JP2002520482A - Cleaning tablets - Google Patents

Abstract

  (57) [Summary] Wherein the tablet comprises: a) a first phase in the form of a molded body having at least one mold therein; and b) a second phase in the form of a particulate solid compacted in said mold. Multiphase wash tablets suitable for use. Multiphasic washed tablets have improved solubility and detergency properties, while at the same time having excellent tablet integrity and strength.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] Technical Field The present invention relates to cleaning tablets of multi-phase.

[0002] The detergent composition of the background tablet of the invention are known in the art. Tablet-type detergent composition
It is understood that it has several advantages over granular detergent compositions, such as ease of dosing, handling, transport and storage. Washed tablets are most commonly made by premixing the ingredients of the detergent composition and forming the premixed detergent composition into tablets using a suitable machine, preferably a tablet press. Tablets are typically formed by compressing the components of the detergent composition such that the resulting tablet is strong enough to withstand handling and transport without sustained damage. Is done. In addition to being strong, the tablet must also dissolve quickly enough so that its ingredients are released into the wash water as quickly as possible early in the wash cycle.

[0003] However, there is a trade-off that increasing the compression force decreases the dissolution rate of the tablet. Thus, the present invention has found a balance between tablet strength and tablet solubility. A solution to this problem involves compressing the tablet with a low compression force, as found in the prior art. However, tablets made in this way, although having a relatively fast dissolution rate, tend to be friable and damaged, making them unacceptable to consumers. Other solutions include making tablets with relatively high compression forces and dissolution aids such as foaming agents to achieve the required strength levels.

[0004] Multiphasic washed tablets described in the prior art are made by compressing a first composition in a tablet press to form a substantially flat layer. Then, another detergent composition is dispensed over the first layer in a tablet press. This second composition is then compressed, forming another substantially flat layer. Typically, the first and second compressive forces are of the same magnitude. Applicants note that, in this case, the compressive force must be sufficient to bond the first and second compositions together, so that the force used in both the first and second compression stages is approximately 4,000 to 20,000 kg (about 10
(assuming a tablet cross-sectional area of ² cm ² ). As a result, the dissolution rate of the tablet is further reduced. Other multiphasic wash tablets that exhibit differential dissolution are made, such as by compressing the second phase with less force than the first phase. However, even if the dissolution rate of the second phase is improved, the second phase is more flexible than the first phase and is therefore more likely to be damaged and damaged due to handling and transport.

[0005] EP 0,055,100 describes a lavatory block formed by combining low solubility moldings and tablets. The lavatory block is placed in the lavatory aquarium and is designed to dissolve over a period of days, preferably weeks.
As a means of reducing the dissolution rate of the lavatory block, this reference teaches the incorporation of one or more solubility modifiers. Examples of such solubility modifiers are paradichlorobenzene, waxes, long chain fatty acids and alcohols and their esters, aliphatic alkylamides. Tablet detergents for washrooms or automatic dishwashers must substantially dissolve within one cycle of the washer or dishwasher, ie, 15 to 120 minutes.

[0006] According to a first aspect of the gist the present invention, multi-phase cleaning tablets for use in washing machine there is provided a tablet comprising: a) at least one type (Mold) therein And b) a second phase in the form of a particulate solid compacted in said mold.

In a preferred embodiment, the first phase is at least about 350 kg / cm ² (3.43 k
N / cm ^2), preferably from about 400 to about 2000 kg / cm ^2, is acted particularly from about 600 to about 1200 kg / cm ² compressive force compression molded body made over (compression force here force The cross-sectional area of the tablet in the transverse plane to the applied force, ie divided by the cross-sectional area of the rotary press). The particulate solid of the second phase (the term is intended to include multiple "second" phases, sometimes referred to as "any additional phase") is smaller than that applied to the first phase It is compressed into the mold by a compression force. This compression force is preferably also less than about 350 kg / cm ² , preferably from about 40 to about 300
kg / cm ² , more preferably in the range of about 70 to about 270 kg / cm ² . Such tablets provide optimal tablet integrity and strength (eg, Child Bite Strength [CBS]
It is preferable from the viewpoint of giving the dissolution characteristics of the product. Tablets of the invention preferably have a CBS of at least 10 kg, preferably greater than 12 kg, more preferably greater than 14 kg. CBS is a US Consumer Product Safety Commission Test Specifica
measurement). The compressive force acting on the first and second phases is generally in a ratio of at least about 2: 1, preferably at least about 4: 1.

Thus, according to a further aspect of the present invention there is provided a multi-phase cleaning tablet for use in a cleaning machine, the tablet comprising: a) compressed molding having at least one mold therein. A first phase in the form of a body, wherein the shaped body is prepared with a compressive force of at least about 350 kg / cm ² ; and b) a second phase in the form of a granular solid compressed in said mold, The second phase is about 350
prepared with a compression force of less than kg / cm ² .

In another preferred embodiment, the second phase is in at least one form of the first phase in a cohesive state, for example, in the form of a compact or a compact by physical or chemical cohesion. . Preferably, the first and second phases are in a relatively high weight ratio to the other, for example, at least about 6: 1, preferably about 10: 1, and the tablet composition has one or more detersive activities. It is also preferable to include components (for example, enzymes, bleaching agents, bleaching activators, bleaching catalysts, surfactants, chelating agents, etc.). They are mainly concentrated in the second phase, for example at least about 50%, preferably at least about 60%, in particular 80%, by weight of the active ingredient (based on the total weight of the active ingredients of the tablet), It is in. Further, such compositions are optimal for tablet strength, dissolution, cleaning and pH adjusting properties, eg, 10, 5, 4 or 3 at the beginning of the cleaning process.
To release at least 50%, preferably at least 60%, more preferably at least 80%, by weight, of the cleaning active, relative to the cleaning liquid, even within minutes.
Provided is a tablet composition that can be dissolved in a washing solution.

Thus, according to another aspect of the present invention there is provided a multi-phase washed tablet for use in a washing machine, the tablet comprising the following components: a) at least one mold therein And b) a second phase in the form of a particulate solid compacted in said mold, wherein said tablet comprises at least one detersive active and has at least one by weight Formulated such that 50%, preferably at least 60%, more preferably at least 80% of the cleaning active is released into the cleaning liquid within the first 10 minutes, preferably within 5 minutes, more preferably within 3 minutes of the cleaning process. Have been.

[0011] Not only has sufficient strength that the detailed description withstand handling and transportation of the invention, the cleaning tablet as at least a substantial portion is rapidly released rapidly dissolved detergent active ingredients to the wash water It is an object of the present invention to provide. At least one phase of the tablet dissolves in the wash water within the first 10 minutes, preferably within 5 minutes, more preferably within 4 minutes of the first wash cycle of the automatic dish washer or washing machine; Is preferred. Preferably, the washing machine is either an automatic dishwasher or a washing machine. The time for dissolution of the multiphasic tablet, or one of its phases or the cleaning active ingredient, should be minimum using a dishwasher available from Bosch, at normal 60 ° C. in 18H water, to ensure reproducibility. Determined according to DIN 44990 using 6 or a sufficient number of duplicates.

[0012] The multiphasic washed tablet of the present invention includes a first phase, a second phase and any additional phases. The first phase is in the form of a molding of the cleaning composition comprising one or more of the cleaning components described below. Preferred cleaning ingredients include builders, bleaches, enzymes, and surfactants. The components of the cleaning composition are mixed together, for example, by mixing dry components or spraying liquid components. These components are then formed into a first phase using suitable equipment, but preferably by compression, eg, a tablet press. Alternatively, the first phase can be prepared by extrusion, casting or the like.

[0013] The first phase is prepared to include at least one mold on the surface of the molded body. In a preferred embodiment, the mold is such that when the surface of the press contacts and presses the cleaning composition, the surface pushes the mold or molds into the first phase of the multi-phase cleaning tablet. It is made using a specially designed tablet press so that the surface of the punch in contact with the cleaning composition is shaped. Preferably, the mold has an inwardly recessed or generally concave surface to provide better adhesion to the second phase.

[0014] The tablets of the present invention also include one or more additional phases prepared from a composition that includes one or more of the following cleaning ingredients. The at least one phase (herein referred to as the second phase) preferably comprises a particulate solid (this term refers to powders, granules, agglomerates and other particulate solids, including mixtures thereof with liquid binders, molten solids, sprays, etc.). ), Which is pressed into one or more molds of the first phase of the cleaning tablet, such that the second phase itself is in the form of a molded body. Preferred cleaning ingredients include builders, colorants, binders, surfactants, disintegrants, and enzymes, especially amylase and protease enzymes.

[0015] In another preferred aspect of the invention, the second and optional additional phase comprises a disintegrant selected from degrading or blowing agents. Suitable disintegrants include agents that swell in contact with water, or agents that form channels in the cleaning tablet to facilitate water inflow and / or outflow. Any known disintegrant or foaming agent suitable for use in laundry or rewashing applications of clothing is contemplated for use herein. Suitable degrading agents include starch, for example, starch derivatives such as Arbocel (trade name) and Vivapur (trade name) available from Rettenmaier, Nymcel (trade name) available from Metsaserla, alginate, acetate trihydrate, brookite, Formula Na ₂ CO ₃ .H ₂ O
Monohydrated carbonate, hydrated STPP having at least about 40% phase I content, carboxymethylcellulose (CMC), CMC base polymer, sodium acetate, aluminum oxide. Suitable blowing agents are those that generate gas on contact with water. Suitable blowing agents are species that generate oxygen, nitric oxide, or carbon dioxide. Examples of preferred blowing agents are selected from the group consisting of perborate, percarbonate, carbonate, bicarbonate in combination with citric acid, sulfamic acid, malic acid, or maleic acid.

The components of the cleaning composition are mixed together, for example, by mixing the dry components and mixing or spraying the liquid components. The components of the second and any additional phases are then pumped into the mold provided by the first phase and retained therein. A preferred embodiment of the present invention comprises two phases; a first phase and a second phase. The first phase usually contains one type and the second phase usually consists of a single cleaning active. However, the first phase may comprise more than one type and the second phase may be prepared from one or more cleaning active ingredients. Further, the second phase may include one or more detersive actives contained within one type. It is also envisioned that some types of cleaning actives may be included in other types. In this way, chemically sensitive cleaning components can be separated to avoid loss of performance caused by reaction between the components and to avoid potential inactivation or depletion.

In a preferred aspect of the invention, the first, second and / or any additional phases may include a binder. If a binder is present, it is an organic polymer, such as granular and liquid polyethylene and / or polypropylene glycol, especially those having a molecular weight of 4000,6000 and 9000, polyvinylpyrrolidone (PVP), especially PVP with a molecular weight of 90000, polyacrylate, Sucrose, sucrose derivatives, starch and starch derivatives such as hydroxypropylmethylcellulose (HPMC)
And carboxymethylcellulose (CMC); and inorganic polymers such as hexametaphosphate.

In a preferred aspect of the invention, the first phase weighs more than 5 g. More preferably, the first phase weighs between 10 g and 30 g, even more preferably between 15 g and 25 g, and most preferably between 18 g and 24 g. The second and any additional phases weigh less than 4 g. More preferably, the second and any additional phases weigh between 1 g and 3.5 g, most preferably between 1.3 g and 2.5 g.

In another embodiment of the present invention, the barrier layer comprising the barrier layer composition comprises a first phase, a second phase and / or
Or between any additional phases, or between the second phase and any additional phases. The barrier layer composition contains at least one binder selected from the group described above. The advantage of the presence of a barrier layer is that it prevents and reduces penetration of components from one phase to another, for example from the first phase to the second and / or any additional phases and vice versa It is. The components of the second phase and / or any additional phases are compressed at a very low pressure compared to the compression force normally used to make tablets. Thus, an advantage of the present invention is that, because of the use of low compression pressure, heat, force or chemically sensitive detergent components suffer from the significant performance loss normally encountered when formulating such components into tablets. Without being added, it can be incorporated into washed tablets.

A further feature of the invention is that the second phase is better protected against damage caused, for example, by handling and transport. As mentioned above, a multi-phase washed tablet was prepared where the second phase was compressed at a lower pressure than the first phase. However, while the dissolution rate is improved, the second phase of these tablets is damaged and tends to crumble or shatter on contact. However, the lightly compressed phase of the washed tablet of the present invention is protected in the form provided by the first phase of the washed tablet.

[0021] Yet another advantage of the present invention is that one can make multi-phase wash tablets such that one phase can be designed to dissolve, preferably significantly before the other. In the present invention, the second phase and / or any additional phases dissolve before the first phase. According to the preferred weight range described above, the first phase is 5-20 minutes, more preferably 10-15 minutes,
And the second and / or optional additional phases dissolve in less than 5 minutes, more preferably in less than 4.5 minutes, and most preferably in less than 4 minutes. The time for the first, second and / or any additional phases to dissolve is dependent on each other. Thus, in a particularly preferred aspect of the invention, dissolution with a time lag is achieved. A particular advantage of being able to achieve staggered dissolution of the multi-phase washed tablet is that components which are chemically inert due to the presence of other components are separated into different phases. In this case, the inactivated components are preferably in the second phase and / or any additional phases. Yet another advantage of the present invention is that the cohesion between the phases of a multi-phase washed tablet is improved. This improved tackiness results in less exposure of the second phase as compared to multi-phase tablets known in the art, making the tablets of the present invention less prone to cracking along the line of contact between the phases. Conceivable.

Process The multiphase washed tablets are made using a suitable tablet press. Preferably, tablets are prepared by compression in a tablet press capable of making tablets of mold. In a particularly preferred embodiment of the invention, the first phase is prepared using a specially designed tablet press. The punch of this tablet press is modified such that the surface of the punch with which the detergent composition contacts is a convex surface.

The first detergent composition is fed into the tablet press die, the punches are lowered and contacted, and then the detergent composition is compressed to form a first phase. The first cleaning composition is preferably 350 to 2000 kg / cm ² , more preferably 500 to 150 kg / cm ² .
0 kg / cm ^2, most preferably compressed under a pressure of 600~1200kg / cm ^2. The punch is then raised, exposing the first phase including the mold. The second and / or any additional phases are then pumped into the mold. The punch of the specially designed tablet press is lowered twice to lightly compress the second phase and / or any additional detergent composition to form the second phase and / or any additional phases. In another aspect of the invention, if any additional phases are present, any additional phases are prepared in any additional compression steps substantially similar to the second compression step described above. The second and / or optional additional detergent composition is preferably less than 350 kg / cm2, more preferably 40-400 kg / cm2.
300 kg / cm ^2, most preferably compressed at a pressure of 70~270kg / cm ^2. After compression of the second detergent composition, the punch is raised twice and the multiphase washed tablet is removed from the tablet press.

Detergent Ingredients The first, second and / or optional additional phases of the multiphasic cleaning tablets herein are prepared by compressing one or more compositions containing the cleaning active. Is done. Suitably,
Compositions used in any of these phases include builder components, surfactants, enzymes,
Bleaching agent, alkali source, coloring agent, fragrance, calcium soap dispersant, organic polymer compound including polymer dye transfer inhibitor, crystal growth inhibitor, heavy metal ion scavenger, metal ion salt, enzyme stabilizer, corrosion inhibitor A variety of detergent ingredients can be included, including suds suppressors, solvents, fabric softeners, optical brighteners, and hydrotropes. Highly preferred detergent components of the first phase include builder compounds, surfactants, enzymes and bleaches. Highly preferred detergent components of the second phase include builder compounds, enzymes and disintegrants.

Builder Compounds Tablets of the present invention preferably contain a builder compound, typically 1% to 80%, preferably 10% to 70%, most preferably 20% to 6% by weight of active cleaning ingredient.
Present at 0% level.

Water-soluble builder compounds Suitable water-soluble builder compounds include water-soluble monomeric polycarboxylates,
Or their acid forms, or homo- or copolymerizable polycarboxylic acids, or salts thereof, wherein the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by no more than 2 carbon atoms, a carbonate, Including bicarbonate, borate, phosphate, and mixtures of any of these.

