KR910004890B1 - Detergent composition with fabric softening properties - Google Patents

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Description

Detergent composition with fabric softening properties

The present invention relates to a detergent composition for fabric treatment, and in particular, a detergent composition for fabric treatment that can soften the cloth fiber laundry without causing the problem of redepositing on a synthetic fiber fabric during washing. In particular, the present invention relates to an alkaline composition capable of achieving an optimal balance between softening and washing power in a woven fiber laundry. It is desirable to treat the fabric with fabric softener during the fabric washing step or during the fabric rinse process to prevent fabric roughness that may result from repeated washing. Materials proposed as fabric softeners include quaternary ammonium compounds, imidazolinium derivatives, fatty amines, fatty acid amines, soaps, clays and mixtures thereof.

Fabric roughness is particularly problematic when the fabric consists of natural fibers such as cotton and wool or contains natural fibers.

Soap is a particularly preferred fabric softener because it also acts as a detergent active material to remove dirt from the fabric.

The problem associated with the deposition of organic fabric softeners, such as soap, onto the fabric during the laundry process is that to achieve a desirable softening effect on the fabric, the deposition of fatty and granular deposits on the fabric is increased, leading to poor fading on the fabric. Is the point.

Products formulated for fabric laundering contain, in addition to detergent active materials which normally serve to remove the dirt from the fabric, contain anti-sedimentation agents to prevent the removed dirt from redepositing onto the fabric again in the wash liquor. Sodium Carboxymethyl Cellulose (SCMC) is one of the materials used for this purpose. This material can reduce the redeposition of clay and soot (or carbon) granules on hydrophilic fabrics such as cotton but does not reduce the redeposition on hydrophobic fabrics.

The redeposition problem is particularly acute for hydrophobic fabrics such as polyester and acrylic fabrics, since the redeposition problem is also a problem with granular, inorganic and organic fats.

Hydrophobic fabric problems can be alleviated by incorporating nonionic cellulose ether polymers as described in South African Patent Application No. 71/5149 (Unilev).

U.S. Patent Application No. 3920561 (transferred from Desmaris to Procter & Gamble Company) contains fabric softeners and highly substituted in order to impart softness to the fabric during the rinse process and to provide excellent time-removing benefits, particularly for polyester fabrics. The treatment of the fabric with a composition containing the prepared methyl cellulose derivative (eg, methyl cellulose containing 2.14-2.62 methyl groups per anhydroglucose ring) is described. The inventors have found that the above-mentioned materials do not increase soap deposition on natural fiber fabrics during the washing process.

However, the inventors have found a particular class of nonionic cellulose ether derivatives that not only inhibits redeposition on synthetic fibers but also enhances fabric softening by soap in natural fiber fabrics during the washing process.

According to the present invention, soaps which are at least 10% by weight C ₈ -C ₂₄ saturated or unsaturated fatty acid salts, HLB (to be described later) is 3.1-4.3, preferably 3.3-3.8 and gel point (to be described later) 58 Provided is a textile treatment composition containing 0.1 ° C.-3% by weight of a water-soluble nonionic cellulose ether-substituted derivative, which is preferably 33 ° C.-56 ° C. or less, provided that the derivative is a hydroxyalkyl group having three or more carbon atoms It does not contain, the composition is assuming that the pH of 8.0 or more when a concentration of 1% by weight in water at 25 ℃.

Whether cellulose ether substitution derivatives are useful is determined by the HLB of the material.

HLB can be calculated from the molecular structure of the material as a measure of the hydrophilic-lipophilic balance of the material.

Suitable calculation methods for emulsifiers are described in the literature (see J.T Davies, 2nd Int Congress of Surface Activity 1957, Ipp 426-439). This method is used to calculate the relative HLB for cellulose ethers by combining the Davis HLB assignments of substituents that may be substituted at the three hydroxyl sites present in the anhydroglucose ring of the polymer. The HLB value of a substituent is as follows.

