JPH05140869A - Fabric softening product containing mixture of pentaerythritol compound and bentonite as base - Google Patents

Abstract

PURPOSE: To provide the subject composition for softening fibers by being applied for washings during washing, rinsing and/or drying cycle(s) wherein the product comprises the specified pentaerythritol deriv. mixed with the specified bentonite and free of inconvenient problem quaternary ammonium salt. CONSTITUTION: To 3-7% of a partial higher fatty acid ester of pentaerythritol or a partial higher fatty acid ester of pentaerythritol oligomer, a higher fatty acid ester of pentaerythritol lower alkylene oxide deriv. or a higher fatty acid ester of pentaerythritol oligomer lower alkylene oxide deriv. or a mixture thereof, 93-97% of montmorillonite clay such as sodium- or calcium-bentonite having a swelling property in water is mixed, to obtain a sufficiently satisfactory fabric softening product free of known quaternary ammonium salt which has much problems morphologically. Herein, the product can be applied to fibers after formed into a particulate solid, a liq. or an aq. suspension, etc.

Description

Detailed Description of the Invention

[0001]

This invention relates to laundry during a wash, rinse and / or drying cycle for applying a fabric softening amount of a fabric softening component in a fabric softening product to the fibers of a laundry fabric. And a fabric softening product containing the article. More specifically, the present invention provides, as a fabric softening component, pentaerythritol higher fatty acid ester, pentaerythritol oligomer higher fatty acid ester, or ethoxylated derivative higher fatty acid ester of pentaerythritol or oligomeric ester, and any mixture thereof ( These are all PEC (instead of the pentaerythritol compound)
Can be referred to as).

[0002]

BACKGROUND OF THE INVENTION Fabric softening compositions and articles have long been used to make washed laundry soft to the touch and comfortable to wear. The compositions include solutions, emulsions and granular and powder products,
The articles include pieces of paper and sponges impregnated with a fabric softener. A preferred fabric softener for most commercial products is generally a quaternary ammonium salt such as dimethyl ditallowoyl ammonium chloride, which is an emulsion of the softener in order to soften the laundry. It is added to the rinse water. Alternatively, the emulsion or powder product containing the fabric softener can be added to the wash water with the detergent composition, or the detergent composition can include a fabric softening component to provide a so-called "softening wash." Can be a "softagent". An article containing a fabric softening component such as a quaternary ammonium salt is added to a dryer of an automatic washing machine, and the fabric softener is repeatedly contacted with the laundry while the laundry is dried in a heated atmosphere. And can be flexible.

Various fabric softening (and antistatic) compositions containing softening detergents have been commercially available for many years with some or less commercial success, including various fabric softening. Despite the inclusion of compounds, the most successful of these was the quaternary ammonium salt. The compound has the formula

[Chemical 1] (In the formula, R, R ′, R ″ and R ′ ″ are all alkyl groups, and at least one of the alkyl groups has 8 carbon atoms.
To 22 or 24 or 12 to 18) higher alkyl, the rest being lower alkyl of 1 or 2 carbon atoms, and X ⁻ is a salt-forming anion). The quaternary ammonium salt is preferably di-lower alkyl or di-higher alkyl ammonium halide, but in some cases, mono-lower alkyl tri-higher alkyl ammonium halide is also used.

Although the quaternary ammonium salt has been an effective fabric softener for the above-mentioned uses, it has remarkable disadvantageous properties, and attempts have been made to replace it. For example, quaternary ammonium salts, which are cationic, are prone to react with anionic substances such as anionic synthetic organic detergents and builders for synthetic detergents, sometimes impairing their intended fabric softening action. Sometimes. Quaternary ammonium salts may stick to the laundry, appearing as very unpleasant greasy spots. Finally, and perhaps most importantly, it has been found that quaternary ammonium salts are not readily biodegradable as desired and are toxic to aquatic organisms, and wastewater carrying the compound is May have detrimental effects on aquatic organisms in lakes, rivers and other bodies of water that are likely to pour last.

In search of alternatives to quaternary ammonium salts as fabric softeners, neoalkane amides,
It has been proposed to use glyceryl esters, glycol esters, silicones, cation-anion complexes, bentonite and various lubricants alone or with a small amount of quaternary ammonium salt, but their softening effect is not satisfactory. Often sufficient or alternative softeners often had other properties that made them even less desirable than quaternary ammonium salts. However, now the PEC containing oligomers and lower alkoxylated derivatives
When used with a montmorillonite clay such as swellable bentonite, it can make laundry sufficiently soft as substantially quaternary ammonium salts and is quaternary ammonium to aquatic. Applicants have discovered that they do not exhibit the adverse effects of salt. This is recognizing the seriousness of the problem, and some countries have found that quaternary ammonium compounds (hereinafter "quarts") in products that can be discharged into sewage, wastewater, etc.
This is a particularly important discovery at this point in time when the law is being passed and the law is being promulgated.
The compositions of the present invention are surprisingly effective softening detergents that are detersive as well as detergent compositions based on the same detersive ingredients, and also like cleaning cycles and rinse additives. Non-detergent products as well as fabric softening in dryer products, all of which are significantly better than the mixture of PEC and bentonite would have expected from the additive effects of the ingredients. Make treated laundry soft. Furthermore, while fabric softening with PEC and bentonite, respectively, asymptotically approaches the limits below the desired good softening, compositions containing PEC and bentonite perform significantly better and exceed said limits. .

According to the present invention, a fabric softening product, which is a composition or article applied to a fibrous material so as to attach and soften the fabric softening component to the fibrous material, is a pentaerythritol higher fatty acid ester. A pentaerythritol oligomer higher fatty acid ester, a pentaerythritol lower alkylene oxide derivative higher fatty acid ester or a pentaerythritol oligomer lower alkylene oxide derivative higher fatty acid ester or a mixture thereof, PEC and montmorillonite clay as a fabric softening component, and very preferably bentonite. Including. P
Most preferred among the ECs are pentaerythritol distearate and dipentaerythritol dilaurate, with sodium and calcium bentonite being preferred among the montmorillonites. The invention also includes a method of softening laundry with the products of the invention.

A search of the prior art relevant to the present invention has yielded the following results.

US Pat. Nos. 3,928,212; 4,
126,562; 4,412,978; 4,1
62,984; and 4,214,038 European Patent Application No. 276999-A German Patent Application No. 3612479-A and Japanese Patent No. 90 47,370 U.S. Patent No. 3,928,212. Various softeners are described which are polyhydric alcohol esters, none of which are pentaerythritol esters, pentaerythritol oligomeric esters or esters of pentaerythritol or its ethoxylated derivatives of oligomers. U.S. Pat. No. 4,126,562 mentions erythritol and pentaerythritol in the table of alcohols capable of reacting with higher fatty acids to form fabric conditioning agents, which compounds are not described in practice. Neither, nor is it shown in the fabric softening composition or article. Also, U.S. Pat. No. 4,126,562 relates to quaternary unmonium salt fabric softeners and mixtures of nonionic esters of higher fatty acids and alcohols, wherein the esters alone serve as fabric softeners. There is no teaching that it would be effective. U.S. Pat. No. 4,142,978 discloses a phase modifier such as an alkyl sulphate for softening the laundry on the dryer sheet while drying the laundry in the dryer of an automatic washing machine. mod
sorbitan esters with ifing components) are described. This patent does not mention any pentaerythritol ester. U.S. Pat. No. 4,162,984 discloses water-insoluble nonionic fabric softeners and fatty acid esters of mono- or polyhydric alcohols or their anhydrides and aromatic mono- or dicarboxylic acids with quaternary ammonium salts or alkylimidazos. A linium salt relates to a fiber treated emulsion with a preferred water insoluble cationic fabric softener. According to said patent, pentaerythritol is among the polyhydric alcohols which can be esterified, but there is no specific description of pentaerythritol ester, nor is any pentaerythritol oligomer suggested, Also, none are taught to be effective fabric softeners in the absence of quaternary ammonium salts and aromatic carboxylic acids. The patentees are aware of the shortcomings of the quaternary ammonium salt component (reaction with anionic detergent from the wash cycle) and, if pentaerythritol ester and aromatic carboxylic acid are present, the quaternary ammonium salt component. I knew that it might be possible to reduce the content of the ingredients, but I also did not recognize the presence of a fabric softener composition without quaternary ammonium halide or equivalent cationic fabric softener, and It was clear that they did not know about the present invention, since they did not explicitly make it either. US Patent No. 4,2
No. 14,038 relates to polyglycerol esters as a softening agent suitable for adhering to a drying laundry from a paper substrate loaded in the dryer of a laundry washing machine. Although polyglycerol is a polyhydric alcohol such as pentaerythritol, it is not the same as pentaerythritol and the patent does not suggest the use of Applicants' pentaerythritol ester as a fabric softener. European Patent Application No. 27699
No. 9-A describes a fabric conditioning composition comprising a non-cationic fabric softener and a nonionic cellulosic ester. Although polyhydric alcohol esters are mentioned as suitable conditioning agents, pentaerythritol esters are not disclosed. German Patent Specification No. 3612479
-A describes a fiber softening composition comprising a carboxylic acid ester and a quaternary ammonium compound, among which esters are esters of various alcohols and polyols including pentaerythritol. However, no such specific ester is described, even named, and no softening composition is disclosed that does not contain a quaternary ammonium compound as a fabric softener. Japanese Patent No. 9040,370 discloses a fabric softening composition which is based on a quaternary ammonium salt but which can contain pentaerythritol higher fatty acid ester. The abstract does not mention the specific ester.

