JPH06192690A - Detergent composition containing polyimide biopolymer hydrolyzable in cleaning medium - Google Patents

Abstract

PURPOSE: To improve detergency by blending a polyimide biopolymer or its derivative which has a specified amount of COO^- electric charge density per a unit weight of the polymer and which can increase its COO^- electric charge density in a washing medium.

CONSTITUTION: Asparatic acid and/or glutamic acid or precursors thereof are polycondensed to prepare a polyimide biopolymer which has a weight average mol.wt. of about 300-10⁷ and COO^- electric charge density of ≥5×10^-4 mole per 1 g of the polymer and which can increase its COO^- electric charge density in a washing medium. Then, each components of a detergent are blended in specified proportions to obtain a detergent compsn. having superior washing ability which comprises 0.2-80 wt.% (hereinafter referred to %) of the polyimide biopolymer, totally 0.2-80% of builders such as phosphate and zeolite, <25% of a corrosion inhibitor such as silicate, <30% of a bleach such as perborate, <5% of a methyl cellulose type re-adhesion inhibitor, <10% of a washing scale inhibitor such as acrylic acid-maleic anhydride copolymer and 2-50% of a surfactant etc.

COPYRIGHT: (C)1994,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to detergent compositions containing polyimide biopolymers capable of generating at least partially biodegradable polypeptide builders when hydrolyzed in a wash medium and compositions thereof. To the field of detergent power.

According to the invention, a builder is to be understood as meaning any ingredient which improves the performance of surfactants in detergent compositions. Generally speaking, the activity of this builder in the washing medium is manifested in the following aspects. -It allows the removal of undesired ions, especially alkaline earth metal (calcium, magnesium) ions, by sequestration or precipitation to prevent the precipitation of anionic surfactants. -It allows the preservation of alkalinity and ionic concentration. -It holds the extracted dirt in suspension. -It prevents the formation of inorganic laundry scales in the laundry which are observed during washing.

[0003]

BACKGROUND OF THE INVENTION For a very long time, tripolyphosphate has been the most frequently used builder in detergent compositions and cleaning substances. But because of their ecological constraints,
These alternatives are currently being sought after. To this end, zeolites and copolymers of acrylic acid with maleic anhydride have already been proposed. Unfortunately, zeolite alone cannot be a substitute for tripolyphosphate. They have to enhance their action by other additives. Especially with regard to copolymers of acrylic acid and maleic anhydride (or their alkali metal or ammonium salts) intended for use as laundry anti-scaling agents (European Patent No. 25551).
They have the disadvantage of not being biodegradable in their natural environment. Recently, the Applicant has proposed a detergent composition which simultaneously has the excellent properties of primary and secondary detergency and the ability to generate at least partially biodegradable builders when hydrolyzed in a washing medium. (EP Patent Application No. 92
400875.8). The detergent composition has, as an ingredient, a COO ^- charge density which is between 0 and 5 x ^10-4 mol / g polymer and in the wash bath is equal to at least ^10-3 mol / g polymer COO ^- charge density. It is characterized by using a polyimide biopolymer capable of providing

[0004]

SUMMARY OF THE INVENTION In particular, the present invention provides a detergent composition wherein one of the components is at least one polyimide biopolymer or one of its derivatives, wherein the component is more than 5 × 10 ^-4 mol / g polymer. It relates to a detergent composition which is characterized by having a high COO ^- charge density and by being able to increase this COO ^- charge density in the wash bath. The detergent compositions that are the subject of this invention advantageously produce at least partially biodegradable builders upon hydrolysis of the polyimide biopolymer in the wash bath. According to a preferred embodiment of the invention, the initial COO ^- charge density of the polyimide biopolymer or its derivatives is not more than 2 x 10 ^-3 mol / g polymer.

By detergent composition is meant according to the invention a laundry washing substance, a dishwashing washing substance or any other washing substance for household use. “Washing bath” or “washing medium” is understood to mean an aqueous solution of the washing substance (detergent composition) present in the washing machine during the washing cycle. The amount of cleaning material present is as recommended by the manufacturer. It is generally below 20 g / l. The pH of such a solution is 9 or higher.

