then spray dried with the anionic detergent. However, when about 4 or 5% (sometimes more than 2%) of non-ionic detergent is present in the formulation, an additional proportion of
For example, the polyacetal carboxylate and the antistatic agent can be post-added, for example by spraying onto the tumbling particles of detergent beads or base beads. The combination of nonionic detergent and polyacetal carboxylate can be dispersed and/or dissolved in a nonionic detergent (the polyacetal carboxylate can be dissolved in a solvent) and the combination of nonionic detergent and polyacetal carboxylate can be applied onto the detergent beads or base beads. The cationic antistatic +)- agent can then be added. Desirably 11, the particles produced are 8-1
20 or 10 to 100 meshes, and the manufacturing method will be designed accordingly. However, when sieving is used to remove small and large particles and their reprocessing, grinding, agglomeration or other methods are used to reduce the desired size to 8 to 80
It can be made into

The products of the invention can be used as bars, cakes or bars.
When fabricated in the form of an iquette, the composition can be extruded, pressed or formed into shaped objects by known methods. In order to convert them into liquid preparations, the compositions can be dissolved and/or dispersed in a liquid medium, such as water and/or suitable solvent(s).

One of the aforementioned compositions can be added to the wash water in order to carry out the soil and stain removal method of the present invention which leaves the washed items non-stick and clean (and also soft). , or various ingredients can be added as such. usually.

The concentration of the composition used is from 0.05 or 0.1% to 0.4%
or 0.5%, preferably 0.1-0.

35%, more preferably 0.15-0.25 or 0.
It is 35%. Concentrations higher than this, e.g. 0.25~
Less than 0.45% of wood (and less wood) is often used in mechanical cleaning practices, where hot wash water is utilized. In American practice, lower concentrations than above, e.g. O,'05-0.2
5%, often preferably about 0.1-0.2% of the composition is used. Typically, the cleaning temperature in the United States is 10
~55°C, often 10-30°C, whereas in Europe>)S 60-99°C, often 70-30°C
The temperature is 90 or 95°C. However, the compositions of the present invention are useful for removing dirt and contamination from different types of laundry and materials, and for removing static electricity from such laundry regardless of the cleaning method used. Useful for remaining firm and flexible.

In the practice of the present invention, sufficient detergent compositions of the present invention may be applied in conventional domestic laundry washing machines (commercial washing machines may also be used) at desired ratios within the foregoing ranges, e.g. 2% at normal wash temperatures, e.g. 49°C and normal hardness (approximately 50-250 or 300 ppm.
(as calcium carbonate) to the wash water. Then,
Add laundry, normal feed weight is 2.7-4.5kg
, for example, 3.6 kg. Washing the laundry is usually carried out on a regular cycle for 2 to 30 minutes, for example 5 to 30 minutes, as required, depending on the soiling of the laundry. *<Preferably, the compositions of the present invention have a hardness comparison of about 50 to 150 ppm compared to a control composition that uses an equal (and even greater) proportion of sodium tripolyphosphate in place of polyacetal carboxylate. It exhibits similar soil and stain removal properties in soft and medium hard water, but is significantly superior to the control composition at higher hardnesses (250 ppm). Also, in a composition of the invention or a control composition (the composition of the invention contains polyacetal carboxylate and a zeolite, and in the control composition,
An equal weight of sodium tripolyphosphate has been used in place of these) washed terry towels (
terrycloth (terrycloth) appears to have almost the same flexibility and overall static charge. However, such inventive compositions are significantly superior to controls in reducing static charge on acetate fabric foils (and reducing fabric foil adhesion).

The invention is further illustrated by the following examples. In these examples, all parts are by weight and temperatures are in degrees Celsius, unless otherwise indicated.

Linear Tridecylbenzenesulfonic Acid 19.0 Sodium Hilder U (79.7% Sodium 23.8 Mbolyacetal Power Rupoxylate, E Lot No. 25 38422.8034 Range Calculated Supplied by Monosanto Company) Weight average molecular weight] Sodium carbonate (m water) 12.4 Sodium silicate (Na20:Si 7.60, ratio =
1:2.4) Sodium sulfate (anhydrous) 26.7 water

5.7 Distearyldimethylammonium chloride
4.8 um (Arosurf TA-1 00, approximately 90% active, available from Selex Tube Chemical Company) ioo.