[0009]

In any of the above disclosures, any pentaerythritol ester can be used with a montmorillonite clay such as bentonite as a fabric softening mixture instead of a quaternary ammonium compound or a quart softener. May not, and is not taught to exhibit a softening effect that is substantially equal or greater, and neither disclosure mentions any particular pentaerythritol ester, nor is the fabric No mention is made of any pentaerythritol oligomeric ester, lower alkoxylated pentaerythritol ester or lower alkoxypentaerythritol oligomeric ester as a fabric softener in a softener composition. Thus, none of the references, either alone or in combination with any other, predict or clarify the invention.

[0010]

The principal components of the invented compositions and articles of the present invention are the major fabric softening agents in the product other than the fabric softening clays normally and also present in the product, such as bentonite. Of the compounds, higher fatty acid esters of pentaerythritol compounds are preferred, as the term is used herein to refer to pentaerythritol higher fatty acid ester, pentaerythritol oligomer higher fatty acid ester, pentaerythritol lower alkylene oxide derivative higher fatty acid ester and pentaerythritol. Oligomeric lower alkylene oxide derivative Used to indicate higher fatty acid ester. The pentaerythritol compound may be abbreviated herein as PEC, which description and abbreviation refer to any pentaerythritol, its oligomers and its alkoxylated derivatives themselves,
Or, more preferably and more generally, it can be applied to esters which can be shown in context.

The pentaerythritol oligomer has 2
It is preferred that it is an oligomer of 5 to 5, more preferably 2 or 3 pentaerythritol moieties, said moieties being linked together by ether linkages. The lower alkylene oxide derivative preferably has a monomer, dimer or polymer of ethylene oxide or propylene oxide terminated with a hydroxyl and linked to pentaerythritol or pentaerythritol oligomers via an ether bond. It is preferred that there be 1 to 10, more preferably 2 to 6 alkylene oxide moieties in each alkylene oxide chain, and depending on the oligomer, there will be 1 to 10 such groups on the PEC. At least one, preferably at least two, for example 1 or 2 to 4 of the OH groups of the PEC are esterified by a higher fatty acid or other higher aliphatic which can have an even number of carbon atoms.

The pentaerythritol compound higher fatty acid ester is preferably a partial ester, more preferably at least two free hydroxyls are present (on the pentaerythritol, oligomer or alkoxyalkane group) after esterification. Often the number of free hydroxyls is 2 or about 2, but sometimes it is 1 as in the case of pentaerythritol stearate or 8 as in the case of pentapentaerythritol tetrapalmitate.
There can be individuals as well.

The higher aliphatic acids or fatty acids which can be used as the esterifying acid have a carbon atom content of 8 to 24, preferably 12 to 24, more preferably 12 to 18, such as lauric acid, Myristic acid, palmitic acid, oleic acid, stearic acid and behenic acid. The fatty acids can be natural sources such as beef tallow or coconut oil or fatty acid mixtures such as those obtained from hydrogenated natural substances. It is also possible to use synthetic acids with an even or odd number of carbon atoms. Of the fatty acids, lauric acid and stearic acid are often preferred, which may be due to the pentaerythritol compound being esterified.

Examples of some of the esters (PEC) in the present invention are shown below.

[0015]

[Chemical 2] Although some of the preferred pentaerythritol compounds useful in the practice of this invention are listed in the formulas provided herein, for example, pentaerythritol dihydrogenated tallowate, pentaerythritol ditallowate, pentaerythritol dipalmitate and It should be understood that various other such pentaerythritol compounds described herein, including dipentaerythritol tetratallowate, can also be used. Also, references to one compound herein should be considered to include the use of mixtures of compounds of that class unless otherwise specified herein (commercial Compounds are often mixtures).

Although the PECs used in the present invention can have fabric softening effects, such effects are significantly enhanced when montmorillonite clay (bentonite) is also present. If the bentonite is not present, PE
C cannot be substantially dispersed in the wash water or rinse water, and cannot be evenly and firmly attached to the laundry from the softened article. Well-dispersed PECs have been found to have an excellent softening effect. If not dispersed, the PEC may form a dense mass when cold, or may melt when heated.
Does not act to effectively soften the fabric (and in any case may unpleasantly adhere to the treated material, producing some greasy spots). Bentonite acts to disperse PEC, making PEC more effective as a softening agent, and at the same time, the “dispersant” also acts as a softening agent, and the softening effect of ordinary dispersants is not preferable. Eliminates thinning and synergistically improves fabric softening.

The clay which is the active ingredient of the product of the present invention is P
It works synergistically with the EC to make the laundry softer than expected from the mixture. The clay adheres to fibrous materials, especially cotton and cotton / synthetic fiber blends, such as cotton / polyester, so as to impart surface lubricity or softness to the fibers and fabrics made thereof, in water (water). ) And having a montmorillonite containing clay having a smectite structure. The best smectite clay for use in the present invention is bentonite, and the best bentonites are those having substantial swelling capacity in water such as sodium and potassium bentonite. Such swellable bentonite is also called Western or Wyoming bentonite, and is substantially sodium bentonite. Other bentonites, such as calcium bentonite, are usually non-swelling and generally are not themselves acceptable as fabric softeners. However, we have found that in compositions where the flexibility is to be tested, alkali metal or other sources of soluble ions, such as sodium hydroxide added to the composition or a functional ingredient of the composition. The non-swelling bentonite is PE, as long as there is sodium) (which can result from sodium salts such as builders and fillers).
It has been found with C that it exhibits a fabric softening even better than the swelling bentonite. This utility of the normally non-swelling bentonites is surprising, and the superiority of the foregoing over the normally swelling bentonites, such as sodium bentonite, in the compositions of the present invention (when a sodium source is present) is quite surprising. Is. Among the preferred bentonites are the normally swellable sodium and potassium bentonites and the normally non-swellable potassium and magnesium bentonites. Of these, calcium bentonite (when a sodium source is present) and sodium bentonite are preferred. The bentonite used is not limited to those produced in the United States such as Wyoming Bentonite, but can also be obtained as calcium bentonite from Europe including Italy and Spain, which is converted to sodium bentonite by treatment with sodium carbonate. Or it can be used as calcium bentonite. Also, other montmorillonite-containing smectite clays having bentonite-like properties can be substituted for all or part of the bentonites described herein, with similar fabric softening results.

The swellable bentonites and similarly acting clays have an ultimate particle size in the micron range, for example 0.01 to 20 microns, and US standard sieve No. 100 to No. 400 sieve, preferably N
o. 140 to No. It has an actual particle size in the range of 325 sieves. The particle size range also applies to the zeolite builder described later. Bentonite and other such suitable swellable clays agglomerate to form large particle sizes, such as No. No. 60 to No. Such an agglomeration is not preferred unless PEC is also included (in any granular product), which may be in the sieve range of 120.

