JPS63186800A - Stabilized enzyme system containing aqueous liquid composition for tableware washer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aqueous dishwashing builder composition containing a stabilizing enzyme system. The stabilizing enzyme system is a boron compound, α-
Contains hydroxy carboxylic acids, casein and enzymes. The invention particularly includes a stabilized enzyme system consisting of boron compounds (e.g. sodium borax), alpha-hydroxy carboxylic acids (e.g. lactic acid, tartaric acid and citric acid), casein and enzymes (e.g. proteolytic and amylolytic enzymes). The present invention relates to an aqueous liquid thixotropic clay composition for dishwashing racks. Specifically, the present invention provides an automatic dishwashing rack that has enzymatic stability and physical stability, and can be easily dispersed in a cleaning medium to effectively clean tableware, glassware, hard pottery, etc. The present invention relates to a detergent composition containing a stabilized enzyme system.

Currently available powdered dishwashing rack builder detergent compositions and aqueous dishwashing rack builder detergent compositions containing thixotropic dishwashing transport compositions do not contain stabilizing enzyme systems.

The present invention relates to a builder-containing enzyme-containing aqueous liquid detergent composition for dishwashing racks, which is suitable for cleaning tableware, glassware, hard pottery, household utensils, and the like. More particularly, the present invention relates to enzyme-containing aqueous liquid detergent compositions for dishwashing racks, which contain one or more detergent virgoos and are characterized by stable compositions.

Dishwasher detergent compositions (hereinafter also referred to as ADD) generally include the following elements: (1) Tripolyphosphoric acid to soften or bind minerals in hard water and emulsify and/or peptize soils. Sodium (NaTPP); (2)
Sodium silicate to provide the necessary alkalinity for effective cleaning and protect the beautiful luster and patterns of the pottery; (3) Sodium carbonate to enhance alkalinity, generally considered an optional ingredient: (4) A chlorine releasing agent to facilitate the removal of water staining stain spots and aid in the removal of tea and coffee colored stains: and (5)
) Defoamers/surfactants to increase equipment efficiency and provide the necessary cleaning power by reducing foaming.

For example, Thomas Opal (Thomas Ober)
Details of SDA detergent (SDA Deterger)
+t in Depth), [Formation Aspects or Mac
hine Dishwashing) J (1974
)reference.

Cleaning agents equivalent to the aforementioned compositions are usually liquids or powders.

However, chlorine releasing agents react with other chemically active ingredients, especially surfactants (U.S. Pat. No. 4,115,308).
The use of chlorine-releasing agents in some dishwashing rack formulations is undesirable because they have a head that degrades the suspending or thixotropic agent and impairs its effectiveness. It is a feature of the present invention that no chlorine releasing agent is required in the dishwashing rack composition.

The production of stabilized enzyme-containing liquid compositions for dishwashing bars is a difficult problem. The advantage of adding enzymes to dishwasher detergent compositions is that they primarily break down protein and starchy substances present on dirty dishes and household utensils, such as gravy, eggs, tomatoes, etc. during washing in an automatic dishwasher. Due to the effectiveness of proteolytic and amylolytic enzymes in facilitating the removal of uneaten food such as sauces, thicholates, etc. However, enzyme materials suitable for dishwashing racks, especially proteolytic enzymes, are relatively expensive. Additionally, enzymes have been found to be unstable in built aqueous laundry detergent compositions.

It is known that the problem of enzyme instability is particularly acute in the case of liquid laundry detergent compositions containing phosphate builders. This is primarily due to the destabilizing effect of phosphate detergent builders on enzymes. Furthermore, the addition of phosphate bilgoos to liquid dishwashing rack detergent compositions creates an additional problem, namely the possibility of the formation of stable single-phase compositions: for example, the solubility of sodium tripolyphosphate is low in aqueous compositions. , especially in the presence of anionic detergents,
Relatively limited.

Stabilization of enzymes in detergent compositions with high alkalinity is difficult as high alkalinity is known to inactivate enzymes. The pH can be lowered to improve enzyme stability, but this negates some of the effectiveness of the builder. The stabilized enzyme system of the present invention allows enzyme stability even at relatively high Ph values up to pH 10-12. High pH values, such as pH 1O-12, are preferred as they are known to provide good detergency. Lowering the pH of the detergent composition, for example to pH 7.5-9.5, increases the enzyme stability but shortens the life of the soap water and reduces the effectiveness of the builder, i.e. the detergency.

Ulrich U.S. Patent No. 4,431
No. 559 discloses a thixotropic composition for an automatic dishwashing rack that includes an aqueous solvent, a thickener, a chlorine source, an anionic surfactant, a builder salt, and a buffer system to stabilize the chlorine source. are doing.

U.S. Pat. No. 3,558,498 describes the stabilizing enzyme sodium perborate trihydrate, anhydrous trisodium phosphate, anhydrous calcium sulfate and the molecule N52Ooo-i, ooo,
A granular laundry detergent composition comprising a soluble or dispersible protein having a molecular weight of 50.000-20.

U.S. Patent No. 3,560,392 (CINP No. 3°55
8.498) is an organic detergent, an alkaline builder salt,
Stabilizing enzymes and molecules ff152O00-250.00
A granular detergent composition for laundry comprising stabilization of protein collagen with 0 is disclosed.

U.S. Pat. No. 4,238,345 discloses a liquid laundry detergent composition in which antioxidants and hydrophilic polyols having 2-6 hydroxyl groups are added to stabilize enzymes. In column 1, the patentee describes the use of protein-bound calcium salts and protein-bound glycerol to form enzyme stabilizing systems in aqueous liquid laundry detergents. British Patent Application No. 22O79,305 discloses an enzyme-containing laundry builder aqueous liquid detergent composition in which the enzyme is stabilized by a mixture of a polyol and boric acid.

The present invention provides an aqueous phosphate builder liquid composition for dishwashing racks that includes a stabilized enzyme system consisting of a boron compound, a hydroxycarboxylic acid, a proteinaceous material (eg, casein), and an enzyme.

