KR950005380B1 - Detergent compositions - Google Patents

Abstract

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Description

Detergent composition

The present invention relates to detergent compositions, in particular detergent compositions for textile washing.

Detergent compositions generally contain various components including detergent active surfactants which serve to remove contamination from the object to be cleaned and to suspend the removed contamination in the wash liquor. Detergent compositions are used to clean fabrics by mobile fabric washing in containers or washing machines, to clean hard surfaces such as glass, polished surfaces, plastics, metals and enamels, and to clean soft fixtures such as carpets. Various kinds of materials have been used as detergent active materials including anionic and nonionic detergent active materials.

The most widely used anionic surfactant material is alkylbenzene sulfonate. However, there has been a desire to find alternative anionic surfactant materials in which alkylbenzene sulfonates can be used under undesirable circumstances, but the performance of other anionic surfactant materials is usually not satisfactory.

Materials known as anionic surfactants that can be used as substitutes are as follows.

[Formula 1]

a) general formula R ² -CH = CH-R ²

Olefin sulfonates, olefin sulfonates derived from olefins having

[Formula 2]

R ¹ and R ² in the vinylidene olefin to the acid salt of vinylidene acid salt derived from the two formulas in having an alkyl group other than hydrogen.

We have found that the performance of selected internal olefin sulfonates and vinylidene sulfonates can be improved by additional use of certain nonionic surfactant materials.

According to the present invention, there is provided a detergent composition for fabric washing containing a surfactant system consisting of the detergent active material as follows.

i) an internal olefin sulfonate derived from an internal olefin of general formula (I) or a vinylidene sulfonate derived from vinylidene of general formula (II) or mixtures thereof (in the sulfone salts, R ¹ and R ² Is the same or different alkyl group with 10-16 total carbon atoms)

ii) nonionic surfactant materials having HLB values of 10.5 or less.

The weight ratio of (i) to (ii) is in the range of 9: 1-1: 9, preferably 4: 1-1: 4.

The general preparation of internal olefin sulfonates or vinylidene sulfonates is accomplished by sulfonating suitable internal olefins or vinylidene with sulfur trioxide and then neutralizing and hydrolyzing the reaction products.

Preference is given to using such water-soluble salts of sulfonic acids, in particular their alkali metal (sodium or potassium) salts. Aluminum salts or alkanol ammonium salts may also be used.

Since the total number of carbon atoms of R ¹ and R ² is 10-16, the total number of carbon atoms of the internal olefin or vinylidene is 12-18. In particular, the total number of carbon atoms of R ¹ and R ² is 12 or more.

Internal olefin sulfonates, which are distinguished from alpha olefin sulfonates, have olefin bonds in which the internal olefin sulfonates are randomly located in the chain, but internal olefins and their derivatives have different properties from alpha olefins and their derivatives. This means that at least half of the internal olefins of the general formulas cited above have R ¹ and R ² groups each having at least 4 carbon atoms. This also applies to the R ¹ and R ² groups of vinylidene olefin sulfonate.

It is preferred that at least three quarters of the internal olefins or vinylidene have R ¹ and R ² groups each containing at least 4 carbon atoms.

Another point to express the distinguishing feature of the internal olefin sulfonates is that most of the molecules have olefinic bonds between carbons 3 and 4 or between carbons far from the ends of the carbon chain.

The amount of α-olefin sulfonate present with the internal olefin sulfonate is generally 20% or less, preferably 10% or less or 5% or less of the total amount of the olefin sulfonate. Preferred materials as nonionic surfactant materials are alkoxylated nonionic materials.

Particularly preferred nonionic surfactants are hydrophobic moieties having a C ₈ or more continuous carbon chain which is aliphatic or alkylaromatic, and hydrophilic moieties having at least one ethyleneoxy and / or glyceryl residue and terminating at least one hydroxyl group for this moiety. Have Particularly preferred nonionic materials are alkoxylated nonionic surfactants which are reaction products of ethylene oxide and compounds having such hydrophobic groups and reactive hydrogen atoms (e.g. aliphatic alcohols, acids, amines or alkylphenols).

