KR920006028B1 - Bleaching detergent composition - Google Patents

Abstract

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Description

Bleach composition

The present invention relates to detergent compositions, in particular bleach detergent compositions composed of organic synthetic detergents or mixtures of these detergents, polyacetal carboxylate enhancers for the detergent (s) and perborates. Also included in the present invention is a method for washing polyester fiber material soiled with granular dirt and oil.

The need to remove dirt and stains from textile materials has been handed down for many years. Many compositions have been described to achieve this result. One formulation that has been used so far to test the cleaning and staining of detergent compositions is a mixture of granular dirt and oil stains, which is a fibrous material, especially polyester fibers such as polyester knits and polyester-cotton blends. Is extremely dirty with mixed things. These dirts are sometimes used to artificially create "collar colored dirt". As is well known, "collar dirt" is thought to be difficult to remove from a sheer's collar (and cuffs beaks) during automatic laundering. Even when laundering is performed at relatively low temperatures, such as 10-30 ° C, or at higher temperatures such as 50-90 ° C or 95 ° C or higher, as is the case in European practice, it is difficult to remove.

However, once soap is a universal detergent today, almost all household detergent compositions are based on one or more organic detergents. Amphoteric detergents and cationic detergents are also used, but anionic detergents and nonionic detergents are considered to be most effective among these detergents. Sodium perborate has been added to detergent compositions for bleaching effects and has been used for a long time. In recent years, polyacetal carboxylate enhancers have been used in detergent compositions instead of polyphosphate enhancers. The reason is that polyacetal carboxylates do not contain phosphorus, so eutrophication of inland water ( It does not promote wealth. Another advantage of such enhancers is that they can be readily degraded in generally acidic wastewater.

Although the main components of the detergent compositions according to the invention are used in other such compositions, they are believed to have novelty and inventiveness and have particularly beneficial stain removal performance. Of particular importance is the ability of the composition to remove oil stains and granular dirt from the fiber material when washing the polyester blend fiber material in hot wash water containing the detergent composition of the present invention. have. This effect is possible even when hard water is used as washing water.

The bleach detergent composition according to the present invention is an organic synthetic detergent having a ratio of washing effect or a mixture of these detergents, a polyacetal carboxylate enhancer for the detergent (s) at a ratio showing washing force enhancing effect and polyester in hot washing water. It is composed of perborate in proportions that show a bleaching effect, which is particularly effective in removing dirt and oil stains from ports from textiles. Preferred compositions are condensation products of higher fatty alcohols having 10 to 18 carbon atoms and higher alkyl alcohols having 10 to 18 carbon atoms and higher fatty alcohols having 10 to 18 carbon atoms and ethylene oxide. 20 moles of nonionic detergent, about 2-10%, polyacetal sodium carboxylate enhancer with a calculated weight average molecular weight of 5000-9000, about 10-30%, sodium perborate. About 3-20% of the water containing moisture in the form of removable hydrates and the remainder consist of filler (s) and / or other enhancer (s) and / or other adjuvants (s). In addition, the present invention contains an organic synthetic detergent or a mixture of these detergents having a ratio of washing, a polyacetal carboxylate enhancer for the detergent (s) at a ratio of increasing the washing power and a perborate of a ratio having a bleaching effect. A method for removing particulate dirt and oil stains from polyester fiber material, which consists of washing contaminated fiber material at a temperature range of 50-99 ° C. in wash water to which the detergent composition is added at a concentration of 0.05-1.5%. Included.

In the composition according to the present invention, an organic synthetic detergent mainly used to exhibit cleaning characteristics is usually an anionic detergent. Among the anionic detergents, lipophilic sulfated and / or sulfonated materials with alkyl chains having 8-20, preferably 10-18, more preferably 12-16 carbon atoms are generally the best anionic detergents. Various water-soluble salt-forming cations can be used to make the required soluble sulfated and sulfonated detergents, including ammonium and lower alkanolamines (e.g. triethanolamine), using alkali metals such as magnesium, ordinary sodium or potassium. Very preferred cation is sodium. Among the various anionic detergents useful in the practice of the present invention, linear higher alkyl benzenesulfonates having alkyl chains having 10-18, preferably 12-16, particularly preferably about 12 or 13 carbon atoms are present in the invention. It is thought to be very suitable in practice. Also useful among other things are monoglyceride sulfates, higher fatty alcohol sulfates, alkanol components, synthetic or natural, sulfated polyethoxylated higher alkanols with 3-20 or 30 epoxy groups per mole, paraffin sulfo Nate and olefin sulfonate, in which both alkyl groups have 10-18 carbon atoms. Some of these alkyl groups may be somewhat branched, but the carbon chain length should still be in the above range.