The carboxylate or polycarboxylate builders are generally preferred for their cost and performance, although monomeric polycarboxylates may be of the monomeric or oligomeric type. Carboxylates containing one carboxyl group include water-soluble salts of lactic acid, glycolic acid and their ether derivatives. Polycarboxylates containing two carboxyl groups include succinic acid, malonic acid, (ethylenedioxy) diacetate,
Includes water-soluble salts of maleic, diglycolic, tartaric, tartronic, and fumaric acids, as well as ether carboxylate and sulfinyl carboxylate. Polycarboxylates containing three carboxyl groups include, in particular, water-soluble citrates, aconitrates and citraconates and succinic derivatives, such as carboxymethyloxysuccinates as described in GB 1,379,241, GB 1,389.
No. 7,732, lactoxysuccinate, amino acid succinate described in Netherlands Application No. 7205873, and 2-oxa-1,1,1 described in British Patent No. 1,387,447.
Oxypolycarboxylates such as 3-propanetricarboxylate are included.

Polycarboxylates containing four carboxyl groups are described in GB 1,261,82
No. 9, oxydisuccinate, 1,1,2,2-ethanetetracarboxylate, 1,1,3,3-propanetetracarboxylate and 1,1,2,3
-Including propane tetracarboxylate. Polycarboxylates having a sulfo substituent include British Patent Nos. 1,398,421 and 1,398,422 and U.S. Pat.
No. 2 and the sulfonated pyrolytic citric acid described in GB 1,439,000.

Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis,
Cis-tetracarboxylate, cyclopentadienepentacarboxylate,
2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylate, 2,5-tetrahydrofuran-cis-tetracarboxylate, 2,2,5,5-
Includes tetrahydrofuran-tetracarboxylate, 1,2,3,4,5,6-hexane-hexacarboxylate and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol, xylitol. Aromatic carboxylate includes the derivatives of melitic acid, pyromellitic acid and phthalic acid described in GB 1,425,323.

Of these, preferred polycarboxylates are hydroxycarboxylates having up to three carboxyl groups per molecule, especially citrates. The parent acid of a monomeric or oligomeric polycarboxylate chelating agent or a salt of a mixture thereof, ie, citric acid or a citrate / citric acid mixture, can also be expected as a useful builder compound.

[0031] Borate builders, as well as builders containing borate-forming substances capable of forming borates during detergent storage or under laundering conditions, can also be used, although laundering conditions below 50 ° C., especially below 40 ° C. Is not preferred. Examples of carboxylate builders include alkaline earth metals and alkali metal carbonates, including sodium carbonate, sesquicarbonate, and mixtures thereof;
Ultrafine calcium carbonate as described in German Patent Application No. 2,321,001, published Jan. 15, 2015.

A highly preferred builder compound for use in the present invention is a water-soluble phosphate builder. Specific examples of water-soluble phosphate builders include alkali metal tripolyphosphate, sodium, potassium and ammonium pyrophosphate, sodium, potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polyphosphate having a degree of polymerization of 6-21. Meta / phosphoric acid and phytate. Highly preferred builder compounds for use in the present invention are water-soluble phosphate builders. Specific examples of water-soluble phosphate builders include alkali metal tripolyphosphate, sodium, potassium and ammonium pyrophosphate, sodium, potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polyphosphate having a degree of polymerization of 6-21. Meta / phosphoric acid and phytate.

Partially soluble or non-soluble builder compound The tablet of the present invention contains a partially soluble or non-soluble builder compound. Partially soluble or non-soluble builder compounds are particularly suitable for use in tablets prepared for use in laundry cleaning methods. Examples of partially water-soluble builders are:
For example, European Patent Application 0164514, German Patent Application 3417649 and German Patent Application 37
No. 42043, including crystalline layered silicates. Preferably, it is a crystalline layered sodium silicate of the following general formula. _{NaMSi x O 2 + 1 · yH} 2 O wherein, M is sodium or hydrogen, x is the number of 1.9 to 4, y is a number of 0 to 20. This type of crystalline layered sodium silicate is described in European Patent Application 016451.
As described in Nos. 4 and 0293640, it preferably has a two-dimensional sheet structure such as a so-called δ-layer structure. The preparation of crystalline layered silicates of this type is described in German Patent Application No. 3417649 and German Patent Application No. 3742043. For the purposes of the present invention, x has a value of 2.3 to 4 in the above general formula, and is preferably 2.

The most preferred crystalline layered sodium silicate compound has the formula δ-Na ₂ Si ₂ O ₅ , known as NaSKS-6 (trade name) available from Hoechst. The crystalline layered sodium silicate material is preferably a PCT patent application no.
As described in US Patent No./18594, it is present in particulate detergent compositions as particles intimately mixed with a solid, water-soluble, ionizable material. The solid, water-soluble ionizable substance is selected from organic acids, salts of organic and inorganic acids, and mixtures thereof, with citric acid being preferred.

An example of a largely water-insoluble builder is sodium aluminosilicate.
Suitable aluminosilicates include aluminosilicate zeolites of the following unit cell formula: Na _z [(AlO ₂ ) _z (SiO ₂ ) _y ] xH ₂ O where z and y are at least 6. The molar ratio of z to y is 1.0 to 0.5, and x is at least 5, preferably 7.5 to 276, more preferably 10 to
264. The aluminosilicate material is in hydrated form, preferably crystalline, and contains 10% to 28%, more preferably 18% to 22% water in bound form.

Aluminosilicate zeolites are naturally occurring substances, but are preferably derived synthetically. The synthetic crystalline aluminosilicate ion-exchange material is zeolite A, zeolite A, zeolite B, zeolite P, zeolite X, zeolite H
S and their mixtures are available. A preferred synthesis of aluminosilicate zeolites is described in Zeolite (1994) 14 (2), 110
-116, which describes a method for preparing a colloidal aluminosilicate zeolite. The colloidal aluminosilicate zeolite particles have less than 5% of particles larger than 1 μm in diameter and 0.05 μm in diameter.
Less than 5% of particles smaller than m. Preferably, the aluminosilicate zeolite particles are from 0.01 μm to 1 μm, more preferably from 0.05 μm to 0.9 μm,
Most preferably it has an average particle between 0.1 μm and 0.6 μm.

Zeolite A has the formula: Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] .xH ₂ O where x is from 20 to 30, in particular 27. Zeolite X has the formula: Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] .276H ₂ O Zeolite MAP is preferred for the zeolite builder herein, as described in EP 384,070.

A preferred aluminosilicate zeolite is a colloidal aluminosilicate zeolite. When used as a component of a detergent composition, the colloidal aluminosilicate zeolite, especially colloidal zeolite A, enhances the builder's performance in providing stain removal. Enhanced builder performance also shows reduced fabric deposits and improved retention of fabric whiteness, problems that were associated with poor builder detergents. A surprising finding is that a mixed aluminosilicate zeolite detergent composition comprising colloidal zeolite A and colloidal zeolite Y provides equivalent calcium ion scavenging capacity for the same weight of commercially available zeolite A. Another surprising finding is that the aluminosilicate zeolite detergent composition described above provides equivalent magnesium ion scavenging capacity for the same weight of commercially available zeolite A.

Surfactants Surfactants are the preferred detersive actives of the compositions herein. Suitable surfactants are selected from anionic, nonionic, amphoteric and zwitterionic surfactants and mixtures thereof. The automatic dishwashing product must be low-foaming, so that foaming of the surfactant system for use in dishwashing must be suppressed, or preferably low-foaming and typically nonionic Sex. Foams generated in surfactant systems used in laundry cleaning do not need to be reduced to the same extent as for dishwashing. Surfactants are typically 0.2% to 3% by weight of the composition of the detersive active.
It is present at a level of 0%, more preferably 0.5% to 10%, most preferably 1% to 5%.

A typical list of anionic, nonionic, amphoteric and zwitterionic classes and types of these surfactants can be found in US Pat. No. 3,929,678 to Laughlin and Heuring, issued Dec. 30, 1975. Is shown in A list of suitable cationic surfactants is provided in Murphy U.S. Pat. No. 4,259,217, issued Mar. 31, 1981.
A list of surfactants included in the automatic dishwashing detergent composition can be found, for example, in European Patent Application 04
No. 14549, PCT Application Nos. WO93 / 08876 and WO93 / 08874.

Nonionic Surfactants Nonionic surfactants that are essentially useful for cleaning purposes can be included in the cleaning tablets. Non-limiting examples of preferred useful nonionic surfactants are provided below.

Nonionic Ethoxylated Alcohol Surfactants Alkyl ethoxylated condensates of 1 to 25 moles of ethylene oxide of a fatty alcohol are useful for the purposes herein. The alkyl chain of the aliphatic alcohol may be linear or branched, primary or secondary, and generally has 6 to 22 carbon atoms. Particularly preferred is a product obtained by condensing an alcohol having an alkyl group having 8 to 20 carbon atoms with 2 to 10 moles of ethylene oxide per mole of alcohol.

End-capped alkylalkoxylated surfactants Suitable end-capped alkylalkoxylated surfactants are epoxy-capped poly (oxyalkylated) alcohols of the formula: R ₁ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ₂ ] (I) wherein R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms;
2 is a linear or branched aliphatic hydrocarbon radical having 2 to 26 carbon atoms;
An integer with a mean value of 1.5, more preferably 1; and y is at least 15,
More preferably, it is an integer of at least 20.

Preferably, the surfactant of formula (I) comprises a terminal epoxy unit [CH ₂ CH (OH)
R ₂ ] has at least 10 carbon atoms. According to the present invention, suitable surfactants of the formula I are described, for example, in WO 94/22800, published on November 13, 1994 by Olin Corporation.
As described in a POLY-TERGENT ^R SLF-18B of Olin Corporation.

Ether-Capped Poly (oxyalkylated) Alcohols Preferred surfactants for use herein include ether-capped poly (oxyalkylated) alcohols of the formula _{^{R 1 O [CH 2 CH (}} R 3) O] x [CH 2] k CH (OH) [CH 2] j OR 2 wherein, R ¹ and R ² are linear or branched C1-30 A saturated or unsaturated, aliphatic or aromatic hydrocarbon radical; R ³ is a hydrogen atom or a linear aliphatic hydrocarbon radical having 1 to 4 carbon atoms; x is an integer having an average value of 1 to 30 , X is 2 or more, R ³ may be the same or different, and k and j are integers having an average value of 1 to 12, preferably 1 to 5.

R ¹ and R ² are preferably straight-chain or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, most preferably having 8 to 18 carbon atoms. preferable. R ³ is most preferably H or a linear aliphatic hydrocarbon radical having 1 to 2 carbon atoms. Preferably, x is an integer having an average value of 1 to 20, more preferably 6 to 15.

As described above, in a preferred embodiment, when x is 2 or more, R ³ may be the same or different. That is, R ³ may vary between any of the aforementioned alkyleneoxy units. For example, if x is 3, R ³ is selected from ethyleneoxy (EO) or propyleneoxy (PO), and (EO) (PO) (EO), (EO) (EO) (PO), (EO) ( (EO) (EO), (PO) (EO)
It may be changed in the order of (PO), (PO) (PO) (EO) and (PO) (PO) (PO). Of course, the integer 3 has been chosen as an example, but for larger integer values of x the change is very large, for example comprising a large number of (EO) units and a smaller number of (PO) units. As mentioned above, particularly preferred surfactants are those having a low cloud point of less than 20 ° C. These low cloud point surfactants are employed in combination with high cloud point surfactants as described below for excellent grease cleaning performance.

The most preferred ether-capped poly (oxyalkylated) alcohol surfactants are those wherein k is 1 and j is 1, such as surfactants of the formula: R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² where R ¹ , R ² and R ³ are as defined above and x is 1 to 30, preferably 1 to 20, still more preferably Is an integer having an average value of 6 to 18. The most preferred surfactant is a range of R ¹ and R ² is 9-14, is H R ³ to form an ethyleneoxy and x ranges from 6 to 15.

[0049] Ether-capped poly (oxyalkylated) alcohol surfactants include three common components: straight or branched chain alcohols, alkylene oxides, and alkyl ether endblockers. Alkyl ether endblockers and alcohols act as hydrophobic, oil-soluble portions of the molecule, while alkylene oxide groups form the hydrophilic, water-soluble portion of the molecule. These surfactants, when used in combination with high cloud point surfactants, significantly improve spot and film formation properties and improve grease-like oil removal compared to conventional surfactants. .

Generally, the ether-capped poly (oxyalkylated) alcohol surfactants of the present invention react an aliphatic alcohol with an epoxide to form an ether and then react with a base to form a secondary epoxide. This secondary epoxide then reacts with the alkoxylated alcohol to form the novel compounds of the present invention. An example of a method for preparing an ether-capped poly (oxyalkylated) alcohol surfactant is described below.

Preparation of C _12/14 alkyl glycidyl ether C _12/14 aliphatic alcohol (100.00 g, 0.515 mol) and tin (IV) chloride (0.58 g)
, 2.23 mmol, available from Aldrich) in a 500 mL three-necked round bottom flask equipped with a condenser, argon inlet, attached funnel, magnetic stirrer and internal temperature probe. The mixture is heated to 60C. Epichlorohydrin (47.70 g, 0.515 mol, available from Aldrich) is added dropwise while maintaining the temperature at 60-65 ° C. After stirring for an additional hour at 60 ° C., the mixture is cooled to room temperature. The mixture is stirred mechanically with a 50% solution of sodium hydroxide (61.8%).
(0 g, 0.773 mol, 50%). After the addition is complete, the mixture is brought to 90 ° C. for 1 hour.
. Heat for 5 hours, cool and filter with ethanol aid. Separate the filtrate and wash the organic phase with water (100 mL), dry over MgSO ₄ , filter and concentrate. 100
Distillation of the oil at -120 ° C (0.1 mmHg) gives the glycidyl ether as an oil.

Preparation of C _12/14 alkyl-C _9/11 ether-blocked alcohol surfactant Neodol R91-8 (20.60 g, 0.0393 mol ethoxylated alcohol, Shell Chemica
Co.) and tin (IV) chloride (0.58 g, 2.23 mol) were charged to a 500 equipped with a condenser, argon inlet, attached funnel, magnetic stirrer and internal temperature probe.
Combine in a mL 3-neck round bottom flask. The mixture is heated to 60 ° C., at which temperature C _12/14 alkyl glycidyl ether (11.00 g, 0.0393 mol) is added dropwise over 15 minutes.

After stirring at 60 ° C. for 18 hours, the mixture is cooled to room temperature and dissolved in the same proportions of dichloromethane. The solution is passed through a 1 inch pad of silica gel eluting with dichloroethane. The furnace liquor is concentrated on a rotary evaporator and then evaporated in a Kugelrohr oven (100 ° C., 0.5 mm Hg) to give the surfactant as an oil.

Nonionic ethoxylated / propoxylated fatty alcohol surfactants C6-C18 ethoxylated fatty alcohols and C6-C18 ethoxylated / propoxylated mixed fatty alcohols are used herein, especially if they are water-soluble. Suitable for use. Preferably, the ethoxylated fatty alcohol is a C10-C18 ethoxylated fatty alcohol having a degree of ethoxylation of 3 to 50, most preferably a C12-C18 ethoxylated fatty alcohol having a degree of ethoxylation of 3 to 40. . Preferably, the ethoxylated / propoxylated mixed fatty alcohol has an alkyl chain of 10 to 18 carbon atoms and a degree of ethoxylation of 3 to 30 and a degree of propoxylation of 1 to 10 carbon atoms.

Nonionic EO / PO Propylene Glycol Condensate The condensation product of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol is suitable for use herein. The hydrophobic portion of these compounds preferably has a molecular weight of 1500-1800 and is water-insoluble. Examples of compounds of this type include the commercially available Pluronic ^™ surfactant sold by BASF.

Nonionic EO condensate of ethylenediamine / propylene oxide adduct The ethylene oxide condensate of the product obtained from the reaction of propylene oxide with ethylenediamine is suitable for use herein. The hydrophobic portion of these products consists of the reaction product of ethylene diamine and excess propylene oxide, and generally has a molecular weight of 2500-3000. Examples of this type of nonionic surfactant are commercially available Tetronic sold by BASF.
Contains TM compounds.

Mixed Nonionic Surfactant System In a preferred embodiment of the present invention, the cleaning tablet comprises at least one low cloud point nonionic surfactant and at least one high cloud point nonionic surfactant. As used herein, "cloud point" is a well-known property of nonionic surfactants that results from a decrease in solubility of the surfactant with increasing temperature, where the appearance of the second phase is observed. The temperature that can be measured is called the "cloud point" (Kirk Othmer's Enctc
lipedia of Technology, 3rd Ed. Vol.22 pp.360-379).