Certain ethoxylated nonionic surfactant compounds are condensation products of alkyl (C ₆ -C ₂₂ ) phenol-ethylene oxide condensates, aliphatic (C ₈ -C ₁₈ ) primary or secondary linear or branched alcohols with ethylene oxide .

Ethylene oxide adducts of fatty substances can preferably be used as nonionic surfactants. The number of ethylene oxide groups per molecule has a significant impact on the HLB of nonionic surfactants. Since the chain length and type of fatty material also affects, the number of preferred alkylreoxides per molecule thus depends on the chain length and type of fatty material.

As described above, the nonionic surfactant has an HLB value of 10.5 or less. Preferably, the HLB value of the nonionic surfactant is 10 or less, more preferably 9 or less.

It is well known that ethoxylated nonionic surfactants are mixtures of molecules that vary in the number of ethylene oxide groups, including some nonethoxylated material.

In the present invention (when present as a pure compound) it is advantageous to use purified surfactants to increase the proportion of molecules having the desired HLB value. This tablet consists of the removal of the non-ethoxylated material which provides the so-called "peelable non-ionic material" or the further purification which provides the so-called "peaky non-ionic material", ie the concentrated distribution of ethylene oxide water. Such purified materials are commercially available.

Other nonionic surfactants that may be used in addition to the ethoxylated nonionic surfactants include fatty alkyl monoesters of glycerol and fattyamide monoethanolamides.

Preferred compositions according to the invention contain 1-50% by weight, preferably 2-35% by weight of surfactant system.

The surfactant system may contain other surfactant materials in addition to the specific sulfonate and nonionic surfactants specified above. Such other surfactant materials are selected from other anionic surfactant materials, zwitterionic or amphoteric surfactant materials or mixtures thereof.

Such additional surfactant materials should be present at levels not exceeding trace amounts of the total amount of surfactant in the composition.

The actual wash solution should contain an electrolyte to provide an ionic strength of at least 5 × 10 ⁻³ . It is particularly desirable that the electrolyte be sufficient to provide an ionic strength of at least 2 × 10 ⁻² mol / l. The electrolyte is suitably present in the detergent composition to provide such ionic strength during washing when using the composition. The concentration of surfactant in the wash liquor is 0.05-2 g / l, preferably 0.1-1.5 g / l.

Ion intensity is related to concentration and the number of ions and multiple charge ions in the molecule are considered. Ionic strength is calculated from the water concentration (m) of each ionic material present in solution and the charge (z) provided by each ionic material. Ionic strength (I) is 1/2 of the sum of mZ ² for all ionic materials present. That is expressed as follows.

[Equation 1]

I = 1 / 2Σm.Z ²

If both ions are monovalent salts, the ionic strength is equal to the water concentration. However, this is not the case when more than two ions or multiple charges are included. For example, a 1 mole solution of sodium carbonate contains 2 moles / liter of sodium ions. Therefore, the ionic strength is expressed as

[Equation 2]

I = 1/2 [2 (1 ² ) + 1 × (2 ² )] = 3 mol / ℓ

A description of ionic strength is described in Physical Chemistry Walter J. Moore, 4th Ed. 1963. Both ionic strength and electrolyte concentration will be at the level of 5 × 10 ⁻³ mol / l, with preferred levels of at least 0.02 mol / l. In general, it is not practical for electrolyte concentrations to exceed 0.5 moles.

The amount of electrolyte in the wash liquor is actually a parameter determined by the amount of the water-soluble salt in the detergent composition and the amount of the composition used. Detergent compositions are generally used in amounts of at least 1 g / l, preferably in amounts of 4 g / l-10 g / l. Detergent compositions that provide the required ionic strength when used in such amounts will contain at least 5% by weight of water soluble salts. When the amount of the composition used is 10 g / l, it is very sufficient to provide an ionic strength of 0.1 mol / l or more.

The water soluble salts present in the detergent composition include a water soluble detergency builder material.

When the composition of the present invention contains a detergency builder material, it is a material capable of reducing the amount of free calcium ions in the wash liquor, and further advantageous properties such as alkaline pH formation and suspension of contamination removed from the fabric. To the composition.