The liquid preparations according to the invention can be emulsions, which term is intended herein to refer not only to emulsions, but also to dispersions and suspensions in a liquid medium. An "emulsion" is usually an aqueous emulsion in which the aqueous phase is the continuous phase. However, solvents and cosolvents such as ethanol, isopropanol, propylene glycol and various mono- and di-lower alkyl esters of diethylene glycol (Carbit).
ols ^™ ) can also be present in the emulsions and microemulsions to help form a more stable product and can also be in a continuous medium. Suitable dispersants such as emulsifiers can be used with the clay to further aid the PEC in dispersing in the aqueous medium. The above are liquid products and solid (including granular)
Effective for products.

A variety of emulsifiers can be used, many of which are included in this specification by Joh.
n W. Annual publications Detergents and Emulsif from McCutcheon
Most of the iers , especially 1969, 1973, 1980
And the 1981 edition. Preferred such emulsifiers are those of alkyl ethers or amines containing one or more hydroxyalkyl substituents. Most preferred of these are alkyl dialkanol amines or alkyl trialkanol propylene diamines, in which the alkanol moiety has 2 to 4, preferably 2 to 3, more preferably 2 carbon atoms, and the alkyl poly ( Ethylene oxide) ethers are those which have 2 to 24 ethylene oxide units, preferably 8 to 12 ethylene oxide units and the alkyl in the emulsifier has 8 to 24, preferably 12 to 18 carbon atoms. More preferred said emulsifier is Hoechst A .; G. From Genamin ^TM
Stearyldiethanolamine sold under the name S-020; A. CECA from Dinora
Tallow triethanol propylene diamine sold under the name mox ^™ S3; and Hoechst
A. G. Commercially available under the name Genapol ^™ OH-100 from R—O— (CH ₂ CH ₂ O) ₁₀ H, where R is a mixture of C _12-15 alkyl.

If it is desired that the composition of the invention be in the form of granules, powder, solid or gel instead of emulsion form, less or even no moisture or moisture is present. However, bentonite still generally has a small (micron range) ultimate particle size. Other swellable montmorillonite clay can be present in place of or in addition to bentonite, and with bentonite, other non-functional, substantially water-insoluble carriers such as calcium carbonate and silica. Alternatively, a dispersant may be present. Even water-soluble carriers such as sodium sulphate or other "filler salts" can be used, at least in part, and the article can sometimes act as a dispersant. The bentonite used forms a gel in water,
It must be capable of softening the fibrous material and, even if it has a large particle size, US standard sieve, is generally No. 8 to No. It is desirable to have an ultimate particle size in the micron range, even if it agglomerates into the 140 sieve range.

If the pentaerythritol compound softener is to be applied to laundry being dried in a dryer of a washing machine such as an automatic dryer, PEC and bentonite can be applied to the substrate material, and then , Can be transferred to the drying laundry by the effect of the heat of the dry air and the frictional action of the substrate on the moving laundry. The substrate used can be paper or other fibrous material, sponge, preferably cellulose or polyurethane, or other suitable substrate, the pentaerythritol compound being solid at room temperature, liquefied and / or dried at the temperature of the dryer. Use something that can be softened. PEC
If desired, other suitable waxy substances, plasticizers or hardeners can be incorporated in order to adjust its conversion point. When using the article, bentonite helps spread or spread PEC on the substrate, and PEC helps promote adhesion of bentonite to the substrate. Moreover, the positive charge of bentonite is usually negative for laundry, which is negatively charged.
Helps EC attach. Usually, in the various applications mentioned above, PECs are used without the presence of any other fabric softening substances (except clays such as bentonite, montmorillonite or other effective smectites), but ecologically. It is also possible to use such other substances with PEC, provided that they are within the proportions and amounts used that would not be unacceptable for PEC, and do not interfere with the fabric softening action of PEC. In fact, in some cases, where antistatic activity is desired in the product, PEC may have some antistatic properties but may be insufficient for its intended purpose, so such addition may be important. .. Thus, PECs reinforced with other antistatic agents and also other fabric softeners can be used to formulate fabric softener compositions and articles. The most important antistatic agent is the quaternary ammonium salt, but its presence can cause ecological problems due to its toxicity to aquatic organisms. For example, in a standard toxicity test against daphnia, in the case of quaternary ammonium compounds such as ditallowalkyldimethylammonium chloride, or quarts, a 50% effective concentration is 1 mg. / L. , Which is often environmentally unacceptable, and thus quotes are not used in such situations. Other antistatic agents and fabric softeners include higher alkyl neoalkane amides such as N
-Stearyl neodecanamide; isostearamides; amines; for example, N, N-ditallowalkyl N
-Methylamine; esterified quaternary salts or esterquats; amidoamines;
There are amidoquats; imidazolines; imidazolinium salts; di-higher fatty acid esters of di-lower alkanolamines such as dicocoamine esters of diethanolamine; silicones; and alkoxylated silicones, such compounds as described above. Some representative examples of the following are given below (preferably avoiding those that may cause significant ecological harm).

[0023]

[Chemical 3] When using supplementary antistatic agents and fabric softeners, ecotoxicity (ecotoxicity) beyond that permitted by law and the local regulatory authorities intended for use.
It should be borne in mind that a composition with ty) should not be made. Therefore, the quaternary ammonium compound is
As with compounds that have similar adverse effects on aquatic organisms, they are usually shunned or their use is limited so that they are not adversely affected.

Other materials that may be included in the compositions of the present invention include the common auxiliaries typically present in other fabric softening compositions, including softening detergents, such as perfumes, sticks. There are agents, solvents, cosolvents, hydrotropes, antioxidants, stabilizers, pH adjusters, buffers, biodegradable antibacterial agents, builders, fillers, enzymes, thickeners and optical brighteners. Both are of the type known in the field of fabric softening compositions, some examples of which are given in the art mentioned herein, and all of which are incorporated herein by reference. There is.

The last component present in the composition of the invention which is an aqueous emulsion (or dispersion) is water. Usually, the CaCO ₃ is 0 to 500 p. p. m. Any clean water of any hardness in the range of can be used, but with a hardness of only 150 p. p. m. , And more preferably 5
0p. p. m. It is preferred to use less than water, and most preferably the water is irradiated deionized water.

The foregoing description of the ingredients in the products of the present invention is primarily concerned with the ingredients in the fabric softening composition that are added to the wash or rinse water, especially during automatic laundering operations. In a relatively simple aspect, the present invention also includes a detergent composition (softening detergent) containing PEC and bentonite (or other suitable montmorillonite clay) as described above. The cleaning composition is P
It contains at least one synthetic organic detergent, preferably in anionic or nonionic form (or mixtures thereof), which may also act as a dispersant for the EC.

Anionic detergents can be commonly referred to as "sulfated (or sulfonated) detergents" and include water-soluble sulfates and / or sulfonates containing a lipophilic moiety and a sulfate (or sulfonate) moiety. Similar phosphates (also phosphonates) can be used, but with type affinity. Among the synthetic anionic organic sulphate (or sulphonate) detergents, the preferred ones are higher alkyl (preferably linear alkyl) benzene sulphonates, higher aliphatic alcohol sulphates, higher aliphatic alcohol ethoxylated sulphates, olefin sulphonates and paraffin sulphonates. is there. Usually, the compound is a water-soluble alkali metal salt, such as a sodium salt, and contains a higher aliphatic alkyl or other aliphatic moiety which acts as a lipophilic moiety and enhances detergency, especially against greasy soils. . The higher alkyl or higher aliphatic moiety is usually 8 to 2
2 carbon atoms, preferably 10 or 12 to 16
Or having 18 carbon atoms, especially in the case of alkyl sulphates and alkyl benzene sulphonates,
It is further preferred that the alkyl moiety has 12 to 14 carbon atoms. Useful higher fatty alcohol ethoxylate sulphates are usually 1 to 2 per mole.
It has 0, preferably 3 to 10 or 15, for example 3 or 7, ethoxy groups. Typical anionic detergents include linear sodium dodecylbenzene sulfonate, linear sodium tridecylbenzene sulfonate, sodium lauryl alcohol sulfate, coconut oil alcohol sodium triethoxylated sulfate, sodium C ₁₆ paraffin sulfonate and C ₁₄ olefin. Mention may be made of sodium olefin sulfonate derived from

Among the nonionic detergents, the most preferred ones are higher aliphatic alcohols or ethylene oxide condensates with alkylphenols, for example higher aliphatic alcohols of 10 or 12 to 18 or 13 to 17 carbon atoms. Or alkylphenols having 7 to 10 carbon atoms in the alkyl group and 3 to 2
0 mol, 5 to 15 mol, 6 to 12 mol or 7
To 11 mol of ethylene oxide condensate, such as Dobanol ^™ 25-7, Synperonic ^™
A7, Neodol ^™ 25-3, Neodol ^™ 25-
7, Neodol ^™ 45-11 and C _13-17 alcohols condensed with 7 or 11 moles of ethylene oxide per mole. Although the excellent softening obtained when using bentonite with PEC is significant in anionic, nonionic and anionic / nonionic detergent compositions, the improvement in softening effect is not significant with PEC alone (without bentonite). This is even more surprising in the case of nonionic detergent compositions, since there is no fabric softening effect in ionic detergent compositions (although there is some effect in anionic detergents).