A granular detergent in the form of spray-dried beads is prepared as follows: 1) from the ingredients of 100% omitted from cationic compounds: 0. Prepare an aqueous crutcher mixture (55% solids concentration) of the listed ingredients at about 55°C. and spray dry the crutcher mixture. The spray drying tower used is a countercurrent type operated under mild conditions, approximately 300°C.
Prevent carbonization of the beads and decomposition of the sodium polyacetal carboxylate using dry air and other equipment at a temperature of (1) to prevent contact between the spray and the tower wall. The product obtained is No. of the American sieve series.

Approximately 0.3 g/ml with particle size ranging from 10 to 100 sieves
It has a bulk density of about 8% and a moisture content of about 8%. 20 parts of the detergent composition thus prepared are mixed with 1 part of the Selex Chemical Q Company product. Desirably, such a product has a particle size similar to that of the base composition, but that it is a fine powder and has a particle size of 100 to 325
Even when the particle size is in the mesh range, the antistatic agent is well distributed throughout the detergent composition and adheres to the particles, which still range in size from 10 to 100 mesh and about 0.3 g/ml. yields a product with a bulk density of . The product produced is tested for soil and contamination removal.

Utilizing a Tergotometer laboratory test cleaning machine, standard swatches of various materials soiled and contaminated in a standard manner were washed with a composition concentration of 0.21% and 49% in cleaning water. Wash with a stirrer rotating at 1100 rpm for a wash period of 10 minutes at a wash temperature of °C. The hardness of the water used is 50.1
3:2 Ca at hardness of 50 and 250 rpm
: M g ratio of calcium and magnesium hardness. Taking the reflection readings of the cleaned and dried swatches and calculating an index representing the weighted sum of the reflections, which index, based on experience, indicates the soil and stain removal ability of the detergent composition being tested. (The higher the index, the better the cleaning performance), 50,150 and (/25
At a hardness level of 0 ppm, the previous experiments of this example yield indices of 256.242 and 234, respectively. If the same composition is made using sodium tripolyphosphate instead of builder U in the above formulation (which creates a product with a higher active builder content than the experimental formulation), the index is 254.24, respectively.
0 and 222. Thus, the cleaning and decontamination efficacy of one inventive composition in hard water (250 rpm) is that of a control composition containing pentapotassium tripolyphosphate, the most successful commercial builder known in the art. Better, and even better when more polyphosphate is used in this control.

In the formulation of Example 1, half of the builder U was replaced with zeolite 4A (20% hydrate), and this zeolite was added to the crutcher as a fine powder with a particle size ranging from 100 to 325 mesh; When the quaternary ammonium halide is then mixed with the spray-dried beads in the manner described in Example 1, the resulting antistatic detergent composition
and a control based on sodium tripolyphosphate builder instead of zeolite, with essentially the same cleaning properties (measured by essentially the same soil and soil removal index) and with less "stickiness" of the cleaned material. When tested for electrostatic charge indicative, the results for the products of the invention containing Builder U and zeolite are essentially identical to those for the "control" compared to detergent compositions containing no cationic compounds. An improved result is obtained. The reduction in electrostatic charge for the acetate cloth foil obtained using the experimental formulation compared to that of the control (containing no builder U and no zeolite) containing sodium tripolyphosphate builder and the aforementioned cationic compounds Recognized for excellence. Thus, after washing using the comparative composition and drying in an automatic laundry dryer, the acetate swatches
The control has a static charge of 5.5 kV after washing and drying and the experimental product of the invention has a static charge of 1.6 kV after washing and drying. When tested for softening properties, the control composition described above and the experimental composition described above are rated nearly identical in the test. In this test, six respondents rate sets of terry towels cleaned with one or the other composition between softest and hardest. The test conditions were the same as those for detergency described above, except that a light settling load was used (approximately 0.5 kg charge for 65 prongs of wash water) and the concentration of the detergent composition was 0.5 kg. 15% (100 g per 65 JJ of wash water).

In another variation of this example, the ratio of Builder U and zeolite is changed to 3:2. The soil and stain removal indices obtained are essentially identical to those for the control in which polyphosphate builder is present instead.