Preferred as nonionic detergents, which are often used to supplement the cleaning action of basic anionic detergents, but in some cases also serve as basic detergent (s), are usually solid materials (especially when added in solid or granular solid products) and oxidation. Condensation product of ethylene and higher fatty alcohols, in which the higher fatty alcohols usually have 10-18 carbon atoms, preferably 12-15 average carbon atoms, such as about 12-13, and the ethylene oxide content is fatty alcohol. In the range of 3-20 moles per mole, preferably 3-12 moles, more preferably 5-9 moles, such as about 6.5 or 7 moles.

Also useful among other nonionic detergents are condensation products of alkylphenols having 5-12 carbon atoms in the alkyl group, such as nonylphenol, with ethylene oxide, where the content of ethylene oxide is 3-30 moles per mole. Condensation products of propylene oxide and ethylene oxide, which are sold under the Pluronic trademark, are available in various nonionic detergents.

Can be used.

Preferred as cationic detergents which can be used in limited proportions, usually less than 10%, preferably less than 5%, are di-higher alkyl ammonium halides and higher carbon atoms having a higher alkyl group having 10-18 carbon atoms, preferably 16-18 carbon atoms. Di-lower alkyl ammonium halides having a lower alkyl group of 1 to 3, preferably 1, wherein halogen is chlorine or bromine. Among these materials are distearyl dimethyl ammonium chloride, di-tallow dimethyl ammonium chloride (where the alkyl group is from animal fat) and this hydrogenated tallow dimethylammonium bromide.

However, other cationic materials, including N-cetyl-ethyl morpholinium ethosulfate, which are often classified as antistatic agents (often deodorant and bactericidal) can also be used. Among the amphoterics there are things like Miraol, which is called Miranol C2MConc. It is marketed under the name. Other such detergents, including anionic detergents, nonionic detergents, amphoteric detergents and cationic detergents, are all listed in various annual publications (eg, McCutcheon's Detergents and Emulsifiers, 1969).

Polyacetal carboxylates are described in US Pat. No. 4,144,226 and may be prepared according to the methods herein. Typical polyacetal carboxylates have the following general formula:

In the above formula, M is an alkali metal, ammonium, an alkyl group having 1 to 4 carbon atoms, a tetraalkyl ammonium group (where the alkyl group has 1 to 4 carbon atoms) and an alkanolamine group (where the alkyl group has 1 to 4 carbon atoms) N is at least 4 on average, and R ₁ and R ₂ are any groups with chemical stability that stabilize the polymer in rapid alkaline depolymerization in alkaline solution. Preferred polyacetal carboxylates are M is an alkali metal (e.g. sodium), n is 20-200, and R ₁ is

Or mixtures thereof

이며, n의 평균값이 20-100, 더욱 바람직하게는 30-80인 것이다. 이 중합체의 계산중량 평균 분자량 범위는 2,000-20,000인 것이 좋은데 3,500-10,000인 것이 바람직하고 더욱 바람직한 것은 5,000-9,000 즉, 7,000-9,000, 특히 약 8,000인 것이다.R ₂

And the average value of n is 20-100, more preferably 30-80. The calculated weight average molecular weight range of this polymer is preferably 2,000-20,000, preferably 3,500-10,000 and more preferably 5,000-9,000, ie 7,000-9,000, especially about 8,000.

Preferred polyacetal carboxylates have been described above, but it should be noted that related organic enhancer salts or other polyacetal carbohydrates disclosed in various Monsanto patents for these compounds, methods for their preparation, and compositions using them. It is possible to replace some or all of the compound with a carboxylate. In addition, as described in various patents, especially US Pat. No. 4,144,226, it has the desired stability, and in acidic media, the above-mentioned heavy forcing agent causes depolymerization, which facilitates biodegradation in waste water while maintaining stability in alkaline media such as washing solutions. Chain terminators can be used.