As used herein, a “low cloud point” nonionic surfactant is at 30 ° C.
It is defined as a nonionic surfactant system having a cloud point of less than 20 ° C, preferably less than 20 ° C and most preferably less than 10 ° C. Typical low cloud point nonionic surfactants are nonionic alkoxylated surfactants, especially ethoxylated products derived from primary alcohols, and polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) reverse block polymers. Such low cloud point nonionic surfactants also include ethoxyl carpropoxylated alcohols (eg, WO 94/22 published October 13, 1994 to Olin Corporation).
Olin Corporation's Poly-Tergent® SLF18B series as described in US Pat. No. 800) and ether-capped poly (oxyalkylated) alcohol surfactants.

[0059] The nonionic surfactant may optionally include propylene oxide in an amount of up to 15% by weight. Another preferred nonionic surfactant is Buill on September 16, 1980.
It can be prepared by a process such as that described in US Patent No. 4,223,163 issued to oty. This is incorporated herein by reference.

The low cloud point nonionic surfactant additionally contains a polyoxyethylene-polyoxypropylene block polymer compound. Polyoxyethylene-polyoxypropylene block polymerization compounds include those based on ethylene glycol, propylene glycol, glycerin, trimethylolpropane, and ethylenediamine as reactive hydrogen compounds that are reactive with the initiator. BASF-Wyandotte Corp. Wyandotte, Mi
PLURONIC ^R of chigan, REVERSED PLURONIC ^R, and TETRONIC certain block polymer surfactant compounds represented by ^R are suitable in ADD compositions of the present invention. Preferred examples include REVERSED PLURONIC ^R 25R2 and TETRONIC ^R 702. Such surfactants are typically used as low cloud point nonionic surfactants.

As used herein, a “high cloud point” nonionic surfactant is a nonionic surfactant system having a cloud point above 40 ° C., preferably above 50 ° C., most preferably above 60 ° C. Is defined as Preferably, the high cloud point nonionic surfactant system comprises ethoxylation derived from the reaction of a monohydric alcohol or alkylphenol having 8 to 20 carbon atoms with an average of 6 to 15 moles of ethylene oxide per mole of alcohol or alkylphenol. Contains a surfactant. Such high cloud point nonionic surfactants include, for example, Tergitol 15S9 (supplied by Union Carbide), Rhodasurf TMD8.5 (supplied by Rhone Poulenc) and Neodol 91-8 (supplied by SHELL).

It is also for the purposes of the present invention that the high cloud point nonionic surfactant additionally has a hydrophilic / hydrophobic balance value (HLB; see Kirk Othmer) of 9-15, preferably 11-15. Preferred. These include, for example, Tergitol 15S9 (Union
Carbide), Rhodasurf TMD8.5 (supplied from Rhone Poulenc), and Neodo
l Includes 91-8 (supplied by SHELL).

[0063] Other preferred high cloud point nonionic surfactants are C6-20 (C6-C20) straight or preferably branched C6-C20 (C6-C20) carbon-containing surfactants, including secondary alcohols and branched primary alcohols. Or a secondary aliphatic alcohol. Preferably the high cloud point nonionic surfactant is an ethoxylate of a branched or secondary alcohol,
More preferably, the C9 / 11 or C11 / 15 mixed branched alcohol has an average of 6 to 15 moles, preferably 6 to 12 moles, most preferably 6 moles per mole of alcohol.
~ 9 moles of ethylene oxide condensate. Preferably, such ethoxylated nonionic surfactants have a narrow ethoxylate distribution as compared to the average.

Anionic Surfactant Any anionic surfactant useful for substantially any cleaning purpose is suitable. These can include salts of anionic sulfates, sulfonates, carboxylate, and sarcosinates, including, for example, sodium, potassium, ammonium and substituted ammonium, such as mono, di, triethanolamine salts. Anionic sulfate surfactants are preferred.

Other anionic surfactants include isethionates such as acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinates ( In particular, saturated and unsaturated C12-C18 monoesters), diesters of sulfosuccinates (especially saturated and unsaturated C6-C14 diesters), N-acyl sarcosinates are included. Resin acids and hydrogenated resin acids, such as, for example, rosin, hydrogenated rosin, are also suitable, the resin acids and hydrogenated resin acids being present in derivatives of tallow oil.

Anionic Sulfate Surfactants The anionic sulfate surfactants useful herein include linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oleyl glycerin sulfate, alkyl phenol ethylene oxide Ether sulfate, C5-C17 acyl-N- (C1-C4 alkyl) and -N- (
Included are alkyl polysaccharide sulfates, such as (C1-C2 hydroxyalkyl) glucamine sulfate, and alkyl polyglucoside (the nonionic surfactants described herein) sulfate.

The alkyl sulphate surfactants are preferably linear and branched primary C10s.
-C18 alkyl sulfates, preferably selected from C11-C15 branched alkyl sulfates and C12-C14 linear alkyl sulfates. The alkyl ethoxy sulfate surfactant is selected from the group consisting of C10-C18 alkyl sulfate ethoxylated with 0.5 to 20 moles of ethylene oxide per mole. More preferably, the alkyl ethoxy sulfate surfactant is a C11-C18, most preferably a C11-C15 alkyl sulfate ethoxylated with 0.5 to 7 moles, preferably 1 to 5 moles of ethylene oxide per mole. . Particularly preferred for the purposes of the present invention are mixtures of the preferred alkyl sulphates and alkyl ethoxy sulphate surfactants. Such a mixture is disclosed in PCT patent application WO 93/18124.

Anionic Sulfonate Surfactants Useful anionic sulfonate surfactants herein include C5-C20 linear alkyl benzene sulfonates, alkyl ester sulfonates, C6-C22.
Primary and secondary alkane sulfonates, C6-C24 olefin sulfonates,
Includes sulfonated polycarboxylic acids, alkyl glycerin sulfonates, aliphatic acyl glycerin sulfonates, aliphatic oleyl glycerins and any mixtures thereof.

Anionic Carboxylate Surfactants Suitable anionic carboxylate surfactants include alkyl ethoxy carboxylate, alkyl polyethoxy polycarboxylate, and soaps (alkyl carboxoxy), especially certain secondary carboxylic acids described herein. Including grade soap. Suitable alkyl ethoxy carboxylate surfactants of the formula _{RO (CH 2 CH 2 O)} x CH 2 COO - in M ⁺ [wherein, R is C6~C18 alkyl group, x ranges from 0 to 10, ethoxy The distribution of rates includes those where x is 0 by weight and less than 20%, and M is a cation.

Suitable alkyl polyethoxy polycarboxylate surfactants are of the formula RO (C
HR ₁ -CHR ₂ -O) -R ₃ wherein R is a C6-C18 alkyl group, x is 1-25, and R1 and R2 are a hydrogen atom, a methyl acid halide, a succinic radical, a hydroxysuccinic radical And mixtures thereof, wherein R 3 is selected from a hydrogen atom, a substituted or unsubstituted hydrocarbon having 1 to 8 carbon atoms, and a mixture thereof.

[0071] Suitable soap surfactants include secondary soap surfactants that contain a carboxyl group attached to a secondary carbon. Preferred secondary soap surfactants herein are 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-
It is a water-soluble substance selected from the group consisting of water-soluble salts of butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps are also included as suds suppressors.

Alkali metal sarcosinate surfactants and other suitable anionic surfactants are R-CON (R ¹ ) CH ₂ COOM [
Wherein R is a C5-C17 linear or branched alkyl or alkenyl group, and R ¹ is C1
A C4 alkyl group, and M is an alkali metal ion]. Preferred examples are in the form of the sodium salts of myristyl and oleyl methyl sarcosinate.

Amphoteric Surfactants Suitable amphoteric surfactants for use herein include amine oxide surfactants and alkyl amphocarboxylic acids. Suitable amine oxide has the formula _{^{R 3 (OR 4) X N}} 0 (R 5) 2 [ wherein, R ³ is selected alkyl 8-26 carbon atoms, hydroxyalkyl, acyl amidopropyl, and alkylphenyl groups R ⁴ is selected from C 2-3 alkylene or hydroxyalkylene or mixtures thereof; x is 0-5, preferably 0-3; and each R ⁵ is C 1-3 alkyl or hydroxy. An alkyl group or a polyethylene oxide group containing 1-3 ethylene oxides]. Preferably, it is C10-C18 alkyl dimethylamine oxide, and C10-C18 acylamidoalkyl dimethylamine oxide. A suitable example of an alkyl amphocarboxylic acid is Miranol (TM) C2M Conc., Manufactured by Miranol Inc., Dayton, NJ.

[0074] Zwitterionic surfactants suitable betaines have the formula ^{_{R (R ') 2 N +}} R 2 COO - [ wherein, R C6-C18
Wherein each R ¹ is typically a C1-C3 alkyl group, and R ² is a C1-C3
5 is a hydrogen-sensitive group]. Preferred betaines are C12
-C18 dimethylaminohaysanoate and C10-C18 acylamidopropane (or ethane) dimethyl (or diethyl) betaine. Complex betaines are also suitable for use herein.

Cationic Surfactants The cationic ester surfactants used in the present invention are preferably surfactant properties containing at least one ester bond (ie, —COO—) and at least one cationic charged group. Is a water-dispersible compound having Other suitable cationic ester surfactants include, for example, U.S. Patent Nos. 4,228,042, 4,239,660,
And chlorine ester surfactants as described in US Pat. No. 4,260,529. Suitable cationic surfactants are mono C6-C16, preferably C6-C6, wherein the remaining N positions are substituted with methyl, hydroxyethyl, or hydroxypropyl groups.
10-N-alkyl or alkenyl ammonium surfactants are included.

Enzymes Enzymes are preferred detergent components of the first phase, and more particularly the second phase and / or any additional phases. If the enzyme is present, the enzyme may be a cellulase, hemicellulase, peroxidase, protease, glucoamylase, amylase, xylanase, lipase, phospholipase, esterase, cutinase, pectinase, keratanase, reductase, oxidase, phenoloxidase, lipoxygenase, ligninase, It is selected from the group consisting of pullulanase, tannase, pentosanase, malanase, β-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase, and mixtures thereof.

[0077] Preferred enzymes include proteases, amylases, lipases, peroxidases, cutinases, and / or cellulases in combination with one or more plant cell wall degrading enzymes. Cellulases useful in the present invention include both bacterial and fungal cellulases. Preferably, it has an optimum pH of 5 to 12 and an activity of 50 CEVU (cellulose viscosity units) or higher. Suitable cellulases are described in U.S. Patent No., 435,307, Barbesgoard et al., J6107.
8384 and WO 96/02653. These are respectively Humicola insolens
, Trichoderma, Thielavia and Sporotrichum are described. EP 739,982 describes a novel cellulase isolated from Bacillus species. Suitable cellulases are described in GB 2,075,028, UK 2,075
No. 95,275, British Patent 2,075,028, German Offenlegungsschrift 2,247,832 and WO 95/26398.

Examples of such cellulases include Humicola insolens (Humicola grisea var. Th.
ermoidea), especially cellulases produced by Humicola sp. DSM 1800. Other suitable cellulases have a molecular weight of 50 KDa, an isoelectric point of 5.5 and
A cellulase of Humicola insolens origin comprising 5 amino acids; a 43 kD endoglucanase of Humicola insolens origin of DSM 1800 exhibiting cellulase activity;
A preferred endoglucanase component has the amino acid sequence described in PCT Patent Application No. WO 91/17243. Suitable cellulases are also those described in Trichoderma longibrachiatum as described in WO 94/21801 of Geneocor published September 29, 1994.
EGIII cellulase. Particularly suitable cellulases are cellulases having a color protecting effect. Examples of such cellulases are described in European Patent Application No. 91202879.2, filed Nov. 6, 1991 (Novo). Carezyme and Cellznme (Novo Nor
disk A / S) is particularly useful. See WO91 / 17244 and WO91 / 21801. Other suitable cellulases for the protection and / or cleaning properties of textiles are WO96 / 34092, WO96 /
17994 and WO95 / 24471.

Such cellulases usually contain 0.0001% of active enzyme by weight of the detergent composition.
Formulated in detergent compositions at levels of ~ 2%.

The peroxidase enzyme is used in combination with an oxygen source such as percarbonate, perborate, persulfate, hydrogen peroxide and the like. These are used to prevent "solution bleaching", i.e., the removal of dyes or pigments from a fabric during a wash investigation into another fabric in the wash liquor. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidases such as chloro- and bromoperoxidase. Peroxidase-containing detergent compositions are described in PCT Patent Application No. WO 89/099813, European Patent Application No. 91, filed Nov. 6, 1991 (Novo).
No. 202879.2 and European Patent Application No. 9687013.8 filed on Feb. 20, 1996. Laccase enzymes are also suitable.

Preferred enhancers are substituted phenthiazines and phenoxazines, 10-phenothiazinepropionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPT
), 10-phenoxazine propionic acid (POP) and 10-methylphenoxazine (
WO94 / 12621) and substituted syringates (C3-C5 substituted alkyl syringates) and phenol. Sodium percarbonate and sodium perborate are preferred peroxide sources. Such cellulases and / or peroxidases usually incorporate the active enzyme into the detergent composition at a level of 0.0001% to 2% by weight of the detergent composition.

Another preferred enzyme that may be included in the detergent composition of the present invention is a lipase. Suitable lipases for dyes are described in Pseudomonas described in GB 1,327,034.
Includes microorganisms of the genus, such as those produced by Pseudomonas stutzeri ATCC 19.154. Suitable lipases include those produced by the microorganism Pseudomonas fluorescent IAM 1057, which show an immunologically positive cross-reactivity with lipase antibodies. This lipase is available from Amano Pharmaceutical (Nagoya, Japan) under the trade name Lipase P "Amano" (hereinafter "Amano-P"). Other suitable commercially available lipases are
Amano-CES, Chromobacter viscosum lipase, for example, Toyo Brewery, Japan
Chromobacter viscosum var.lipolyticum NRRLB 3673; US Biohemical Corp.
(USA) and Chromobacter viscosum lipase from Disoiynth Co., (Netherlands), and
ex Pseudomonas gladioli. Particularly suitable lipases are, for example, M1Lip
Lipases such as ase ^R and Lipomax ^R (Gist Brocades) and Lipolase ^R and Lipolase Ultra ^R (NOVO), which have been found to be very effective when used with the compositions of the present invention. Novo EP 258,068, WO 92/05249 and WO 95 /
Also suitable are the enzymes described in 22615 and Unilever WO94 / 03578, WO95 / 35381 and WO96 / 00292.

Also suitable are cutinases [EC 3.1.1.5.], Which can be considered a special class of lipases that do not require interface activation. The addition of cutinase to detergent compositions is described, for example, in WO-A-88 / 09367 (Genencore), WO 90/09446 (Pl
ant Genetic Systems), WO 94/14693 and WO 94/14693 (Unilever). Lipase and / or cutinase are usually present in an amount of 0.0001% by weight of the detergent composition.
The active enzyme is incorporated into the detergent composition at a level of ~ 2%.

Suitable proteases are B. Subtilis and B. Licheniforms (subtilisin BPN and BPN '
) Is a subtilisin obtained from the specific strain of (1). One suitable protease is
Bacill with maximum activity in the pH range of 8-12, developed and sold as ESPERASE ^R by Novo Industries A / S (Novo) in Denmark
Obtained from US strains. An enzyme similar to the preparation of this enzyme is disclosed in Novo UK Patent 1,243,78.
It is described in No. 4. Other suitable proteases, ALCALASE of Novo ^R, DURA
Including ZYM ^R and SAVINASE ^R, and Gist-Brocades of MAXATASE ^R, MAXACAL ^R, the PROPERASE ^R and Maxapem ^R (protein treated with Maxacal). Proteolytic enzymes are also included in denatured bacterial serine proteases, which are referred to herein as "proteases B" and are described in European Patent Application No. 97-303761.8, filed October 29, 1987 (especially 17-17).
Venega, published October 29, 1986, cited herein as a modified bacterial serine protease referred to as "Protease A".
s European Patent Application 199,404. A suitable one is called "Protease C", which is a variant of the alkaline serine protease from Bacillus, where lysine is arginine at position 27, tyrosine is valine at position 104,
Serine replaces asparagine at position 123, and alanine replaces threonine at position 274. Protease C corresponds to WO 91/06637 and is described in Venegas EP 90915958.4 issued May 16, 1991. Genetically altered variants, particularly those of protease C, are also included herein.