As can be seen from the experiments above, the experimental compositions of these examples compared to control compositions using sodium tripolyphosphate in place of Builder U or in place of a mixture of Builder U and zeolite. Equal or superior in critical dirt and contamination removal, static charge reduction and flexibility properties.

It is believed that such results can be obtained when changes are made to the experimental formulation and/or when changes are made in the manufacturing and/or cleaning methods. Thus, the aforementioned antistatic agents can be combined with other such substances, e.g.
Di-hydrogenated tallow dimethyl ammonium chloride, the corresponding quaternary ammonium bromide and other known antistatic agents can be used instead. Similarly, sodium tridecylbenzenesulfonate can be substituted with other water-soluble high M alkylbenzenesulfonates, such as sodium dodecylbenzenesulfonate or a mixture (equal parts) of linear sodium tridecylbenzenesulfonate and sodium lauryl sulfonate. Satisfactory products within the scope of the present invention can also be obtained when using other anionic detergents as mentioned above. Instead of the specific sodium polyacetal carboxylate, other such compounds of different molecular weights, such as molecular weight 5,
250 compounds (Monosanto Lot No. 2547
321) or other such compounds having molecular weights within the ranges described above and end groups as described and would result in useful antistatic detergents, as well as builders, fillers, etc. Agents and adjuvants can be varied as described herein.

For example, zeolite 4A can be transformed into other zeolites type A or into zeolites) X and/or Y types. Additionally, the proportions of the various components may be varied by ±10 or ±25% without losing the benefits of the invention, as long as the proportions remain within the aforementioned ranges.

In a manufacturing modification, the above-described compositions incorporate Builder U powder in the form of spray-dried particles of similar size or in the form of finer (ioo ~ 325 mesh) particles of similar size and charge. It can be made by post-addition to the spray dried beads before, after, or in conjunction with inhibitor particles or fine powders. The polyacetal carboxylate can be premixed with the antistatic agent and then mixed with the spray dried material. It can be blended with. In some cases, various components can be added to the wash water as individual feeds. In a preferred method, the polyacetal carboxylate is post-added rather than spray-dried with the various other components of the final product, thus better preserving all cleaning enhancement and static charge reduction effects (such builders When such changes are made in the manufacturing procedure described (by exposure to possible excessive heat and thereby preventing decomposition), the products obtained are equivalent in the described properties to those described above. mosquito,
Or even better. In the method described, the product obtained is 0.2 as in spray-dried beads.
It has a bulk density of 5 to 0.5 g/ml, and both No.
, with a particle size ranging from 10 to 100 sieves, whereas the polyacetal carboxylate builder and antistatic agent distearyldimethylammonium chloride usually have a high bulk density (0.6 to 0.9 g/ml), And with a small particle size (No. 100-325 sieve), the smaller particles satisfactorily retain the larger particles in the final composition to produce the desired product.

The cleaning method of this example can also be modified to
0ppm, and even higher, sometimes 300p
Water of various mixed calcium/magnesium hardnesses ranging from 10 to 5 pm is available and cleaning
It can be carried out at a temperature range of 5° C. and a concentration in the range of 0.05 to 0.5% of the detergent composition, and satisfactory results are obtained without undue loss of detergency;
The No. 4 formulation will then be equal to or better than the "control" containing sodium tripolyphosphate instead of the polyacetal carboxylate builder or instead of the mixture of said builder and zeolite.

Kaoden 1'' 4. 15 parts of linear sodium tridecylbenzene sulfonate and 25 parts of sodium tripolyphosphate.
5 parts of 70 surf (Arosurf) TA-100 approx. 9
0% active distearyldimethylammonium chloride), all ingredients are fine powders with particle sizes in the range of about IO-200 mesh. Using such material, Control, terry towels are washed and weighed according to essentially the same method as described in Examples 1 and 2. The towels were subsequently evaluated by an experienced rater: and given a grade of 9 on a standard scale of 1 to 10 for softness, where IO is the most soft. In another control experiment, 3 parts of 70 Surf TA-100 is used, mixed with 15 and 25 parts of other ingredients, and a similar flexibility test is performed. Washed towels are rated an 8 on this scale.

Instead of 25 parts of sodium tripolyphosphate,
In such compositions 25 parts of Builder U (Lot 25
38422) and repeating the test, the obtained flexibility rating is 10 and Allosurf AT
Such a grade is also obtained when the content of -100 is reduced to 3 parts in the aforementioned formulation.