Examples of polyimide biopolymers having a COO ⁻ charge density and which can be used according to the invention are derived from the polycondensation of aminodiacids, in particular aspartic acid or glutamic acid or precursors of these aminodiacids. An example is a polyimide that is used. These polymers dissolve in water at basic pH to form free COO ^-1 functional groups. These polymers are homopolymers derived from aspartic acid or glutamic acid,
Or a copolymer derived from aspartic acid and glutamic acid in any proportion or derived from aspartic acid and / or glutamic acid and other amino acids (for example up to 15% by weight, preferably up to 5% by weight of other amino acids). May be a copolymer. Examples of the copolymerizable amino acid include glycine, alanine, valine, leucine, isoleucine, phenylalanine, methionine, tryptophan, histidine, proline, lysine, arginine, serine, threonine and cysteine. The polyimide biopolymer of the present invention or a derivative thereof is about 300 to 10 ⁷ , generally 500
It can have a weight average molecular weight of about 60,000. These biopolymers, as well as polyimides derived from aspartic acid or glutamic acid, are described in J.
A. C. S. , 80 , 3361 (1958); Me
d. Chem. , 16 , 893 (1973); Poly
Mer, 23 , 1237 (1982) or US Pat.
As described in No. 052655, it can be produced by heat condensation of an amino acid in a substantially anhydrous medium. .

Also, the COO ^-- required according to the present invention.
The charge density can be met by using a partially hydrolyzed polyimide biopolymer. The availability of these compounds (also referred to as the term "polyimide derivatives") can be achieved, inter alia, by controlling the opening of at least one of the imide rings of the polyimide backbone to form a carbochelate group. . The amount of polyimide biopolymer incorporated into the detergent composition which is the subject of the present invention may be between 0.2 and 80% by weight, preferably between 2 and 5% by weight of the detergent composition. In the detergent composition, in addition to the polyimide biopolymer or its derivative, a surfactant is contained in an amount of 2 to 50% by weight of the detergent composition.
%, Preferably present in an amount which may be between 6 and 30%.

The surfactants which may be incorporated into the detergent composition which is the subject of the present invention include: Alkali metals and soaps (alkali metal salts of C ₈ -C ₂₄ fatty acids), alkali metal sulfonates (C ₈ -C ₁₆ alkylbenzene sulfonates, C ₁₂ -C ₁₆ alkyl sulfonates, oxyethylenated - sulfation C ₆ -C ₁₆
Fatty acids, oxyethylenated - sulfated C ₈ -C ₁₃ alkylphenol), the type of anionic surfactant comprises an alkali metal sulfosuccinate (C ₁₂ -C ₁₆ alkyl sulfosuccinate), and the like, poly oxyethylenated C ₆ -C ₁₂ alkylphenols, oxyethylenated C ₈ -C ₂₂ aliphatic alcohols, ethylene oxide - propylene oxide block copolymers, optionally nonionic types including polyoxyethylenated carboxylic acid amide Alkyl dimethyl betaine type amphoteric surfactant, Alkyl trimethyl ammonium chloride or alkyl dimethyl ammonium bromide type cationic surfactant. Further, various ingredients may be present in the detergent composition of the present invention to provide the cleaning or cleaning material in powder form.

Thus, the following ingredients can be present in the detergent composition of the present invention. (i) Builders of the following types: -Phosphate in a proportion of up to 25% of the total formulation weight-Zeolites up to about 40% of the total formulation weight-Sodium carbonate up to about 80% of the total formulation weight, -Nitriloacetic acid up to about 10% of the total formulation weight-Citric acid, tartaric acid up to about 20% of the total formulation weight. The total amount of builders (polyimide precursor of builders + other builders) is about 0.2-80% of the total weight of the detergent composition,
It preferably corresponds to 20 to 45%. (ii) Corrosion inhibitors such as silicates, up to about 25% of the total weight of the detergent composition. (iii) Perborate, chloroisocyanate or N, N, N '
, N'-tetraacetylethylenediamine (TAE
D) type bleach, up to about 30% of the total weight of the detergent composition. (iv) Carboxymethylcellulose or methylcellulose type anti-redeposition agent, an amount which may be up to about 5% of the total weight of the detergent composition. (v) An anti-wash agent of the type comprising a copolymer of acrylic acid and maleic anhydride, an amount which may be up to about 10% of the total weight of the detergent composition. (vi) Sodium sulphate type fillers for powder detergents, amounts which may be up to about 50% of the total weight of the detergent composition.