By premixing a mixture of boron and mono-hydroxy carboxylic acids with a mixture of enzyme and casein to block enzyme contact sites with casein and simultaneously blocking the enzyme structure with a mixture of boron compounds and mono-hydroxy carboxylic acids. , enzyme stabilization is achieved.

In addition to stabilizing protease very well, the enzyme stabilization system of the present invention also stabilizes amylase very well, making a dual protease/amylase stabilization system possible in highly alkaline detergent compositions. Become. It is surprising that amylase enzymatic activity is effectively stabilized, since amylase activity is expected to be degraded at pH values higher than 9.

In the present invention, cleaning of soiled dishes and household utensils in a dishwasher is accomplished by contacting the dishes and household utensils with a heavy builder aqueous liquid composition for dishwashing bars containing a stabilizing enzyme system. .

The aqueous liquid dishwashing rack composition of the present invention allows for thorough cleaning of dishes and household utensils containing both oil stains and particulate food stains. Furthermore, the composition can be used for presoaking heavily soiled dishes to be cleaned in an automatic dishwasher.

The present invention is based on the discovery that an enzyme stabilizing system comprising a boron compound, a dihydroxy carboxylic acid, a protein material (e.g., casein), and an enzyme provides an effective and sufficient enzyme stabilizing effect in aqueous dishwashing liquid compositions. It is something.

In one embodiment of the present invention, a built aqueous liquid composition for dishwashing racks is prepared that includes an enzyme stabilization system and a suspension of phosphate detergent Bilgoo in an aqueous liquid anionic surfactant detergent.

In another embodiment of the invention, an aqueous liquid thixotropic clay composition for dishwashing bars is produced, comprising an enzyme stabilization system and a suspension of phosphate detergent Bilgoo in an aqueous liquid anionic surfactant detergent. .

Applicant has discovered that an enzyme stabilizing system comprising a mixture of a boron compound, a hydroxycarboxylic acid, a proteinaceous substance (e.g., casein), and an enzyme is stable and effective over a relatively long period of time in an aqueous dishwashing liquid composition. discovered that it enables the enzyme activity to increase.

The dishwashing rack formulation of the present invention is a physically stable composition. The aqueous liquid detergent compositions of the present invention are easily pourable, easily dispensed, and easily addable into automatic dishwashing machines.

It is desirable to produce aqueous liquid compositions or aqueous liquid thixotropic clay compositions for dishwashing racks that contain stabilizing enzyme systems and optionally physical stabilizers.

It is therefore an object of the present invention to produce an aqueous liquid composition for dishwashing bars containing a stabilized enzyme system.

It is another object of the present invention to produce an aqueous liquid thixotropic clay composition for dishwashing bars containing a stabilized enzyme system.

Furthermore, boron compounds, thihydroxycarboxylic acids,
A stabilized enzyme system comprising casein and an enzyme is added to an aqueous dishwashing rack composition and an aqueous liquid thixotropic composition to provide effective proteolytic and/or amylolytic enzyme cleaning activity to the dishwashing rack composition. That is,
It is another object of the invention.

In addition, a small amount of an active fatty acid metal salt, a physical stabilizer such as sodium stearate, and a stabilizing enzyme system can be added to the thixotropic clay composition for dishwashing to create an aqueous liquid thixotropic gel composition for dishwashing racks. It is another object of the present invention to improve the physical stability to prevent sedimentation of suspended particles and to prevent phase separation.

These and other objects of the present invention, which will be readily understood from the following detailed description of the present invention and preferred embodiments thereof, include the addition of a stabilizing enzyme system to an aqueous thixotropic composition, such as a conventional gel-like composition. achieved by. To improve the physical stability of the dishwashing rack composition, small effective amounts of physical stabilizers, such as fatty acids or fatty acid metal salts, can be added to the composition. More particularly, preferred embodiments of the invention include a stabilizing enzyme system comprising a boron compound, a bi-hydroxy carboxylic acid, casein and an enzyme, and a long chain fatty acid metal salt effective to inhibit sedimentation of suspended particles. A conventional gel-like composition for automatic dishwashing racks is prepared with the addition of a physical stabilizing amount.

The present invention provides a phosphate builder aqueous liquid composition for dishwashing bars containing a relatively simple stabilizing enzyme system consisting of a boron compound, a -hydroxy carboxylic acid, a protein material (e.g., casein), and an enzyme. do. Enzyme stabilization systems stabilize the active ingredient enzyme over a relatively long period of time so that only small amounts of expensive enzymes are used.

The present invention provides an aqueous liquid phosphate builder anionic surfactant composition containing a stabilizing enzyme system for dishwashing bars that can be used at an effective high pH HIO212. The present invention also provides an effective and sufficient dishwashing rack composition that does not require the use of chlorine compounds.

In a preferred embodiment of the present invention, the following composition (heavy standard)
: (a) 8-35% alkali metal tripolyphosphate (b) 0-20% sodium silicate, e.g. 2.5-20% (C) 0-9% alkali metal carbonate (d) Dispersible in water 0-5%, e.g. 0.1-5%, of organic detergent actives (e) 0-10.0, e.g. about 2.5-10 741 in the thixotropic clay thickener composition.
0.5-2.0% (g) rj%-Hydroxy
Carboxylic acid 1.5-4% (h) Casein 1-4.0% (i) Enzyme 0.5-2.0% (j) Foam suppressant 0-5% (k) Sodium hydroxide 0-8 % (1) Long chain fatty acid metal salts 0-2% (m) Water The remainder With respect to this embodiment, the present invention also provides for the use of an aqueous dishwasher containing an effective amount of the liquid automatic dish rack detergent (LADD) composition described above in an automatic dishwashing machine. To provide a method for washing tableware using a washing bath. According to this aspect of the invention, the LADD composition can be easily poured into the dispensing cup of an automatic dishwasher and rapidly thickens within seconds to its normal gel-like or base-like consistency; It remains safely within the dispensing cup until shear stress is applied again, such as by water splash from a dishwasher.

According to the present invention, the enzyme activity is stabilized over a relatively long period of time, so that a small amount of enzyme exhibits effective enzyme cleaning activity. Enzyme activity is stabilized by adding a small amount of a stabilizing enzyme system consisting of a boron compound, a di-hydroxy carboxylic acid, a protein substance (eg, casein), and an enzyme.

