EP1045022A1 - Use of gelatine in washing agents - Google Patents

Abstract

The use of gelatin as graying inhibitor in laundry detergents is claimed. An Independent claim is also included for capsules with a wall of gelatin and filling of laundry detergent containing fatty alcohol-(12-14 carbon) polyethylene glycol (2EO) ether sulfate monoisopropanolammonium salt.

Description

The present invention relates to the use of gelatin in detergents.

Detergents and cleaning agents are subject to contradictory delivery forms Requirements: On the one hand there is a desire to use detergents or cleaning agents in offer as concentrated a form as possible to avoid packaging material and energy costs save. On the other hand, the handling and dosing of the The more concentrated the detergents are, the more difficult detergents or cleaning agents are. Not only an underdosing but also an overdosing leads especially in the case of highly concentrated ones Detergents for unsatisfactory washing results. An exact one Dosage requires a measurement in the milliliter and gram range. This is e.g. in the Everyday operation of a household is not practical and would also depend on the substance Tools such as Scales, and protective devices (against toxic, allergic Effect of surfactants at high concentrations). The increasing viscosity of liquid detergents with increasing concentration also causes considerable Detergent residues in the dosing device of the washing machine.

These problems are solved in the prior art by encapsulating the detergents solved. The encapsulation is done by water-soluble or water-dispersible polymeric substances such as Gelatin, gum arabic, alginates etc. Detergents or cleaning agents enclosed in gelatin capsules and together with these added to the washing or cleaning process are in various Described documents, such. B. in US 3,528, 925, US 4,597,885, EP 261 754, DE 43 01 358, EP 339 707 and WO 95/28182. The capsule shells dissolve and disintegrate during the washing process through contact with water, whereby the dosed capsule contains is released in the washing drum.

In recent years, the development has focused on the construction of dishwashers and washing machines For reasons of environmental protection also on a water and energy reduction during the washing and rinsing processes. While the detergent removes dirt If water saving programs remain unchanged, the inevitably increased Dirt load in the wash liquor to a noticeable graying of the fabric.

Under the term "graying" is the gray color of textiles when washing or understood during dry cleaning, which is due to a re-opening of already detached dirt is caused on the tissue in finer distribution. The re-opening is probably triggered by electrostatic forces (Römpp chemical lexicon, Ed. J. Falbe, M. Regiz, Georg Thieme Verlag, Stuttgart, 9th edition, 1992, Page 4,895). The extent of the reattachment depends, among other things, on tissue and type of dirt, the degree of contamination of the fabric, the amount of water in the Washing process and the degree of mechanical movement in the washing drum.

Detergents contain washing agents, the so-called graying inhibitors, which in the essentially prevent the dirt detached from the fiber from the fleet again on the fiber. For this purpose, mainly cellulose derivatives, especially carboxymethyl cellulose, used.

Gelatin is a polypeptide with a molecular weight in the range of approximately 15,000 to 250,000 g / mol. Gelatin is mainly produced by hydrolysis of the skin and bones Collagen obtained under acidic or alkaline conditions. Under standard conditions at 25 ° C and 1 bar gelatin in water is essentially in a helical conformation in front.

It is known from various studies that surfactants influence the helical order of gelatin ' change ("Influence of surfactants on the helical conformation of gelatin", R. Hüttenrauch, S Fricke, P. Zielke, Pharmazie 40, H. 1, 1985; Pp. 56-57; "Interaction of Sodium N - Methyl N -oloyl taurine with gelatin ", B.H. Tavernier, Journal of Coloid and Interface Sience Vol. 93, No. 2, June 1983, pp. 419 - 423). In particular, the ionogenic Character of the cationic and anionic surfactants discontinuities of the helical Conformation of the gelatin. Most of all is from the anionic surfactants Known to be a surfactant-protein complex with the cationic groups of gelatin form, which is responsible for the conformational change of the polypeptide shows. However, complex formation was also observed with cationic surfactants.