The present invention also relates to the use of the above polyimide biopolymers in powdered detergent compositions. The detergent compositions which are the subject of the present invention have good efficiencies in both primary and secondary detergency. further,
The composition of polyimide that can be hydrolyzed only in the cleaning medium,
It ensures that the detergent composition has greater storage stability than compositions that directly contain biodegradable polypeptides.

[0011]

EXAMPLES The following examples and the accompanying FIG. 1 illustrate the invention and should not be considered as limiting it. The accompanying FIG. 1 shows the change in the amount of calcium carbonate precipitate with polymer concentration.

Example 1 Preparation of a low molecular weight polysuccinimide 450 g of anhydrous ammonium maleate are cast on an unrimmed rectangular stainless steel tray over an area of about 95 cm ² . Place the tray in a "THERMOSI SR2000" (R) airless ventilation oven preheated to 230 <0> C. After reacting for 2 hours, the extract content was calculated to be 1.64% (w / w). A powder was recovered which had a number average molecular weight Mn of 900 (0.
Polysuccinimide (IR spectroscopy) equal to (by viscometrics in 5N NaOH).

Example 2 Formulation of a detergent composition for cleaning in a roundy using the polysuccinimide of Example 1 Various additives were introduced into the powder prepared in Example 1 by dry mixing to obtain the following detergent composition (for cleaning). Substance).

[0014]

[Table 1] The term "control cleaning material" is used to mean a cleaning material of the above composition but containing no polysuccinimide. The performance of this cleaning material was tested and is described in detail in the examples below.

Example 3 This example demonstrates the calcium ion sequestering ability of the polysuccinimide of Example 1 after in situ hydrolysis to polyaspartic acid in basic medium. Calcium ion sequestration ability is measured using an electrode with a calcium ion permeable selective membrane. First, pH 10.5 containing 3 g / l sodium chloride
100 ml of the solution was used to plot a calibration curve, then to this solution an amount of calcium ions between 10 ^{−5 and} 3 × 10 ⁻³ mol / l was added and a function of the free Ca ²⁺ ion concentration. Plot the curve representing the potential applied by the electrode as. The polysuccinimide of Example 1 is hydrolyzed with concentrated sodium hydroxide solution until a pH 10.5 solution containing 20% by weight of sodium polyaspartate is obtained. The resulting solution is called "hydrolyzate". This solution is diluted until 100 g of an aqueous solution containing 10 g / l sodium polyaspartate are obtained. The pH is adjusted to 10.5 with concentrated sodium hydroxide solution. 0.3 g of powdered sodium chloride is added.
In addition, calcium ions are ^added at 10 ^{-5 to} 3 × 10 ^-3 mol / l
[Ca ²⁺ ] release / [Ca ²⁺ binding] =
Plot f ([Ca ²⁺ ] free). In this way, the following parameters are determined.・ Calcium ion complexation constant K of polymer ・ The following formula

[Equation 1] So the number of complexing sites on the polymer defined by According to this evaluation method, the polyaspartic acid obtained by hydrolyzing the polysuccinimide of Example 1 was 1 g of the polymer.
It was found to have 2.6 × 10 ⁻³ complexing sites per unit and its affinity was log K = 3.6.

Example 4 This example demonstrates the calcium carbonate dispersancy of the polysuccinimide of Example 1 after in situ hydrolysis to polyaspartic acid in basic medium. PH 10.5 (NaOH) containing 3 g / l NaCl, 3 × 10 ⁻³ mol / l CaCl ₂ and various concentrations of hydrolysates in a 100 cm ³ measuring cylinder (height 26 cm, diameter 3 cm). 2g in 100ml of aqueous solution
Disperse the precipitated calcium carbonate. The amount of sediment cm ³ is measured after 10 minutes and the curve representing the amount of sediment as a function of the polymer concentration ppm (expressed as dry matter) is plotted. The attached FIG. 1 shows first the agglomeration phenomenon (the particles are coated with the polymer too low) and then the restabilization phenomenon. The stabilizing ability of this inorganic particle is particularly beneficial. The reason for this is that it is known that the inorganic particles are responsible for the phenomenon of scale formation caused by the deposits deposited on the cotton.