In addition to the examples of suitable anionic and nonionic detergents described above, an extensive table of useful detergents is given below.
It can be found in standard textbooks on synthetic organic detergents, for example the text of McCutcheon mentioned above.

Among the water-soluble builders for anionic and nonionic detergents it is desirable to use water-soluble salts, such as sodium or potassium salts, more preferably sodium salts, among which: Carbonates, silicates, borates, bicarbonates and phosphates, especially polyphosphates, for example sodium carbonate, sodium bicarbonate, Na ₂ O: SiO ₂ ratios of 1: 1.6 to 1: 3,
Preferably 1: 2 to 1: 3, for example about 1: 3,
Preference is given to 1: 2.35 or 1: 2.4 sodium silicate, sodium tripolyphosphate and tetrasodium pyrophosphate, but where appropriate sodium sesquicarbonate as well as the corresponding potassium and other soluble salts. It is also possible to use sodium sesquisilicate. Although the builder also has a water softening property, among the water-insoluble builders, the most preferable one is zeolite, especially hydrated zeolite. The zeolites include synthetic and naturally occurring crystalline, amorphous and mixed crystalline / amorphous zeolites, which have a sufficiently rapid and effective function to eliminate the effect of calcium hardness ions in the wash water. Have The zeolite used is preferably one which is said to have a high exchange capacity for calcium ions, which exchange capacity is usually about 200 to 400 milligram equivalents of calcium carbonate per gram of zeolite. Although other ion-exchangeable zeolites can be used, the zeolite has the formula

[Chemical 4] (In the formula, x is 1, y is 0.8 to 1.2, and z is 1.3.
To 3.5 and w is 0 to 9 and 2.5 to 6
Are preferred). Among the useful crystalline zeolites, preferred are Zeolites A, X and Y, with A being more preferred, of which Zeolite 4
A is most preferred. These zeolites are preferably in finely divided form when added to the clutcher with the synthetic detergent prior to drying, and have an ultimate particle size, with the actual particle size close to that of bentonite. Other builders that can be used are organic compounds, which are often sequestrants of hardness ions. The compounds include organic acids, especially hydroxy and aminopolycarboxylic acids such as citric acid and gluconic acid and ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NT).
A) and all are usually included as water-soluble salts such as sodium salts. Other useful builders are organophosphorus chelating agents such as D from Monsanto Co.
request ^{™ s} , such as Dequest 2046.

The proportions of the ingredients in the compositions and articles of the present invention are such that they result in a stable and effective product for fabric softening. In the case of PEC, the concentration in the liquid and gel softening detergent composition is usually about 1 to 25%, preferably 2 to 20%, more preferably 2 to 15%.
%, Most preferably 3 to 10%, eg about 5
Or in the range of 6%. In the case of liquid rinse cycle and wash cycle additive compositions, the range is preferably 1 to 40 parts (60 to 99) in the aqueous liquid medium.
Along with some bentonite). The composition is PEC
Of 1 to 10%, more preferably 3 to 7%, for example 6% or about 6%.

Granular softening detergents usually have 1 to 25% PEC, preferably 2 to 20%, more preferably 2 to 15%, most preferably 3 to 10%.
%, Eg 6%, and before addition of a granular non-washable rinse and wash water cycle, the PEC content ranges from 1 to 25% or 40%, 1 to 10%, 3 to 10 respectively. % And 3 to 7%, for example 6%. PE in the case of dryer articles
The effective, preferred, more preferred, and most preferred ranges of C and bentonite (or equivalent clay) content, as well as the corresponding ratios of PEC: bentonite for rinse and wash cycle additive, respectively, are:
5 to 99%, 5 to 95%, 10 to 90% and 20 to 80%.

The bentonite or suitable clay content in the liquid or gel softening detergent has an effective range of 1
To 50%, preferably 5 to 40%, more preferably 10 to 30% and most preferably 15 to 20%, for example 16% or 18%. In the case of granular softening detergents, the range is 10
To 30%, 10 to 25%, 12 to 20%,
And 15 to 20%. In the case of granular and solid wash and rinse cycle additives, the percentage of bentonite (or clay) is in the effective, preferred, more preferred and most preferred range from 10 to 9.
9%, 60-99%, 90-99% and 93
To 97%, for example 94% or about 94%.

In liquid or gel and granular softening detergents, the effective percentage of synthetic effective detergent is 1 or 2.
To 35%, preferably 3 to 25%, more preferably 3 to 20%, and most preferably 5 to 15%. Preferably, the synthetic organic detergent is a mixture of anionic and nonionic detergents, the respective percentages of which are 1 to 10%, preferably 1 each.
To 5% and more preferably 1 to 3% anionic detergent and 3 to 5% nonionic detergent, for example:
It is in the range of about 2% and about 4%, respectively. In the case of granular or solid builder softening detergents, the builder percentage is usually in the range of 5 to 80%, preferably 10 to 60%, more preferably 20 to 50% and most preferably 30 to 40%. And the percentages of sodium tripolyphosphate, sodium carbonate and sodium silicate are 10 to 50%, 2 to 20%, and 2 to 15%, respectively, preferably 15 to 15% when the three builders are present, respectively. 35%, 2
To 10% and 2 to 10%, most preferably 20 to 30%, 3 to 8% and 2 to 6
%, For example in the range of about 23%, 6% and 4% respectively. In the case of a liquid softening detergent, the content range of the synthetic detergent and the builder can be determined by multiplying by a coefficient proportional to the solid content of the liquid composition and dividing by the limit solid content of the range of the granular or solid product. Many. Generally, the rinse cycle composition does not contain any builders, but the wash cycle additive may be used to improve the washability of the detergent composition in which the wash cycle composition may be used and to aid PEC. It can serve as a positive carrier (in addition to bentonite). When a builder is used, its percentage range is often similar to that of the softening detergent.

In the case of the composition according to the invention containing an emulsifier,
The content of the emulsifier is usually in the range of 0.2 to 10%, preferably 0.4 or 0.5 to 5%, more preferably 0.7 or 1 to 3%, for example about 1.25 or 2%. It is in. When the emulsifier comprises alkyl poly (ethylene oxide) ethers as well as alkyl alkanol amines, as desired, the proportion of alkanol amines is usually equal to or greater than the proportion of alkyl poly (ethylene oxide) ether alkanols. Desirably, and preferably, exactly 2 to 5
Double, for example just about four times. Therefore, the percentage is
0.2 to 5% alkanolamine and 0.05 to 5% ether alkanol, preferably 0.3 to 3% and 0.1 to 2%, more preferably
It can be 0.5 to 2% and 0.2 to 1%. If no detergents, builders or auxiliaries are present and the composition is liquid, the content of aqueous medium or water can be residual, usually 20 to 98%, preferably 50 to 94%. , More preferably 63 to 87%, most preferably 81 to 74%, eg about 78%. It should be understood that the presence of any detergents, builders, auxiliaries or co-ingredients in the emulsion is compensated by a corresponding decrease in the water content in the composition. Usually, the total content of auxiliaries is at most 25%, preferably at most 15% and in many cases does not exceed the limit of 5%. In the amounts used, any of the auxiliaries may be acceptable enough to adversely affect aquatic life, including fish, to the extent that it prohibits pouring washing water containing the composition into lakes and running water. It does not cause any level of toxicity. Thus, the compositions of the present invention can be considered to consist essentially of the aforementioned ingredients in the form of additives or softening detergents, with only environmentally acceptable proportions of auxiliaries in the composition. Can be present in. As mentioned above, the compositions and articles of the present invention are preferably substantially free of quaternary ammonium compounds. The presence of zero percent of the ingredients is most preferred, but in such circumstances, where the final composition and article are not ecologically toxic, respectively,
More preferred, preferred and acceptable limits,
Extension limits of 0.1%, 0.3% and 0.5% can be provided that are within the broader scope of the invention. Although the emulsifiers mentioned are more often used in aqueous compositions, they can also be present in solid or granular products, the proportion of which in the product is proportional to that of liquids based on solids. Is the same.