The perborate used is a water soluble perborate which is capable of releasing active bleaching oxygen in an aqueous medium at high temperatures, as in washing water. Preferred examples of this borate salt are alkali metals and equivalent salts, with sodium perborate and tetrahydrate being very preferred. Usually perborate is hydrated, but it is not necessary. Generally, tetrahydrate is used as a hydrate, but some perborates having a water content of less than 1 mole per mole of hydrate can be used, especially when charged to a specific use or in a vapor-tight container (where hydration degree is The larger the is, the easier it is to liquefy or the easier to cake the detergent composition).

Usually, higher fatty acid soaps such as sodium soap are used as detergents, but these are generally not considered organic synthetic detergents, and thus they do not belong to the range of detergent types that are suitable for the purpose of the present invention. These soaps have a detergency but can also be used for other purposes such as bubble restriction. Among the soaps that may be used in the compositions of the present invention are soaps of 10-18 carbon atoms and preferably highly saturated soaps, alkali metal soaps such as sodium. These soaps include sodium soaps made from hydrogenated tallow, four tallow soaps with sodium stearate and sodium palmitate, and mixtures of tallow and coconut groups, such as uji: coconut oil = 4: 1. It can also be used as a composition component.

Although the other enhancer other than polyacetal carboxylate may be unnecessary in the composition of this invention, it can also be used. What is often needed is to avoid the presence of phosphorus in the detergent composition, so that polyphosphates (particularly 5-sodium tripolyphosphate), which have been selected and used as enhancers in the detergent field for many years, are not included in the compositions of the present invention. Nevertheless, in some cases at least relatively small amounts of less than 5 or 10% are used. Among the enhancers other than polyphosphates, such as sodium tripolyphosphate and tetrasodium pyrophosphate, may be added to the composition of the present invention to compensate for the enhancement of polyacetal carboxylates, such as sodium carbonate, sodium bicarbonate, sodium sesquicarbonate, silicic acid Sodium, zeolites (eg Zeolite A), NTA, sodium citrate, sodium gluconate, borax, other borate salts and other enhancers known in the detergent field.

Fillers, such as sodium sulfate and sodium chloride, can be added to give volume to the product when deemed desirable to give bulk to the product. In liquid compositions that normally have to be used immediately upon preparation, solvents or extenders such as water, ethanol and isopropanol can be used.

As auxiliaries, colorants such as dyes and pigments, flavorings, enzymes, stabilizers, activators (particularly activators that release free radicals from perborates), fluorescent brighteners, buffers, fungicides, fungicides, and fluids There is a promoter. There are also impurities that are present as supplements to the ashes, along with various additional or other ingredients. For example, it can be seen that sodium carbonate and rule are mixed in the polyacetal carboxylate marketed as the builder U, which is a polyacetal carboxylate used in the present invention.

The moisture in the compositions of the present invention is in free moisture or in one or more hydrate forms. Moisture is not an essential ingredient in these bleaching detergent compositions but is usually contained because water is used in the preparation and may help dissolve and bind other composition ingredients.

The ratio of each component in the composition according to the present invention is as follows for a granular product having a particle size of 8 or 10-100 or 140 (or mesh) on a US Sieve grade basis. Are shown. However, this ratio also applies to other solids such as rods and cakes, to fine powders or to coarse powders, to granulated compositions and to agglomerates, and that aqueous liquid preparations should be used relatively quickly at the time of manufacture because of the relatively low stability of liquid preparations. The same applies to water. In addition, the proportions of all components except water are almost the same as for liquid formulations, so these products are often much more diluted to allow a much larger proportion of water or other solvents or solvent mixtures. Some features of the present invention allow the ingredients to be added directly to the wash water, in which case the detergent composition may be considered to be wash water containing various active ingredients and other ingredients.

In the granular solid detergent composition and other solid detergent compositions according to the present invention, the total ratio of the detergent is usually 5-40%, more preferably 10-25%, and most preferably about 12%. Among these detergents, it is preferable to include sulfated or sulfonated anionic detergents or nonionic detergents, but both of these detergents may be included. The proportion of anionic detergent is usually 3-30%, preferably 4-20%, more preferably 4-10, such as about 8%, and the ratio of non-ionic detergent is about 2-25%, preferably 2-10%. Preferred is 2-6%.