EXAMPLE 5 This example demonstrates the ability of the polysuccinimide of Example 1 to prevent crystallization of calcium carbonate after in situ hydrolysis to polyaspartic acid in basic medium. The property of this substance to prevent crystallization of calcium carbonate is Z. LANGMUI by AMJAD
R, 1987, 3 , 224-228. The measurement was carried out in a temperature-controlled closed cell with 10 ⁻³ mol / l sodium bicarbonate and 2 × 10 ^−3.
Supersaturated aqueous solution containing 1 mol / l calcium chloride (p
H = 8.6) and 5 g / l of synthetic calcium carbonate (specific surface area = 80 m ² / g; theoretical diameter = 20 nm) are added to this solution. 500 as produced in Example 3
The decrease in the crystallization rate of the calcium carbonate obtained upon addition of ppm of hydrolyzate (expressed as dry substance) is measured. The results obtained are shown in Table 2 below.

[Table 2]

Example 6 Effect of Anti-Washing Agent This effect was achieved by the following test results for unsoiled test pieces, test woven fabric 405 cotton fabric (4) and Krefeld 12A cotton (8) in the absence of soiled fabric. It was measured after washing twice. The mineral laundry scale is calculated from the ash content (% of the total weight of cotton) of the washed and dried fabrics burned at 950 ° C. for 3 hours. The anti-washing effect is evaluated by the ratio of the ash content when the additive is used and the ash content when the additive is not used. The results obtained are shown in Table 3 below.

[Table 3]

[Brief description of drawings]

FIG. 1 is a graph showing changes in the amount of calcium carbonate precipitate depending on the polymer concentration.

Claims (17)

[Claims] 1. A detergent composition wherein one of the components is at least one polyimide biopolymer or one of its derivatives, wherein the component is 5 × 10 ^{−4 /} g of polymer.
Detergent composition characterized in that it has a COO ^- charge density of greater than molar and that this COO ^- charge density can be increased in the wash bath. 2. The polyimide biopolymer is polymer 1.
The detergent composition according to claim 1, having an initial charge density of not more than 2 × 10 ^-3 mol per gram. 3. A detergent composition according to claim 1 or 2 wherein the polyimide biopolymer is derived from the polycondensation of aminodiacids or aminodiacid precursors. 4. The detergent composition according to claim 1, wherein the polyimide biopolymer is derived from polycondensation of aspartic acid and / or glutamic acid or precursors of these acids. 5. The detergent composition according to any one of claims 1 to 4, wherein the polyimide biopolymer is partially hydrolyzed. 6. The polyimide biopolymer is 300 to 1
The detergent composition according to any one of claims 1 to 5, characterized in that it has a weight average molecular weight of about ^0-7. 7. The polyimide biopolymer is 500 to 6
The detergent composition according to claim 6, which has a weight average molecular weight of about 10,000. 8. The detergent composition according to claim 1, wherein the polyimide biopolymer accounts for 0.2 to 80% by weight of the detergent composition. 9. The detergent composition of claim 8, wherein the polyimide biopolymer comprises 2-5% by weight of the detergent composition. 10. The surfactant is 2 to the weight of the detergent composition.
2. It is present in an amount between 50%.
The detergent composition according to any one of 9 above. 11. A polyimide biopolymer or one of its derivatives which has a COO ⁻ charge density of greater than 5 × 10 ⁻⁴ mol / g of polymer and is capable of increasing its COO ⁻ charge density in a washing medium. , A powdered detergent composition containing an at least partially biodegradable polypeptide builder component as a substance generating in a washing medium. 12. The detergent composition of claim 11, wherein the polyimide biopolymer is derived from the polycondensation of aminodiacids or aminodiacid precursors. 13. A polyimide biopolymer derived from polycondensation of aspartic acid and / or glutamic acid or precursors of these acids.
The detergent composition according to 1 or 12. 14. The detergent composition according to claim 11, wherein the polyimide is further partially hydrolyzed. 15. The polyimide biopolymer having a molecular weight of 300 to 300 is used.
The detergent composition according to any one of claims 11 to 14, which has a weight average molecular weight of about 10 ⁷ . 16. The polyimide biopolymer is from 500 to
The detergent composition according to claim 15, having a weight average molecular weight of about 60,000. 17. The detergent composition according to claim 11, wherein the polyimide biopolymer is present in an amount of between 0.2 and 80% by weight of the powdered detergent composition.