JPH06100889A - Composition for dish washing machine - Google Patents

Abstract

PURPOSE: To provide a compsn. for a dishwasher with suppressed scale forming by blending polyamino acid.

CONSTITUTION: This phosphate-free dishwasher compsn. comprises a non- phosphate builder (such as zeolite, alkali metal citrates, alkali metal carbonates and bicarbonate) wherein the amount of the builder does not exceed 50 wt.% of the compsn. and also comprises an effective amount of a biodegradable poly-amino acid compd. of the formula: Poly (X)_n [wherein, each X is independently aspartic acid or salts thereof, glutamic acid or salts thereof, glutamine, asparagine, or mixtures thereof; and n is 3-1000].

COPYRIGHT: (C)1994,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a dishwasher composition. In particular, the invention relates to improved dishwashing compositions containing polyamino acids and free of phosphate.

[0002]

PRIOR ART AND PROBLEMS TO BE SOLVED BY THE INVENTION In a dishwasher, carbonate ion species (CO
^- ₃₎ If it is a high concentration, the cleaned articles (e.g., dishes, glasses, formation of cutlery, etc.) and calcium carbonate deposits on the machine part (scaling) occurs. Current phosphorus-free formulations contain builders (eg, citrates, carbonates, zeolites) that are inherently weak in builder action and insufficient in scale protection, and the risk of scaling these products. Is higher than conventional sodium triphosphate based products. If the hardness of tap water is relatively high or the water softening in the machine is not sufficient, the above problems will occur immediately. Other parameters involved in the scale formation process are temperature (high temperature increases adhesion) and pH (high pH increases scale formation).

Therefore, scale formation on dishware and machine parts is associated with phosphate-free dishwasher products,
Especially when used in hard water areas and / or when the builder system comprises sodium carbonate and / or when the bleach system comprises sodium percarbonate it is a significant problem.

[0004]

## STR3 ## Formula: Poly (X) _n [wherein each X is independently aspartic acid or a salt thereof, glutamic acid or a salt thereof, glutamine, asparagine or a mixture thereof; n is 3 ˜1000, preferably 3 to 500] of the polyamino acid compound, when incorporated into a phosphate-free dishwashing composition at a particular critical amount, and in the composition of carbonate and / or heavy salts. It has been found that when the amount of carbonate builder does not exceed 50% by weight of the composition, it can be effectively used as a scale inhibitor.

Accordingly, the present invention comprises a non-phosphate builder, when formulated, wherein the amount of carbonate and / or bicarbonate builder does not exceed 50% by weight of the composition and has the formula: poly (X) _n [ Wherein each X is independently aspartic acid or salt thereof, glutamic acid or salt thereof, glutamine, asparagine or mixture thereof; n is 3 to 1000,
Preferably 3 to 500], at least 1% by weight or more, preferably at least 2 to 10% by weight of the polyamino acid compound.
Disclosed is a phosphate-free dishwasher composition, which is included in an amount of not more than wt%.

In the above formula, the X amino acid may consist of any of the X groups (ie, polyaspartate, polyglutamate, polyglutamine, polyasparagine), or any combination of X group types. For example,
Poly (Asp) ₅ (Glu) ₅ ].

Builder materials (phosphate and non-phosphate builders) are known in the art and various types of organic and inorganic compounds have been described in the literature. They are typically used in all types of cleaning compositions to provide alkalinity and buffering capacity, prevent agglomeration, retain ionic strength, extract dirt-derived metals from cleaning solutions and / or remove alkaline earth metal ions. To do.

The term "builder material" as used herein refers to various non-phosphate builder materials [eg,
Alkali metal salts of citric acid, carbonic acid and bicarbonate; nitrilotriacetic acid (NTA); dipicolinic acid (DPA); oxydisuccinic acid (ODS); succinic acid alkenyl salt (AKS); and zeolite] It may be. These may be incorporated in the compositions of the present invention at 5 to about 90% by weight, preferably 10-80% by weight.

Particularly preferred builders include citrate, alkenyl succinate, carbonate, bicarbonate, zeolites and mixtures thereof. When the carbonate and / or bicarbonate builders are used alone or in combination with other builders, the amount is 50% of the composition as described above.
It was found that it should not exceed wt%.

0 carbonate and / or bicarbonate builders
Compositions containing from about 40% by weight are preferred.