The compositions of the invention described are all satisfactory detergents and have excellent antistatic and fabric softening properties.

Instead of mixing the various components, other compositions of this example can be made by spray drying and other procedures described in Example 1 and described above. The compositions described are also useful for washing soiled and contaminated laundry and for softening it, and after washing said laundry, it is usually obtained from drying in an automatic laundry dryer. It can be used to reduce its adhesion due to static electricity. Instead of linear sodium tridecylbenzenesulfonate, sodium lauryl sulfate and higher aliphatic alcohol polyalkoxysulfates can be used, and zeolite A or zeolite x can be used instead of half of builder U. Also,
70 Surf AT-1 with the other anti-static agent 11 mentioned above.
00 and the various ratios can be varied as described above and a satisfactory detergent with excellent softening and antistatic properties will be obtained.

, -743-

Claims (1)

[Claims] 1. A synthetic anionic organic detergent with a cleaning ratio, a polyacetal carboxylate builder of the detergent with an enhancing ratio or a mixture of the polyacetal carboxylate builder and a zeolite builder with an enhancing ratio, and a static charge with an antistatic ratio. An antistatic builder-containing granular detergent composition comprising an antistatic cationic compound. 2. The detergent composition according to claim 1, wherein the antistatic compound is a quaternary ammonium compound. 3. essentially free of phosphates, and the synthetic anionic detergent is a sulfated or sulfonated detergent;
The polyacetal carboxylate builder is 3,5
00 to 10,000, the zeolite builder is type A, type X or type Y, and the quaternary ammonium salt is a di-higher alkyl, di-lower alkyl ammonium halide. and
3. The detergent composition of claim 2, wherein said higher alkyl has 10 to 18 carbon atoms and said alkyl has 1 to 3 carbon atoms. 4. The synthetic anionic detergent has an alkyl group of 10 to 18
the polyacetal carboxylate is one in which the carboxylate is sodium carboxylate, and the zeolite has the formula (Na_2O)x·(Al_2O_3)y·(SiO_
2)_2·wH_2O In the formula, x is 1, y is 0.8 to 1.2, preferably about 1, and z is 1.5 to 3.5, preferably 2 to 3 or about 2. Yes, and w is 0 to 9, preferably 2.5
~ 6, and the quaternary ammonium salt has a higher alkyl of 10 to 18
4. A detergent composition according to claim 3, wherein the detergent composition is a di-higher alkyl dimethyl ammonium halide having 5 carbon atoms. 5. About 5-30% sodium linear higher alkylbenzene sulfonate, where said higher alkyl has 12-14 carbon atoms; 5-40% polyacetal carboxylate builder or a mixture of said builder with a zeolite builder. ; 2-10% distearyldimethylammonium chloride; 2-20% moisture; and the balance, if present, one or more fillers and/or
or other builders and/or adjuvants. 6. About 10-25% linear sodium tridecylbenzene sulfonate; 15-30% 5,000-9,000
a polyacetal carboxylate builder or a mixture of said builder and a zeolite builder having a calculated weight average molecular weight in the range of , wherein at least 5% of said composition is polyacetal carboxylate builder; 3 to 8% distearyl dimethyl chloride; Ammonium; 3-15% moisture; 8-18% sodium carbonate;
5-10% Na_2 in the range of 1:1.6-1:3.0
Sodium silicate with O:SiO_2 ratio; and 20-3
A detergent composition according to claim 5 comprising 5% sodium sulfate. 7. About 13-23% linear sodium tridecylbenzene sulfonate; 17-23% sodium polyacetal carboxylate builder with a calculated weight average molecular weight in the range of about 8,000; 4-6% distearyl chloride Dimethylammonium; 5-12% moisture: 10-
15% sodium carbonate; 6-9% 1:2.0-1:
7. A detergent composition according to claim 6, comprising sodium silicate with a Na_2O:SiO_2 ratio in the range of 2.6 and 22-30% sodium sulfate. 8. about 13-23% linear sodium tridecylbenzene sulfonate; a mixture of sodium polyacetal carboxylate builder and Type A zeolite having a calculated weight average molecular weight in the range of about 8,000 from 17-23%; and x is 1, y is 1, z is 2-3, and w is 2.5-6, and the ratio of polyacetal carboxylate builder to zeolite in the mixture is 2:3-2: 1:2; 4-6% distearyldimethylammonium chloride; 5-12% moisture; 10-15% sodium carbonate; 6-9% 1:2