Residual hydroxyl group: 1.9

Methyl: 0.825

Ethyl: 0.350

Hydroxyethyl: 1.63

Cellulose ether derivatives useful in the present invention are polymers that are water soluble at room temperature. The gel point of the polymer can be measured in several ways. Gelation points herein are measured for polymer solutions prepared by dispersing at 60/70 ° C. at 10 g / l concentration in de-ionized water and cooling to 20 ° -25 ° C. 50 ml of this solution is placed in a beaker and heated at a heating rate of about 5 ° C./min with stirring. The temperature at which the solution becomes cloudy is the gelling point of the tested cellulose ether and this temperature is measured using a Sybron / Brinkmann colorimeter at 450 nm and transmittance of 80%.

The degree of substitution (DS) of the anhydroglucose ring can be any value less than or equal to the maximum inon value of 3, provided that the HLB and gelling points of the polymer are within a desired range, but about 1.9-2.9 is preferred, and anhydrohydroglucose of cellulose is preferred. The maximum value of hydroxyl for each unit is three. The expression 'molar substitution' (MS) is also a term often used in connection with such polymers and refers to the number of hydroxyalkyl substituents per anhydroglucose ring, which may be three or more if the substituent substituting another substituent. Do.

Particularly preferred polymers are those wherein the number or weight average degree of polymerization of the average anhydroglucose units in the cellulose polymer is about 50-1,200. It is preferable to use polymers of relatively low degree of polymerization in certain product forms, such as liquids, in order to obtain a satisfactory viscosity of the product.

Several cellulose ether derivatives suitable for use in the present invention are commercially available, such as the following.

Many other cellulose ether derivatives are known in the art but have been found to be inadequate for use in the present invention. GB Patent No. 2038353B (Colgate-Palmolyb) has a gelation point of 58 ° C. tyrose MH 300 (Hoestst) and Methocel XB 8861 (dough chemical with 0.1 hydroxybutyl substituent per anhydroglucose ring) Company's product, now known as Methocel HB12M), is published in Japanese Patent Specification No. 59-6293 (Lion KK) .Crussel H (Hercules Chemical Corp. product) having an HLB of about 4.4 and a gelation point of about 69 ° C. Phosphorus Metocel K4M (Dough Chemical Company) and Natrosol 250H (Hercles Chemical Corp.) with HLB of about 6.9 are disclosed. The amount of cellulose ether derivative used in the composition according to the invention is on the order of 0.1% -3% by weight of the composition.

The term "soap" is used to include not only alkali and alkaline earth metal salts of fatty acids, but also organic salts produced by the reaction of fatty acids with organic nitrogen-containing substances such as amines and derivatives thereof. Soaps generally consist of salts or mixtures of higher fatty acids containing 10-20 carbon atoms in the molecule. Examples of suitable soaps include sodium stearate, sodium palmite, tallow, coconut oil, sodium salts of palm oil fats and stearic and / or palmitic fatty acids and / or tallow and / or coconut oil and / or palm oil fatty acids. Water-soluble alkanol amines and morpholines, such as ethanolamine, di- or tri-ethanolamine N-methylethanolamine, N-ethylethanolamine, 2-methylethanolamine and 2,2-dimethylethanolamine, 2'-pyrroli Reaction products with N-containing ring compounds such as don and its methyl derivatives.

Mixtures of sodium and potassium salts of mixed fatty acids derived from coconut oil and tallow, ie soaps such as sodium and potassium tallow and coconut soap, can also be used.

Particularly preferred are mixtures of oleate and coconit soap with a weight ratio of about 3: 1-1: 1.

The amount of soap in the composition is at least 10% by weight (calculated as the weight of the corresponding sodium soap). However, it is preferable to use soap in an amount of up to 50% by weight in order to leave room for the composition of the other components.

The composition according to the invention also contains at least one non-soap detergent active material selected from anionic, nonionic, zwitterionic and amphoteric synthetic detergent actives. Compounds suitable as such detergent actives are described fully in the literature (see, eg, "Surface Active Agent and Detergents", VOL. I and II, Schwartz, Perry and Berch).

Non-soap anionic detergent actives are usually water soluble alkali metal salts of organosulfuric acid and sulfonic acid having an alkyl group of about C ₈ -C ₂₂ .