The proportion of polyacetal carboxylate enhancer is usually 4-50%, with 10-30% being preferred and more preferably 10-25%, such as 18%. The content of perborate is usually 10-50%, preferably 10-40%, more preferably 15-30%, such as 22%, which is sodium perborate. Since it is based on the rate of tetrahydration, when using anhydrous salts or different hydrates, the dosage can be changed. When soap is used, the amount of addition is usually in the range of 1-10%, preferably 2-6%, and the moisture content is usually 3-20%, preferably 5-15%, for example, about 10%. Do. This content contains water in the form of a hydrate which is released during heating at 105 ° C. for 2 hours (analysis by standard moisture analyzer).

The addition of other ingredients such as fillers is usually limited to less than 40%, usually in the range of 0-30% or 5-20%. Likewise, the content of enhancers other than polyacetal carboxylates is usually limited to less than 25% (eg 3-20% or 5-15%), which is sometimes not added. The total adjuvant content usually does not exceed 10% or 20% and is preferably less than 5% and the content of each adjuvant is preferably not more than 3% or 5% and preferably less than 1% or 2%. For example, the content of sodium carboxymethyl cellulose used as a reattachment inhibitor is usually 0.3-3%, preferably 0.5-2% (eg 1%).

Preferred is a granular solid composition of particle size as described above, and it is often desirable to spray dry as much of the composition as possible so that a substantially uniformly shaped spherical particle is obtained. Because perborate is heat labile, it is usually post-added to the remainder of the composition. Of course, to ensure that the final product is not separated during shipment or storage, the perborate must have the same particle size and shape as the rest of the composition.

Occasionally, polyacetal carboxylate may be spray dried together with the detergent composition, with care being taken not to decompose by heat. However, it may be post-added and the particle size for post-addition again is the same as previously described so that no separation of components in the product occurs. Another method of preparation allows for the simple mixing of the various components in their finely divided form. In addition, if the initial particle size of these components is below the desired particle size in the range of 160-325 mesh, the particles may be coagulated to a desired size by a coagulant such as a dilute aqueous solution of sodium silicate and may also be coagulated by water at other times.

When anionic detergents are used as dominant in the desired compositions, they are spray dried together with fillers such as sodium sulfate, enhancers such as sodium carbonate, sodium bicarbonate, borax and sodium silicate, and auxiliaries such as optical brighteners, pigments and dyes. A spray drying tower is used to spray dry the conventional air into the drying air introduced at about 200-600 ° C. (if the polyacetal carboxylate is contained, the temperature is preferably 150-300 ° C. or 350 ° C.). After this, the polyacetal carboxylate and the perborate are mixed in order or simultaneously, or the perborate and the polyacetal carboxylate are mixed in advance and then mixed with the spray dried beads.

When it is necessary to contain a relatively small amount of nonionic detergent together with an anionic detergent, it can be spray dried together with an anionic detergent, filler, etc., and the stable amphoteric and cationic substances to be added are crushed into the air and then spray dried together with the anionic detergent. have. However, if at least about 4% or 5% (sometimes more than 2%) of nonionic detergent is added to the composition, any additional ratios are post-added by spraying onto the detergent particles or basic beads that are rolling over. do.

These basic beads are made using any of the enhancers, fillers and stable auxiliaries in the final product and then post-added polyacetal carboxylate and perborate. In some cases, the polyacetal carboxylate may be dispersed and / or dissolved in a nonionic detergent and heated to liquid (or dissolved in a solvent) and the nonionic and polyacetal carboxylate mixtures may be added to the detergent beads or base ratio. Spray onto the sheet and add perborate. Preferably, the particle size of the particulate material is 8-120 mesh or 10-100 mesh, thus designing the manufacturing process accordingly. However, screening removes the fine particles and the particles that are too large and reuses them, pulverizes, aggregates or otherwise treats them to the desired particle size.

To make the products according to the invention into rods, cakes or briquettes, the composition is extruded, pressed or molded by known methods to the desired shape. To convert this composition into a liquid phase, each component is dissolved and / or dispersed in a liquid medium such as water and / or a suitable solvent (s).

To carry out the staining process according to the present invention, the above composition is added to "washing water" or various components are added as such. Usually the concentration range of the composition used is 0.05 or 0.1-1.0 or 1.5%, preferably 0.1-1.3%, more preferably 0.15-1.1 or 1.2%. According to the European style, where hot wash water is used, a high concentration of 1.0-1.5% or more in the washing machine is sometimes used. In this method, active bleaching oxygen is released by perborate.