Although not strictly critical, surfactants may be included for detergency, soil removal, foam control and / or rinsing aids. When incorporated, they may be used in amounts up to about 60% by weight, depending on their type and properties. Usually, it is customary in a composition containing a proper amount of builder or a large amount of builder, but in order to promote the detergency and suppress the extreme foaming caused by the dirt of the protein, a non-foaming nonionic 0.1-5 small amount of surfactant
It is preferably used in weight percent. Large amounts (ie 5-60% by weight) of high detergent efficacy surfactants (eg high HLB nonionic surfactants, anionic sulfate or sulfonate surfactants and surfactant alkyl polyglycoside species). Can usually be used in activator-based compositions containing small amounts of builders.

The compositions of the present invention may include one or more of the following special ingredients for particular purposes during the multi-stage wash cycle, which is typically typical of dishwasher compositions.

Alkali metal silicate- about 1 to about 40% by weight,
It is preferred to include sodium silicate at a level of preferably 5 to 35% by weight. This substance is a cleaning ingredient, an alkalinity source,
It can be used as a metal corrosion inhibitor and a gloss protector for porcelain dishes. A particularly effective example is sodium silicate, commonly referred to as sodium disilicate, having a molar ratio of SiO ₂ : Na ₂ O of about 1.0 to about 3.3, preferably about 1.8 to about 2.5.

Bleach system -When compounded, it is preferably compounded in an amount of 1 to 30% by weight. The alkali metal hypochlorite may be incorporated into the liquid composition. Other chlorine bleaching agents that may be included include di- and tri-chloro and alkali metal salts of di- and tri-bromocyanuric acid.

Preferred bleaches are peroxygen bleaches, eg
And sodium perborate (tetra or monohydrate) or sodium percarbonate. They are preferably used in combination with bleach activators which liberate reactive oxygen species at low temperatures. Many examples of activators of this type, called bleach or peracid precursors, are known in the art. Preferred bleach activators include International Application Publication (WO) 91/107
Tetraacetylethylenediamine (TAE
D), glucose pentaacetate (GPA) and mono-long chain acyl tetraacetyl glucose, but other active agents such as choline sulfophenyl carbonate (CSPC) described in US Pat. Nos. 4,751,015 and 4,818,426. Can also be used. The amounts of perboric acid or sodium percarbonate and bleach activator in the composition preferably do not exceed 20% and 10% by weight, respectively.

Another type of peroxygen bleaching agent is potassium monopersulfate. Peroxygen bleaches that can be used include organic peroxy acids and their metal salts.
Typical peroxy acids include: (i) peroxybenzoic acid and ring-substituted peroxybenzoic acids (eg, peroxy-α-naphthoic acid); (ii) aliphatic and substituted aliphatic monoperoxy acids (eg, peroxylauric acid and Peroxystearic acid); (iii) 1,12-diperoxidedecanedioic acid (DPDA); (iv) 1,9-diperoxyazelaic acid; (v) diperoxybrassic acid; diperoxysebacic acid and diperoxyisophthalic acid. (Vi) 2-decyldiperoxybutane-1,4-dioic acid; and (vii) phthaloylamide peroxycaproic acid (PAP).

Instead of or together with the bleach activator, a bleach catalyst (eg EP-A-45).
Manganese complexes described in 8,397 and US Pat. No. 5,041,2
No. 32 and No. 5,047,163, sulfonimines) may also be added.

Enzymes -starch-degrading enzymes and proteolytic enzymes are commonly used. As used herein, a "starch-degrading enzyme" may be derived from bacteria or fungi. A preferred amylolytic enzyme is described and produced in British Patent No. 1,296,839 and is produced by B. lichenif
ormis) NCIB 8061, NCIB 8059, ATCC 6334, ATCC 659
8, ATCC 11945, ATCC 8480 and ATCC 9945A strains. Examples of such a starch-degrading enzyme include SP-95 and Termanyl (registered trademark; Novo industri A /
S, manufactured by Copenhagen, Denmark) and produced and distributed. These amylolytic enzymes are usually granular and may have an enzyme activity of about 2-10 maltose units / mg. These have a final composition of 10 in the composition of the present invention.
^It may be formulated to have a starch degrading enzyme activity of ³ to 10 ⁶ maltose units / kg.

As used herein, the term "starch-degrading activity" refers to P. Bernfeld "Method of Enzymology", vol.
I (1955), p149.