The term alkyl is used herein to include alkyl moieties of higher acyl groups. Examples of suitable synthetic anionic detergent compounds include sodium and potassium alkyl sulfates, in particular sodium and potassium alkyl sulfates obtained by the sulfation of higher (C ₈ -C ₁₈ ) alcohols, for example produced from tallow or cornone oil; Alkyl (C ₈ -C ₂₀ ) benzene sulfonic acid sodium and potassium, in particular linear secondary alkyl (C ₁₀ -C ₁₅ ) benzene sodium sulfonate; Alkyl ethers of sodium glyceryl ethers, especially of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum: coconut oil fatty acid monoglyceride sulfuric acid and sodium sulfonate; Reaction products of sodium and potassium salts of sulfate esters of higher (C ₈ -C ₁₈ ) fatty alcohol-alkylnel oxides (especially ethylene oxide), fatty acids such as coconet fatty acids, esterified with isethionic acid and neutralized with sodium hydroxide: Sodium and potassium salts of fatty acid amides of methyltaurine; A substance induced by the reaction of alpha-olefin (C ₈ -C ₂₀ ) with sodium bisulfite or a substance induced by hydrolysis with a base to generate a random sulfonate after the reaction of paraffin with SO ₂ and Cl ₂ ; Same alkanonosulfonates; Olefin sulfonates, which refer to substances obtained by neutralizing and hydrolyzing the reaction products after the reaction of olefins (especially C ₁₀ -C ₂₀ alpha-olefins) with SO ₃ . Preferred anionic detergent compounds are sodium (C ₁₁ -C ₁₅ ) alkylbenzenesulfonate and sodium (C ₁₆ -C ₁₈ ) alkyl sulfate.

Materials used as suitable nonionic detergents are in particular reaction products of compounds having hydrophobic groups and reactive hydrogen atoms (e.g. aliphatic alcohols, acid amines or alkylphenols) with alkylene oxides (especially ethylene oxide or ethylene oxide / propylene oxide). to be.

Particularly suitable nonionic detergent compounds include alkyl (C ₆ -C ₂₂ ) phenol-ethylene oxide condensates (usually ethylene oxide 25 or less, ie 25EO or less) per molecule; Condensation products of aliphatic (C ₈ -C ₁₈ ) primary or secondary linear or branched alcohols with ethylene oxide (usually 40 EO or less); It is the product of the reaction product of propylene oxide and ethylenediamine and the condensation of ethylene oxide. Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and polyalkyl sulfoxides.

It is particularly advantageous to use mixtures of anionic and nonionic compounds in detergent compositions to impart low foaming properties. This is useful for compositions for use in automatic washing machines that do not allow foam. Amphoteric or zwitterionic detergent compounds may also be used in the compositions of the present invention but are undesirable because they are relatively expensive.

If amphoteric or zwitterionic detergent compounds are used, their amounts are usually in small amounts.

The effective amount of the non-soap detergent active material used in the composition of the present invention is generally in the range of 50% by weight or less, more preferably 40% or less, especially 30% or less of the composition, which amount is a small amount compared to the amount of soap. to be.

The composition of the present invention contains a non-soap detergency builder to enhance the detergency of the detergent active material, in particular to remove calcium hard ions from water and impart alkalinity. Builder materials include precipitated builder materials (e.g., alkali metal salts of carbonic acid, bicarbonate, boric acid, orthophosphoric acid and silicic acid), and metal ion disintegrating builder materials (e.g. pyrophosphoric acid, polyphosphoric acid, amino polyacetic acid, phytic acid, polyphosphate) Alkali metal salts of phonic acid, aminopolymethylene phosphonic acid and polycarboxylic acid), ion exchange builder materials (eg zeolites and amorphous aluminosilicates) or mixtures of these materials. Preferred builders are sodium tripolyphosphate, a mixture of this material with sodium orthophosphate, sodium carbonate, a mixture of this material with calcite as a seed, sodium citrate, zeolite and sodium nitrilotriacetic acid.

The amount of such builder material in the composition of the present invention is 80% by weight or less, preferably 20% -70% by weight, more preferably about 30% -60% by weight.