Usually in the United States, the washing temperature range is 10-55 ° C, sometimes 10-30 ° C, compared to 60-90 ° C, sometimes 70-90 ° C or 95 ° C in Europe. In the US, the concentration of the composition is used at a low concentration of 0.05-0.2% and sometimes about 0.07-0.15%.

According to the American style, perborate oxygen is not released to the same extent because of the low washing temperature. Therefore, if the active agent is not present enough to release the active oxygen from the perborate, even if the washing temperature is high, the bleaching effect does not appear.

Various active agents are known for this purpose so that the present invention can be applied according to the American style using these active agents. Among these active agents are TAED (tetraacetylethylenediamine), acyloxybenzene sulfonate (as described in US Pat. No. 4,412,934) and TAGU.

For washing or staining operations, either use a conventional washing machine, such as GE's automatic washing machine (upper charge type), or use the American washing machine or a European washing machine, such as a Miele washing machine. The composition of the present invention is considered to be capable of washing better than the control by washing at high or low temperature using sodium tripolyphosphate instead of polyacetal carboxylate, wherein perborate releases an equivalent ratio of active oxygen, and It is often desirable to follow the European style without the need to add accelerators to promote the release of active oxygen from the borate salts. It can be expected that the hardness of various waters can be used, and the softer the water, the better the stain removal effect. However, it is unexpectedly confirmed that the composition according to the present invention is used under the conditions of using hard water. The dirt removal method was superior to the control using pentasodium tripolyphosphate instead of polyacetal carboxylate. This improved dirt removal capability is usually noticeable at high temperatures (60-90 ° C.), even in normal laundries, even at extremely heavy granular dirt and grease stains in Sheertz collar and cuffs.

The hardness of the water is 250-350ppm as CaCO ₃ , and the dirt removal effect is good even when cone hard water is used. Aside from the fact that the dirt removal effect is better at 90 ° C than 60 ° C, the fact that it is confirmed is that the compositions and methods according to the present invention resulted in significant improvements for the removal of various other typical dirts. Surprisingly, organic detergents (particularly anionic and nonionic detergents) are added, adding a stabilizer that is stable during washing and dedusting treatments, but which decomposes in acidic wastewater, and also omits sodium tripolyphosphate, one of the best known enhancers previously mentioned. And the perborate bleach together, the composition of the present invention shows an excellent dedusting effect, apparently due to the unique combination of each component used. This effect is also present in extremely hard water, which is unexpected in view of the excellent metal ion containment of the sodium tripolyphosphate enhancer and its known stability and widespread utility in laundry or dedusting operations.

The following examples illustrate the invention but do not limit it. In these examples, elsewhere in the specification, and in the claims, all parts are by weight and all temperatures are in degrees Celsius unless otherwise indicated.

Example 1

* In spray dried beads

A crusher mixture containing about 55% solids and 45% water (a tap water with a hardness of about 100 ppm as calcium carbonate) was sprayed into a countercurrent spray drying tower at about 50 ° C and dried to a moisture content of about 10%. Make a detergent composition for removing dirt having a composition of. The inlet temperature of the spray drying tower was about 450 ° C., and the air temperature at the outlet of the tower was lowered to about 150 ° C.

The particle size of the resulting spray dried beads was determined by US Body Grade No. The range is 10-100. Enhancer U and sodium perborate with particle sizes in the range of 10-100 bodies in a tumbling drum beveled using this bead. Mix the tetrahydrate. The ingredients may be supplied as fine powders and aggregated or aggregated to a desired particle size alone or together, without being spray dried. The mixing ratio of such polyacetal carboxylate-perborate aggregates is 1: 5-5: 1, which contains 0.1-5% of sodium silicate (Na ₂ O: SiO ₂ = 1: 1.6-1: 3) as a binder. You can.

Rd값을 측정한다.Test the dirt removal performance using the prepared product and using Miele / multi-dirty light reflection method.

Measure the Rd value.