“Proteolytic enzyme” as used herein
The subtilisin obtained from a specific strain of Bacillus subtilis and B. licheniformis is, for example, a commercially available subtilisin.
Maxatase (registered trademark: Gist-Brocades NV, Delft, Holland
Made) and Alcalase (registered trademark: NOVO Industri A / S Cope
nhagen, made by Denmark). Particularly preferred examples include proteases obtained from Bacillus strains that have maximum activity at pH 8 to 12, such as Esperase and Savbin.
ase (registered trademark: NOVO Industri A / S) is commercially available. The production of these and similar enzymes is described in British Patent 1,243,
No. 784. These enzymes are usually granular [eg malm, prills, T-granules, etc.] and may have an enzyme activity of 500 to 1700 glycine units / mg.
MLAnson “Journal of Genera
It can be determined by the method described in “L Physiology” Vol. 22 (1938), p79 (1 Anson unit / g = 733 glycine unit / mg).

The proteolytic enzyme in the composition of the present invention may be incorporated in an amount such that the final composition has a proteolytic enzyme activity of about 10 ⁶ to 10 ⁸ glycine units / kg.

Other enzymes, such as lipolytic enzymes, may also be included to promote fat removal. Typical examples of commercially available lipolytic enzymes include Lipase YL, Amano CE, Wallerstein
AW, Lipase My and Lipolase (manufactured by Novo Ind.) Can be mentioned.

Other optional ingredients that may be incorporated in even smaller amounts include mineral clays, especially layered mineral clays, to reduce film and spot formation in the wash. Generally, a particularly preferred commercial viscous product is Laporte In
Lapo manufactured and supplied by ductries LTD, England
nite [eg Laponite S, Laponite XLS, Laponite R
D and Laponite RDS (registered trademark)]. Zinc salts (both soluble and insoluble zinc salts) may also be included as additives to minimize glass corrosion.

In the compressed powder composition it is preferred to omit it as substantially as possible, but inert particulate fillers, especially sodium sulphate, may also be incorporated.

Polyamino Acid Compounds The polyamino acid compounds used in the present invention include homopolymers of aspartic acid, glutamic acid, glutamine or asparagine, or copolymers of any combination of the above amino acids, where the amino acids are L, D or L. It may be / D type. n is preferably 5 to 150, and 10 to
100 is more preferable.

Preferred compounds include Sigma Chem. Cor
and polyaspartate and polyglutamate, which are widely commercially available from P. and Ajinomoto. Cygnus-32® is a polyamino acid product (Cygnus Corporation, USA) containing about 40% by weight of polyaspartate.

Other polyamino acids of the invention are also preferred for other reasons.

As mentioned above, the amount of polyamino acid compound which can be used in the present invention should be at least 1% by weight or more, preferably at least 2% to 10% by weight or less of the composition, and the polyamino acid compound in the washing liquid should be at least 1% by weight. Amino acid concentration of about 30-300ppm
You can

Even at low concentrations, especially high carbonate content,
There is no noticeable effect on the appearance of the glass, and at a high concentration of 10% by weight or more, another undesirable phenomenon (that is, thin crystals that are considered to have been caused by the adherence of fine calcium carbonate crystals to the glass and metal surfaces) It is very important that this range be adhered to as it is ineffective due to the formation of the blue film). A preferred range for best results is from 3 to about 8% by weight of polyamino acid in the composition.

When used at these levels, the polyamino acid compounds of the present invention are effective in reducing scale build-up on glass, dishes, etc., which can improve the appearance of the glass. They are also biodegradable and can prevent metal corrosion.

Accordingly, a dishwasher composition within the scope of the present invention may include the following ingredients.

[0032]

[Table 1]

[0033]

The present invention is further described by the following non-limiting examples.

Examples I and II Setup Scale Formation Experiments The deposition of scale (calcium carbonate) on the dishes during the dishwasher washing process was studied in a small scale model scale formation experiment. The wash cycle in such an experiment is simulated by heating the wash solution containing a pre-weighed glass slide. The weight gain of these slides during the 9 cycle deposition experiment is considered to be due to the deposition scale. A combined main wash and final rinse experiment was conducted to study scale protection for the main wash composition.