In addition to the components described above, the detergent compositions of the present invention may generally contain small amounts of conventional additives added to the textile laundry detergent composition. Such additives include auxiliary fabric softeners and the like. The inventors have found that the effect is particularly high when the fabric softener is a mixture of soap and cationic fabric softener or fatty amine. Other additives include foam accelerators (e.g., alkanol amides, in particular monoethanolamides derived from palm kernel fatty acids and coconut fatty acids), foam control agents, oxygen-releasing bleaches (e.g. sodium perborate and sodium percarbonate), Peracid bleaching precursors, chlorine-releasing bleaches (e.g. trichloroisocyanuric acid), inorganic salts (e.g. sodium sulfate), and fragrances including fluorescent deodorant flavors, enzymes (e.g. cellulase, protease and amylase) , Fungicides and coloring agents are usually added in trace amounts.

The compositions may have the form of aqueous or non-aqueous, structured or unstructured liquids, pastes, powders or bars as desired.

Detergent compositions are prepared in a manner suitable for the physical form of the components by dry-mixing, co-aggregating or dispersing them in a liquid carrier. Preferred physical forms, however, are very conveniently prepared by spray-drying at least part of the composition in the form of granules incorporating detergency builders. The cellulose ether derivative is added to the composition by dry mixing (if any, with other ingredients as additives added later) or by incorporating with other ingredients in the slurry and then spray drying.

This detergent composition is used in a conventional manner. The amount of use is suitably about 1g / l-12g / l. The washing temperature may be any temperature between room temperature (about 20 ° C.) and boiling point.

The invention will be described based on the following non-limiting examples.

Example 1-8

The cellulose ether derivatives used in this example are as follows. BermoCol CST 035 (Berrol Chemie), which has a gelation point of 35 ° C., an ethyl hydroxy derivative having a HLB of 3.40, and a hydroxy ethyl derivative; Tyroze MH 300 (product of Hohest) which is a methyl, hydroxy ethyl derivative having a gel point of 58 ° C., HLB of 4.05; Bermocol E 230 (Berrol Chemie), which has a gelation point of 63 ° C., an ethyl hydroxy having a HLB of 4.09, and a hydroxy ethyl derivative; Methocel J12MS (manufactured by Dough Chemical Company), which is a methyl, hydroxypropyl derivative having a gelation point of 62 ° C and an HLB of 3.85.

A detergent composition having the following composition was prepared. The composition was prepared by dry mixing the following components.

Note 1.Dobanol 45-7EO, an ethoxylated fatty alcohol with an average of 7 units of ethylene oxide per molecule

2. tallow soap

3. Dovan, Alkylbenzenesulfonate 113

The pH was above 8.0 when the two compositions were added to 25 ° C. water at a concentration of 1% by weight.

The composition was added to water in an amount of 5 g / l. The laundry solution thus prepared was used to wash laundry fabrics including terry towels and polyester monitors on an experimental scale facility. The hardness of the water was 24˚FH, and the wash solution to fabric ratio was about 20: 1. Washing time was performed at 50 ° C. for 15 minutes, diluted 50%, flowed for 2 minutes, and then rinsed three times for 5 minutes. The washed fabric was hung on a string and dried. After drying, the softness of the terry towel monitor was evaluated by the expert by setting it to zero for comparison and comparing the corresponding values of the monitors. Positive values indicate better softening than controls. The results are shown in the following table.

TABLE 1

Compared to the control in the above results, the cellulose ether derivative having a gelation point of less than 58 ℃ and HLB of 3.1-4.3 showed a significant softening effect, while the other cellulose ether derivative did not show a significant effect and in one case rather than the control Lagged behind.

Example 9-12

The procedure of Examples 1-8 was repeated using the following composition.

The following table shows the results obtained when the amounts of cellulose ether derivatives were varied.

TABLE 2

The results demonstrate that there is an appropriate amount of salose ether derivative that exhibits the best softening properties and that addition of the derivative material above that amount does not improve the softening properties any more.

Example 10-13

Dobanol 45-9EO (the same material except containing an average of 9 units of ethylene oxide per molecule) was used instead of dobanol 45-7EO in Composition C and 2.0% of Dovan 113 was added. the results are as follow.

TABLE 3

The results show that the softening effect of the present invention does not depend greatly on the presence of non-soap anionic detergent active materials. In addition, when comparing these results with the results of Table 2, it is clear that any kind of nonionic detergent active material used can obtain a significant effect from the present invention.