This stabilizing enzyme system is used in aqueous phosphate builder anionic detergent compositions.

Stabilizing Enzyme Systems Preferably, the stabilizing enzyme systems are prepared separately and added to the dishwashing rack composition.

The stabilized enzyme system is preferably prepared in three steps as follows: 1. Adding the boron compound to the bi-hydroxy carboxylic acid or its salt to obtain a primary mixture; 2. Adding the protein substance (
For example, casein) is added to an aqueous alkaline solution, and the enzyme is added to this aqueous alkaline solution to obtain a secondary mixture: 3. The protein obtained in step 2 is added to the boron/(7(-hydroxycarboxylic acid mixture obtained in step 1). The substance/enzyme mixture is mixed to obtain a premix stabilized enzyme system of the invention.

The Step 1 mixture and the Step 2 mixture above can be added separately to the dishwashing rack composition, but the Step I mixture and the Step 2 mixture can
The best enzyme stabilization results are obtained by premixing the mixture and adding the premixed mixture to the dishwashing rack composition.

Although Applicants do not wish to be limited to theories of how the stabilizing enzyme system works, it is believed that boron compounds react with bi-hydroxy or polycarboxylic acids to form borate esters. It is possible to do so. It is believed that borate esters react with enzymes and block the structure of the enzyme in the active form, preventing denaturation of the enzyme. Protein substances are believed to prevent digestion of enzyme molecules during product storage by blocking enzyme contact sites.

The stabilizing enzyme system consists of a diboron compound (e.g. borax), 0.4-2.5. Preferably 0.75-2.0°, more preferably 0.9-1.2 parts by weight: 〆-hydroxycarboxylic acid, l-5, preferably 1.5-4.0°. More preferably, S to 3.6 parts by weight: Protein substance (eg, casein), 1-6. , Q, preferably 1-4.0, e.g. about 1,
0-2.0 parts by weight enzyme 0.5-3.5. Preferably 0.5-2.
0. More preferably 0.5-1.0 parts by weight Hiro-hydroxy carboxylic acid/boron compound weight ratio is 7:1-1:1, preferably 4:1-1=1, still more preferably 3:1-2 : It is 1.

The weight ratio of protein material (e.g. casein)/enzyme is 8:
l-1:1, preferably 4:1-1:L, more preferably 4:1-2:1.

Preferred stabilized enzyme systems of the invention contain the following components in the stated amounts: Ingredients Parts by weight Borax (Na,
B, 07-101T, O) 0, 75-2,
0- and a carboxylic acid
C5-42O casein 1.0
- 4.0 enzyme 0.5- 2
．． The stabilized enzyme system 7 contains 10-30 parts by weight/90-70 parts by weight of the stabilized enzyme system 7 dishwashing composition.
It can be added in an amount such that the amount is preferably 15-25 parts/85-75 parts by weight, more preferably 15-20 parts/85-80 parts by weight. The stabilized enzyme system is added to the dishwashing composition such that the weight percent of the active ingredient of the enzyme system in the dishwashing composition is equivalent to the weight part of the active ingredient in the stabilized enzyme system.

A detailed description of the stabilizing enzyme system can be found in the above-mentioned patent application no. 925.4.
It is stated in No. 37. This patent application is incorporated herein by reference in its entirety.

The stabilized enzyme system of the present invention can be used in aqueous liquid dishwashing rack compositions, aqueous liquid dishwashing rack thixotropic compositions, and powder or granular dishwashing rack compositions.

A preferred embodiment of the stabilized enzyme system of the present invention is added to a liquid dishwasher thixotropic composition.

U-Hydroxycarboxylic acid The 6-hydroxycarboxylic acid that can be used in the present invention is an organic carboxylic acid having 3 to 8 carbon atoms and having 1 to 3 carboxyl groups and 1 to 2 hydroxyl groups.

Preferred carboxylic acids are monohydroxy carboxylic acids having 3 to 6 carbon atoms and having 1 to 3 carboxyl groups and 1 to 2 hydroxyl groups. Suitable hydroxy carboxylic acids include malic acid (HOOCCnOllCllyCoo
lT), tartaric acid (lT00CCFIORCI'1OHC
OOH), lactic acid (1100cc11011cH,) and citric acid (HooCCll, C(Oll)COOII
CH, C00I+). preferred - hydroxy
Carboxylic acids are tartaric acid, lactic acid and citric acid. Citric acid is most preferred. Pi-hydroxy carboxylic acids can be used as such or as their alkali metal salts, such as the sodium and potassium salts.

Boron Compounds The boron compounds that can be used in the dishwashing composition of the present invention are water soluble and, when added to water, form boric acid or an alkali metal salt of boric acid. Boron compounds that can be used include boric acid, boron oxide or alkali metal borates.

Suitable alkali metal borates include sodium and potassium ortho-borates, biro-borates, meta-borates, polyborates and borax (NaJaOt.xon).
zo). Preferred boron compounds include boric acid, sodium borate (Na5BO-) and borax (NatB
40? -10110).

Enzymes Enzymes that can be included in the dishwashing compositions of the present invention are proteolytic enzymes or amylolytic enzymes or mixtures thereof. Proteolytic enzymes suitable for the present invention are a variety of commercially available liquid, powder or slurry enzyme formulations suitable for use in detergent compositions.

Although it is most convenient to incorporate the enzyme into the composition in liquid form, enzyme slurry forms have also been found to be useful.

Suitable liquid enzyme formulations include Novo Industries (Nov
“Alcalase” sold by O Industries (Copenhagen, Denmark)
ase) J and [Esperase
) J, Gist-Brocade
s) sold by (Delft, Netherlands)
Maxacal J and Optimase J, commercially available from Maxacal J and Miles Kali Chemie.
There is. Suitable proteolytic enzymes include subtilisin, bromelin, papain, tryfusin and pepsin. Suitable enzymes are liquid proteases and liquid amylases. These enzymes are preferably used in their solutions. A particularly preferred enzyme is Esperase 8L in solution form.
It is. Suitable amylase liquid enzyme preparations are available from Novo Industries and Gistau Brocades, respectively, from "Termamyl J" and "Maxamyl".
This is a formulation sold under the trade name lllyI)J.