Typically detergent compositions containing detergency builder materials will contain 5 or 10-90 or 95% by weight water soluble salts, whether or not the builder material itself is a water soluble salt and preferably 30-80% by weight water soluble salts. It may contain. The amount of cleaning builder material, whether water soluble or not, is generally 5 or 10-60% by weight, preferably 20-50% by weight. One form of the invention is a composition containing 10-60% by weight of a water insoluble detergent builder and 5-50% by weight of a water soluble salt.

Examples of phosphorus-containing inorganic cleaning builders used are water-soluble salts, in particular alkali metal salts of pyrophosphoric acid, orthophosphoric acid metaphosphoric acid, polyphosphoric acid and phosphonic acid. Specific examples of inorganic phosphate builders include the tripolyphosphoric acid, orthophosphoric acid, sodium and potassium salts of hexametaphosphate.

Examples of phosphorus-free inorganic detergency builders are water-soluble alkali metal salts of carbonic acid, bicarbonate, silicic acid and crystalline and amorphous aluminosilicates. Specific examples are sodium carbonate (with or without interference seedlings), potassium carbonate (with or without interference seedlings), sodium bicarbonate and potassium, sodium silicate and potassium.

When containing an organic detergency builder there are, for example, alkali metal, ammonium and substituted ammonium salts of polyacetic acid, carboxylic acid, polycarboxylic acid, polyacetyl carboxylic acid, polyhydroxysulfonic acid. Specific examples are ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, melic acid, benzenepolycarboxylic acid, sodium, potassium, lithium, ammonium and substituted ammonium salts of citric acid.

The composition according to the invention is preferably alkaline. That is, the pH should be at least 8, preferably at least 10 at 25 ° C. and at least 1 g / l in distilled water. For this purpose the composition may contain a water soluble alkaline salt. This salt may be a detergency builder or an alkaline material with no special capacity.

The composition may also contain various optional components in addition to the components described above.

Examples of other components that may be contained in the composition include polymers having carboxylic acid or sulfonic acid groups in acid form or carboxylic acid or sulfonic acid groups partially or completely neutralized with sodium or potassium salts. Preferred polymers are copolymers and homopolymers of acrylic acid and / or maleic acid or maleic anhydride. Particularly preferred polymers are polyacrylate acrylic / maleic acid copolymers, and acrylic phosphinates.

Suitable polymers that can be used alone or in combination are as follows. Polyacrylic acids, such as Versicool (trademark) E5, E7, E9 (manufactured by Allied Colloids), Narlex (trademark) LD30 and LD34 (from National adhesives and Resins Ltd), acrysol (Acrysol: Trademark) LMW-10, LMW-45, Al-N (manufactured by Rohm & Hass), Sokalan (Sokalan trademark) PA-20, PA-40, PA-70, PA-110 (manufactured by BASF): Ethylene / Maleic acid copolymers, such as the EMA (trademark) series (manufactured by Monsanto), methyl vinyl ether / maleic acid copolymers, such as Gantrez (trademark) AN 119 and AN 149 (manufactured by GAF Corporation): acrylic acid / Maleic acid copolymers, such as Sokalan (Sokalan®) CP4, CP5, CP7 (manufactured by BASF), Alcospese (Alcosperse®) series (manufactured by Alco): acrylic phosphinate, eg DKW (Trademark) 125 (product of National Adhesives and Resins Ltd), Belsperse (trademark) series (product of Ciba-Geigy)

The molecular weight of the homopolymers and copolymers is generally 1000-150,000, preferably 1500-100,000. The amount of polymer used is in the range of 0.5-5% by weight of the composition. Other suitable polymer materials include carboxyethyl cellulose, methylcellulose, cellulose ethers such as hydroxyalkyl cellulose, mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose and methyl carboxymethyl cellulose. Mixtures of other cellulose ethers, in particular mixtures of carboxymethylcellulose and methylcellulose, are also suitable. Also suitable are polyethylene glycols having a molecular weight of 400-50,000, preferably 1000-10,000, copolymers of polyethylene oxide and polypropylene oxide, and suitable copolymers of polyacrylate and polyethylene glycol. It is also suitable as a copolymer of polyvinyl pyrrolidone, polyvinylpyrrolidone and other polypyrrolidone having a molecular weight of 10,000-60,000, preferably 30,000-50,000. Also suitable are polyacrylic phosphinates and corresponding copolymers of molecular weights 1000-100,000, in particular 3000-30,000.