It has now surprisingly been found that the gelatin structure in particular under because the influence of surfactants at 40 ° C is changed in such a way that the gelatin is particularly advantageous as a graying inhibitor in detergents. The term "graying indicator is primarily intended to describe and is the function of gelatin in the washing process not to be understood as a quantitative statement about the degree of whiteness achieved. The gelatin causes a reduction in the graying visible to the human eye, ever after the interaction of the influencing factors already described completely prevents graying.

Without depending on the exact structure of the conformation caused by the surfactants Wanting to set gelatin is believed to be the original helical Structure of the gelatin in the direction of a disordered ball of surfactant-gelatin complex is moved. On the one hand, this changed structure is ensured by its spatial or tertiary structure for inclusion of the emulsified or the suspended Dirt. On the other hand, the dirt particles through the primary and secondary structure of the complex (electrostatic and intermolecular interactions) in the wash liquor is held, which also causes the dirt to be re-absorbed on the Tissue is reduced. Failure of the gelatin or the "gelatin-dirt-surfactant associate" has so far not been observed to a large extent, what the removal of the "associate" relieved by rinsing.

Detergents are those that are required when washing textile products, in the form of Pieces, powders, pastes or liquids available commercially available tools that are generally used in mechanically vigorous aqueous solutions. Detergents always contain surfactants that, depending on the intended use, with other substances be combined. These are usually builders, bleaching components, optical Brighteners, enzymes, stabilizers, perfumes, dyes, adjusting agents and others Auxiliaries such as Corrosion and foam inhibitors. The individual detergent ingredients are described in numerous publications. To define the terms, in connection with the present invention, on Römpp Chemielexikon, Hersg. J. Falbe, M. Regitz, Georg Tieme Verlag, 9th edition, Stuttgart.

The term surfactants should be understood to mean all substances that have the ability reduce the interfacial tension. Surfactants have a characteristic Structure from at least one hydrophilic and at least one hydrophobic Group. Commercial surfactants can be divided into four groups: anionic surfactants, Cationic surfactants, nonionic surfactants (nonionic surfactants) and amphoteric surfactants. As a general rule gelatin is suitable in combination with all four groups of surfactants as a graying inhibitor. However, particularly advantageous results are obtained in combination with anionic surfactants achieved.

Anionic surfactants generally have carboxylate, sulfate or functional groups Sulfonate groups that are present in the dissociated form at the appropriate pH.

In a preferred embodiment of the present invention, the detergent is encapsulated. The gelatin can act as a graying inhibitor as part of the detergent are present, and is therefore part of the capsule ingredient.

In a particularly advantageous embodiment, however, the capsule shell is essentially made from gelatin. In this embodiment, the gelatin thus fulfills at the same time two functions. First, it acts as a graying inhibitor during the Washing process, on the other hand, as capsule shell material, it is environmentally friendly Disposable packaging for detergents with all the advantages already described.

The capsules are those with a one-piece capsule shell (soft gelatin capsules) if the Capsule ingredient is liquid or pasty. Is the capsule content solid, in the form of powders, Granules or tablets, so two-part capsule shells (hard gelatin capsules) be used. Solid, but free-flowing (powder, granules) detergents are can also be encapsulated in one-piece capsule shells. Be advantageous for the present Invention detergent encapsulated in one-piece capsule shells, in particular by means of Rotary die processes are made.

In the embodiment as a capsule shell, the large surface area (diameter = 0.5-5 cm, surface area = 3-300 cm ² ) ensures that the gelatin dissolves in water within 2-5 pure at 60 ° C. and thus enables rapid interaction with the surfactants . The effect as a graying inhibitor also occurs to the full extent for the gelatin in the machine wash programs. The amount of detergent required for a wash cycle can be in a single "large" capsule shell. An advantageous embodiment, however, is the division of the required amount of detergent into at least two capsules, the capsule volume of which is then naturally smaller. The division of the amount of detergent into at least two capsules with the same capsule shell thickness has an advantageous effect on (1.) the stability of the capsules and (2.) advantageously on the surface volume ratio (with regard to the function of the gelatin as a graying inhibitor).