Suitable auxiliaries for the above products, especially rinse cycle additives, are those in which the pH of the emulsion or other aqueous composition is in the range of 2.5 to 5.5, preferably 2.5 to 4, eg 3.5. Acidifying agents such as hydrochloric acid and other suitable acids that are effective in controlling. In order to adjust the pH, the percentage of HCl (concentrated hydrochloric acid based) or other equivalent acidifying agent present is usually 0.01 to 0.4%, preferably 0.05 to 0.2%. In range. A sodium-containing compound can be present (or a potassium compound can be present) to transform the alkaline earth metal or magnesium bentonite into a swelling alkali metal bentonite by providing sodium ions and used in this case The ratio can usually be at least stoichiometric and up to 20% excess of stoichiometric. Sodium hydroxide can be a suitable source of sodium ions, especially in the case of softening detergents where alkaline is desired.

Producing the solid, granular and gel-like compositions of the present invention and making said article is a relatively simple matter (sometimes gelling, agglomerating) requiring little but the mixing of the components. And an application step), but follows a particular method of making Applicant's dispersion (ie, the example method). In this case, it is preferable to melt the PEC before adding it to the aqueous medium,
The heating temperature of PEC is preferably within 10 ° C from the melting point. When melted with an alkanolamine / ether alcohol mixed (or alkanolamine / ethoxylated alcohol) emulsifier, PEC is any meltable emulsifier, especially one that is lipophilic (or any other emulsifier present). Are also highly lipophilic), eg alkanolamines, or the two fusible substances, PEC and alkanolamines, are melted separately and together or at the same time, also at approximately 60 ° C., for example. It can be added to an aqueous medium (usually water) that must be at the same elevated temperature. Smectite clay can be added before, simultaneously with, or after the emulsifier / PEC case. The water used has a final pH of 2.5 to 5.5, preferably 2.
It is often desirable to add HCl or other suitable acid to it to acidify it to a range of 5 to 4.0, eg, about 3.5. After emulsification, the emulsion formed is cooled to room temperature and the remaining emulsifiers are added before or after cooling, preferably before. The result is a stable emulsion which, under normal high temperature conditions, resists separation for more than 6 months.

PEC for making granular or powder products
Need only be mixed with the smectite clay and any other ingredients of the formulation. PE melted at high temperature
C is sprayed onto a rotating agglomerate of granular agglomerated smectite or montmorillonite powder (eg bentonite) or agglomerates thereof with any other particulate matter in the product to evenly distribute throughout. Is preferred. The mixer used may also include grinding means to ensure that the particle size is as small as possible so that the PECs can evenly adhere to the laundry being treated. Bentonite and other smectite clay particles can be at room temperature when PEC is applied to it, and the PEC solidifies when in contact with the particulate aggregates, usually with little agglomeration, but the PEC application, temperature. And by controlling the speed of the mixer, it may be possible to obtain some agglomeration if required.

To make a softened article, a continuous strip of substrate material, with or without an emulsifier, is used for PEC.
It is usually preferred to pass the melt through the melt, emulsion or other bath and remove excess with a doctor blade or squeeze roll and bentonite or other acceptable clay can be applied to the PEC coated strip. The strips containing PEC and other materials can be chilled or dried and then cut into solids for subsequent use.

Softening detergents can be made in the usual way, PEC and bentonite being added after the process, including by clutching and spray drying, taking into account exposure to unstable or detrimental temperatures. Add at an appropriate stage of the manufacturing process.

In use, the compositions and articles of the present invention are used in the same manner as other softening detergents, emulsions, powders and articles for imparting fabric softeners to laundry.
The softening detergent can be loaded into the washing machine as if it were a detergent, and the desired concentration for adjusting the various washing conditions used is 0.1 to 1%, preferably 0.
In the range of 1 to 0.5%, for example about 0.1 in the US
5% and about 0.5% in Europe. The rinse cycle additive emulsion can be added to the rinse water,
It can therefore be powdered and granular composition, PEC
The concentration of rinsing water is in the range of about 0.01 to 0.05%, and the concentration of bentonite is proportionally higher as described above. Alternatively, the composition can be added to the wash water, in which case the concentration can often be increased about 1 to 3 times. The dryer treated article can be used similar to the products currently marketed for that purpose, with paper (or paper towels) or equivalent sponge added to the dryer, usually 300 to 800 square cm sheets or paper pieces. Is used.

The following examples illustrate the invention but do not limit it. Unless stated otherwise, all parts and percentages in this specification and the appended claims are by weight and all temperatures are in ° C.

Example 1 Component Weight% Linear sodium dodecylbenzenesulfonate 2.00 Stearyl hydroxyethyl imidazoline 1.00 * Nonionic detergent 3.90 ** Sodium silicate 4.00 Sodium tripolyphosphate 23.00 Anhydrous Sodium carbonate 6.00 Ethylenediaminetetra (methylenephosphonic acid) 0.38 Sodium salt *** Optical brightener 0.21 **** Methyl silicone 0.18 Sodium hydroxide 1.00 Sodium perborate tetrahydrate 12.00 ・ Proteolytic enzyme 0.30 ・ ・ Calcium montmorillonite Swelling clay 16.00 Potassium methyl siliconate 0.50 Hydroxylamine sulfate 0.30 Perfume 0.50 Tetraacetylethylenediamine 0.89 Sodium aluminosilicate Two ... pentaerythritol distearate 6.00 condensates ** Na ₂ O with anhydrous sodium sulfate 10.59 Water 11.00 100.00 * C _13-17 mixed alcohol 1 mole of ethylene oxide 7 moles: of SiO ₂ The ratio is 1: 2 *** Diaminostilbene disulfonate type **** Dow-Corning X2-3302. Alcalase 2T .. Calcium bentonite ... Industrial products (monostearate 14%, distearate 45% and tristearate. 40%) Spray dry a portion of the formulation to make base beads and further mix the beads with a mixture of the remaining ingredients excluding perfume,
A fabric softening detergent composition (softening detergent) containing granular builders of the above formulation is prepared by spraying a fragrance on a mixture of beads and other substances. Sodium sulfate, linear sodium dodecyl benzene sulfonate, stearyl hydroxyethyl imidazole, nonionic detergent, sodium silicate, sodium tripolyphosphate, sodium carbonate,
Ethylenediaminetetra (methylenephosphonic acid) sodium salt, optical brightener, silicone, sodium hydroxide,
A clutcher formulation having about 55% solids of various heat stable ingredients in a product containing PEC and water was spray dried to No. US Sieve No. No. 10 to No. Make spray-dried beads with a particle size range of 100 fuzzy. Bentonite is agglomerated to the same particle size range, agglomerated bentonite and other ingredients including sodium perborate tetrahydrate, enzyme, hydroxylamine sulfate and sodium aluminosilicate are mixed with base beads, then the resulting mixture Spray silicone and perfume into final softening detergent. As a variant of the manufacturing method, the PEC can be added later to the composition as a powder or as a co-aggregate with bentonite.