In this method, the test composition and the control detergent composition (with trisodium polyphosphate added instead of the enhancer U) are put into a Miele washing machine and tested separately. In this case, it is 200 ppm or more (300 ppm) as calcium carbonate, Calcium ion: Magnesium ion: Wash the water at 60 ° C with a concentration of about 1.1% (225 g per 20 탁 of washing water) added with water having a hardness of 4: 1. The specimens used were different materials and were contaminated with different dirt.

Using the experimental compositions of this example, the average reflectance and dirt from a number of fabric pieces after normal washing and drying were measured and compared with the test cloth pieces of the control detergent composition in which 22% of sodium tripolyphosphate was added instead of the enhancer U. . The above procedure is repeated at 90 ° C., except that half of the detergent composition and half of the control detergent composition are used in the pre-washing step and the other half is used in the main washing step.

이중 편직물의 입상 오물/기름 얼룩, 면 퍼케일(cotton percale), 퀴아나 저어지(Qiana jersey) 및 Dacron 이중편직물에 대한 액체 첨부물, Dacron -면 혼방물에 대한 Bic

혹색 펜 잉크 얼룩 및 Dacron 이중 편직물에 대한 프렌치 드레싱(French dressing)을 비롯한 세탁 대상물상에 있는 각종의 전형적인 오물을 60℃에서 제거하며, Dacron 이중 편직물의 입상오물/기름 얼룩, 면퍼케일, Dacron -면 혼방물 및 퀴아나 저어지에 대한 액체 첨부물 및 Dacron 이중 편직물에 대한 유색 쇼오트닝 얼룩을 90℃에서 제거함에 있어서 상당히 큰 향상을 보았다.According to the above test method, which is considered as a basic method for testing the decontamination property of the detergent composition, the results according to the present invention of the present embodiment and the washing method of the present example were used.

Granular Filth / Oil Stain of Double Knitted Fabric, Cotton Percale, Liquid Attachment to Qiana jersey and Dacron Double Knitted Fabric, Bic for Dacron-Cotton Blend

Various typical dirt on laundry objects, including hard pen ink stains and French dressing for Dacron duplex knits, is removed at 60 ° C. Significant improvements were seen in removing liquid attachments to blends and quiana jerseys and colored shortening stains on Dacron duplex knits at 90 ° C.

The compositions and methods of the present invention were subjected to soil removal test at 60 ° C. by a controlled detergent composition containing tripolyphosphate on boiled tea stains on polyester / cotton blends and barbecue source stains on Dacron duplexes. The French dressing dirt removal test on the liquid attachment and Dacron duplex knits at 90 ° C. with the base detergent composition showed poor removal performance.

Results like the one above, without the use of non-ionic detergents and soaps, increase the alkylbenzene sulfonate content to 16%, and instead of 29% sodium sulfate, sodium bicarbonate, sodium carbonate and sodium silicate (Na ₂ O: SiO ₂ = about It also appears when the above experimental composition is changed by using 1/3 of each of 1: 2.4).

Similarly, a mixture of alkylbenzene sulfonate and sodium laurylsulfate (16% in total) or no containing alkylbenzene sulfonate and instead a post-sprayed nonionic detergent (Neodol 25-7 or Neodol23-) 6.5) and a secondary composition was made by mixing sodium perborate and enhancer U with a base bead containing nonionic detergent. In this case, an improved dirt removal effect was shown due to the combination of polyacetal carboxylate and perborate in this formulation.

Instead of the nonionic detergents mentioned above, other detergents, including condensation products of ethylene oxide and nonylphenol, such as Pluronics such as F-68 and Neodol 45-11, and mixtures containing two or four components thereof can be used. have.

In addition to and / or using other enhancers and fillers, including small amounts, 1-10 or 2-5% of amphoteric and / or cationic detergents (cationic detergents can be used as antistatic agents) in addition to those used in the formulation. Other changes can be made in this embodiment by varying the additive component ratios by ± 10 and ± 25% while keeping them within the corresponding usage ranges. It is also possible to change the conditions of manufacture by spray-drying essentially all the ingredients (usually perborate, flavoring and enzymes) together under mild conditions (to prevent degradation of the enhancer U).