A preferred protease, referred to as “Protease D”, is a carbonyl hydrolase variant having an amino acid sequence not found in nature, wherein for a plurality of amino acid residues, at the position of said carbonyl hydrolase corresponding to position +76, It is derived from a carbonyl hydrolase precursor that has been replaced by a different amino acid. Preferably, according to the numbering of Bacillus amyloliquefaciens subtikisin, +
99, + 101, + 103, + 104, + 107, + 123, + 27, + 105, + 109, + 126, + 128, + 135, + 156, + 166, + 195,
One at a position corresponding to one selected from the group consisting of +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and / or +274 It is replaced by more amino acid residues. This is described in WO95 / 10591 and U.S. application Ser.No. 08/3, filed Oct. 13, 1994.
No. 22,677, C. Ghosh et al., In a patent application entitled "Bleaching Compositions Containing Protease Enzymes."

Suitable proteases of the present invention include the proteases described in European Patent Applications 251446 and WO 91/06637, the protease BLAPR described in WO 91/02792, and WO 9
Variants thereof described in 5/23221. See also the high pH protease from Bacillus sp. NCIMB 40338 described in Novo WO 93/18140. Enzyme detergents containing proteases, one or more other enzymes, and reversible enzyme inhibitors are described in Novo WO 92/03592. If desired, Procter & Gamble is a protease with low adsorptivity and high hydrolysis
Can be used as described in WO95 / 07791. Suitable recombinant trypsin-like proteases for detergents herein are described in Novo WO 94/25583. Other suitable proteases are described in Unilever EP 516,200.

Another preferred protease enzyme is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived by substitution of a plurality of amino acid residues of a carbonyl hydrolase precursor substituted by different amino acids. You. Here, this amino acid residue is one or more of the following residues: +33, +62, +
67, + 76, + 100, + 101, + 103, +104, +107, +128, +129, + 130, + 132, + 135, + 156, +158
, +164, +166, +167, +170, +209, +215, +217, 218 and +222 in combination with the precursor enzyme corresponding to position +210. Here, the numbered position is Bacillus
Corresponds to the naturally occurring subtilisin from amyloliquefaciens or the equivalent amino acid residue of another carbonyl hydrolase or subtilisin (such as Bacillus lentus subtilisin). Preferred enzymes of this type are +210, +76, +103, +104, +15
Includes those with position changes of 6, and +166. The protein hydrolase is present in the present invention at a level of pure enzyme of 0.0001 to 2%, preferably 0.001 to 0.2%, more preferably 0.005 to 0.1% by weight of the detergent composition. To the detergent composition.

Amylases (α and / or β) can be included for the removal of carboxyhydrate-based strains. Novo Nordisk AS WO94 / 0259 issued February 3, 1994
No. 7 describes a detergent composition incorporating a mutant amylase. April 1995
See also Novo Nordisk AS WO95 / 10603, issued on the 20th. Other amylases known for use in detergent compositions include α and β amylase.
Alpha-amylases are known in the art and are described in U.S. Pat.
52,666, WO91 / 00353, French Patent 2,676,456, European Patent 285,123,
EP 525,610, EP 368,341 and UK Patent Specification 1,298,839
Includes those listed under Novo. Other suitable amylases are found in 1994
Stability enhancing amylases described in WO 94/18314 issued August 18 and Genencor WO 96/05295 issued February 22, 1996, and Novo Nordisk AS issued April 1995.
Amylase variants with additional parental changes available from WO 95/10603.
EP 277216, WO95 / 26367, WO96 / 23873 (all Novo Nordisk) are also suitable.

Examples of commercially available α-amylase products include Purafect OX Am from Genencor, Termamyl ^R , Ban ^R , Fungamyl ^R , Duramyl ^R , all available from Novo Nordisk AS, Denmark.
Natalase ^R. The No. WO95 / 26397, describes other suitable amylases: That was measured by Phadebas ^R alpha over-amylase activity evaluation method, 25 ° C. to 5
An α-amylase characterized by having a specific activity at least 25% higher than that of Temamyl ^R in a temperature range of 5 ° C and a pH range of 8-10. WO96
Also suitable are variants of the above enzymes described in US Pat. No. 23873 (Novo Nordisk). Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and high activity level are described in WO 95/35382.

Preferred amylase enzymes include those described in WO 95/26397 and simultaneously Novo
Includes those described in PCT / DK96 / 00056, filed by Nordisk. The amylolytic enzyme is 0.0001 to 2%, preferably 0.1% by weight of the composition.
It is incorporated into the detergent compositions of the present invention at a level of pure enzyme of from 0.0018 to 0.06%, more preferably from 0.00024 to 0.048%.

[0091] In a particularly preferred embodiment, the washed tablets of the present invention comprise an amylase enzyme, in particular WO
No. 95/26397 and PCT / DK96 / 0 pending at the same time as Novo Nordisk
No. 0056 and combinations of coenzymes.

“Supplement” means the addition of one or more amylases suitable for washing purposes. Examples of co-amylases (α and / or β) are described below. Novo Nordisk AS WO 94/02597 and WO 95/10603 describe detergent compositions incorporating a mutated enzyme. Other known amylases suitable for use in detergent compositions are α and β amylase. Α-amylases known in the art include
U.S. Patent No. 5,003,257, European Patent No. 252,666, WO91 / 00353, French Patent No.
2,676,456, EP 285,123, EP 525,610, EP 368,341
And UK Patent Specification No. 1,298,839 (Novo).
Other suitable amylases are the stability enhancing amylases described in WO 94/18314 and Genencor WO 96/05295, and amylase variants with additional parental changes available from Novo Nordisk AS WO 95/10603. is there. European Patent No. 277216 (No
vo Nordisk) are also suitable.

Examples of commercially available α-amylase products include Purafect OX Am from Genencor, all denmers
Termamyl available from Novo Nordisk AS^R, Ban^R, Fungamyl^R, And Duramyl ^R It is. WO 95/26397 describes other suitable amylases:
, Phadebas^RTemperature of 25 ° C. to 55 ° C. measured by α-amylase activity evaluation method
In the temperature range, pH range of 8-10, specific activity is Termamyl^RAt least than that of
Α-amylase characterized by having a 25% higher value. WO96 / 23873
Also suitable are variants of the above enzymes described in Novo Nordisk. Active level
And other starches with improved properties with respect to the combination of thermal stability and high activity levels
Proteolytic enzymes are described in WO95 / 35382. Preferred supplemental amilla for the present invention
Intended for WO 94/18314, WO 96/05295 sold by Genencor
Amylase sold under the trade name Purafect OX Am, all Novo Nordi
Termamyl available from sk AS^R, Ban^R, Fungamyl^R, Natalase^RAnd Duramyl^R,
Maxamyl of Gist-Brocades^RIt is.

The co-amylase is generally present at 0.0001 to 2%, preferably 0.00018 to 0.06%, more preferably 0.00024 to 0.04% by weight of the composition.
It is incorporated into the detergent composition of the present invention at a level of 8% pure enzyme. The pure enzyme ratio by weight of the specific amylase to co-amylase is between 9: 1 and 1: 9, preferably 4: 1.
: 1 to 1: 4, most preferably between 2: 1 to 1: 2.

The enzymes described above are of suitable origin, such as vegetables, animals, bacteria, fungi, yeast. The origin can also be mesophilic or extremophilic (cryophilic, thermophilic, hyperbaric, alkalophilic, acidophilic, halogenophilic, etc.). Both purified and non-purified forms of these enzymes can be used. Mutants of the original enzyme are also included by definition. Mutants can be obtained, for example, by protein and / or genetic engineering, chemical and / or physical modification of the native enzyme. A common method is also the representation of the enzyme vs. host tissue in which the genetic material for the production of the enzyme was cloned.

[0096] Such enzymes are typically incorporated into detergent compositions at levels of 0.0001 to 2% active enzyme by weight of the detergent composition. The enzymes can be added as separate single components (including one enzyme such as prills, granules, stabilizing liquids, etc.) or as a mixture of two or more (eg, co-granules). Other detergent components that can be added are 19
Enzymatic oxidant scavengers described in European Patent Application No. 920018.6 filed on Jan. 31, 1992. An example of such an enzymatic oxidant scavenger is ethoxylated tetraethylene polyamine.

The range of enzyme substances and their means of incorporation into synthetic detergent compositions are described in Genencor Inter
national WO93072634A and WO9307260A, Novo WO8908694A and January 1971
It is also described in McCarty et al., U.S. Pat. No. 3,553,139, issued on May 5. Enzymes are further described in Place et al., U.S. Patent No. 4,101,457, issued July 18, 1978 and Hughes, U.S. Patent No. 4,507,219, issued March 26, 1985. Enzyme substances useful in liquid detergent formulations and their incorporation into the formulation are described in U.S. Pat. No. 4,261,868 to Hora et al., Issued April 14, 1981. The enzymes used in detergents can be stabilized by various techniques. Enzyme stabilization techniques are described in U.S. Pat.No. 3,600,319 issued to Gedge et al.
No. 200,586 and is exemplified. Enzyme stabilization systems are also described, for example, in US Pat. No. 3,519,570. Useful Bacillus, sp. AC13 to provide proteases, xylanases and cellulases are described in WO9401532.

[0098] Highly preferred components of the bleach detergent composition is a bleaching agent. Suitable bleaches include chlorine and oxygen releasing bleaches. In one preferred aspect, the oxygen releasing bleach comprises a source of hydrogen peroxide and an organic peracid bleach precursor compound. The production of organic peracids occurs by the reaction of a precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydration bleaches. In an alternative preferred aspect, a preformed organic peroxyacid is directly incorporated into the composition. Compositions comprising a mixture of a hydrogen peroxide source and an organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisioned.

The composition of the inorganic perhydrate bleach detergent component preferably includes a source of hydrogen peroxide as an oxygen releasing bleach.
Suitable sources of hydrogen peroxide include inorganic perhydrate salts. The inorganic perhydrate salt is usually in the form of a sodium salt, from 1% to 40% by weight of the composition.
, More preferably from 2% to 30%, most preferably from 5% to 25%.

Examples of inorganic perhydrate salts include perborates, percarbonates, perphosphates, persulfates, and
Contains persilicate salts. The inorganic perhydrate salt is usually an alkali metal salt. inorganic
The perhydrate salt may be included as a crystalline solid without additional protection. However
For certain perhydrates, the preferred use of such granule compositions is
, A coating that gives better storage stability to perhydrates in granular products
A logging configuration is used. Sodium perborate has the formula NaBO_TwoH_TwoO_TwoMonohydrate or NaBO_TwoH_TwoO _Two ・ 3H_TwoIt can be in the form of tetrahydrate of O.

Alkali metal percarbonates, especially sodium percarbonate, are more preferred hydrates for inclusion in the compositions of the present invention. Sodium percarbonate is an adduct having the formula corresponding to 2Na ₂ CO ₃ .3H ₂ O ₂ and is commercially available as a crystalline solid. Sodium percarbonate, a hydrogen peroxide adduct, tends to dissolve and release hydrogen peroxide rapidly, which tends to locally increase the bleach concentration. The percarbonate is most preferably formulated in a coated form that provides stability to the product.

Suitable coating materials to provide product stability include mixed salts of water-soluble alkali metal sulfates and carbonates. Such coatings and coating methods were previously described in British Patent No. 1,466,799, granted to Interox on March 9, 1977. The weight ratio of the mixed salt coating material to the percarbonate is in the range of 1: 200 to 1: 4, more preferably 1:99 to 1
: 9, most preferably in the range of 1:49 to 1:19. Preferably, the mixed salt has the general formula Na ₂ SO ₄ . n. Sodium sulfate with Na ₂ CO ₃ , wherein n is 0.1 to 3, preferably n is 0.3 to 1.0, and most preferably n is 0.2 to 0.5. It is a mixed salt of sodium.

Another suitable coating material that provides product stability is a SiO: Na ₂ O ratio of 1
. 8: 1 to 3.0: 1, preferably 1.8: 1 to 2.4: 1 sodium silicate;
And / or sodium metasilicate, preferably 2% to 10% by weight of perhydrate
% (Usually 3-5%) applied in SiO ₂ level. Magnesium silicate can also be included in the coating. Coatings comprising silicate and borate or boric acid or other minerals are also suitable.

Other coatings, including waxes, oils, fatty soaps can also be used to advantage in the present invention. Potassium peroxymonopersulfate is another inorganic hydrolyzate salt useful in the compositions herein.

Peroxy Acid Bleach Precursor A peroxy acid bleach precursor is a compound that reacts with hydrogen peroxide in a perhydration reaction to generate peroxy acid. Generally, the peroxyacid bleach precursor is represented by the following formula:

[0106]

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Here, L is a leaving group, X may have any functionality, and the structure of the peroxyacid generated by perhydration is as follows.

[0108]

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The peroxyacid bleach precursor compound is preferably present in an amount of 0.5% to 2% by weight of the composition.
It is present at a level of 0%, more preferably 1% to 10%, most preferably 1.5% to 5%.

Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, which precursors can be selected from a wide variety of ranges. Suitable classes include anhydrides, esters, imides, lactams and acyl derivatives of imidazoles and oximes. Examples of useful substances that fall into this class are
No. 1,586,789. Suitable esters are described in British Patent Application No. 836988 No. 8
Nos. 64798, 1147871, 2143231 and European Patent Application 0170386.

Leaving group The leaving group, hereafter the L group, must be sufficiently reactive to the hyperhydration reaction to occur in an optimal time frame (eg, a wash cycle). However, if L is too reactive, the activator is difficult to stabilize for use in bleach compositions. Preferred L groups are selected from the group consisting of and mixtures thereof:

[0112]

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In the formula, R ¹ is an alkyl, aryl, or alkaryl group having 1 to 14 carbon atoms, R ³ is an alkyl chain having 1 to 14 carbon atoms, and R ⁴ is H or R ³ Yes,
R ⁵ is an alkenyl chain of 1 to 8 carbon atoms, and Y is H or a solubilizing group. Any of R ¹ , R ³ and R ⁴ may be substituted by substantially any functional group, such as alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammonium groups.

[0114] Preferred solubilizing _{^{groups, -SO 3 - M +, -CO}} 2 - M +, -SO 4 - M +, -N + (R 3
) ₄ X ^-, and O <-N (R ³⁾ ₃ and most preferably _{^{-SO 3 - M +, -CO 2}} -
M ⁺ . Here, R3 is an alkyl chain having 1 to 4 carbon atoms, M is a cation that gives solubility to the bleach activator, and X is an anion that gives solubility to the bleach activator. Preferably, M is an alkali metal, ammonium, or substituted ammonium, most preferably sodium and potassium, and X is a halide, methyl sulfate, or acetate anion.

Perbenzoic acid precursor The perbenzoic acid precursor compound gives perbenzoic acid by perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds include substituted and unsubstituted benzoyloxybenzene sulfonates, for example, benzoyloxybenzene sulfonate of the formula:

[0116]

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Also suitable are benzoylated products of sorbitol, glucose and all saccharides with benzoylating agents, for example those of the formula

[0118]

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The imide type perbenzoic acid precursor compound includes N-benzoylsuccinimide, tetrabenzoylethylenediamine, and N-benzoyl-substituted urea. Suitable imidazole-type perbenzoic acid precursors include N-benzoylimidazole, N-benzoylbenzimidazole, and other useful N-acyl groups, including N-benzoylpyrrolidone, dibenzoyltaurine, benzoylpyroglutamic acid. Perbenzoic acid precursors.

Other perbenzoic acid precursors include benzoyl diacyl peroxide, benzoyl tetraacyl peroxide, and compounds of the following formula:

[0121]

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[0122] Phthalic anhydride is another suitable perbenzoic acid precursor compound herein.

[0123]

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A preferred N-acylated lactam perbenzoic acid precursor has the formula:

[0125]

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In the formula, n is 0 to 8, preferably 0 to 2, and R ⁶ is a benzoyl group.