The percentages of softening detergent and bentonite and PEC produced were varied, the percentages of all remaining ingredients remained the same, except that sodium sulphate was varied to adjust the increase or decrease in the total amount of bentonite and PEC. Make a variation of the formulation to test the detergency and fabric softening efficiency. In testing against various oily and clay-like soils, the softening detergent was found to be effective using visual observations of cleaning of soiled laundry and test watches as well as comparison of refractometer readings with controls. Recognized as a commercially acceptable cleaning agent. In composition,
When tested comparatively with the best commercially available softening detergents known to the inventors that include clays, tertiary amines, polysiloxanes and soaps or quaternary ammonium compounds, the composition of the invention of the above formulation is: Whether the washing machine and method is American or European, and whether the material of the laundry article is natural such as cotton or synthetic such as polyester or blends thereof Using 60 ° C. laundry in a normal wash load washer for laundry or test watch, the fabric softening effect is comparable or superior to the “best” composition. In the test, a washed swatch (or equivalent article), usually at least four experienced panelists of evaluators, one washed with the control detergent composition and the other with the softening detergent to be evaluated To compare. To determine the difference in softness between the control detergent and the swatch washed with the softening detergent, a number was added to indicate the difference, 1 was a slight difference, 2 was a significant difference, and 3 was a large difference. And Of course, in all cases, the softened detergent washed swatches are softer than the control washed in wash water containing the detergent composition excluding the softened bentonite-PEC mixture.

The softening detergents of the invention of the formulation of this example were tested in comparison with a control detergent from which bentonite and PEC were removed and replaced with sodium sulphate (inert filler), showing a softening effect. The difference is estimated to be 2.3. When 6% PEC is present in the formulation but bentonite is excluded, sodium sulphate replaces it with a rating of 0.7, sodium sulphate replaces PEC and bentonite (16%) is present with an evaluation. It is 0.8. As described above, the addition effect of the PEC blend and the bentonite only blend is supposed to be 1.5, but in reality, the addition effect was found to be 2.3, which shows a very remarkable improvement (synergistic action). .. As is apparent from the accompanying drawings, it can be seen that a further excellent softening effect can be obtained, and that the drawings show that bentonite does not provide a similar improvement by merely increasing the proportion of PEC. Increasing the PEC percentage (separately) by 30% and 20% results in a reduced softening effect.

The synergistic results for the fabric softening action of the softening detergent of the present invention will be readily apparent from the accompanying drawings.

In FIG. 1, curve 11 shows the improvement in the fabric softening effect of the washed laundry when the bentonite content is increased from 0 to 25%, and the points on the curve represent the content of the specific bentonite. . The best softening obtained was estimated to be about 2.7, which is about the best value ever obtained for a softening detergent. Curve 13 shows the fabric softening effect when PEC is removed from the formulation and the bentonite content is increased. It is worth noting that at bentonite contents above 25% the tip of the curve points downwards, indicating a decrease in softening. Pseudo-curve 15 shows the expected effect of addition on fabric softening action when the indicated percentage of bentonite is added to 6% PEC. Since most of curve 15 is substantially lower than curve 11, it can be seen that a synergistic fabric softening effect is associated with the presence of both bentonite and PEC in the softening detergent composition.

In the experiment of FIG. 2, clay (bentonite) was used.
Content is kept constant, but PEC content is 0 to 20
2 is the same as FIG. 1 except that it varies up to%. Curve 17 is 16% clay and 1 to 10
Although the softening detergent of the present invention containing up to 10% PEC shows an improved fabric softening effect, curve 19 shows that at a clay content of 0, the softening effect improves as the PEC content increases at a lower rate. It shows that too much PEC content actually reduces softening. Curve 21 is a plot of the expected (addition) effect of adding the indicated percentage of PEC to 16% clay. The curve is substantially lower than the actual curve 17, demonstrating that a mixture of bentonite and PEC synergistically improves the fabric softening of laundry washed with the softening detergent.

The above effect, a synergistic improvement in fabric softening, is also obtained with PECs described herein and various other mixtures of montmorillonite clays as described above, but with PECs being pentapentane. Best results are obtained with erythritol partial esters and pentaerythritol oligomeric partial esters containing at least one, preferably two hydroxyls, and when the clay is calcium bentonite or sodium or potassium bentonite capable of swelling in wash water. can get. In the experiment plotted above in the graph of the drawing, the bentonite used was calcium bentonite, and the wash water contained only sodium ions (from builder salts and sodium hydroxide) that converted it to swellable sodium bentonite. is there. Quite surprisingly, calcium bentonite has a much better fabric softening power than sodium and potassium bentonite when used in these conditions.

Another significant advantage of the softening detergents of the invention is that they overcome the observable "softening barriers". From FIGS. 1 and 2, an increase in the content of bentonite or PEC alone shows that the softening effect asymptotically approaches the limit of less than or about 1 and even the additive effect that may be expected is less than 2. Furthermore, it is clear that in any case, the larger amount of the softener mentioned reduces the fabric softening, so that it does not lead to an excellent softening detergent. However, in the case of the composition of the present invention, beyond this apparent limit of softening power,
The relatively low total amount of the mixture of PEC and bentonite produces excellent results, and the fabric softening effect approaches that of the rinse cycle additive composition previously thought of as a "impossible dream." The effect is a nonionic detergent only, anionic detergent only, a water insoluble builder such as zeolite, a builder composition or a zeolite, a phosphorus-free formulation which can be a mixture of carbonate and silicate, and polyacetal carboxylate. , NT
It can also be obtained in the case of other types of softening detergents, including those based on softening detergents with organic builders such as A, EDTA, citric acid and gluconic acid. Further, the synergistic softening effect can also be obtained in the case of detergent-free wash cycle and rinse cycle additive softening compositions, and whether in the liquid, granular or gel form, the rinse cycle. In the additive composition, the softening effect may be better than the composition without said mixture of clay and PEC.

Example 2 Component Weight% Linear sodium dodecylbenzenesulfonate 3.00 Stearyl hydroxyethyl imidazoline 1.50 * Nonionic detergent 3.50 Sodium silicate (Na ₂ O: SiO ₂ = 1: 2) 5 .50 Zeolite 4A 19.00 Sodium maleate methacrylate copolymer 1.10 Sodium carboxymethyl cellulose 0.50 Anhydrous sodium carbonate 4.00 Ethylenediaminetetra (methylenesulfonic acid) 0.44 Sodium salt Stilbene optical brightener 0.25 Sodium hydroxide 0.10 proteolytic enzyme (Alcalase ^TM 2T) sodium 0.36 perborate tetrahydrate 10.60 calcium Mont Mori Ron stone clay (calcium 18.00 bentonite) hydroxylamine sulfate 0.50 Te La acetyl ethylene diamine 1.00 aluminosilicate Sodium 0.40 ethylenediaminetetraacetic acid sodium 0.13 ... pentaerythritol distearate 3.00 anhydrous sodium sulfate 19.07 Water 7.50 Perfume 0.55 100.00 * C _{13 -17} Condensation product of 1 mol of mixed alcohol and 7 mol of ethylene oxide ・ ・ ・ Monostearate 14%, Distearate 45
% And 40% tristearate A granular product of this example was made by the method described in Example 1 and tested for detergency and fabric softening performance according to the method set forth in the example to show that PEC and bentonite Content shows good detergency and synergistic fabric softening. The synergistic improvement in fabric softening compared to the expected effect of individual PECs and bentonites in the composition was not as pronounced as in Example 1 (6% PEC and 16% bentonites present). Not quite, but quite. This phosphorus-free variant reduces the PEC content to 1.5% and the corresponding sodium sulfate content to 2%.
Increasing to 0.57% synergistically still softens the fabric softening, but to a lesser extent. The synergistic fabric softening effect is even more pronounced when the PEC content is increased to 6% and the sodium sulfate content is reduced to 16.07% for adjustment.