Other components that may be included in the composition include fabric softeners such as fatty amines, fabric softening clay materials, foam inhibitors, oxygen release bleaching precursors such as sodium perborate and sodium percarbonate, and oxygen such as trichloroisocyanoic acid. Luminescent bleaches, inorganic salts such as sodium sulphate, and flavours, including deodorant flavors, enzymes (cellulases, proteases, amylases, etc.), bactericides and coloring agents, which are usually present in very small amounts.

The detergent composition according to the present invention may be in any form such as powder, bar, liquid, paste. For example, suitable liquid compositions may be non-aqueous or water soluble, or may be isotropic or may be ladela, if water soluble. The composition can be prepared by a variety of different methods depending on its physical form. In the case of granular products, the composition may be prepared by dry mixing or coagulation. Preferred physical forms are granules containing a detergency builder. It may be prepared by conventional granulation processes, or by spray drying at least a portion of the composition. This process produces a slurry containing components that are not heat sensitive, such as surfactants, builder materials, and packed salts. The slurry is spray dried to form basic powder granules, and then mixed with heat sensitive solid constituents including bleach and urea. Certain nonionic surfactants specified above are liquefied by melting or solvent dissolution and then sprayed onto the basic powder granules, rather than being mixed into the slurry to be spray dried.

The invention will now be described in more detail in the following nonstable examples.

EXAMPLE

Numerous examples and comparative examples were performed. In each example, two surfactants were used in different proportions to compare decontamination from the polyester test cloth (especially triolein removal). The test cloth was changed in each example. As a result, each example shows whether or not a specific pair of surfactants is synergistic upon mixing and exhibits a synergistic effect, but the resin result of one example cannot be directly compared with the resin result of another example.

Experimental conditions are the same in each example. The wash liquor was used to wash the laundry fabric in a tigotometer, where the ratio of wash liquor to cloth was 40: 1. Washing was performed at 40 ° C. for 20 minutes under stirring at 70 rpm. The laundry fabric consisted of several polyester test cloths precontaminated with C ₁₄ labeled triolein. The degree of detergency (decontamination) was indicated by measuring the amount of labeled triolein after washing using radiotrace method.

The experiment was carried out using vinylidene sulfonate derived from symmetric vinylidene (ie R ¹ and R ² are equal). Experiments were also performed using internal olefin sulfonates derived from internal olefins, which were any mixtures of olefins at various positions (but the amount of α-olefins were 2% or less).

Nonionic surfactants are ethoxylated C ₁₂ alcohols having different average numbers of ethylene oxide, as described below, and are materials which are peeled off to remove non-ethoxylated alcohols. Other nonionic surfactants have also been used somewhat. Such materials are C ₁₀ and C ₁₂ alkyl glyceryl monoethers and coconut monoethanolamides.

C ₁₂ alcohols having residues of ethylene oxide on average 3 have an HLB value of about 8.3, and C ₁₂ alcohols having ethylene oxide-residues of average 8 have an HLB value of about 13.1. Coconut ethanolamide has an HLB value of about 7.9. The HLB value of glyceryl monoether is not exactly known but is 10 or less.

In the first series of experiments for each test composition, sodium carbonate and sodium chloride were added to provide 1 g / l surfactant mixture and 0.1 mol / l ionic strength (to express the amount of electrolyte derived from the other components of the composition). A wash liquor containing the mixture was prepared and its pH was 10.

Two series of experimental results are shown in Table 1 (vinylidene sulfonate) and Table 2 (internal olefin sulfonate).

TABLE 1

TABLE 2

* Cn3EO means Cn alcohol with average ethylene oxide residue of 3.

CnGME means Cn alkylglycerol monoether.