Example 14-17

The procedure of Example 10-13 was repeated except that tallow soap was used instead of curing tallow soap. the results are as follow.

TABLE 4

Example 18-21

A slurry of predetermined ingredients except sodium perborate was spray dried to form a basic powder, and then sodium perborate was added thereto to prepare an alkaline composition having the following composition.

The composition was tested according to the method of Examples 1-8 by adding Bermochol CST035 and cured tallow dimethylamine to the composition. the results are as follow.

TABLE 5

The results show that a secondary benefit is obtained by adding the auxiliary fabric softener to the composition.

Example 22-25

The slurry of the following components except sodium tripolyphosphate and sodium perborate was spray cooled to form a basic powder, and then the remaining components were added thereto.

Bermo was added to the composition in varying amounts of CST 035 and the composition was tested according to the method of Examples 1-8 except that the concentration of the composition was used at the level of 6 g / L.

TABLE 6

The results show that there is an advantage of the present invention even without the addition of a non-soap detergent active material.

[Example 26-33]

A liquid composition with the following composition was prepared.

The liquid composition was prepared by mixing a co-melt of oleic acid and lauric acid with an aqueous / ethanol solution of EDTA, potassium hydroxide and potassium chloride at 60 ° C. After cooling the liquid composition, the desired amount of cellulose ether derivative was added.

Different amounts of cellulose ether derivatives were added to the composition, followed by the method described in Examples 1-8, except that the amount of the composition used and the hardness of the water were changed. Details are as follows.

TABLE 7

From the above results, it can be seen that, when compared under the same conditions, vermicol CST 035 always has a higher softening value than other cellulose ether derivatives.

In addition, a good result can be obtained by using a modified composition by adding 2% coconet ethanolamide or 2% dobanol 45-7EO to the composition G.

Example 34-39

Soap and soap mixtures were added differently and the methods of Examples 9-12 were repeated using 1% or 3% Bermochol CST 035.

The results for softening are as follows.

TABLE 8

The results show the advantage of using an oleate / coconit soap mixture, in particular when adding a higher amount of 3% cellulose ether derivative and using the soap mixture.

Example 40-45

The method of Example 1-4 was repeated using Composition A by adding 3% Bermochol CST 035 and adding various other soaps and soap mixtures.

The softening results are as follows.

The results show the advantage of using an oleate / coconet soap mixture.

Claims (7)

(i) at least 10% by weight of a soap that is a C ₈ -C ₂₄ saturated or unsaturated fatty acid; (ii) a nonionic having an HLB (described herein) of 3.1-3.8 and a gel point (described herein) of 58 ° C. or less; A fabric treating composition containing 0.1% -3% by weight of the substituted derivative which does not contain a hydroxy alkyl group having three or more carbon atoms as the cellulose ether substituted derivative, wherein the composition is water at a concentration of 1% by weight at 25 ° C. When added to the pH of the fabric treatment composition, characterized in that more than 8.0. The textile treatment composition of claim 1, further comprising up to 50% by weight of a non-soap detergent active material. 3. A textile treatment composition according to claim 2, wherein the non-soap detergent active material is contained in an amount less than the amount of soap. The fabric treatment composition of claim 1, further comprising an auxiliary fabric softener selected from cationic fabric softeners, fatty amines, fabric softening clays and derivatives thereof and mixtures of these materials. The composition of claim 1, wherein the cellulose ether derivative has an LHB (described herein) of 3.3-3.8. The fabric treatment composition of claim 1, wherein the cellulose ether derivative has a gel point (described herein) of 33 ° C-56 ° C. (i) at least 10% by weight of a soap that is a C ₈ -C ₂₄ saturated or unsaturated fatty acid; (ii) a nonionic having an HLB (described herein) of 3.1-3.8 and a gel point (described herein) of 58 ° C. or less; Contacting the fabric with a wash solution having a pH of at least 8.0 which is produced by adding to the water a composition containing 0.1% -3% by weight of said substituted derivative which does not contain a hydroxy alkyl group having at least 3 carbon atoms as a cellulose ether substituted derivative. Fabric washing method comprising a.