Example 3 Component wt% Nonionic Detergent 12.00 Sodium Silicate (Na ₂ O: SiO ₂ = 1: 2) 5.50 Zeolite 4A 23.00 Sodium Maleate Methacrylate Copolymer 1.50 Sodium Carboxymethyl Cellulose 0.55 anhydrous sodium carbonate 13.00 ethylenediaminetetra (methylenephosphonic acid) 0.65 sodium salt stilbene optical brightener 0.30 sodium hydroxide 0.15 sodium perborate hydrate 9.00 proteolytic enzyme ( Alcalase 2T) 0.70 Calcium bentonite 18.00 Hydroxylamine sulfate 0.50 Tetraacetylethylenediamine 3.86 Sodium aluminosilicate 0.50 ... Pentaerythritol distearate 3.50 Water 6.54 Fragrance 0.75 100.00 * C _13-17 mixed alcohol 1 mole of ethylene oxide 7 condensate of molar ... monostearate 14% distearate 45
% And tristearate 40% The zeolite builder, non-phosphorus, non-ionic granular detergent composition of this example is made by the method of Examples 1 and 2 and similarly tested for detergency and fabric softening performance. . The composition is a good nonionic detergent and does not have the ecologically disadvantageous properties of phosphate or nonbiodegradable anionic detergents. Also, due to the content of calcium bentonite and PEC, the composition has excellent fabric softening performance which is synergistically better than expected from the effect of the addition of the fabric softener present in the formulation (in addition, PEC is biodegradable). Is).

To improve the detergency of the composition, even one or more biodegradable anionic detergents such as 5% sodium lauryl sulphate or 10% sodium C _14-15 paraffin sulphonate. Can also be included in the composition, and in some cases the total detergent content can be about the same as in the formulation of this example and the anionic detergent can be used in place of the nonionic detergent. The product also exhibits excellent fabric softening performance of the formulations of this example, with the fabric softening being synergistically improved over the effect of adding the fabric softening component in the product.

Example 4 Ingredient % by Weight Linear Sodium Tridecyl Benzene Sulfonate 6.00 + Neodol ^™ 25-7 4.00 Pentaerythritol Distearate 7.00 Swellable Calcium Bentonite 18.00 Sodium Carbonate 8.00 Sodium silicate (Na ₂ O: SiO ₂ = 1: 2.4) 4.00 ++ Emulsifier 2.00 Water 51.00 100.00 + Aliphatic alcohol having 12-15 carbon atoms and 7 mol ethylene oxide Nonionic detergent which is a condensate of ++ 4 parts of N-stearyldiethanolamine and C
_{12-15 Alkyldecaethoxy} Ethanol 1 part Mixture This basic liquid softening detergent formulation results in excellent detergents and fabric detergents, with the synergistic effect of the fabric softening ingredients described above in Examples 1-3. Show.

Example 5 Ingredient % by Weight Calcium Bentonite 93.7 Pentaerythritol Dipalmitate 5.8 Sodium Hydroxide 0.5 100.0 For Granular or Powder Wash Cycle Additives (including non-softening detergent composition) This base formulation (for addition to normal wash water) mixes sodium hydroxide in powder or aqueous solution with bentonite and then melts PEC to the surface of moving aggregates of bentonite (and NaOH). It is made by spraying or dropping to give an agglomerate or powder. When the product was added to the wash water in such a proportion as to give 0.06% PEC in the wash water and proportionally more calcium bentonite, the laundry washed with the obtained wash liquid gave an unexpectedly superior wash liquid. Shows fabric softening performance. The wash cycle additive can be liquid rather than granular or powdery, of which 2
% Emulsifier may also be present and the water content may be about 70 to 90%, eg 80%.

Alternatively, the rinse cycle softener composition is made in substantially the same formulation shown for granules, with the bentonite being sodium bentonite and the sodium hydroxide being replaced by hydrochloric acid to acidify the product. be able to. Liquid rinse cycle compositions can likewise be made without the presence of detergents or builders and with emulsifiers to help keep the liquid product homogeneous. In the case of the product, the water content may be similar to that of the liquid wash cycle additive, but also water
Can be used in place of detergents and builders, pH
Appears to be in the range 2.5 to 5.5, eg 3.5. Similarly, 0.5 to 5% gelling agent, eg 3%
Of sodium alginate and the other ingredients are the same as for the liquid product (reducing the water content to control the presence of the gelling agent) to make a gelled product. If desired, the rinse cycle composition can reduce the concentration of bentonite and PEC, for example, even if the concentration in the softening detergent is reduced to 1/3, it is still effective.

All of the above compositions containing not only bentonite but also PEC are all effective fabric softeners and exhibit synergistic softening as represented by the data and figures presented above.

Example 6 Component Weight% Calcium bentonite 16.0 Sodium hydroxide 0.2 ... Pentaerythritol distearate 6.0 ++ Emulsifier 3.0 Water 74.8 100.0 ... 14% monostea Rate, 45% distearate and 40% tristearate ++ N-stearyldiethanolamine 4 parts and C
_{12-15 Alkyldecaethoxyethanol} 1 part Mixture The indicated ingredients are mixed together to make a wash cycle additive suspension which improves the conditioning of the fabric by the wash water containing suspension. Concentrate all ingredients except water by half or 1 /
It can be reduced to 3 to increase the water content to adjust and the resulting suspension can be used for rinse cycle softening. Alternatively, the compounded product is used directly in rinse cycle softening of washed laundry using a normal charge of the softener in rinse water (often about 1.3 fl oz in the end of 64 liters). be able to.

As already mentioned in the other examples, any kind of use results in synergistically superior fabric softening.

Example 7 Ingredient % by Weight Cellulose Sponge 13.0 Sodium Bentonite 54.0 ・ ・ ・ Pentaerythritol Distearate 18.0 ++ Emulsifier 5.0 Water 10.0 100.0 ・ ・ ・ See Example 6 ++ See Example 6 PEC, bentonite and emulsifier are mixed with half the amount of water, the remaining half amount of water is used to moisten the sponge, after which the sponge is saturated with a mixture of the other ingredients and the water is further evaporated. The final product is used to soften the laundry while being dried in the dryer of the automatic washing machine. The laundry is softened sufficiently to obtain the above-mentioned synergistic softening. In a similar manner, saturate a paper towel with the formulation,
Used as a dryer softener with essentially the same results.

Example 8 In this example, a cotton terry swatch is washed in an automatic washing machine with 60% wash water containing 0.5% of the softening detergent composition of Example 1. Rinse and dry. Other such swatches have the same formulation except that bentonite and PEC may be replaced with inert filler (sodium sulphate), but with the same cleaning composition, followed by a rinse water of about 0.05%. % (Or higher)
Rinse water (with final rinse) with any quaternary ammonium or amine salt rinse cycle fabric softening composition to include the fabric softening quarts or amines and dry the swatch.

A piece of cloth was cut out from the swatch subjected to these various treatments, and the lower end of the vertical piece of cloth was immersed in an aqueous solution of a water-soluble dye (Red Iragon), and after 30 seconds, 1 minute, 3 minutes and The water absorption is tested by measuring the height at which the water rises after 5 minutes. A piece of cloth washed with the softening detergent of the present invention is about 2 times as large as a piece of cloth from a swatch that is washed as above and further treated with a rinse cycle softener.
Absorbs water up to twice as high.

By using the rinse cycle softener of the present invention in which PEC and bentonite are present, similar results are obtained when compared to rinse cycle fabric softening compositions based on quart and / or amine fabric softeners. Obtainable. Nevertheless, the softening detergent and rinse cycle compositions of the present invention soften cotton (and other fabrics) in much the same way as the best contrasting softener compositions, which has very good results. is there.

These and similar absorption test results for towels and fabrics show that fabrics treated with the composition of the present invention, rather than commercial quart products, are more important (to towels) than the commercial products. Water and (underwear,
It is important because it shows that it can absorb more body sweat (which is important for textiles such as T-shirts and sportswear).

In the embodiments of the present invention described above, various modifications can be made within the scope of the present invention, and the synergistic result is still obtained. For example, various other swellable bentonites and montmorillonites can be used in place of calcium and sodium bentonite, and dipentaerythritol tetralaurate, monopentaerythritol 10 ethylene oxide distearate and pentapentaerythritol tetrapalmitate can be used. Other PECs including can be used. Various detergents, PECs and clays as described above may be used in the compositions and articles of the present invention, and various auxiliaries and active ingredients may be included and acceptable clay and A synergistic fabric softening effect can be obtained as long as the PEC combination is present. The same applies when the ratio is changed within the above-mentioned range and when various concentrations of the product are used within the given range. In the presence of the bentonites and PECs according to the invention, in all variants, probably by the mutual promotion of the attachment of the individual required softeners to the laundry fibers,
Sometimes excellent softening occurs due to the favorable dispersing effect of bentonite on PEC. However, the resulting synergistic effect appears to be more than just the adhesion promoting and dispersing effects already mentioned, and the applicants are not bound by any of the theories set forth herein.