CEA means coconut monoethanolamide.

In Examples 1 and 3 of Table 1 and Examples 6-8 and 11-13 of Table 2, the use of a mixture of a nonionic surfactant and sulfonate having a low HLB value was found to be more effective than the case of using these components alone. Shows excellent. This synergistic effect is not observed in non-ionic surfactants with high HLB values used in Examples 2, 4 and 9, but in Example 10 where such nonionic surfactants are used with sulfonic acid salts of C ₁₈ or higher. The synergistic effect of is observed.

Further experiments were performed using C ₁₆ internal olefin sulfonates and low HLB values with varying ionic strengths. The run was performed at 40 ° C and 20 ° C. For comparison purposes a mixture of the same nonionic surfactants as linear alkylbenzene sulfonates (LAS) was used. The ratio of anionic surfactant to nonionic surfactant was a predetermined ratio that could maximize the maximum triolein removal at the ionic strength and temperature.

The results are shown in Table 3. From this, it can be seen that excellent cleaning power is observed when the content of the electrolyte is high.

TABLE 3

From Table 3, it can be seen that under low temperature and low electrolyte conditions, nonionic surfactants having low IOS / HLB values and LAS / nonionic surfactants have almost the same level.

Claims (13)

(i) an anionic surfactant material as follows: (a) an internal olefin sulfonate derived from an internal olefin having the general formula (I) R ² -CH = CH-R ² (I) General formula (II) as follows

Vinylidene sulfonate derived from vinylidene having a compound or a mixture thereof (c) wherein R ¹ and R ² are the same or different alkyl groups having 10 to 16 carbon atoms in total; And (ii) a nonionic surfactant material having an HLB value of 10.5 or less, and a surfactant composition containing a surfactant system having a weight ratio of (i) to (ii) in the range of 9: 1-1: 1. The detergent composition according to claim 1, wherein the ratio of (i) to (ii) is in the range of 4: 1-1: 4. 3. A detergent composition according to claim 1 or 2, wherein the nonionic surfactant is an alkoxylated, preferably ethoxylated, nonionic surfactant. The detergent composition according to claim 1, which contains 5-95% by weight of a water-soluble salt. The method of claim 1, wherein at least a majority of the anionic surfactant in the surfactant is an internal olefin sulfonate and the composition contains 10-60% by weight of a water-insoluble detergency builder with 5-50% by weight of a water soluble salt. Detergent composition. The detergent composition according to claim 1, wherein the nonionic surfactant has an HLB value of 10 or less. 2. A detergent composition according to claim 1, wherein the composition contains an amount of alkaline salt sufficient to have a pH of 8 or more, preferably 10 or more, when the composition is added to distilled water at 25 DEG C in an amount of 1 g / L or more. The detergent composition according to claim 1, which is a granular composition suitable for fabric washing. The detergent composition according to claim 1, which contains at least one of fabric softener, fabric softening clay, foam accelerator, foam inhibitor, bleach, fluorescent agent, organic polymer having carboxylic acid or sulfonic acid group, and perfume enzyme. (i) an anionic surfactant substance as follows: (a) an internal olefin sulfonate derived from an internal olefin having the general formula (I) R ² -CH = CH-R ² (I) General formula (II) as follows

Vinylidene sulfonate derived from vinylidene having a compound or a mixture thereof (c) wherein R ¹ and R ² are the same or different alkyl groups having 10 to 16 carbon atoms in total; And (ii) a nonionic surfactant material having an HLB value of 10.5 or less, wherein the weight ratio of (i) to (ii) is in contact with the contaminated fabric with an aqueous solution that is a solution of the surfactant in the range of 9: 1-1: 9. A cleaning method comprising the step. The cleaning method according to claim 10, wherein the washing liquid contains an electrolytic material having an ionic strength of 4 × 10 ^-3 mol / L or more. The method of claim 10, wherein at least a majority of the anionic surfactants in the surfactant system are internal olefin sulfonates and the wash liquor contains an electrolyte of ionic strength in the range of 0.005-0.1 mol / l. 11. The method of claim 10, wherein the washing liquid has a pH of 8 or more.