The amount of gelatin per kg dry weight of the textiles Dirt to a noticeable extent should generally be at least 150mg / kg Dry weight, tissue, preferably 200 mg / kg dry weight tissue and even more preferred at least 300 mg / kg dry weight, tissue. Obtain this information gelatin with a water content between 9 and 11 % By weight based on the total weight of the gelatin.

In addition to the absolute amount of gelatin, there is also the weight ratio for a good washing result Gelatin decisive for surfactants. The amount of gelatin is in a range from 1 to 40 percent by weight of the surfactant weight of the detergent, that's it Ratio of weight gelatin: surfactant depending on the given conditions such as e.g. the degree of contamination and the type of dirt in a range from 1: 2 to 1: 100.

The invention is not intended to be limited to spherical capsules. Under the term "Capsule" should include all technically feasible designs, such as elliptical or figural designs of the capsule.

In any case, the amount of gelatin present in the capsule results from the film thickness and gelatin content the mass forming the capsule shell (initial mass), and the dimensions of the capsule body in x, y, and z axis. To ensure the stability of the rotary die Process manufactured capsule shell especially with large ball diameter so far support as possible, the volume of the ball is almost filled with washing or cleaning agents. In addition, hygroscopic agents can be added to the ingredient caused by the effect of "inflating" the ingredient by ingestion of humidity through the capsule shell after encapsulation and welding for increased Ensure stability against mechanical stress.

The thickness of the capsule shell is primarily limited by the encapsulation technique. The washing capsules are advantageously produced by means of the rotary die process. This Process allows film thicknesses up to 2mm, preferably up to 1mm and more preferably up to 0.8mm. The size of the capsules depends, among other things, on the shape Tool (see Die Kapsel, Hersg. W. Fabrig, U.Hofer, Wissenschaftliche Verlagsgesellschaft mbH, Stuttgart, 1983).

Depending on the ingredient, the washing capsules are also known by means of others Methods such as Injection molding, extrusion, etc. manufactured.

When used as a capsule shell, the gelatin is characterized by bloom numbers from 100-250. It can come from beef, pork or fish. The molecular weight of the gelatin used as a graying inhibitor is in a range between 10 ² to 10 ⁸ g / mol.

The capsule shell also contains plasticizers from the group of polyhydric alcohols, such as. Glycerin, sorbitol, etc. but also polyglycols and polyglycerols in one Range from 10 to 30% by weight based on the weight of the capsule shell compositions. The plasticizer content of the capsule shell material is determined first Production line.

The capsule shell or the detergent can also be native and / or physical and / or chemically modified macromolecular natural products and / or synthetic polymers be added. This classification includes starches, cellulose, Galactomannans, alginates, casein, etc. Among the suitable synthetic polymers include primarily water-soluble and -dispersible polyvinyl alcohols and Polyacrylates.

In the embodiment, the gelatin becomes one or more of these substances as a capsule shell added, so the film thickness or the diameter of the capsule or the number increase the capsules per wash cycle compared to capsules without the relevant additive, if the added substances are not themselves effective as graying inhibitors. The addition of the amount of gelatin required to prevent graying will occur thereby guaranteed. The absolute amount of gelatin can be tissue per kg dry weight per capsule, as long as the gelatin: surfactant ratio does not exceed or fall below becomes.

Carboxymethyl cellulose or other cellulose derivatives can be from 0.1 to 10% by weight. based on the weight of the gelatin or based on the surfactant of the capsule shell composition be added.

In cases where gelatin is encapsulated with the other detergent ingredients the capsule shell can also be made entirely of said macromolecular natural substances or synthetic polymers exist. However, these substances must meet the requirements disintegration in water at the required washing temperatures is sufficient.

The surprising use of gelatin as a graying inhibitor is illustrated the following examples are illustrated.