A preferred enzyme is Termamil 120L. For the purpose of the present invention, Esperase J8L is preferred as it is active at high pH values corresponding to detergent compositions with builders.Esperase 8.OL also has low activity at room temperature but high activity at 60'C. Moreover, Esperase 8.OL is stable at high pH values, thus allowing high pH values in the final product and ensuring good detergency.

Protein Materials One of the enzyme stabilizing material components of the present invention is a protein material (eg, casein). Protein substances are used as their water-soluble alkali metal salts (eg, sodium and potassium salts) and/or as dispersions in an aqueous medium with added enzymes.

In the present invention, a water soluble or dispersible protein is used in an effective amount to stabilize the enzyme. Examples of water soluble or dispersible proteins suitable for use in the present invention include casein (average molecular fi 50.000-200, 0(1(
1) ;Wilson's protein wsp
-x-1ooo <average molecule m approximately 10. Solubilized Collagen with QQQ) and Wilson's Hydrolyzate Cosmetic 50 (both sold by Wilson's Pharm.
Aceutical & Chemical Comp
any): and Collagen Hydrolyzate Cosmetic 50 (sold by Maybrook)
Inc.).

A preferred casein protein is manufactured by Bridal Co., Ltd.
) (France) or Dena (A, G,
Sodium caseinate is a mixture of several caseins with different molecular sizes. Proteins (e.g. casein) are usually obtained as powders. For example, proteins such as casein exist as long-chain chemicals.The long-chain chemicals, as a powder, fold onto their bodies, forming hydrogen bonds and keeping the protein in a spherical shape.

Unlabeling, or denaturation, of proteins breaks these bonds and forms more gradual,
It means forming a random structure. Proteins can be denatured by boiling, the use of acids, alkalis, and various detergents. Unlabeled proteins, or denatured proteins, are easily digested by enzymes;
exerts a good stabilizing effect, ie leads to good enzyme stabilization. Denaturation makes the protein more effective as a stabilizer. Proteins (eg casein) are used in sufficient quantities to stabilize enzyme activity.

Dishwashing Frame Detergent Compositions Generally, the effectiveness of an aqueous thixotropic dishwashing clay clay composition is related to (a) alkalinity, (b) solubility in the cleaning medium, and (c) suds control.

In the present invention, the pH of the LΔDD composition is at least about 9.
5, more preferably about 10.5-12.5, most preferably at least about 11.5.
l I % Lshi -～n'l h [1%
-'rv? '# -yx IJ nn
:Jt+-441101 The detergent product is too viscous, i.e., solid-like, and is difficult to fluidize at the shear force levels that occur in the dispensing cup under normal equipment operating conditions. The composition inherently has its thixotropic properties,
You will lose most, if not all. Therefore, addition of NaOH is often necessary to raise the pH to the above range and improve flowability. The presence of carbonate is also often necessary, as carbonate serves as a buffering agent that helps maintain favorable pH levels.

However, excess carbonate should be avoided as it leads to the formation of carbonate needles, impairing the stability, thixotropy and/or detergency of the LADDg product, and impairing the dispersibility of the product from, for example, squeeze tube bottles. No. Caustic soda (NaOH) If a phosphate or phosphonate foam suppressant is present,
It also has a function to neutralize this. About 0.5-3% by weight NaOH and about 2% sodium carbonate in the LADD composition
-9 fflfil% is typical, but above NaTPP and sodium silicate. A cloth 4) or flu IV
It should be noted that the II degree is given. Sodium silicate is used in an amount of 0-20% by weight, preferably 2.5-20% by weight, more preferably 5-15% by weight.

NaTPP is used in the LADD composition in a range of about 8-35% by weight, preferably about 20-30% by weight. NaT
PP may be anhydrous or hydrated (containing hexahydrate or higher hydrates with a degree of hexahydration corresponding to approximately 18Mf1% water; in fact, the stability of the hexahydrate is In view of this, the presence of some hydration water is considered to be very effective as it forms stable hexahydrate seeds that promote the hydration and solubilization of residual NaTPP particles. If only anhydrous NaTPP is used, the detergent product will be too liquid and exhibit little thixotropic properties.On the other hand, if only anhydrous NaTPP is used, the product will sometimes be too thick;
Inappropriate. For example, anhydrous NaTPP/hexahydrate NaT
Particularly preferred LADD compositions are obtained when the PP fiffl ratio is 0.5+1-2:1, with values of about 1:1 being particularly preferred.

Foam control is important in order to increase the efficiency of dishwashers and reduce the destabilizing effects that can occur due to the presence of excessive foam within the dishwasher during use. Foam can be sufficiently suppressed by appropriately selecting the type and/or amount of the detergent active ingredient, which is the main foam-generating component. Since the degree of foaming depends to some extent on the hardness of the washing water in the dishwasher, a desired degree of foaming inhibition can be easily obtained by appropriately adjusting the proportion of NaTPP, which has a water softening effect. However, if a low foaming LADD is desired, it is most preferred to include an antifoam or suppressant.
Phosphonic acid alkyl ester (PCUK-P
AE), and especially for example Hooker (
SAP) and K napzack (L
Particularly preferred are hydrogen phosphate alkyl esters having the formula: ). This 2
Mixtures of different types of esters or mixtures of the same types of monoesters and diesters can also be used. for example,
Mixtures of hydrogen phosphate mono-C, -C,, alkyl esters/hydrogen phosphate di-c+a-c+a alkyl esters, such as monostearyl hydrogen phosphate/distearyl hydrogen phosphate -,2/1 (Nutpsack) is particularly preferred. If an antifoaming agent is used, the proportion of antifoaming agent in the composition is from 0.1 to 5% by weight, preferably about 0.1-5% by weight.
Detergent active ingredient (d)/, typically 0.5% by weight.
The weight ratio of defoamers (j) is generally about 10:1-1:1, particularly preferably about 4:1-1:1. Other uses i
Fr device fp M 'tkJ 31111? For example, there are known silicones.