Perbenzoic acid derivative precursor The perbenzoic acid derivative precursor gives a substituted perbenzoic acid by perhydrolysis. Suitable perbenzoic acid derivative precursors include benzoyl groups of the perbenzoic acid precursors described herein that are substantially non-positively charged (ie, non-cationic), such as alkyl, hydroxy, alkoxy, Includes any substituted by halogen, amine, nitrosyl, and amide groups. A preferred class of substituted perbenzoic acid precursor compounds are amide substituted compounds represented by the following general formula:

[0128]

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In the formula, R ¹ is an aryl or alkaryl group having 1 to 14 carbon atoms; R ² is an arylene or alkaryl group having 1 to 14 carbon atoms; R ⁵ is H or carbon atom 1-10 alkyl, aryl, alkaryl groups; and L can be virtually any leaving group. R ¹ preferably contains from 6 to 12 carbon atoms. R ² is preferably a branched, with substitution or both of them, including the 4-8 carbon atoms. R ¹ may be an aryl or substituted aryl and may be supplied from any of synthetic sources or natural sources including, for example, tallow. Variations on similar structures can be acceptable with respect to R ^2. Substitutions can include alkyl, aryl, halogen, nitrogen, sulfur, and other typical substituents or organic compounds. R ⁵ is preferably H or methyl. R ¹ and R ⁵ should not contain more than 18 carbon atoms in total.
Amide-substituted bleach activator compounds of this type are described in European Patent Application No. 0170386.

Cationic Peroxyacid Precursor The cationic peroxyacid precursor compound produces a cationic peroxyacid by perhydrolysis. Typically, the cationic peroxyacid precursor replaces the peroxyacid moiety of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonia, alkyl ammonium group, preferably an ethyl or methyl ammonium group. Generated by The cationic peroxyacid precursor is typically present in the compound as a salt of a suitable cation, such as a halide or methyl sulfate ion.

The peroxyacid precursor compound so cationically substituted is perbenzoic acid, or a substituted derivative thereof, the precursor compounds already described. Instead,
The peroxyacid precursor compound may be an alkylpercarboxylic acid precursor compound or an amide substituted alkylperoxyacid precursor described below. Cationic peroxyacid precursors are described in U.S. Pat.Nos. 4,904,406, 4,751,015,
No. 4,988,451, No. 4,397,757, No. 5,269,962, No. 5,127,852, No. 5,093,022
No. 5,106,528; British Patent No. 1,382,594; European Patent Nos. 475,512, 458,396
No. 284,292, and Japanese Patent No. 87-318,332.

Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyloxybenzene sulfonates, N-acylated caprolactam, and monobenzoyl tetraacetylglucose benzoyl peroxide. A preferred cationic substituted benzoyloxybenzenesulfonate is a 4- (trimethylammonium) methyl derivative of benzoyloxybenzenesulfonate:

[0133]

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Preferred cationically substituted alkyloxybenzene sulfonates have the formula:

[0135]

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Preferred cationically substituted peroxyacid precursors of the class of N-acylated caprolactams include trialkyl ammonium methylene benzoyl caprolactam, especially trimethyl ammonium methylene benzoyl caprolactam:

[0137]

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[0138] Preferred cationic peroxyacid precursors of the other preferred N-acylated caprolactam class include trialkyl ammonium methylene alkyl caprolactams:

[0139]

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In the formula, n is 0-12, especially 1-5. Another preferred cationic peroxyacid precursor is 2- (N, N, N-trimethylammonium) ethyl sodium 4-sulfophenyl carbonate chloride.

Alkyl percarboxylic acid bleach precursor The alkyl percarboxylic bleach precursor produces percarboxylic acid by perhydrolysis. Preferred precursors of this type provide peracetic acid by perhydrolysis. Preferred alkyl percarboxylic acid bleach precursor compounds of the imide type are N, N
, N ¹ , N ¹ tetraacetylated alkylenediamines. Here, the alkylene group contains 1 to 6 carbon atoms, and in particular, a compound in which the alkylene group contains 2 to 6 carbon atoms. Tetraacetylethylenediamine (TAED) is particularly preferred. Other preferred alkyl percarboxylic acid bleach precursors are 3,5,5-trimethylhexanoyloxybenzenesulfonate (iso-NOBS), sodium nonanoyloxybenzenesulfonate (NOBS), sodium acetoxybenzenesulfonate (ABS) and pentane Contains acetyl glucose.

Amide-Substituted Alkyl Peroxy Acid Precursors Amide-substituted alkyl peroxy acid precursor compounds are also suitable, including compounds of the general formula:

[0143]

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Wherein R ¹ is an aryl group having 1 to 14 carbon atoms; R ² is an aryl group having 1 to 14 carbon atoms
R ⁵ is H or an alkyl group having 1 to 10 carbon atoms;
And L can be virtually any leaving group. R ¹ preferably contains from 6 to 12 carbon atoms. R ² preferably contains from 4 to 8 carbon atoms. R ¹ may be a linear or branched alkyl group containing branched, substituted or both, and may be supplied from any of synthetic raw materials or natural raw materials including, for example, tallow. Variations on similar structures can be acceptable with respect to R ^2. Substitutions can include alkyl, halogen, nitrogen, sulfur, and other typical substituents or organic compounds. R ⁵ is preferably H or methyl. R ¹ and R ⁵ should not contain more than 18 carbon atoms in total. Amide-substituted bleach activator compounds of this type are described in European Patent Application No. 0170386.

Benzoxazine organic peroxyacid precursors are described, for example, in EP-A-332,294 and EP-A-482,807, and also particularly suitable are benzoxazine-type precursor compounds of the formula

[0146]

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This also includes substituted benzoxazines of the formula:

[0148]

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Wherein R ¹ is H, alkyl, alkaryl, aryl, arylalkyl, and R ² , R ³ , R ⁴ and R ⁵ are H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, The same or different substituents selected from amino, alkylamino, COOR ⁶ (where R ⁶ is H or an alkyl group) and a carbonyl function. A particularly preferred precursor of the benzoxazine type is of the formula:

[0150]

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Preformed Organic Peroxy Acids The organic peroxy acid bleach system additionally or alternatively comprises an organic peroxy acid bleach precursor compound, a preformed organic peroxy acid, typically, by weight of the composition. At a level of 0.5% to 25%, more preferably 0.5% to 25%. A preferred class of organic peroxyacid compounds are amide substituted compounds of the general formula:

[0152]

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Wherein R ¹ is an alkyl, aryl or alkaryl group having 1 to 14 carbon atoms; R ² is an alkylene, arylene or alkarylene group having 1 to 14 carbon atoms; R ⁵ is H Or an alkyl, aryl, or alkaryl group having 1 to 10 carbon atoms. R ¹ preferably contains from 6 to 12 carbon atoms. R ² is preferably 4 to 8
Containing carbon atoms. R ¹ may be a branched or substituted or both linear or branched alkyl, substituted aryl or alkylaryl, and may be supplied from any synthetic source or natural source including, for example, tallow. Variations on similar structures can be acceptable with respect to R ^2. Substitutions are alkyl, aryl, halogen, nitrogen, sulfur,
And other typical substituents or organic compounds. R ⁵ is preferably H or methyl. R ¹ and R ⁵ should not contain more than 18 carbon atoms in total. Amide-substituted organic peroxyacid compounds of this type are disclosed in European Patent Application No. 01
No. 70386.

Other organic peroxy acids include diacyl and tetraacyl peroxides, especially diperoxydecandionic acid, diperoxytetradecandionic acid, and diperoxyhexadecandionic acid. Dibenzoyl peroxide is a preferred organic peroxyacid. Also suitable herein are mono- and di-perazelaic acid, mono- and di-per-brachiluric acid, and N-phthaloylaminoperoxycaproic acid.

Controlled Release Rate-Means Means are provided for controlling the release rate of bleaches, especially oxygen bleaches, into the washing solution. Means for controlling the release rate of the bleach provide a controlled release of the peroxide species into the washing solution. Such measures include, for example, controlling the release of inorganic perhydrate, which acts as a source of hydrogen peroxide, into the washing solution. Another mechanism for controlling the release rate of bleach is by coating the bleach with a coating designed to provide a controlled release. Therefore,
The coating may comprise, for example, poorly water-soluble substances, or may be of sufficient thickness such that the kinetics of dissolution of the thick coating provides a controlled release rate.

[0156] The coating material is applied using various methods. The coating material is typically present in a weight ratio of coating material to bleach of 1:99 to 1: 2, preferably 1:49 to 1: 9. Suitable coating materials include triglycerides, (eg, partially) hydrogenated vegetable oils, soybean oil, cottonseed oil, mono- or diglycerides, microcrystalline wax, gelatin, cellulose, fatty acids, and mixtures thereof. Other suitable coating materials can include alkali metal and alkaline earth metal sulfates, silicates, and carbonates, including calcium carbonate and silica.

Preferred coating materials, especially for the bleaching raw materials of the inorganic perhydrate salts, are SiO 2 _Two : Na_TwoThe ratio of O is 1.8: 1 to 3.0: 1, preferably 1.8: 1 to 2.4: 1.
Sodium silicate and / or sodium metasilicate, preferably inorganic peroxide
2% to 10% (usually 3% to 5%) SiO 2 by weight of the hydrate salt_TwoApply Silicic acid
Magnesium can also be included in the coating. The inorganic salt coating material is combined with an organic bath to provide an inorganic salt / organic binder composite coating.
It may be combined with the indah material. Suitable binders include alcoholic
C10-C20 alcohol containing 5-100 moles of ethylene oxide per mole
Ethoxylate, and more preferably 20 to 100 per mole of alcohol.
C15-C20 primary alcohol ethoxylate containing molar ethylene oxide
Including

Other preferred binders include certain polymeric substances. Polyvinylpyrrolidone having an average molecular weight of 12,000 to 700,000 and an average molecular weight of 600
５5 × 10 ⁶ , preferably 1000-400,000, most preferably 10
00 to 10,000 polyethylene glycols are examples of such polymeric materials. Maleic anhydride, a copolymer of maleic anhydride and ethylene, methyl vinyl ether, or methacrylic acid, maleic anhydride comprising at least 20 mol% of the polymer, is a further example of a polymeric material useful as a binder. These polymeric materials may be on their own or C10-C20 containing from 5 to 100 moles of ethylene oxide per mole of water, propylene glycol and the alcohols mentioned above.
May be used in combination with the alcohol ethoxylate. Further examples of binders also include C10-C20 mono- and di-glycerin esters and C10-C20 fatty acids.

[0159] Cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, and homo- or copolymerizable polycarboxylic acids or salts thereof are other examples of binders suitable for use herein. One method for applying the coating material is agglomeration. Preferred agglomeration processes include the use of any of the organic binder materials described above. Any conventional aggregator / stirrer can be used, including, but not limited to, pan, rotary drum, and vertical blender types. The melt coating composition can also be applied either by pouring over a moving layer of bleach or by spraying.

Other means of providing the desired controlled release include mechanical means for altering the physical properties of the bleach to control its solubility and release rate. Suitable procedures include compression, mechanical injection, manual injection, and adjusting the solubility of the bleach compound by selecting the particle size of the particular component. The choice of particle size depends both on the composition of the particular component and on meeting the desired controlled release kinetics, but the particle size should be at least 500 μm, preferably with an average particle size of 800-1200 μm. is there.

[0161] Additional procedures to provide controlled release means include the ability of the ionic strength environment therein to achieve controlled release kinetics to be achieved when the composition is placed in a wash liquor. And appropriately selecting other components of the detergent composition matrix as such.

Metal-Containing Bleaching Catalyst The compositions herein containing a bleaching agent as a detergent component may additionally contain a metal-containing bleaching catalyst as a preferred component. Preferably, the metal containing bleach catalyst is a transition metal containing bleach catalyst, more preferably a manganese or cobalt containing bleach catalyst. Suitable bleach catalyst types include heavy metal cations with defined bleaching catalytic activity, such as copper and iron cations, auxiliary metal cations with little or no bleaching activity, and defined solubility constants for the catalyst and auxiliary metal cations. A sequestering agent having
Particularly, it is a catalyst containing ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) and a water-soluble salt thereof. Such catalysts are disclosed in U.S. Pat.
No. 423,243.

Suitable bleaching catalyst types are described in US Pat. Nos. 5,246,621 and 5,244,594.
Manganese-based complex compounds. Preferred examples of these catalysts are M
n^IV _Two(U-O)_Three(1,4,7-trimethyl-1,4,7-triazacyclononane)_Two-PF ₆ )_Two, Mn^III _Two(U-O)₁(U-OAc)_Two(1,4,7-trimethyl-1,4,7-trimethyl
Azacyclononane)_Two-(ClO_Four)_Two, Mn^IV _Four(U-O)₆(1,4,7-triazashi
Chrononan)_Four-(ClO_Four)_Two, Mn^IIIMn^IV _Four(U-O)₁(U-OAc)_Two(1,
4,7-trimethyl-1,4,7-triazacyclononane)_Two-(ClO_Four)_ThreeAnd these
Contains mixtures. Others are described in EP-A-549,272. Book
Other ligands suitable for use herein are 1,5,9-trimethyl-1,5,9-triaza
Cyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4
, 7-Triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclono
Nan and mixtures thereof.

[0164] Bleaching catalysts useful in the compositions herein are also suitably selected for the present invention.
See U.S. Patent Nos. 4,264,612 and 5,227,084 for examples of suitable bleaching catalysts. See U.S. Pat. No. 5,246,621, which is Mn (1,4,7-trimethyl-1,4,7-triazacyclononane) (OCH _{3) 3} mononuclear manganese (IV) complex compounds such as -PF ₆₎ Is described.

Yet another preferred type of bleach catalyst is a non-carboxylate-polyhydroxy compound having at least three consecutive C-OH groups, as described in US Pat. No. 5,114,606. Manganese (III) and / or (IV) with ligand
) Is a water-soluble complex compound. Preferred sorbitols include sorbitol, iditol,
Includes darcitol, mannitol, xylitol, arabitol, adonitol, mesoerythritol, meso-inositol, lactose and mixtures thereof.

US Pat. No. 5,114,611 discloses Mn, Co, F with a non- (macro) cyclic ligand.
It teaches a bleach catalyst comprising a complex compound of a transition metal containing e or Cu. This ligand has the formula:

[0167]

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In the formula, R¹, R^Two, R^ThreeAnd R^FourIs a 5- or 6-membered R¹-N = CR^TwoAnd R ^Three -N = CR^FourH, substituted alkyl and aryl groups such that
You. This ring may be further substituted. B is O, S, CR^FiveR⁶, NR⁷And C =
O is a crosslinking group selected from^Five, R⁶And R⁷Represents a substituted or unsubstituted group
H, alkyl or aryl groups. Preferred ligands include pyridine, pyr
Dazine, pyrimidine, pyrazine, imidazole, pyrazole and triazole rings
including. Optionally, the ring is an alkyl, aryl, alkoxy, halide, and nitro
It may be substituted with a substituent such as b. Particularly preferably, 2,2′-bispyridyl a
Min. Preferred bleaching catalysts include Mn, Co, Fe, Cu-bispyridylmethine.
Includes tan and -bispyridylamine complex compounds. A very preferred catalyst is Co
(2,2'-bispyridylamine) Cl_Two, Di (isothiocyanate) bispyridylua
Min-cobalt (II), trispiridylamine-cobalt (II) perchlorate, C
o (2,2'-bispyridylamine)_TwoO_TwoCl_Four, Bis- (2,2'-bispyridylamine
) Copper (II) perchlorate, tris (di-2-bispyridylamine) iron (II) park
Lolate, and mixtures thereof.

Preferred examples include N ₄ Mn ^III (u—O) ₂ Mn ^IV N ₄ ) ⁺ and [Bipy ₂ Mn ^III (u−
Includes polynuclear Mn complex compounds having tetra-N-dentate and bi-N-dentate ligands, including O) ₂ Mn ^IV bipy ₂ ]-(ClO ₄ ) ₃ .

Although the structure of the bleaching catalyst manganese complex of the present invention is unclear, it includes chelates or other hydrogenated coordination complexes resulting from the interaction of the manganese cation with the carbonyl or nitrogen atom of the ligand. Similarly, the oxidation state of the manganese cation during the catalytic process is not reliably known and may be (+ II), (+ III), (+ IV) or (+
V) Will be in a state of valency. It is presumed that polynuclear and / or "cage" structures are present in the aqueous bleaching medium because of the six possible bonds of the ligand to the manganese cation. Whatever the form of the active Mn ligand species actually present, it clearly functions as a catalyst and provides excellent bleaching capacity against stubborn stains such as tea, ketchup, wine, juice, etc. .