Main Wash / Final Rinse Experiment 2.7 g of the composition was added to 1.5 liters of hard water in a 3 liter glass beaker. This water, demineralized water, calcium chloride, magnesium chloride and sodium bicarbonate, the hardness of the entire water French hardness ¹ 40 (molar ratio Ca / Mg: 4 /
1) was prepared by adding in an amount such that the temporary French hardness ² 32 (bicarbonate). Place a pre-weighed glass slide (5 x 5 x 0.1 cm) in this solution and increase the temperature to 2
The temperature was raised from 0 ° C to 65 ° C at a rate of 2.5 ° C / min and kept constant at 65 ° C for 12 minutes. This temperature profile simulated the main wash cycle and was performed using an electric heating element submerged in water and a programmable temperature controller. At the end of this cycle, slides were removed from solution. One slide was used for measuring scale formation during this cycle and replaced with a new slide. The final rinse cycle is then simulated by pouring the remaining slides with 1.5 liters of water of the same hardness. At the same time, 1.5 ml of the main washing solution (simulating the amount of 1/1000 carryover from the main washing) is added. Add this final rinse solution to 20
Heated from ℃ to 70 ℃ (2.5 ℃ / min), and held constant for 10 minutes. At the end of this cycle, one slide is removed again for analysis and replaced with a new slide. This method was usually repeated 9 times.

1) 1 ° FH (Ca and / or Mg) is 0.1 mmol
Equivalent to / l CaCO ₃ .

[0037] _{2) 1 ° FH (HCO 3} -) is 0.2 mmol / l NaHCO ₃
Is equal to

[0038]

[Table 2]

The results are shown in the table below.

[0040]

[Table 3]

The above results show that in all cases scale formation was suppressed by the incorporation of polyamino acids. The above data is for high content of carbonate /
Negative effect of bicarbonate builder and low concentration of Cygnu compared to more pure polyaspartate product (Bayer)
It also demonstrates the low efficacy of s-32 (impure product).

Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C11D 3:33) (72) Inventor Rudolf Willem P. Juan Dornen, 3142 A.M., The Netherlands・ Mars Rice, Poplarendal ・ 20

Claims (12)

[Claims] 1. A non-phosphate builder, when incorporated, wherein the amount of carbonate and / or bicarbonate builder does not exceed 50% by weight of the composition and a formula: poly (X) _n [wherein each X Are independently aspartic acid or a salt thereof, glutamic acid or a salt thereof, glutamine, asparagine or a mixture thereof; n is 3 to 1000].
A phosphate-free dishwasher composition, characterized in that it comprises at least 1% by weight and at most about 10% by weight of the polyamino acid compound of. 2. The polyamino acid compound is at least 2
A composition according to claim 1, characterized in that it comprises by weight. 3. The polyamino acid compound is contained in an amount of 3 to about 8 parts by weight.
The composition according to claim 2, wherein the composition comprises%. 4. The composition according to claim 1, wherein n is 3 to 500. 5. The composition according to claim 4, wherein n is 5 to 150. 6. The composition according to claim 5, wherein n is 10 to 100. 7. A non-phosphate builder selected from the group consisting of citrates, alkenyl succinates, carbonates, bicarbonates and zeolites and mixtures thereof. The composition according to any one of claims. 8. The composition according to claim 1, which contains 0 to 40% by weight of a carbonate and / or bicarbonate builder. 9. A composition according to any one of claims 1 to 8 comprising 5 to about 90% by weight of non-phosphate builders. 10. b) 0 to 60% by weight of surfactant; c) 0 to 40% by weight of alkali metal silicate; d) 0 to 30% by weight of bleaching system; and e) further containing an enzyme as an optional component. The composition according to claim 9, characterized in that 11. A) 10 to 80 weight of non-phosphate builder.
%) B) low foaming to non-foaming nonionic surfactant 0.1 to 5% by weight; c) alkali metal silicate salt 1 to 40% by weight; d) peroxygen bleaching system 1 to 30% by weight; and e) The composition comprises starch degrading enzymes and proteolytic enzymes in an amount such that they have a starch degrading enzyme activity of 10 ³ to 10 ⁶ maltose units / kg and a proteolytic enzyme activity of 10 ⁶ to 10 ⁸ glycine units / kg The composition according to claim 10, characterized in that 12. The alkali metal silicate is, SiO _2:
Composition according to claim 10 or 11, characterized in that it is sodium disilicate with a molar ratio of Na ₂ O of about 1.8 to 2.5.