Carrying out the experiments:

A test tissue contaminated with test dirt is washed together with an untreated one Fabrics of the same size and quality at 80 ° C in a standardized washing process undergoes: After completion of five stirring cycles of three minutes each discard the washing solution (400ml) and with the same amount of tap water (composition: 9533 Kirchberg, Switzerland, 1999) without stirring. After that the test fabrics are dried and subjected to a visual assessment.

Testgewebe (6x6cm):

l. Baumwollgewebe, weiss;

II. Sythetikgewebe, weiss

Testschmutz:

Ketchup : Mayonnaise : Eigelb : Kristallviolett im Verhältnis 4 : 1 : 0.75 : 1 auf 3.2 Teile Wasser

Two different test fabrics were tested in three different detergent compositions (test solutions).

Test fabric (6x6cm):

l. Cotton fabric, white;

II. Synthetic fabric, white

Test dirt:

Ketchup: mayonnaise: egg yolk: crystal violet in a ratio of 4: 1: 0.75: 1 to 3.2 parts of water

Testbeschmutzung:

2 ml Testschmutz wurden in einem definierten Bereich auf das Testgewebe aufgetragen und über Nacht bei 60°C getrocknet. Waschmittellösungen (Prüflösung) [alle Werte als Gewichts.-%] Prüflösung 1 Prüflösung 2 Prüflösung 3 1,25% Fettalkohol-(C₁₂-C₁₄)polyethylenglycol-(2EO)ethersulfatmonoisopropanolammoniumsalz 1,25% Fettalkohol- (C₁₂-C₁₄)polyethylenglycol-(2EO)ethersulfatmonoisopropanolammoniumsalz 1,25% Fettalkohol- (C₁₂-C₁₁)polyethylenglycol-(2EO)ethersulfatmonoisopropanolammoniumsalz 1,25% Gelatine 1,25% CMC 98,75%, Leitungswasser 97,5% Leitungswasser 97,5% Leitungswasser = 100% = 100% = 100%

The components were freshly prepared in a fixed ratio before the start of the experiment

Test soiling:

2 ml of test dirt was applied to the test fabric in a defined area and dried overnight at 60 ° C. Detergent solutions (test solution) [all values as% by weight] Test solution 1 Test solution 2 Test solution 3 1.25% fatty alcohol (C ₁₂ -C ₁₄ ) polyethylene glycol (2EO) ether sulfate monoisopropanol ammonium salt 1.25% fatty alcohol (C ₁₂ -C ₁₄ ) polyethylene glycol (2EO) ether sulfate monoisopropanol ammonium salt 1.25% fatty alcohol (C ₁₂ -C ₁₁ ) polyethylene glycol (2EO) ether sulfate monoisopropanol ammonium salt 1.25% gelatin 1.25% CMC 98.75%, tap water 97.5% tap water 97.5% tap water = 100% = 100% = 100%

Results:

The soiled synthetic rifle (II) is very good from all three test solutions at 80 ° C cleaned. The untreated fabric added to the wash cycle takes away the dirt not at. After drying is between the previously soiled fabric and the untreated Tissue no discernible color difference.

• Das unbehandelte Gewebe aus Prüflösung 1 hat erkennbar Schmutz angenommen und ist zudem rötlich gefärbt.
• Die unbehandelten Gewebe aus Prüflösung 2 und 3 zeigen keine wesentlichen Verfärbung. Auch zog der fetthaltige Schmutz nicht im visuell erkennbaren Rahmen auf das Gewebe auf.

The cotton fabrics (I) contaminated with test dirt are only insufficiently cleaned of all test solutions at 80 ° C. After the treatment has been completed, all fabrics have distinctive stains which are classified as equivalent by the color intensity. However, the untreated fabrics added to the washing cycle show clear differences depending on the test solution:

• The untreated fabric from test solution 1 has evidently taken on dirt and is also colored reddish.
• The untreated fabrics from test solution 2 and 3 show no significant discoloration. The greasy dirt did not appear on the fabric in a visually recognizable frame.

Prüflösung 1:

4;

Prüflösung 2:

10;

Prüflösung 3:

10.