Example 2

The product formulation of Example 1 is changed using enhancer U with a calculated weight average molecular weight of about 5.250 and 83% sodium polyacetal carboxylate polymer. The formulation made by the method according to Example 1 has improved dirt removal properties compared to the control composition containing sodium tripolyphosphate instead of the enhancer Upolymer, the experimental product exhibiting the same dirt removal capacity as the formulation of Example 1. . The same is true if an equivalent proportion of perborate hydroxide tetrahydrate is used and the difference is given by the non-dispersant enhancer (Na ₂ SO ₄ ). The described products can also be prepared in paste form, liquid and rod or cake form by conventional means as previously described.

Example 3

Sodium dodecylbenzene sulfonate, sodium paraffin sulfonate, sodium olefin sulfonate (on average of about 16 carbon atoms), sodium lauryl sulfate and sodium in place of the linear sodium tridecyl benzene sulfonate in the primary formulation of Example 1 Monoglyceride sulfate is used respectively. This product, when tested by the method of Example 1, also demonstrates significantly better laundry removal performance compared to the various control compositions, which use pentasodium tripolyphosphate instead of sodium polyacetal carboxylate and various other enhancers.

The active effect is varied by post-adding to the composition a proportion that represents, such as about 1% of the TAED (and thus correspondingly reducing the amount of sodium sulfate content) to make the composition. Instead of treatment at 60 ° C. according to the method of Example 1, the washing temperature was lowered to 30 ° C. according to the American method, and washed using a GE top filling washing machine to remove dirt compared to the control detergent composition containing sodium tripolyphosphate instead of the enhancer U. The result was improved. In this case, the polyacetal carboxylate active polymer having a molecular weight of about 5000 [Monsanto Lot No. 2547312 (molecular weight = 5,250)] and a polymer having about 8,000 [Monsanto Lot No. 2538422 (molecular weight = 8,034)]. However, it is contemplated here that dirt is best removed when treated according to the method of Example 1 with a composition which has been changed using other polyacetal carboxylates having a calculated weight average molecular weight within a given range.

In changing this embodiment (in the same manner as in Examples 1 and 2), the liquid product may be used in various formulations using water instead of sodium sulfate or other fillers and / or enhancers (except polyacetal carboxylates). Make a slurry. This product is an effective dedusting agent even when it is made to the same concentration of active ingredient as in Example. In another variation of the invention, the desired results are obtained even by separately adding the various components of the composition to the wash water respectively. Of course, for the final commercial product, an adjuvant is added, such as 0.5% fragrance, 1% protease, 2% fluorescent brightener composition, 0.2% colorant (e.g. blue with Polar Brilliant Blue dye and / or Ultramarine Blue pigment). Product preparation) and 3% flow improver (eg magnesium silicate. Hydrate) are added as needed. It is not conceivable to use such benzoic agents having significant side effects on the preferred properties of the process according to the invention or the composition according to the invention.

It is clear from the foregoing description of the composition and the method according to the present invention and from each example that a permeate and a polyacetal carboxylate are used in the composition of the present invention even if the washing medium is in hard water. While it has been difficult to remove both oil stains and granular debris until now, it has led to surprisingly improved products and methods. Considering in particular that sodium tripolyphosphate has been the most effective detergent enhancer used in the past, the fact that the proportion of active polyacetalcarboxylate polymers used in the present invention is less than the proportion of polyphosphates used in the control detergent composition. Of course it is surprising to get these results. Therefore, it can be considered that the present invention has made considerable progress in the field of decontamination and cleaning.

The present invention has been described in terms of these various descriptions and embodiments, but is not limited thereto, for the reason that those skilled in the art can use equivalents and substitutes without departing from the scope of the present invention. Because this is obvious.

Claims (10)