．． 7. A detergent composition according to claim 6, comprising sodium silicate with a Na_2O:SiO_2 ratio ranging from 0 to 1:2.6; and 22 to 30% sodium sulfate. 9. A synthetic anionic organic detergent in a cleaning ratio, comprising a polyacetal carboxylate builder of said detergent in an enhancing ratio or a mixture of said polyacetal carboxylate builder and a zeolite builder in an enhancing ratio, and an antistatic quaternary ammonium in an antistatic ratio. A method of preparing a granular detergent composition containing an antistatic builder, comprising spray drying an aqueous slurry of a synthetic anionic detergent, a filler and/or a builder of the detergent, and water, using a No. into essentially spherical beads with a particle size in the range of 10 to 100 sieves, and characterized in that the spray-dried beads are mixed with a polyacetal carboxylate builder and an antistatic quaternary ammonium salt in an antistatic proportion. Method. 10. The synthetic anionic detergent is a linear sodium higher alkylbenzene sulfonate, where the higher alkyl has 12 to 14 carbon atoms, and the polyacetal carboxylate builder has 5,000 to 9,00 carbon atoms.
0 and the builder in the crutcher mixture is hydrated zeolite A, 1:
premixing said polyacetal carboxylate builder and said antistatic quaternary ammonium halide comprising sodium silicate, sodium carbonate and sodium sulfate in a Na_2O:SiO_2 ratio ranging from 2.0 to 1:2.6; mixed together with the spray dried beads and said detergent composition comprises about 13-23% linear sodium tridecylbenzene sulfonate; 17-23
polyacetal carboxylate builder and type A zeolite having a calculated weight average molecular weight in the range of about 8,000 of the sum of %, wherein the ratio of polyacetal carboxylate builder to zeolite is within the range of 2:3 to 2:1. ; 4-6% distearyldimethylammonium chloride; 5-12% moisture; 10-15% sodium carbonate; 6-9% N ranging from 1:2.0 to 1:2.6
a_2O:SiO_2 ratio of sodium silicate; and 2
10. The method of claim 9 comprising 2-30% sodium sulfate. 11. The bulk density of spray-dried beads is 0.25-0.5
g/ml, the bulk density of the mixture of sodium polyacetal carboxylate builder and antistatic distearyldimethylammonium chloride is greater than the bulk density of the spray-dried beads, and the mixture is No. 11. The method of claim 10, having a particle size in the range of 100 to 325 sieves. 12. The soiled and contaminated textile material is washed in water with a mixed calcium and magnesium hardness ranging from 25 to 250 ppm as calcium carbonate at a temperature ranging from 10 to 55°C and from 0.05 to 0.5% as calcium carbonate. cleaning with a detergent composition, said detergent composition comprising: a synthetic anionic organic detergent in a cleaning ratio;
Soils and contamination from textile materials characterized in that they consist of a polyacetal carboxylate builder of said detergent in an enhanced proportion or a mixture of said polyacetal carboxylate builder and a zeolite builder in an enhanced proportion, and an antistatic cationic compound in an antistatic proportion. How to remove. 13. The temperature of the washing water is in the range of 35 to 55°C,
The concentration of the detergent composition in the washing water is 0.1 to 0.3.
5% and said detergent composition has a
23% linear sodium tridecylbenzene sulfonate; a mixture of sodium polyacetal carboxylate builder and type A zeolite having a calculated weight average molecular weight in the range of about 8,000 from 17 to 23%, where x
is 1, y is 1, z is 2-3, and w is 2.5-6, and in said mixture the ratio of polyacetal carboxylate builder to zeolite is 2:
Within the range of 3-2:1; 4-6% distearyldimethylammonium chloride; 5-12% moisture; 10-1
5% sodium carbonate; 6-9% 1:2.0-1:2
．． 13. The method of claim 12, comprising sodium silicate with a Na_2O:SiO_2 ratio in the range of 6; and 22-30% sodium sulfate. 14. The method of claim 13, wherein the material being washed is cellulose acetate.