IJum, a silicate that provides alkalinity and protects hard surfaces such as beautiful porcelain luster and patterns, is present in the composition at about 2.
M of 5-20% by weight, preferably about 5-15% by weight, can be used. Sodium silicate, Na, 0:SiO, preferably in a ratio of about 1:2.2 to 1:2.8, is generally added as an aqueous solution. It should be mentioned at this point that most of the other components of the composition, especially NaOH, antifoam agents and thixotropic thickeners, are also often added as pre-prepared aqueous dispersions or solutions.

Detergent actives useful in this invention are water-dispersible surfactant types of organic anionic amine oxides, phosphine oxides, sulfoxides or betaines. Anionic surfactants are preferred. The surfactant, e.g. anionic surfactant, is about 0.1-5%, preferably about 0.3-2.0%.
Used in amounts ranging from % to %. Particularly preferred surfactants in this case are, for example, DOWFAX® 3B
-2 and DOWFAX2A-1 are linear or branched alkali metal mono- and/or di-C, -C, alkyl diphenyl oxide mono- and/or di-sulfates. In general, paraffin sulfonates have been found to impair, if not destroy, thixotropy, excessively increase viscosity, and cause severe shear force problems. Additionally, the surfactant must be compatible with the other ingredients of the composition. Other suitable surfactants include primary furkyl sulfates, alkyl sulfonates, alkylaryl sulfonates and secondary furkyl sulfates. Examples include CIoCts sodium alkyl sulfates, such as sodium dodecyl sulfate and sodium tallow alcohol sulfate; CIOCts, such as sodium hexadecyl-1-sulfonate.
, Cl1-CI* sodium alkylbenzene sulfonates, such as sodium alkanesulfonate and sodium dodecylbenzene sulfonate. The corresponding potassium salts can also be used. Examples of suitable alkyl sulfonic acid salts are Tii I C1,-C, sodium and potassium salts of alkyl sulfonic acids, 1C,.

-C,s Sodium normal alkyl sulfonate is preferred.

Amine oxide surfactants as other suitable surfactants or detergents typically have the structure R,R'N-0, where each R represents a lower alkyl group, such as methyl;
R' represents a long-chain alkyl group having 8 to 22 carbon atoms, such as lauryl, myristyl, palmityl or cetyl. Instead of the amine oxide, the corresponding surfactant phosphine oxide R,R'PO or the sulfoxide RR'
S O can be used. Betaine surfactants typically have the structure R,R'N-R'Coo,
In the formula, each R represents a lower alkylene group having 1 to 5 carbon atoms.

Particular examples of these surfactants are lauryl-dimethylamine oxide, myristyldimethylamine oxide, the corresponding phosphine oxides and sulfoxides, and the corresponding betaines, dodecyldimethylammonium acetate, tetradecyldiethylammonium pentanoate, hexadecyldimethyl Also included are ammonium hexanoate and the like. For biodegradability, the alkyl groups of these surfactants should be linear, and such compounds are preferred.

Surfactants of this type are well known in the art and are described, for example, in U.S. Pat.
It is stated in the issue.

Thixotropic thickeners, i.e. thickening or suspending agents that impart thixotropic properties to an aqueous medium, are well known in the art and can be organic or inorganic, water-soluble, water-dispersible or colloid-forming, monomeric or polymeric. Yes, but of course these compositions must be stable, for example stable against high alkalinity. Particularly preferred thickeners are inorganic colloid-forming clays, generally of the smectite and/or attapulgite type.

Organoclay thixotropic thickeners can also be used.

British Patent No. 2,116.199A and British Patent No. 2
Referring to the preferred thixotropy and Bingham plasticity of Assignee's previously published LADD compositions disclosed in US Pat.
It is used in an amount of 5-10, preferably 2-5% by weight.

According to the present invention, the inorganic colloid-forming clay of the smectite and/or attapulgite type is about 0.25
-5%, preferably 0.50-4.0%, especially 1.0-
m in the range of 3% is generally sufficient to obtain favorable thixotropy and Bingham plasticity. When used in conjunction with fatty acid metal salt physical stabilizers, smaller amounts of thixotropic agents can be used.

Smectite clays include montmorillonite (bentonite), hectorite, attapulgite, and sabonite. Preferred is montmorillonite clay, which is manufactured by Georgia Kaolin Co.
olin Coi+pany) to thixogel (Thi
xogel® No. 1 and Gelvhite® CP, H, etc. and Luthurn Clay Products
layPro products) and Etsuki Gum (ECC).
AGUM) (registered trademark) It is available under trade names such as GP and H. Attapulgite clay is manufactured by Engelhard Minerals and Chemicals Corporation.
Chemicals Corporation under the tradename AttagelX® 40. There are Attagel 50 and Abtagel 150. Mixtures of smectite and attapulgite types in weight ratios of 4:1 to 1:5 are also useful in the present invention.

Thickeners or suspending agents of this type are well known in the art and are described, for example, in the above-mentioned US Pat. No. 3,985,668. Abrasives or polishes can damage the surfaces of beautiful tableware, crystal, etc. and should be avoided in LADD compositions.

The amount of water contained in these compositions must not be so high as to result in unreasonably low viscosity and fluidity, nor must it be so low as to result in unreasonably high viscosity and low fluidity, in either case. Thixotropy is reduced or destroyed. Such amounts are readily determined in the particular case by routine testing and are generally in the range of 35-65% by weight, preferably about 40-55% by weight. Preferably, the water is deionized or soft water.

Unless otherwise specified, references to LADD products refer to United Kingdom Patent Application No. 2°116.19, assigned to the applicant's assignee.
9A and 2,140,450A.

UK Patent Application No. 2,166.199A and No. 2.1
40.450 The LADD product of No. A shows improved rheology as evaluated by measuring product viscosity as a function of shear rate. These compositions exhibited high viscosity at low shear rates and low viscosity at high shear rates. These data indicate that fluidization is effective and gelation is sufficient within the shear rate range within a standard dishwasher. In practical terms, this means improved pourability and processability as well as less leakage in dishwasher dispensing cups compared to previous liquid or gel ADD products. Given a shear rate corresponding to 33-30 rp, the corresponding viscosity (Brookfield) is approximately io as measured by an LVT Brookfield viscometer (at room temperature) after 3 minutes using a No. 4 spindle.
,oo.