5-55% of organic synthetic detergents selected from the group consisting of anionic detergents, nonionic detergents and mixtures of anionic detergents and nonionic detergents, 4-50% polyacetal carboxylate enhancers for the detergents and alkali metal perborates 10-50 A bleach detergent composition which, in hot wash water, composed of%, removes particulate dirt and oil stains particularly effectively from polyester fabrics. 10. The sodium perborate hydrate of claim 1 wherein the polyacetal carboxylate enhancer has a calculated weight average molecular weight of about 3,500-10,000 and the perborate is a sodium perborate hydrate having a molar content of up to 4 moles per mole of anhydrous sodium perborate. A granular bleach detergent composition that is substantially free of phosphate, which is an alkali metal perborate selected from the group consisting of. The bleach-free bleach detergent of claim 2 wherein the detergent is a mixture of an anionic detergent and a nonionic detergent, the polyacetal carboxylate has a calculated weight average molecular weight ranging from 5,000-9,000 and the alkali metal perborate is sodium perborate. Composition. The method according to claim 3, wherein about 3-30% of a sulfated anionic detergent or a sulfonated anionic detergent with a lipophilic component having an alkyl chain having 8-20 carbon atoms, ethylene oxide and a nonionic detergent capable of producing a nonionic detergent A bleaching detergent composition comprising about 2-25% of a nonionic detergent, a condensation product of an oily donor compound with ethylene oxide, 4-50% of a polyacetal carboxylate enhancer, and 10-50% of hydrated sodium perborate. The method of claim 4, wherein about 4-20% of a higher alkylbenzenesulfonate having a higher alkyl group having 10-18 carbon atoms and ethylene oxide per mole as a condensation product of ethylene oxide and a higher fatty alcohol having 10-18 carbon atoms About 2-10% of nonionic detergents containing 3-20 moles of sodium, about 10-30% of polyacetal carboxylate enhancers whose carboxylate is sodium carboxylate, sodium perborate, about 10-40% of tetrahydrate, 105 Bleach detergent composition comprising about 3-20% of water comprising hydrate moisture removable at < RTI ID = 0.0 > C, < / RTI > the remainder consisting of filler (s) and / or other enhancer (s) and / or adjuvant (s). The higher fatty alcohol polyethoxy ethanol according to claim 5, which is obtained by condensing 4-10% of linear sodium tridecylbenzenesulfonate, 5-9 mol of ethylene oxide, and 1 mol of higher fatty alcohol having an average of 12-15 carbon atoms. 2-6%, polyacetal carboxylate enhancer with a calculated weight average molecular weight of 7,000-9,000, 10-25%, sodium perborate, tetrahydrate 15-30%, higher fatty acids with 10-18 carbon atoms Bleaching detergent composition consisting of fatty acid sodium soap 2-6%, sodium carboxymethyl cellulose 0.3-5% and moisture 5-15%. 7. The higher fatty alcohol polyethoxy ethanol of claim 6, which is a condensation product of about 8% of linear sodium tridecylbenzenesulfonate, about 7 moles of ethylene oxide, and one mole of higher fatty alcohols having an average of 12-15 carbon atoms. 4%, about 18% polyacetal carboxylate enhancer with a calculated weight average molecular weight of about 8,000, sodium perborate. About 22% tetrahydrate, about 4% tallow sodium soap, about 1% sodium carboxymethyl cellulose, and about 10 moisture Bleach detergent composition consisting of%. 5-55% organic synthetic detergent selected from the group consisting of anionic detergents, nonionic detergents and mixtures of anionic and nonionic detergents, polyacetal carboxylate enhancers 4-50% for synthetic detergents and alkali metal perborate 10-50 Granular dirt and oil mixed from polyester fibrous material consisting of washing contaminated fibrous material in a temperature range of 50-99 ° C. in wash water in which a detergent composition consisting of% was added to the wash water at a concentration of 0.05-1.5%. How to remove stains. 9. The detergent composition of claim 8, wherein the detergent composition is substantially free of phosphate and has a calculated weight average molecular weight range of about 3,500-10,000 for the polyacetal carboxylate enhancer, and the perborate has up to 4 moles of water having a hydration per mole. Sodium perborate, the wash water hardness of calcium carbonate more than 200ppm. 10. The detergent composition of claim 9, wherein the detergent composition comprises about 4-20% of a higher alkyl benzene sulfonate having a higher alkyl group having 10-18 carbon atoms and 3-20 mol of ethylene oxide per mole of a higher fatty alcohol having 10-18 carbon atoms. Condensation reaction product, about 2-10% of nonionic detergent, molecular weight range of 7,000-9,000 and carboxylate of sodium carboxylate, about 10-30% of polyacetal carboxylate enhancer, removed at 105 ° C Approximately 3-20% of the moisture, including the possible hydrate moisture, and the remainder are composed of filler (s) and / or other enhancer (s) and / or adjuvant (s), and the laundry has a hardness in the range of 250-350 ppm as calcium carbonate. The method is carried out with an automatic washing machine in the detergent composition concentration 1.0-1.5% in washing water and washing temperature 60-90 ℃ range.