While the invention has been described with respect to the description and examples, it will be apparent to those skilled in the art that substitutes and equivalents may be used in this specification without departing from the invention, so that the invention has been described above. And should not be considered limited to the examples.

[Brief description of drawings]

Figure 1: Bentonite content fluctuates and PEC content is 0%
FIG. 4 is a plot of the fabric softening effect of the base formulation of Example 1 herein with varying bentonite content as compared to the softening effect of the similar composition of FIG.

FIG. 2 PEC content fluctuates and bentonite content is 0%.
FIG. 6 is a diagram in which the fabric softening effect of the basic compounding composition of Example 1 in which the PEC content is changed as compared with the softening effect of the similar composition is plotted.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C11D 3/20 D06M 11/77 23/08 7199-3B D06M 21/00 Z (72) Inventor Jiyang --Paul M. Atsyuev Granmer Belgium 4821 Andrimon, Lieu Soulet Syato 45 (72) Inventor Vyuviane a Tatsk Belgium Belgium 4630 Einault, Reux Boardlier 17 (72) Inventor Jan El Pae Domus Belgium 3700 Tongeren, Romense Katssei 245 (72) Inventor Marcel Zieg Zili Belgium 4601 Argiyanto, Are de Srizier 26 (72) Inventor Pierre・ M Lambert Belgium −5380 Cortaire-Voudon, Rieu de Sardines 31 (72) Inventor Paul A. Eccle, Belgium 4-4190 Avengyou Do La Grot, Talf, 18

Claims (27)

[Claims] 1. A fabric softening product, which is a composition or article applied to a fibrous material such that a fabric softening component is applied to and softens the fibrous material, wherein the product is a pentaerythritol higher fatty acid ester, Pentaerythritol oligomer higher fatty acid ester, pentaerythritol lower alkylene oxide derivative higher fatty acid ester or pentaerythritol oligomer lower alkylene oxide derivative higher fatty acid ester or a mixture thereof, which is PEC and montmorillonite clay as a fabric softening component. Fabric softening products. 2. The fabric softening product of claim 1 wherein the montmorillonite clay is a wash cycle or rinse cycle composition, dryer article or softening detergent that is capable of swelling during use. 3. The montmorillonite clay is sodium, potassium, calcium or magnesium bentonite or a mixture of two or more thereof, and the PEC is pentaerythritol partial higher fatty acid ester or pentaerythritol oligomer partial higher fatty acid ester. Fabric softening products. 4. The fabric softening product of claim 3 which is substantially free of quaternary ammonium compound fabric softening agents. 5. The fabric softening agent according to claim 4, wherein the softening detergent is a softening detergent containing anionic and / or nonionic synthetic organic detergent, PEC and bentonite. Product. 6. A softening detergent composition according to claim 5 wherein the synthetic organic detergent is in the form of granules and comprises 3 to 35% of the composition, 2 to 20% of PEC and 10 to 30% of bentonite. 7. A synthetic organic detergent is a mixture of anionic as well as nonionic detergents, the proportion of which in the composition is in the range of 3 to 25%, the composition being 10 to 60% builder, PEC. And the ratio of bentonite is 2
7. The granular softening detergent composition of claim 6 in the range of 15 to 15% and 10 to 25%. 8. Anionic detergent is a sulfated and / or sulfonated detergent, a nonionic detergent is a condensate of higher aliphatic alcohol and ethylene oxide, and a builder is a water-soluble alkali metal polyphosphate, carbonate or silicic acid. Selected from the group consisting of salts, borates, citrates, bicarbonates, gluconates, nitrilotriacetic acid salts, and ethylenediaminetetraacetic acid salts, water-insoluble water-softenable zeolites and mixtures thereof, PEC being pentaerythritol. The granular softening detergent composition according to claim 7, wherein the higher fatty acid partial ester of 1 or the higher fatty acid partial ester of pentaerythritol oligomer, and bentonite are sodium and / or calcium bentonite. 9. A nonionic detergent which is a condensate of 1 to 10% sodium higher alkylbenzene sulfonate, 1 to 10% higher aliphatic alcohol 1 mol and ethylene oxide 5 to 10%, 2 to 10% silicic acid. Sodium, 15-35% sodium tripolyphosphate, 2-10% sodium carbonate, 3-10
9. The particulate softening detergent composition of claim 8 which comprises% pentaerythritol higher fatty acid partial ester and 12 to 20% sodium and / or calcium bentonite. 10. The granular softening detergent composition according to claim 9, wherein the pentaerythritol higher fatty acid partial ester is pentaerythritol distearate and the bentonite is calcium bentonite. 11. A softening detergent composition according to claim 5, which is in the form of a liquid or a gel and contains 3 to 20% synthetic organic detergent, 2 to 20% PEC and 10 to 30% bentonite in an aqueous medium. object. 12. The fabric softening rinse cycle or wash cycle additive composition of claim 4 which is in the form of granules or powder and comprises about 1 to 40% PEC and about 60 to 99% granules or powder bentonite. 13. The fabric softening product of claim 12 wherein PEC is dispersed in bentonite which acts as a carrier. 14. Granular or powdered fabric softener according to claim 13 comprising 1 to 10% pentaerythritol higher fatty acid partial ester or pentaerythritol oligomer higher fatty acid partial ester, or mixtures thereof, and 90 to 99% bentonite. Chemical composition. 15. 3 to 7% pentaerythritol C _12-18 higher fatty acid partial ester and 93 to 97.
15. The fabric softening composition of claim 14 comprising% sodium bentonite or calcium bentonite. 16. PEC is pentaerythritol distearate and bentonite is calcium bentonite.
There is no quaternary ammonium compound, and there is an ionizable sodium compound in the composition, and / or sodium ions that convert calcium bentonite to sodium bentonite in the wash or rinse water in which the composition should be used. The fabric softening composition according to claim 15. 17. The composition of claim 16 comprising about 6% pentaerythritol distearate and about 94% calcium bentonite. 18. The composition of claim 4 which is liquid and comprises about 1 to 40 parts PEC and about 60 to 99 parts bentonite in the liquid medium. 19. 1 to 10% pentaerythritol higher fatty acid partial ester or pentaerythritol oligomer higher fatty acid partial ester, 10 to 30%
19. The composition of claim 18 comprising bentonite and 50 to 89% aqueous medium. 20. _3-7 % pentaerythritol C _12-18 higher fatty acid partial ester, _10-24 % sodium and / or calcium bentonite and 60-85% aqueous medium, the aqueous medium being substantially water. 20. The composition of claim 19, which is 21. About 6% pentaerythritol distearate, about 16% calcium bentonite and 6%.
21. The fabric softening wash cycle additive composition of claim 20, comprising 5 to 76% water. 22. A fabric softening dryer comprising from about 1 to 25%, based on a fabric softening article, of a fabric softening component attached to or absorbed by an absorbent fibrous or cellular material. Goods. 23. The fabric softening article of claim 22 comprising a piece of paper impregnated with 5 to 95% of a fabric softening component comprising pentaerythritol partial higher fatty acid ester, pentaerythritol oligomeric partial ester or mixtures thereof and bentonite. 24. A laundry comprising applying a fabric softening component to a laundry to soften it and applying the fabric softening product of claim 2 to the laundry under said conditions. How to be flexible. 25. A fabric softening product applied to laundry is an anionic type and / or applied to laundry in wash water.
25. The method of claim 24 which is a softening detergent composition comprising a nonionic synthetic organic detergent, PEC and bentonite. 26. The method of claim 24, wherein the fabric softening product is a rinse cycle or wash cycle composition comprising PEC and bentonite applied to laundry in wash water or rinse. 27. A dryer article comprising a PEC and bentonite wherein the fabric softening product is applied to laundry in a dryer of a washing machine, wherein the article has PEC and bentonite attached or absorbing. 25. The method of claim 24, having a viscous fibrous or spongy material.