Other bleaching catalysts are, for example, EP-A-408,131 (cobalt complex catalysts), EP-A-384,503 and EP-306,089 (metal pyridine catalysts), US Pat. No. 4,728,952 (manganese / multidenate) Ligand catalyst), U.S. Pat.
No. 11,748 and European Patent Application Publication No. 224,952 (manganese adsorbed on aluminosilicate), US Pat. No. 4,601,845 (manganese and zinc or manganese salt supported on aluminosilicate), US Pat. No. 4,626,373 (manganese / ligand catalyst), U.S. Patent No. 4
, 119,557 (iron complex salt catalyst), German Patent Specification 2,054,019 (cobalt chelate catalyst), Canada 866,191 (transition metal containing catalyst), US Patent 4,430,243 (chelate of manganese cation and non-catalytic metal cation), And U.S. Pat. No. 4,728,455 (manganese gluconate catalyst).

Other preferred examples include cobalt (III) catalysts of the formula: Co [(NH ₃ ) _n M ′ _m B ′ _b T ′ _t Q _q P _p ] Y _y where cobalt is N is an integer from 0 to 5 (preferably 4 or 5, most preferably 5); M 'represents a monodentate ligand; m is 0
B 'represents a bidentate ligand; b is 0-2; T' represents a tridentate ligand; t is an integer from 5 to 5 (preferably 1 or 2, most preferably 1); 0 or 1; Q represents a tetradentate ligand; q is 0 or 1; P represents a pentadentate ligand; p is 0 or 1;
m + 2b + 3t + 4q + 5p = 6; Y is one or more approximately selected counterions present at the number y, where y is 1-3 (preferably 2 or 3, when Y is an anion charged to -1, most preferably an integer of 2). Preferably, Y is chloride, nitrate, nitrite, sulfate, citrate, acetate, carbonate, and combinations thereof. Further, at least one coordination site attached to cobalt is unstable under the conditions of use of the automatic dishwasher, and the reduction potential of cobalt (III) to cobalt (II) under alkaline conditions is a normal hydrogen electrode. Under such automatic dishwasher conditions, such as less than 0.4 volts (preferably 0.2 volts), the remaining coordination sites stabilize.

A preferred cobalt catalyst of this type has the formula: [Co (NH ₃ ) _n (M ′) _m ] Y _y where n is 3-5 (preferably 4 or 5, most preferably 5 ); M
'Is an unstable coordinating group, preferably chlorine, bromine, hydroxide, water, and (m
M) is selected from the group consisting of those combinations;
Preferably an integer of 1 or 2, most preferably 1); m + n = 6; and Y
Is appropriately selected from a number y of counterions, and y is 1 to obtain a charge-balanced salt.
To 3 (preferably 2 or 3, most preferably 2 when Y is an anion charged to -1).

A preferred cobalt catalyst of this type useful herein is the cobalt pentaamine chloride salt of the formula [Co (NH ₃ ) ₅ Cl] Y _y , especially [Co (NH ₃ ) ₅ Cl] Cl 2.

More preferably, the compositions of the present invention use a cobalt (III) bleach catalyst of the formula: [Co (NH ₃ ) _n (M) _m (B) _b ] T _y where cobalt is N is an integer from 4 to 5 (preferably 5); M is one or more ligands with one site coordinated to cobalt; m is 0,1 Or B is an integer coordinated to cobalt at two sites; b is an integer of 0 or 1 (preferably 0);
When 0, m + n = 6, when b = 1, m = 0, n = 4; and T is suitably selected from a number y of counterions, where y is an integer to obtain a charge-balanced salt. (Preferably y is 1-3, most preferably 2 when T is a -1 charged anion); and the catalyst further comprises 0.23M ^-1 s ^-1 (25 ° C) base. Has a hydrolysis rate constant.

Preferably, T is chloride, iodide, I ₃ ⁻ , formate, nitrate, sulfate, sulfite, citrate, acetate, carbonate, bromide, PF ₆ ⁻ , BF ₄ ⁻ , B (Ph) ₄ ^-,
It is selected from the group consisting of phosphate, phosphite, silicate, tosylate, methanesulfonate, and combinations thereof. Optionally, one or more anionic groups in T, e.g., HPO ₄ ^2-, HCO ₃ ^-, if H ₂ PO _4-like are present, T is can be protonated. Further, T may be an anionic surfactant (e.g., linear alkyl benzene sulfonate (LAS), alkyl sulfate (AS), alkyl ethoxy sulfonate (AES), etc.) and / or an anionic polymer (e.g., polyacrylate, Polymethacrylate).

The group M can be, but is not limited to, for example, F^-, SO_Four ^-2, NCS^-, SCN^-, S _Two O_Three ^-2, NH_Three, PO_Four ^3-And carboxylate (preferably monocarboxylate)
However, the bond to cobalt is reduced to only one carboxylate per group.
Thus, as long as they are attached, they are one or more carboxylates, in which case
Other carboxylate may be protonated or in the form of its salt
). Optionally, M has one or more anionic groups (eg, HPO_Four ^2-, HCO_Three ^-, H_TwoP
O_Four-, HOC (O) CH_TwoC (O) O^-M) is protonated when
Can be Preferably, M is a substituted or unsubstituted C1-C30 carboxylic acid of the formula
RU:

[0178] RC (O) O ^- wherein, R is a hydrogen atom, and C1-C30 (preferably C1-C18) unsubstituted and substituted alkyl groups, C6-C30 (preferably C6-C18) unsubstituted and substituted aryl group, and C3-C30 (preferably C5-C18) selected from the group consisting of heteroaryl groups, wherein the substituents ^{_{NR '3, NR' 4 +}} , -C (O) oR ', -
OR ′, —C (O) NR ′ ₂ , wherein R ′ is a hydrogen atom and C1-
It is selected from the group consisting of C6 groups. Thus, such a substituted R is represented by-(
CH ₂ ) _n OH and — (CH ₂ ) _n NR ′ ₄ ⁺ , wherein n is 1 to 16, preferably 2 to 1.
0, most preferably 2-5.

Most preferably, M is a carboxylic acid having the above formula, and R is selected from hydrogen, methyl, ethyl, propyl, straight or branched chain C4-C12 alkyl, and benzyl. Most preferably, R is methyl. Preferred carboxylic acids M are formic acid, benzoic acid, octanoic acid, dodecanoic acid, malonic acid, maleic acid, succinic acid, adipic acid, phthalic acid, 2-ethylhexanoic acid, naphthenic acid, oleic acid, palmitic acid,
Tartaric acid, stearic acid, butyric acid, citric acid, acrylic acid, fumaric acid, lauric acid,
Linoleic acid, lactic acid, malic acid, especially acetic acid.

The groups B are carbohydrates, di- and higher carboxylates (eg, oxalate, malonate, succinate, maleate), picolinic acid, and α and β amino acids (eg, glycinalanine, beta-alanine, phenylalanine). . Cobalt bleaching catalysts useful herein are described, for example, in MLTobe, "Base Hydrolysis of Transition Metal Complexes", Adv. Inorg. Bioinorg. Mech., (1983) 2, pp. 1-94. It is known that it is described in. For example, Table 1 on page 17 shows a composite catalyst of cobalt pentaamine and oxalic acid (k _OH = 2.5 × 10 ⁻⁴ M ⁻¹ s ⁻¹ (2
5 ° C.)), a composite catalyst of formic acid (k _OH = 5.8 × 10 ⁻⁴ M ⁻¹ s ⁻¹ (25 ° C.)) and a composite catalyst of acetic acid (k _OH = 9.6 × 10 ⁻⁴ M ^{−). 1} s ⁻¹ (25 ° C.)), given as base hydrolysis rate (expressed as k _OH ).

The most preferred cobalt bleach catalyst herein is of the formula [Co (NH_Three)_FiveOAc] T _y (Where OAc represents an acetate group)
In particular, cobalt pentaamine acetate chloride [Co (NH_Three)_FiveOAc] Cl _Two And [Co (NH_Three)_FiveOAc] (OAc)_Two[Co (NH_Three)_FiveOAc] (
PF₆)_Two[Co (NH_Three)_FiveOAc] (SO_Four); [Co (NH_Three)_FiveOAc] (
BF_Four)_TwoAnd [Co (NH_Three)_FiveOAc] (NO_Three)_Two(Here "PAC")
You.

These cobalt catalysts are described, for example, in Tobe, supra, and 19, cited therein.
U.S. Pat. No. 4,810,410 to Diakun, issued Mar. 7, 1989, J. Chem. Ed. (1989) 66.
(12), 1043-45, WLJolly's “The synthesis and characterization of inorga.
nic compounds ”(Prentice Hall) pp.461-3, Inorg. Chem., 18, 1497-1502 (19
79), Inorg.Chem., 21, 2881-2885 (1982), Inorg.Chem., 18, 2023-2025 (1979).
), Inorg.Synthesis., 173-176 (1960), Journal of Physical Chemisty, 56, 22.
-25 (1952), together with synthetic examples.

Cobalt catalysts suitable for incorporation into the washed tablets of the present invention are described in US Pat. No. 5,559,26.
1, US Pat. No. 5,581,005 and US Pat. No. 5,597,936, which are incorporated herein by reference. These catalysts may be treated with accompanying substances to reduce the color impact if necessary in terms of product aesthetics, or may include particles containing the enzymes exemplified below. Alternatively, the composition may be made to include spots of catalyst.

Organic Polymerizable Compound An organic polymerizable compound is added as a preferred component of the washed tablet of the present invention. Organic polymerizable compound means virtually any organic polymerizable compound commonly found in detergent compositions having dispersants, anti-redeposition agents, soil dispersants, and other detergent properties. The organic polymerizable compound is typically present in the detergent composition of the present invention in an amount of 0% by weight of the composition.
. It is present at a level of from 1% to 30%, preferably from 0.5% to 15%, most preferably from 1% to 10%.

Examples of organic polymerizable compounds include water-soluble, organic homo- or copolymerized polycarboxylic acids,
It includes modified polycarboxylates or salts thereof, wherein the polycarboxylic acid contains at least two carboxyl groups separated from each other by no more than two carbon atoms. Examples of these salts are polyacrylates having a molecular weight of 2,000 to 10,000 and their modified acrylic acid, fumaric acid, maleic acid itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid or salts thereof, maleic acid Copolymers with other suitable monomer units, including acid anhydrides, acrylamide, alkylene, vinyl methyl ether, styrene, and mixtures thereof. Preferably, the molecular weight is 5,000 to 100,000, more preferably 20,000 to 1,
It is a copolymer of acrylic acid and maleic anhydride of 00000.

Preferred commercially available acrylic acid-containing polymers having a molecular weight of 15,000 or less include Sokalan PA30, PA20, PA15, PA10 and Sokalan CP10 under the trade names of BASF GmbH.
And Rohm and Haas trade names Acusol 45N, 480N, 460N.

Preferred acrylic acid-containing copolymers include, as monomer units, a) 90% by weight
10 to 10% by weight, preferably 80 to 20% by weight of acrylic acid or a salt thereof;
b) 10% to 90% by weight, preferably 20% to 80% by weight, of the general formula-[
CR ₂ -CR ₁ (CO—O—R ₃ )] —- containing substituted acrylic monomers or salts thereof. Here, at least one of the substituents R ₁ , R ₂ or R ₃ , preferably R ₁ or R ₂ is an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms, and R ₁ or R ₂ is a hydrogen atom and R 1 ₃ can be a hydrogen atom or an alkali metal salt. Most preferably, R ₁ is a substituted acrylic monomer having methyl and R ₂ being a hydrogen atom (ie, a methacrylic acid monomer). The most preferred copolymers of this type have a molecular weight of 3
500, comprising 60% to 80% by weight of acrylic acid and 40% to 20% by weight of methacrylic acid. Polyamine and modified polyamine compounds are available from European Patent Application No. 30
Useful as well as derivatives of aspartic acid as described in 5282, EP-A-305283 and EP-A-351629.

Other optional polymers include modified and unmodified polyvinyl alcohol and acetate, cellulose and modified cellulose, polyoxyethylene, polyoxypropylene, copolymers thereof, modified with polyoxyalkylene units, Unmodified ethylene or propylene glycol terephthalic acid esters or mixtures thereof. Suitable examples include U.S. Pat.Nos. 5,591,703, 5,597,789 and U.S. Pat.
No. 4,490,278.

Antifouling agents Suitable polymerizable antifouling agents are (a) (i) a polyoxyethylene segment of at least two degrees of polymerization, or (ii) linked to adjacent groups at each end by an ether linkage. If not, the hydrophilic segment does not contain any oxypropylene units, the oxyprorylene or polyoxypropylene segment of a degree of polymerization of 2 to 10, or (iii) an oxyalkylene containing oxyethylene and 1 to 30 oxypropylene units A mixture of units, wherein the hydrophilic segment preferably comprises at least 25% oxyethylene units, more preferably at least 50% for such components having from 20 to 30 oxypropylene units. (B) one or more nonionic hydrophilic components consisting essentially of; or (b)
(I) a C3 oxyalkylene terephthalate segment wherein the ratio of oxyethylene terephthalate to C3 oxyalkylene terephthalate units is 2: 1 or less, provided that the hydrophobic component also comprises oxyethylene terephthalate;
6 (alkylene) or oxy C4-C6 alkylene segment, (iii) poly (vinyl ester) segment having a polymerization degree of 2 or more, preferably polyvinyl acetate, (i
v) C4-C6 alkyl ether or C4 hydroxyalkyl ether segments or mixtures thereof, wherein said substituents are present in the form of C4-C6 alkyl ether or C4 hydroxyalkyl ether cellulose derivatives or mixtures thereof. , One or more nonionic hydrophobic components consisting of these, or an antifouling agent which is a combination of (a) and (b).

Typically, the polyoxyalkylene segments of (a) (i) can be used in a degree of polymerization from 200 to higher, but are preferably from 3 to 150, more preferably 6
Of 100 to 100. Suitable oxy C4-C6 alkylene hydrophobic segments include, but are not limited to, for example, Gosselink U.S. Patent No. 4,721.
No. 5,580, MO ₃ S (CH ₂ ) _n OCH ₂ CH ₂ O—
M is sodium, n is an integer of 4-6].

The polymerizable antifouling agent useful in the present invention also includes a hydroxyethyl cellulose polymer, a copolymer block of ethylene terephthalate or propylene terephthalate and polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and include hydroxy ethers of cellulose such as METHOCEL (Dow). Useful cellulosic soil inhibitors for use herein are selected from the group consisting of C1-C4 alkyl and C4 hydroxyalkyl cellulose. See US Patent No. 4,000,093 to Nicol et al., Issued December 28, 1976.

Antifouling agents characterized by poly (vinyl ester) hydrophobic segments include poly (vinyl ester) graft copolymers, eg, C1-C6 vinyl esters grafted onto a polyalkylene oxide skeleton such as a polyethylene oxide skeleton. , Preferably polyvinyl acetate. See European Patent Application No. 0219048 to Kud et al., Issued April 22, 1987.

[0193] Other suitable polymerizable antifoulants are copolymers having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight of the polymerizable stain inhibitor ranges from 25,000 to 55,000. See Hays U.S. Pat. No. 3,959,230 issued May 25, 1976, and Basadur U.S. Pat. No. 3,893,929 issued Jul. 8, 1975.

Other suitable polymerizable antifoulants include from 10 to 15% by weight of ethylene terephthalate units, together with 90 to 80% by weight of polyoxyethylene terephthalate units, derived from polyethylene glycol having an average molecular weight of 300 to 5000 It is a polyester having repeating units of ethylene terephthalate units.

Other suitable polymerizable antifouling agents are the sulfonated products of substantially linear ester oligomers comprising an oligomeric ester backbone of terephthaloyl and oxyalkylene repeat units and a terminal group covalently bonded to the backbone. It is. These antifouling agents are disclosed in US Pat. No. 4,968, JJScheibel and EP Gossenkink, issued Nov. 6, 1990.
No. 451. Other suitable polymerizable antifoulants are 1987
Gossenkink et al., U.S. Pat.No. 4,711,730 issued Dec. 8, U.S. Pat.No. 4,711,730, Gossenkink U.S. Pat. Issued Gossenkink U.S. Patent No.
No. 4,702,857 is a block polymerizable oligomer compound. Other polymerizable antifoulants also include the antifoulants of Maldonado et al., US Pat. No. 4,877,896, issued Oct. 31, 1989, which describes anionic, especially sulfoallyl, end-blocked terephthalates.