-302O00cps to about 32O00-72O00c
The range was up to ps. A shear rate of 7.4 sec-' corresponds to approximately 3 spindle rpm.

An increase in shear rate of about 10 times results in a decrease in viscosity of about 3-9 times. For conventional ADD gels, the corresponding decrease in viscosity was only about twice that.

Furthermore, such compositions had an initial viscosity of only about 2,500-2.700 cpS measured at about 3 rpm. Assignee's prior invention compositions exhibit a significantly greater range of flow thresholds in terms of shear rate increase versus viscosity decrease at low shear rates. This property of the prior invention LADD products is summarized as the thixotropic index (TI), which is the ratio of the apparent viscosity at 3 rpm and 3 Orpm. Prior compositions have TI values of 2-10. The LADD compositions tested substantially and rapidly return to their previous quiescent consistency when the shear force is discontinued.

The above patent application no. 903.924 is UK Patent Application No. 2
．． The physical stability, i.e., resistance to phase separation, of the liquid aqueous ADD compositions of the '116,199A patent and the East 2.140°450 patent is improved by adding a small but effective amount of a long chain fatty acid metal salt to the composition. is based on the discovery that their rheological properties are significantly improved, without adversely, and in some cases favorably, affecting their rheological properties.

As an example of rheology improvement, the viscosity at low shear rates (e.g., spindle rpm of about 3), the apparent viscosity, of fatty acid metal salt stabilizers is on the order of 0.2% or less, e.g.
Adding 16% often increases 2-3 times. At the same time, the compositions containing fatty acid metal salt stabilizers exhibit physical stability to such an extent that they do not exhibit visible phase separation over a temperature range extending from approximately the freezing point to over 40°C even after long periods of time, such as 12 weeks or more. is improved.

Preferred long chain fatty acid metal salts are disclosed in the above patent application No. 903.9.
No. 24 (which is incorporated herein by reference). Suitable fatty acid metal salts are higher aliphatic fatty acid metal salts having about 8-22 carbon atoms, more preferably 10-20 carbon atoms, and particularly preferably about 12-18 carbon atoms, including the carbon atoms of the carboxyl group of the fatty acid. Aliphatic radicals can be saturated or unsaturated and straight or branched. Straight chain saturated fatty acids are preferred. Fatty acid mixtures can also be used, such as fatty acids derived from natural sources such as tallow fatty acids, coconut oil fatty acids, soybean fatty acids, or fatty acids from synthetic sources obtained from industrial manufacturing methods. Examples of fatty acids that can form polyvalent metal salt stabilizers are, for example, decanoic acid, valmitic acid, myristic acid, stearic acid, oleic acid,
Eicosanoate tallow fatty acid, coconut oil fatty acid, soybean fatty acid,
mixtures of these acids, etc. Stearic acid and mixed fatty acids are preferred.

Preferred metals are polyvalent metals such as magnesium, calcium, aluminum, and zinc.

Many of these metal salts are commercially available. For example, the aluminum salt is aluminum tristearate [AI (CI
? H3SCOO)3] is available in tri-acid form such as aluminum stearate. -acid acid, e.g.-
Aluminum stearate [A I (OR) t(C
,,H35COO)], and diacid salts such as aluminum nistearate [AI(OR)(C,?H3SCO
O)] and monoacids, diacids and two or three mixtures of diacids of metals such as AI with a valence of +3 and monoacids of metals such as Zn with a valence of +2 Mixtures of salts and diacids can also be used.

Calcium stearate or calcium nistearate, aluminum stearate or aluminum tristearate, and other lead stearate or zinc nistearate are preferred polyvalent fatty acid salt stabilizers.

Stable with respect to LADD compositions as well as with respect to other uses, such as where the compositions of the present invention come into contact with objects used in the handling, storage or presentation of food products or objects that come into contact with or are consumed by people or animals. The use of fatty acids as agents is of course particularly advantageous since fatty acids are known to have low toxicity. For this purpose, calcium stearate or calcium nistearate and magnesium stearate or magnesium nistearate are particularly preferred as generally safe food additives. The amount of fatty acid metal salt stabilizer to preferably enhance physical stability depends on the nature of the fatty acid metal salt, thixotropic agents, detergent active compounds, inorganic salts, especially T
It depends on factors such as the nature and amount of the PP, other LADD components, and anticipated storage and transportation conditions. However, generally about 0.2-2%, preferably about 0-5-1.0
%, particularly preferably in the range of 0.5-0.8%, to achieve the long-term stability and shelf life at both low and high temperatures required for a commercially acceptable product. or ensure that there is no phase separation during transportation.

Depending on the amount, proportion and type of physical stabilizer and thixotropic agent, the addition of fatty acid metal salts may cause physical/++h yuzu to be mixed with ancient Buddha pu^1. Zu collar / Old 1J / 1% Increases your face at the same time. Since proportions of fatty acids and thixotropic agents in the range of about 0.08-0.4% by weight of fatty acids and about 1.3-2.5% by weight of thixotropic agents are usually sufficient to simultaneously confer such benefits, The use of these components in such proportions is most preferred.

In one method of preparing these compositions, all of the inorganic salts, carbonate (if used), silicate, and tripolyphosphate, are first dissolved or dispersed in an aqueous medium. Thickener (
(if used) is added immediately before the stabilizing enzyme system. Antifoaming agent (
(if used) is formed in advance as an aqueous dispersion, similar to the thickener. The antifoam dispersion, caustic soda (if used) and inorganic salts are first mixed into an aqueous solution (deionized water) at elevated temperature and then cooled while stirring.

The room temperature surfactant, fatty acid stabilizer and thickener dispersion are then added to the cooled (25-25°C) solution. The stabilizing enzyme system of the invention is added last. Total salt concentration in the composition (Na
T P P, sodium silicate and carbonate) is generally about 2
0-50% by weight, preferably about 30-40% by weight. The stabilizing enzyme system generally comprises about 15-25 parts by weight of the composition;
Preferably about 15-20 parts by weight.