A classification of the gelatin in comparison to CMC and test solution 1 shows the following assessment (scale 1 = bad; 10 = very good)

Test solution 1:

4;

Test solution 2:

10;

Test solution 3:

10th

The same experiments were repeated at a wash liquor temperature of 50 ° C. Again, Test Solution 2 and Test Solution 3 gave the same results in terms on the untreated test fabrics (II) added to the washing cycles. Neither the fatty one the intensely colored test dirt also appeared on a visually noticeable scale the tissue on.

Alternatively, fatty alcohol (C ₁₂ -C ₁₄ ) polyethylene glycol (2EO) ether sulfate monoisopropanolammonium salt was encapsulated by means of the rotary die process, the ratio of gelatin (in capsule shell to surfactant as capsule filling) correspondingly being 3:30 g. With a gelatin content of 8 - 15% by weight based on the total weight of the capsule shell ((starting material) and a film thickness of 0.1 - 2 mm, this results in a diameter of 4 - 4.5 cm.

Fatty alcohol (C ₁₂ -C ₁₄ ) polyethylene glycol (2EO) ether sulfate monoisopropanol ammonium salt is particularly well suited for encapsulation using the rotary die process, since it can be encapsulated directly without further preparation steps. The test results were almost identical to the tests with test solution 2. Test solution 4: Lauryl alcohol polyethylene glycol - (2EO) ether sulfate monoisopropanolamine 50% Fatty alcohol ethoxylate (4EO) 15% (Merlipal 24/40) ethanolamine 15% Coconut palm kernel acid 8th% PEG 200 10% Perfume 2%

1. 45% Gelatine, 20% Weichmacher, Rest Sonstige; absolute Gelatinemenge von 2.2 g.

2. 45% Gelatine. 5% Stärke, 20% Weichmacher. Rest Sonstige: absolute Gelatinemenge von 2.2 g.

The test solution 4 was encapsulated with a capsule shell material consisting of

1. 45% gelatin, 20% plasticizer, the rest other; absolute amount of gelatin of 2.2 g.

2. 45% gelatin. 5% starch, 20% plasticizer. Rest of others: absolute amount of gelatin of 2.2 g.

With regard to the graying inhibitor effect, the capsules according to 1 and 2 showed the same results.

Claims (11)

Use of gelatin as a graying inhibitor in detergents. Use of gelatin according to claim 1, characterized in that the Detergent is enclosed in a capsule shell. Use of gelatin according to claim 1 or 2, characterized in that the capsule shell contains gelatin. Use of gelatin according to one of claims 1 to 3, characterized in that that the gelatin is present in a range of 1 to 40% by weight on the surfactant weight of the detergent. Use of gelatin according to one of Claims 3 or 4, characterized in that that the thickness of the capsule shell is in a range from 0.1 to 2 mm. Use of the gelatin according to one of claims 3 to 5, characterized in that that the ball diameter of the capsule is at least 1 cm. Use of gelatin according to one of claims 1 to 6, characterized in that the detergent composition contains anionic surfactants, in particular fatty alcohol (C ₁₂ -C ₁₄ ) polyethylene glycol (2EO) ether sulfate monoisopropanol ammonium salt. Use of gelatin according to one of claims 1 to 7, characterized in that the gelatin comes from beef, pork or fish with a molecular weight in a range between 10 ² to 10 ⁸ daltons. Use of gelatin according to one of claims 1 to 8, characterized in that selected that the capsule shell contains other macromolecular substances from the group consisting of native starches, chemically and / or modified Starches, chemically modified cellulose, native galactomannans, chemically and / or physically modified galactomannans, alginates, casein, Polyvinyl alcohols and polyacrylates and auxiliaries. Use of gelatin according to one of claims 1 to 9, characterized in that that the capsule shell plasticizer from the group of mono, di or contains polyfunctional alcohols. Capsule with a capsule shell made of gelatin and a capsule filling consisting of a detergent which contains fatty alcohol (C ₁₂ -C ₁₄ ) polyethylene glycol (2EO) ether sulfate monoisopropanol ammonium salt.