Other antifouling agents are oligomers having terephthaloyl units, sulfoisoterephthaloyl units, and repeating units of oxyethyleneoxy and oxy-1,2-propylene units. The repeating units form the backbone of the oligomer and are preferably end-capped with isethionate. Particularly preferred antifouling agents of this type are one sulphoisoterephthaloyl unit, five terephthaloyl units, and 1.7 to 1.
It contains oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of 8 and both end-blocking units of sodium 2- (2-hydroxyethoxy) ethanesulfonate.

Heavy Metal Ion Scavenger The tablet of the present invention preferably contains a heavy metal ion scavenger as an optional ingredient. The heavy metal scavenger as used herein means a component that acts to trap (chelate) heavy metal ions. These components may have the ability to chelate calcium and magnesium, but preferably exhibit selectivity for the capture of heavy metal ions such as iron, manganese and copper.

Heavy metal ion scavengers generally comprise from 0.005% to 20%, preferably from 0.1% to 10%, more preferably from 0.25% to 7.5% by weight of the composition, most preferably Preferably it is present at a concentration of 0.5% to 5%. Heavy metal ion scavengers that are acidic in nature and have phosphonic acid or carboxylic acid functions, for example, may be in acid form, complexes / salts with suitable counter cations such as alkali metal ions, ammonium or substituted ammonium ions or mixtures thereof. May exist as. Preferably, the complex / salt is water-soluble. The molar ratio of these counterions to heavy metal ion scavengers is preferably 1: 1 or more.

[0199] Heavy metal ion scavengers useful herein include aminoalkylene poly (alkylene phosphonates), alkali metal ethane-1-hydroxydiphosphonates, and organic phosphonates such as nitrilotrimethylene phosphonate. Preferred among the above are diethylenetriaminepenta (methylenephosphonate), ethylenediaminetri (methylenephosphonate) hexamethylenediaminetetra (methylenephosphonate) and hydroxyethylene 1,1 diphosphonate.

Other heavy metal ion scavengers useful herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic acid, ethylenediaminediglutaric acid, 2-hydroxypropylenediaminedisuccinic acid. And salts thereof. Particularly preferred is ethylenediaminedisuccinic acid (EDDS) or an alkali metal, alkaline earth metal, ammonium, or substituted ammonium salt thereof, or a mixture thereof. Preferably, the EDDS compound is in a free acid form or a sodium or magnesium salt or a double salt thereof.

The crystal growth inhibiting component washing tablet preferably contains a crystal growth inhibiting component, preferably an organodiphosphonic acid component, in an amount of 0.01% to 5%, more preferably 0.1% to 2% by weight of the composition. Included at a% concentration.

[0202] The term "organodiphosphonic acid" means an organodiphosphonic acid that does not contain a nitrogen atom in any of its chemical structures. Thus, this definition excludes organoaminophosphonates, which may be included in the compositions of the present invention as heavy metal scavenger components. The organodiphosphonic acid is preferably C1-C4 diphosphonic acid, more preferably C2 diphosphonic acid such as, for example, ethylene diphosphonic acid, most preferably ethane-1-hydroxy-1,1-diphosphonic acid, It may be in a fully or fully ionized form, especially as a salt or double salt.

The water-soluble sulfate washed tablet optionally contains a water-soluble sulfate. When present, the water-soluble sulfates
It comprises from 0.1% to 40%, more preferably from 1% to 30%, most preferably from 5% to 25% by weight of the composition. The water-soluble sulfate can be a sulfate of virtually any counter cation. Preferred salts are selected from alkali metal and alkaline earth metal sulfates, with sodium sulfate being particularly preferred.

Alkali metal silicate Alkali metal silicate is a preferred component of the tablet of the present invention. Preferred alkali metal silicates have a SiO ₂ : Na ₂ O ratio of 1.8-3.0, preferably 1.8-2.
. 4, most preferably 2.0 sodium silicate. Sodium silicate is preferably, by weight of SiO _2, 20% or less, preferably present from 1% to 15%, most preferably at a concentration of 3% to 12%. The alkali metal silicate may be either an anhydrous salt or a hydrate salt. The alkali metal silicate is also present as a component of the alkaline agent system.

The alkaline agent system is present in at least 0.4% by weight of SiO ₂ . Sodium metasilicate has a nominal SiO ₂ : Na ₂ O ratio of 1.0. The weight ratio of sodium silicate to sodium metasilicate is preferably 5 as measured as SiO _2.
0: 1 to 5: 4, more preferably 15: 1 to 2: 1, most preferably 10: 1 to 1
5: 2.

Colorant As used herein, the term "colorant" refers to any substance that absorbs a particular wavelength from the visible light spectrum. Such colorants have the effect of changing the apparent color when applied to the detergent composition and altering the appearance of the detergent composition. The colorant may be, for example, either a dye or a pigment. Preferably, the colorant is stable in the composition in which it is formulated. Thus, in high pH compositions, the colorant is preferably alkali stable, and in low pH compositions, the colorant is preferably acid stable.

The first phase, and / or the second phase, and / or any additional phases may be a colorant, a colorant mixture, a colored particle or a mixture of colored particles, such that each phase has a different appearance. May be included. Preferably, either the first phase or the second phase comprises a colorant. If both the first and second phases and / or the additional phase include a colorant, the colorants preferably have different appearances.

Examples of suitable dyes include reactive dyes, direct dyes, azo dyes. Preferred dyes include phthalocyanine dyes, anthraquinone dyes, quinoline dyes, monoazo, diazo and polyazo. More preferred dyes are anthraquinone dyes, quinoline dyes and monoazo dyes. Preferred dyes include SANDOLA available from Clariant UK
N E-HRL 180% (brand name), SANDOLAN MILLING BLUE (brand name), TURQOISE AC
ID BLUE (trade name) and SANDOLAN BRILLRANT GREEN (trade name); HEXACOL QUINOLINE YELLOW (trade name) and HEXACOL BRILLRANT BLUE available from Pointings UK
(Trade name); ULTRA MARINE BLUE (trade name) available from Holliday; or Bayer
Includes LEVAFIX TURQUISE BLUE EBA (trade name) available from USA, USA.

[0209] The colorant is incorporated into the phase in a suitable manner. Suitable methods include mixing all or selected detergent components with the colorant in a drum, or spraying all or selected detergent components with the colorant in a rotating drum. The colorant, when present as a component of the first phase, may comprise from 0.001% to 1.5%, preferably from 0.01% to 1.0%, most preferably from 0.1% to 0.3%. Present at the level. The colorant, when present as a component of the second phase and / or any additional phases, is generally 0.001% to 0.1%, more preferably 0.005% to 0.0%.
It is present at a level of 5%, most preferably 0.007% to 0.02%.

Corrosion Inhibiting Components The washed tablets of the present invention suitable for dishwashing are preferably organic silver coating agents, especially paraffins, nitrogen-containing corrosion inhibiting compounds, and Mn (II) compounds, especially the organic ligand Mn (II). ) Including a corrosion inhibitor selected from salts.

Organic silver coating agents are described in PCT Publication No. 94/16047, pending European patent application EP
-A-690122. European Patent Application EP-
It is described in A-634478. Mn (II) compounds for use in corrosion inhibitors are described in European Patent Application EP-A-672749. The organic silver coating agent is present at a level of from 0.05% to 10%, preferably from 0.1% to 5% of the total weight of the composition.

[0212] The functional role of the organic silver coating agent is to form an in-use protective film on silver dishes to which the composition of the present invention is applied. The silver coating agent should have a high affinity for adhesion to the solid silver surface, especially when present as a component of an aqueous wash and bleach solution treating the solid silver surface. Suitable organic silver coating agents include fatty acid esters of mono- or polyhydric alcohols having 1 to 40 carbon atoms in the hydrocarbon chain.

[0213] The fatty acid portion of the fatty acid ester can be obtained from a mono- or polyhydric alcohol having 1-40 carbon atoms in the hydrocarbon chain. Suitable examples of monocarboxylic acids include behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid, lauric acid, acetic acid, propionic acid, butanoic acid, isobutanoic acid, valeric acid, lactic acid, glycolic acid, and β, β '-Dihydroxyisobutanoic acid is included. Examples of suitable polycarboxylic acids include n-butylmalonic acid, isocitric acid, citric acid, maleic acid, malonic acid, and succinic acid.

[0214] The fatty alcohol residue of the fatty acid ester can be represented by a mono- or polyhydric alcohol having 1 to 40 carbon atoms in the hydrocarbon chain. Examples of suitable fatty alcohols include behenyl, arachidyl, cocoyl, oleyl, and lauryl, ethylene glycol, glycerin, isopropanol, vinyl alcohol, diglycerin, xylitol, sucrose, erythritol, pentaerythritol, sorbitol, or sorbitan. Preferably, the fatty acid and / or fatty alcohol residues of the fatty acid ester binding substance have 1 to 24 carbon atoms in the hydrocarbon chain.

Preferred fatty acid esters herein are esters of ethylene glycol, glycerin, and sorbitan, wherein the fatty acid moiety of the ester is typically of a species selected from behenic acid, stearic acid, oleic acid, palmitic acid, or myristic acid. is there. Glycerin esters are also highly preferred. These are mono-, di- or triesters of the above-mentioned fatty acids and glycerin.

[0216] Particular examples of fatty alcohol esters used herein include stearyl acetate, palmityl diacetate, cocoyl isobutyrate, oleyl maleate, oleyl dimaleate, and tallow propionate. Fatty acid esters as used herein include xylitol monopalmitate, pentaerythritol monostearate, sucrose monostearate, glycerin monostearate, ethylene glycol monostearate, sorbitan esters. Suitable sorbitan esters are sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan monomyristate, sorbitan monobehenate,
Includes sorbitan monooleate, sorbitan dilaurate, sorbitan distearate, sorbitan dibehenate, sorbitan dioleate, and mixed tallow mono and diesters.

Glycerin monostearate, glycerin monooleate, glycerin monopalmitate, glycerin monobehenate and glycerin distearate are preferred glycerin esters herein. Suitable organic silver coating agents include triglycerides, mono- or diglycerides and their fully or partially hydrogenated derivatives. Preferred sources of fatty acid esters are vegetable oils, fish oils and animal fats. Suitable vegetable oils include soybean oil, cottonseed oil, castor oil, olive oil, sunflower oil, rapeseed oil, grape seed oil, palm oil, and corn oil.

[0218] Waxes including microcrystalline wax are suitable as organic silver coating agents. Preferred waxes have a melting point in the range of 35 ° C to 110 ° C and generally consist of 12 to 70 carbon atoms. Preferably, it is a paraffin petroleum wax composed of a long-chain saturated hydrocarbon compound and a microcrystalline type. Alginate and gelatin are here suitable organic silver coatings. Also suitable are dialkylamine oxides such as C12-C20 methylamine oxide and dialkylquaternary ammonium compounds such as C12-C20 methylammonium halide.

Other suitable organic silver coating agents include certain polymerizable materials. Polyvinylpyrrolidone having an average molecular weight of 12,000 to 700,000, polyethylene glycol (PEG) having an average molecular weight of 600 to 10,000, a polyamine N-oxide polymer, a copolymer of N-vinylpyrrolidone and N-vinylimidazole, and methylcellulose; Cellulose derivatives such as carboxymethylcellulose and hydroxyethylcellulose are examples of such polymerizable substances. Certain fragrance materials, especially those that exhibit high realities on metal surfaces, are also useful here as organic silver coating agents.

[0220] Polymerizable stain inhibitors can also be used as organic silver coating agents. Preferred organic silver coating agents are paraffin oils, typically branched aliphatic hydrocarbons having predominantly 20 to 50 carbon atoms; preferably a cyclic to acyclic ratio of 1:10 to 2: 1, preferably from 1: 5 to 1: 1 predominantly branched C25-C45 species.

A paraffin oil meeting these characteristics, having a ratio of cyclic to non-cyclic hydrocarbons of 32:68, is sold by Wntershall (Salzbergen, Germany) under the trade name WINOG 70.

Nitrogen-containing corrosion inhibitors Suitable nitrogen-containing corrosion inhibitors include imidazole, benzimidazole, 2-
Heptadecyl imidazole, and Czech patent 139,279 and British patent GB-A-1,137,
No. 741, which also describes a method for producing imidazole compounds, including those imidazole derivatives described in US Pat. Suitable nitrogen-containing corrosion inhibiting compounds are those pyrazole compounds and their derivatives, in particular pyrazole substituted by a substituent R _1, R _3, R ₄ and R ₅ at the position of the 1, 3, 4, or 5. Here, R ₁ is any of H, CH ₂ OH, CONH ₃ , or COCH ₃ , R ₃ and R ₅ are any of C1-C20 alkyl or hydroxyalkyl, and R ₄ is H, NH ₂ or NO ₂ is either.

Other suitable nitrogen-containing corrosion inhibiting compounds include benzotriazole, 2-mercaptobenzothiazole, 1-phenyl-5-mercapto-1,2,3,4-tetrazole, thionalide, morpholine, melamine, distearylamine , Stearoyl stearamide, cyanuric acid, aminotriazole, aminotetrazole, and indazole.

Also suitable are amines, especially distearylamine and ammonium compounds such as ammonium chloride, ammonium bromide, ammonium sulfate or diammonium hydrogen citrate.

Mn (II) Corrosion Inhibitor Compound Cleaning Tablets may include a Mn (II) corrosion inhibitor compound. The Mn (II) compound preferably comprises from 0.005% to 5%, more preferably 0.01% by weight of the composition.
１1% by weight, most preferably 0.02% to 0.4% by weight. Preferably, the Mn (II) compound is 0.1% by weight of Mn (II) in the bleaching solution.
It is blended at a level giving from ppm to 250 ppm, more preferably from 0.5 ppm to 50 ppm, most preferably from 1 ppm to 20 ppm.

The Mn (II) compound may be an anhydrous or hydrated form of an inorganic salt. Suitable salts include manganese sulfate, manganese carbonate, manganese phosphate, manganese nitrate, manganese acetate, and manganese chloride. The Mn (II) compound may be a salt or double salt of an organic fatty acid such as manganese acetate or manganese stearate. The Mn (II) compound may be a salt or a double salt of an organic ligand. One preferred example is a heavy metal ion scavenger. Examples of other preferred organic ligands are crystal growth inhibitors.

Other Corrosion Inhibiting Compounds Other suitable additional corrosion inhibiting compounds include mercaptans, diols, especially lauryl mercaptan, thiophenol, thionaphthol, thionalide, thioanthranol. Saturated or unsaturated C10-C20 fatty acids or salts thereof,
Particularly, aluminum tristearate is also suitable. C12-C20 hydroxy fatty acids or salts thereof are also suitable. Other antioxidants such as phosphonated octadecane and beta hydroxytoluene (BHT) are also suitable.

Copolymers of butadiene and maleic acid, especially those supplied by Polysciences Inc. at deal reference 07787, have been found to be particularly useful as corrosion inhibiting compounds.

Hydrocarbon Oils Other preferred detergent components for use in the present invention are hydrocarbon oils, typically long chain aliphatic hydrocarbons having predominantly 20 to 50 carbon atoms; preferred hydrocarbons. Is saturated and / or branched; preferred hydrocarbons are predominantly branched C25- having a ratio of cyclic to acyclic hydrocarbons of from 1:10 to 2: 1, preferably from 1: 5 to 1: 1. Selected from C45 seeds. The preferred hydrocarbon oil is paraffin. A paraffinic oil having a ratio of cyclic to acyclic hydrocarbons of 32:68, which meets the above-mentioned properties, is sold under the trade name WINOG 70 by Wntershall (Salzbergen, Germany).

Water-soluble bismuth compound The washing tablet of the present invention suitable for dish washing contains a water-soluble bismuth compound preferably in an amount of 0.005% to 20%, more preferably 0.01% to 5% by weight of the composition. , Most preferably at a level of 0.1% to 1%. The water-soluble bismuth compound is a salt or double salt of substantially bismuth and any inorganic or organic counter anion. Preferred inorganic bismuth salts are bismuth trihalides,
Selected from bismuth nitrate and bismuth phosphate. Bismuth acetate and bismuth citrate are preferred salts with organic counter anions.