Another method of mixing the ingredients of the LADD composition is to first mix water, suds suppressant (if used), detergent, physical stabilizer (
for example, fatty acids) (if used) and thixotropic agents (eg, clay) (if used). These ingredients are mixed together under high oxidation conditions, preferably starting at room temperature, to form a homogeneous dispersion. The remaining ingredients are introduced into this premixed portion under low shear mixing conditions. For example, introduce the required amount of premix into a low shear mixer and then add the remaining ingredients with continuous or simultaneous mixing. Although it is preferred to add the ingredients sequentially, it is not necessary to complete the addition of all of one ingredient before beginning the addition of other ingredients. Additionally, one or more of the ingredients can be added in small portions and not at the same time. The same result is obtained by adding the remaining ingredients in the following order: sodium hydroxide, alkali metal carbonate, sodium silicate, alkali metal tripolyphosphate (
hydration), alkali metal tripolyphosphate (anhydrous or containing up to 5% water), sodium hydroxide and finally a stabilized enzyme system.

These compositions may contain fragrances such as benzenesulfonic acid,
Other customary ingredients such as hydro-loving agents such as the sodium salts of toluenesulfonic acid, xylenesulfonic acid and cumenesulfonic acid, preservatives, dyes and pigments etc. [all, of course, depending on the nature of the ingredients as a whole]. stable to certain high alkalinities] can be included in small amounts, generally up to about 3% by weight. Particularly preferred for coloring are polysulfides of chlorinated phthalocyanines and aluminosilicates, which give the preferred green and blue colors, respectively. For whitening or off-shade neutralization, Tie is used.

The liquid ADD compositions of the present invention are readily employed in a known manner for cleaning dishes, utensils, etc. in an aqueous wash bath containing an effective amount of the composition in an automatic dishwasher equipped with a suitable detergent dispenser.

Although the present invention has been particularly described in connection with its application to aqueous thixotropic clay detergents for automatic dishwashing racks, the benefits obtained by the addition of the stabilizing enzyme system of the present invention can be applied to aqueous liquid dishwashing compositions and dishwashing rack powders. It will be readily understood by those skilled in the art that compositions may equally well be provided.

The invention may be embodied in a variety of forms, and a number of specific embodiments are set forth below in connection with the accompanying examples for the purpose of illustrating the invention.

All units and proportions herein are by weight of the composition, unless otherwise indicated.

Example I A stabilized enzyme system was prepared according to the invention using the following method.

(1) 12.6 g of sodium borate (Na,BO,') was added to 56.1 g of tartaric acid in 90 g of water with stirring. The mixture was neutralized to approximately pH 7 with 56.1 g of NaOH (50% solution).

In [supplied by Brdel] 60g
was added with stirring and heating. After completely dissolving,
Esperase8. OL was added at 50oC and Termamil 2OL was added at room temperature to form a casein enzyme mixture.

(3) The mixture obtained from steps (1) and (2) above were mixed together to obtain a premixed stabilized enzyme system of the present invention.

The entire premixed stabilized enzyme system, i.e. approximately 570.6
g to the aqueous dishwashing transport composition or dishwashing rack aqueous thixotropic clay composition, plus about 300 g of a dishwashing rack composition in which the stabilizing enzyme system of the present invention is present in the following amounts:
can be obtained.

Weight% Na=80. 0.4 tartaric acid
1.9 Casein 2.0 Esperase 8. OL 0.5 and Ichimamil
191''lL n-3 Dishwasher compositions containing the stabilized enzyme system of the present invention are found to effectively clean dirty dishes even in the absence of active chlorine providing compounds.

Example 2 A stabilized enzyme system containing the following components was prepared according to the method of Example 1.

Weight % NatB, O, ・1 oH, o o-s Citric acid 2.6 Casein 2.0 Polysperase g-QL O,5 Termamyl 1
A 2OL 0.3 dishwasher thixotropic clay detergent composition was prepared, and about 19 parts by weight of the above-mentioned stabilizing enzyme system was added to about 81 parts by weight of this composition to obtain the following dishwasher transport detergent composition.

Weight % Deionized water 43.7 Caustic soda solution (50% NaOH) 2, 2 Sodium carbonate (
anhydrous) 5.0 Sodium silicate (47.5% solution with a NatO:SiO ratio of 1:2.4) 15.74 NaTP
P (substantially anhydrous, 0-5% moisture, preferably 3%) (Thermphos N1f)
1 2.0NaTPP (hexahydrate) (No.-mu7tsuN hexahydrate)
12.0NaxBaot・1 oH, o O
,8 citric acid 2.6 casein
2.0 Esperase 8. OL
O,5 term mill 120L
Oi Monostearyl Phosstate 0.16 Daufax 3B-2 (45% Na 7-nodecyl/dif-cyl diphenyl oxide disulnate aqueous solution)
0.80 Aluminum stearate 0.2
0 Pharmagel H (thixo)oE-clay) 2.0100
．． 0 Example 3 Esperase 8. OLo, 5% by weight and Termamill 12
OLo, containing 3% enzyme by weight The proteolytic and amylolytic activities of the aqueous liquid thixotropic composition for dishwashing bars of Example 2 containing the stabilized enzyme system of the present invention were determined to be 1.4 and 1.4 at room temperature at 4°C and 35°C. Tested after 8 weeks of aging. This dishwasher composition had a pH of approximately 11.7. The results obtained are shown in the following table.

Aging temperature 4°C Room temperature 35°C New Jersey 124 124124 Proteolytic activity 77-58 - - 5138-32 Starch degrading activity -50--22--4 Borax-citric acid, casein-esperase and termamyl stability of the present invention The enzyme system not only stabilizes amylase under highly unfavorable conditions (amylase is normally destroyed at pH 9), but also allows pronounced amylolytic activity even at high alkaline pH.This dishwashing detergent composition In fact, even after 5 months of storage at room temperature, other tests showed that the effectiveness of the composition on hard waste was greater than that of the commercially available ADD, especially at a low concentration of 5 g/l of dishwashing formulation. It turned out to be high.