Enzyme Stabilizing System Preferred enzyme-containing compositions herein comprise from 0.001% to 10%, preferably from 0.005% to 8%, most preferably from 0.01% to 6% enzyme by weight. A stabilizing system may be included. The enzyme stabilizing system may be any stabilizing system that can be used in combination with the detersive enzyme. Such stabilizing systems consist of calcium ions, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, chlorine bleach scavengers, and mixtures thereof. Such a stabilizing system can also include a reversible enzyme inhibitor, such as a reversible protease inhibitor.

Calcium soap-dispersed compound The washed tablet of the present invention comprises 0.1% to 40% by weight of the composition, more preferably 1% by weight.
It may contain calcium soap dispersion compounds present at a level of 20%, most preferably 2% -10%. Calcium soap dispersion compounds are substances that prevent precipitation of alkali metal, ammonium or amine salts of fatty acids by calcium or magnesium ions.
Preferred calcium soap dispersion compounds are described in PCT Application No. WO 93/08877.

Foam Suppressing System The cleaning tablets of the present invention, when formulated for use in a machine laundering composition, are preferably 0.01% to 15%, more preferably 0.05%, by weight of the composition. % To 10%
, Most preferably at a level of 0.1% to 5%. Suitable suds control systems for use herein may comprise essentially known suds suppressors, including, for example, silicone suds suppressors, 2-alkyl and alkanol suds suppressors. Preferred foam control systems and compounds are described in PCT application WO 93/08876 and EP-A-7.
No. 05324.

Polymerizable Dye Transfer Inhibitor The washed tablet of the present invention may contain 0.01% to 10% by weight, more preferably 0.05% to
% To 0.5% of a polymerizable dye transfer inhibitor. The polymerizable dye transfer inhibitor is preferably a polyamine-N-oxide polymer,
It is selected from a co-polymer of N-vinylpyrrolidone and N-vinylimidazole, a polyvinylpyrrolidone polymer or a combination thereof.

Optical Brighteners Washable tablets suitable for use in the laundry of clothing described herein may optionally comprise from 0.005% to 5% by weight of certain hydrophilic optical brighteners. Including. Hydrophilic optical brighteners useful herein include those having the following structural formula:

[0236]

Embedded image

Wherein R ₁ is selected from anilino, N-2-bishydroxyethyl and NH-2-hydroxyethyl; R ₂ is N-2-bishydroxyethyl, N-2-hydroxyethyl-N-methyl Selected from amino, morpholino, chloro and amino; and M is a salt-forming cation such as sodium, potassium. In the above formula, where R ₁ is anilino, R ₂ is N-2-bishydroxyethyl, and M is a cation such as sodium, the lightening agent is 4,4′-bis [(4-anilino -6- (N-2-bishydroxyethyl) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid and disodium salt. This particular lightening agent is CibaGe
Commercially sold by igy Corporation as Tinopal-UNPA-GX. Tinopal-UNPA
-GX is a preferred hydrophilic optical brightener useful in the detergent compositions of the present invention.

In the above formula, when R ₁ is anilino, R ₂ is N-2-hydroxyethyl-N-methylamino, and M is a cation such as sodium, the lightening agent is 4,4 ′ -
Disodium salt of bis [(4-anilino-6- (N-2-bishydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid.
This particular lightening agent is commercially available from CibaGeigy Corporation under Tinopal-5BM-GX.

In the above formula, when R ₁ is anilino, R ₂ is morpholino, and M is a cation such as sodium, the lightening agent is 4,4′-bis [(4-anilino-6- Morpholino-s-triazin-2-yl) amino] -2,2'-stilbene disulfonic acid. This particular lightening agent is available from Tibapal-AMS-G from CibaGeigy Corporation.
Commercially sold under X. Another preferred optical brightener is that known as Brightner 49, available from CibaGeigy.

Clay Softening System Washing tablets suitable for use in clothing laundering may include a clay softening system consisting of a clay mineral substance and optionally a clay flocculant. The clay mineral material is preferably a smectite clay material. Smectite clays are described in U.S. Patents 3,862,058, 3,948,790, and 3,954,632. Procter and Gamble No. 4,062,647, European Patent Nos.EP-A299,575, EP-A313,
No. 146 describes suitable organic polymerizable clay flocculants.

Cationic Fabric Softeners Cationic fabric softeners can also be incorporated into the compositions of the present invention suitable for clothing washing methods. Suitable cationic fabric softeners include water-soluble tertiary amine or dilong chain amide materials, as described in GB 1514276 and EP-B-0011340. The cationic fabric softener is typically 0.5% to 15% by weight, usually 1%
Formulated at a level of ~ 5%.

Other Optional Ingredients Other optional ingredients suitable for inclusion in the compositions of the present invention are fragrances and filler salts, with sodium sulfate being the preferred filler salt.

Composition pH The washed tablets of the present invention are preferably not formulated to have a particularly high pH, but preferably have a pH of 7.0 to 12.5, more preferably measured as a 1% solution in distilled water. Preferably 7.5
It has a pH of １１11.8, most preferably 8.0-11.5.

Mechanical Dishwashing Methods Any suitable method for washing dishes or cleaning dirty dishes can be envisioned. A preferred mechanical dishwashing method is to treat a dirty article selected from porcelain, glassware, silverware, metalware, cutlery and mixtures thereof with an aqueous solution in which an effective amount of a cleaning tablet according to the invention is dissolved or dispersed. It consists of doing. An effective amount of a washing tablet is the amount of a typical product commonly used in a conventional mechanical dishwashing method and the volume of a washing solution, and 8 g to 60 g of a product is added to a washing solution having a volume of 3 to 10 liters. It means dissolving or dispersing. Preferably, the washed tablets are from 15 g by weight
40 g, more preferably 20 g to 35 g.

Clothes Washing Method The mechanical washing method herein typically involves soiling with an aqueous laundry liquor in a washing machine in which an effective amount of a mechanically washed tablet composition according to the present invention has been dissolved or dispersed. Consists of processing clothing. The effective amount of the washing tablet is the amount of a typical product commonly used in a conventional mechanical washing method and the volume of the washing liquid, and the amount of the washing liquid of 5 to 65 liters is 15 g to 300 g of the washing liquid. It means to dissolve or disperse.

In a preferred mode of use, the dispensing device is employed in a washing method. The feeder is filled with detergent product and used to introduce the product directly into the drum of the washing machine before the start of the washing cycle. Its volume capacity should be able to accommodate enough detergent product that would normally be used in a laundering process. Once the laundry has been loaded into the washing machine, a supply containing detergent products is placed in the drum. At the beginning of the washing cycle of the washing machine, water is introduced into the drum and the drum is rotated periodically. The dispensing device is designed to be able to contain the dried detergent product and to release the product during the washing cycle in response to its agitation as the drum rotates and to come into contact with the wash water.

This device has a number of holes through which the product can pass so that the detergent product can be released during washing. Alternatively, the device may be made of a material that is permeable to liquids but impermeable to solids, so that the dissolved product can be released.
Preferably, the detergent product is released rapidly at the beginning of the washing cycle, whereby at this stage of the washing cycle the concentration of the product in the washing machine drum is temporarily high locally.

The preferred dispensers are reusable and are designed to maintain their expected integrity, both in the dry and during the wash cycle. Alternatively, the supply device may be a flexible container such as a bag or pouch. The bag may be a fibrous structure coated with a water-impermeable protective material to hold the contents, as described in European Patent Application No. 0018678. Alternatively, water that provides an end seal or seal designed to break in aqueous media, as described in European Patent Applications Nos. 0011500, 0011501, 0011502, and 0011968. It may be formed of an insoluble synthetic polymeric material. Conventional forms of seals that are friable to water include those in which one end of a pouch formed of a water impermeable film such as polyethylene or polypropylene is treated with a water soluble adhesive and sealed.

Alternatively, but in a preferred embodiment of the present invention, the multi-phase wash tablet is a laundry detergent known as a bleach additive. As used herein, bleach additive means that the multi-phase wash tablet is used in combination with a conventional laundry detergent composition. Multiphasic tablets and conventional detergent compositions are prepared either by placing one or both detergents in a drawer of a washing machine feeder or by placing one or both detergents directly in a drum of a washing machine. , Supplied to the washing machine. More preferably, the multi-phase tablet is placed directly on the drum of the washing machine. Even more preferably, the multi-phase cleaning tablet and the conventional detergent composition are both placed in the drum of a washing machine. The multiphase wash tablet is fed to the main washing cycle of the washing machine prior to, but more preferably at the same time as the conventional detergent composition.

Here, the conventional detergent composition refers to any detergent composition sold as a laundry preparation in the form of granules, liquids, gels, tablets, such as Ariel, Daz, Bold (all trade names). Also means things. An advantage of this particular embodiment is the cleaning capability. In fact, the benefits of the cleaning capacity of the combination of bleach additive and conventional laundry detergent are greater than those obtained with each component alone. Without wishing to be bound by theory, it is believed that this is because the first phase of the multi-phase tablet dissolves relatively quickly, releasing components, eg, enzymes, into the wash liquor faster.

[0251] Abbreviations in the Examples Example STPP: Sodium tripolyphosphate Bicarbonate: sodium bicarbonate citric acid: Anhydrous citric acid Carbonate: Anhydrous sodium silicate carbonate: amorphous sodium silicate (SiO _2: ratio of Na ₂ O = 2.0) SKS-6: crystalline layered silicate of formula δ-Na ₂ Si ₂ O ₅ PB1: anhydrous perborate monohydrate non-ion: average ethoxylation degree 3.8, average propoxylation degree 4.5 C13-C15 mixed ethoxylated / propoxylated fatty alcohol, sold by Basf under the trade name Plurafac. TAED: tetraacetylethylenediamine HEDP: ethane-1-hydroxy-1,1-diphosphonic acid DTPMP: diethylenetriaminepentamethylenephosphonic acid ATMP: aminotrimethylenephosphonic acid PAAC: pentaaminecobalt (III) salt Paraffin: trade name Winog 70 from Wintershall Paraffin oil Protease: Proteolytic enzyme Amylase: Proteolytic enzyme BTA: Benztriazole Sulfate: Anhydrous sodium sulfate PEG3000: Polyethylene glycol with a Hoechst molecular weight of about 3,000 PEG6000: Polyethylene glycol with a Hoechst molecular weight of about 6000 pH: 20 C. Measured in 1% distilled aqueous solution In the following examples, all concentrations are% by weight.

Examples I-IV The following are examples of cleaning tablets of the present invention suitable for use in a dishwasher.

[0253]

[Table 1]

[0254]

[Table 2]

A multiphasic tablet composition was prepared as follows. The Phase 1 cleaning active composition is made by mixing the particulate and liquid ingredients and then sent to a conventional rotary press die. The press has an appropriately shaped punch for forming a molded article. The cross section of the die is about 30 × 38 mm. The composition is then 940 kg
/ Cm ² and then lift the pan to expose the top of the first phase of the tablet containing the molding. A second phase cleaning active composition is prepared in a similar manner and sent to a die. The granular active composition is then subjected to a compressive force of 170 kg / cm ² , the punch is lifted and the multiphase tablet is discharged from the tablet press. The resulting tablet dissolves or disintegrates within 12 minutes as described above, with phase 2 of the tablet comprising 5
Dissolve within minutes. Tablets exhibit good solubility and detergency, as well as good tablet integrity and strength.

Examples VII-XII The following examples illustrate the wash tablets of the present invention suitable for use as a laundry additive in a clothes washing machine.

[0257]

[Table 3]

[0258]

[Table 4]

Lightening agent 49 is available from Ciba Geigy. Acrylic acid - average molecular weight of the maleic acid copolymer is from about 7000 bleach catalyst is NH ₃ and acetic acid and the stable double salts of cobalt. The washed tablets were prepared as described in Examples I to VI above.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C11D 11/00 C11D 11/00 (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, F I, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV , MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZA, ZW (71) Applicant ONE PROCTER & GANBLE PLAZA, CINCINNATI, OHIO, UNITED STATES OF AMERICA (72) Inventor Benny, Brenda Francis England, N.N., N.N. 23, 9FS, Cramlington, Dela Mia, Crescent 34A (72) Inventor Binder, Christopher James New England, UK Castle, Upon, Tyne, N2, 2D, Jesmond, Saint, Georges, Terrace 116 (72) Inventor Del Duca, Valerio 80064 Massarbrenze, Italy, Corso, Esse, Agata 61 / N (72) Inventor Esposito , Andrea Italy 00167 Rome, Via, Car Dinale, Caprara 34 F-term (reference) 4H003 AB04 AC23 BA17 CA08 DA01 DA19 EA06 EA09 EA12 EA15 EA16 EA19 EA24 EB02 EB08 EB13 EB16 EB20 EB24 EB26 EB30 FA28 FA28

Claims (20)

[Claims] 1. The tablet comprises: a) a first phase in the form of a molded body having at least one mold therein; and b) a second phase in the form of a granular solid compacted in said mold. Multi-phase cleaning tablets suitable for use in washing machines. 2. The multi-phase washed tablet of claim 1, wherein the second phase is compressed at a pressure less than about 350 kg / cm ² . 3. The tablet is: a) in the form of a compressed molded body having at least one mold therein, wherein the molded body is compressed at a pressure of at least about 350 kg / cm ² ; And b) a second phase in the form of a granular solid compacted in said mold, said second phase comprising about 350
A multiphasic wash tablet suitable for use in a washing machine, comprising being compressed at a pressure of less than kg / cm ² . 4. The multi-phase washed tablet according to claim 1, wherein the second phase dissolves faster than the first phase. 5. Multiphasic wash tablet according to claim 1, wherein the second phase dissolves in the washing machine within 5 minutes. 6. The tablet comprises: a) a first phase in the form of a molded body having at least one mold therein; and b) a second phase in the form of a particulate solid compacted in said mold. And the tablet comprises at least one detersive active, at least 50%, preferably at least 60%, more preferably at least 8% by weight of the detersive active.
A multi-phase washed tablet suitable for use in a washing machine, wherein 0% by weight is supplied to the washing liquid within 10 minutes, preferably within 5 minutes, more preferably within 3 minutes. 7. The tablet comprises: a) a first phase in the form of a molded body having at least one mold therein; and b) a second phase in the form of a particulate solid compacted in said mold. And wherein the tablet is selected from an enzyme, a bleach, a bleach activator, a bleach catalyst, a surfactant, a chelating agent, and mixtures thereof, wherein the tablet is predominantly concentrated in the second phase, one or more A multi-phase cleaning tablet suitable for use in a washing machine, comprising a cleaning active ingredient of 8. The multi-phase washed tablet according to claim 1, wherein the second phase additionally comprises a disintegrant. 9. Multiphasic washed tablet according to any of the preceding claims, wherein the second phase comprises an enzyme. 10. The tablet comprises: a) a first phase in the form of a molded body having at least one mold therein; and b) a second phase in the form of a granular solid compacted in said mold. A multiphase wash tablet suitable for use in a washing machine, comprising a second phase enzyme. 11. The multi-phase washed tablet according to claim 1, wherein the first and / or the second phase comprises a binder. 12. The binder according to claim 1, wherein the binder is selected from the group consisting of sucrose and sucrose derivatives, starch and starch derivatives, inorganic and organic polymers.
2. The multi-phase washed tablet according to 1. 13. Multiphasic wash tablet according to any of the preceding claims, characterized in that it additionally has a barrier phase between the first and the second phase. 14. The multiphase washed tablet according to claim 11, wherein the barrier phase comprises a binder applied in a liquid state. 15. The tablet comprises: a) compressing the first cleaning active composition to form a first phase comprising a mold; b) dispensing the second cleaning active composition into the mold in particulate form. And c) compressing the granular detergent components in a mold. A method for producing a multi-phase washed tablet suitable for use in a washing machine. 16. The method according to claim 15, wherein the second detergent composition is compressed at a pressure of less than 350 kg / cm ² . 17. A method for washing in a washing machine, comprising charging a multi-phase washing tablet according to any of the preceding claims into a washing machine. 18. The method according to claim 17, wherein the washing machine is charged with a conventional detergent composition in addition to the multiphase washing tablet. 19. The method according to claim 18, wherein the washing machine is charged with the conventional detergent composition simultaneously with the multi-phase washing tablet. 20. Use of a multiphase washed tablet as a bleaching additive.