Example 4 In accordance with the present invention, an aqueous liquid detergent composition for dishwashing racks was prepared which is suitable for hand washing of dishes and for pre-soaking of particularly dirty dishes before machine washing. This composition has the following ingredients as shown in aX.

Weight % Deionized water 46.1 Caustic soda solution (50% NaOH) 2.2 Sodium carbonate (
anhydrous) 5.0 Sodium silicate (N a20 : S i O2 ratio
47.5% solution of 15.741:2.4) NaTPP (Thermphos NW) 12.0Na
TPP (Boom Phos N Hexa) 12.0NazE
l<Ot ・10 N20 0.9 lactic acid
1.8 casein
2.0 Esperase ROT,
f'l ill monostearyl phosphate 0.16 Daufax 3 B-20,
80 (45% N & monodecyl/didecyl diphenyl oxide disulfonate aqueous solution) aluminum stearate) 0.50 ioo
,.

The dishwasher detergent composition of the present invention comprising a stabilizing enzyme system comprises:
It can also be produced as a powder composition for dishwashers.

In the above manufacturing method, the ingredients and their proportions can be varied by those skilled in the art to obtain preferred dishwasher detergent compositions having specific ingredients and proportions.

It will be understood that the above detailed description is for illustration only and that changes may be made without departing from the spirit of the invention.

(4 other people) 3:3δノ

Claims (23)

[Claims] (1) An aqueous liquid detergent composition for dishwashers containing a stabilizing enzyme system containing the following ingredients: water alkali metal phosphate builder organic surfactant boron compound carboxylic acid protein-containing material, and enzymes. (2) The boron compound is borax (Na_2B_4O_
7・10H_2O), sodium borate (Na_3BO
At least one of _3), boric acid, and boron oxide
The aqueous liquid composition for dishwashing machines according to claim 1, which is of the type. (3) The aqueous liquid composition for a dishwasher according to claim 1, wherein the protein-containing substance is casein. (4) The following ingredients: Ingredient weight% water 35-65% Alkali metal phosphate builder 8-35 Sodium silicate 0-20 Organic surfactant 0-5 Boron compound 0.4-2 Carboxylic acid 1-5 Protein-containing substances 1-6 enzyme 1-6 An aqueous dishwasher liquid composition comprising a stabilized enzyme system. (5) The aqueous liquid composition for dishwashing machines according to claim 4, comprising 0-5% by weight of a thixotropic clay thickener. (6) The boron compound is borax (Na_2B_4O_
7.10H_2O), sodium borate, boric acid, and boron oxide, and the carboxylic acid is α-hydroxycarboxylic acid. . (7) The following components: Component weight % Water 40-55 Sodium tripolyphosphate 20-30 Organic surfactant 0-5 Sodium silicate 0-20 Sodium carbonate 0-9 Antifoaming agent 0-5 Borax (Na_2B_4O_7・10H_2O )0.7
5-2.0 α-hydroxycarboxylic acid 1.5-4.0 casein 1.0-4.0 enzyme 0.5-2.0 Aqueous liquid composition for dishwashers according to claim 4 thing. (8) The aqueous liquid composition for dishwashers according to claim 7, wherein the anionic surfactant is linear sodium tridecylbenzene. (9) The aqueous liquid composition for dishwashers according to claim 7, wherein the α-hydroxycarboxylic acid is at least one of lactic acid, tartaric acid, citric acid, and their sodium salts. (10) The aqueous liquid composition for dishwashers according to claim 7, wherein the α-hydroxycarboxylic acid is citric acid and its sodium salt. (11) The following ingredients: Ingredient weight % Water 40-55 Sodium tripolyphosphate 20-30 Thixotropic clay thickener 0.25-5.0 Anionic surfactant 0.1-5 Sodium silicate 0-20 Sodium carbonate 2-9 Antifoaming agent 0.1-0.5 Borax (Na_2B_4O_7・10H_2O) 0.7
5-2.0 α-hydroxycarboxylic acid 1.5-4.0 casein 1.0-4.0 enzyme 0.5-2.0 Aqueous liquid composition for dishwashers according to claim 4 thing. (12) The aqueous liquid composition for dishwashers according to claim 11, wherein the anionic surfactant is linear sodium decylsulfonate. (13) α-hydroxycarboxylic acid is at least one of butyric acid, tartaric acid, citric acid and their sodium salts.
12. The aqueous liquid composition for dishwashing machines according to claim 11, which is of the type. (14) The following ingredients: Ingredient weight % Water 40-55 Sodium tripolyphosphate 20-30 Thixotropic clay thickener 0.5-4.0 Sodium silicate 2.5-20 Sodium carbonate 2-9 Anionic surfactant 0.3-2.0 Borax (Na_2B_4O_7・10H_2O) 0.7
An aqueous thixotropic composition for an automatic dishwasher containing a stabilized enzyme system comprising: 5-2.0 α-hydroxycarboxylic acid 1.5-4.0 casein 1.0-4.0 enzyme 0.5-2.0. (15) The aqueous thixotropic composition for an automatic dishwasher according to claim 14, which comprises a physical stabilizer of a long chain fatty acid metal salt in an amount sufficient to enhance the physical stability of the composition. (16) The composition according to claim 15, wherein the physical stabilizer is aluminum stearate. 17. The composition of claim 15, wherein the physical stabilizer is present in an amount of about 0.1-2%. (18) The composition according to claim 14, wherein the thixotropic thickener is an inorganic or organic colloid-forming clay. (19) The composition according to claim 14, wherein the clay is montmorillonite clay, attapulgite clay, hectorite clay or smectite clay. (20) The composition according to claim 14, containing 0.1-0.5% of an antifoaming agent. (21) A method for cleaning dirty dishes, which comprises bringing the aqueous liquid composition for dishwashers according to claim 1 into contact with the dirty dishes. (22) contacting the soiled dishes in an automatic dishwashing machine with an aqueous cleaning bath in which an effective amount of the composition of claim 7 is dispersed; How to clean dirty dishes that come into contact with dishes. (23) A method for cleaning dirty dishes in an automatic dishwasher having an aqueous cleaning bath in which an effective amount of the composition according to claim 14 is dispersed.