JP2002520478A - Detergent tablet - Google Patents

Abstract

  (57) [Summary] A multi-phase detergent tablet for a washing machine, comprising: a) a first phase in the form of a compact having at least one mold therein; and b) a second phase in the form of compressed granular solids in said mold. The multi-phase tablets provide improved dissolution and cleaning properties with excellent tablet integrity and tablet strength.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] TECHNICAL FIELD The present invention relates to a multi-phase detergent tablet.

BACKGROUND tablet detergent compositions are well known to those skilled in the art. Tablet-type detergent compositions have several advantages over detergent compositions in granular form, such as ease of dosing, handling, transport and storage.

[0003] Detergent tablets are most commonly manufactured by premixing the components of the detergent composition and forming the premixed detergent components into tablets using a suitable device, preferably a tablet molding machine. It is. Tablets are typically formed by compressing the ingredients of the detergent composition such that the manufactured tablet is strong enough to withstand handling and transport without breaking. In addition to being robust, tablets must dissolve fast enough and be released into the wash water as soon as possible at the beginning of the wash cycle.

[0004] However, there is an opposing concept that the tablet dissolution rate decreases with increasing compression force. Therefore, an object of the present invention is to find a balance between tablet strength and tablet dissolution.

[0005] As found in the prior art, solutions to this problem include compressing the tablet at low compression pressure. However, tablets made in this way, despite having a high relative dissolution rate, are prone to crumble or damage and are unacceptable to consumers. Other solutions include making tablets containing a solubilizing agent, such as a foaming agent, with a high relative compression pressure to provide the required level of rigidity.

[0006] The multiphase detergent tablets described in the prior art are made by compressing a first composition on a tablet press to form a substantially planar first layer. Next, the detergent composition is further supplied on the first layer of the tablet molding machine. Thereafter, the second composition is compressed to form another substantially planar second layer. Thus, the first layer is subjected to more than one compression. Because it is compressed during the compression of the second composition. Generally, the first and second compression forces are of comparable magnitude. In such a case, the force used in both the first and second compression stages should be about 4,000 to about 4,000, since the compression force must be large enough to bind the first and second compositions. 20,000 kg range (tablet cross-sectional area is about 10
Applicant has found that (assuming cm ² ). As a result,
Tablet dissolution rates are slower. Other multi-phase tablets with different dissolution rates are made by compressing the second layer with less force than the first layer. However, although the dissolution rate of the second layer is improved, the second layer is softer than the first layer and is therefore more susceptible to handling and transport damage.

[0007] EP-B-0,055,100 describes a toilet block formed by combining slowly dissolving shaped bodies with tablets. The above toilet block
It is placed in a washroom cistern and is designed to dissolve for days, preferably weeks. As a means of slowing the dissolution rate of the lavatory block, this publication teaches the incorporation of one or more solubility inhibitors. Examples of such solubility inhibitors are paradichlorobenzene, waxes, long-chain fatty acids and alcohols and their esters, and fatty alkylamides. Detergent tablets for use in washing or automatic dishwashing should almost dissolve within one cycle of the washing machine or dishwasher, ie, within 15 to 120 minutes.

According to one aspect of the subject matter the present invention, comprising the following multi-phase detergent tablet for use in a washing machine is provided: a) the shape of the molded article having at least one mold A) a second phase in the form of a compressed granular solid in said mold.

In a preferred embodiment, the first phase is at least about 40 kg / cm ² , preferably at least about 250 kg / cm ² , more preferably at least about 350 kg / cm ² (3.43 kN / cm ² ).
cm ² ), more preferably about 400 to about 2000, and especially about 600 to about 1
It is a compression-molded body produced by applying a compression pressure of 200 kg / cm ^{2 (} the compression pressure in the present invention refers to the applied force, the tablet cross-sectional area across the applied force—actually, of a rotary press). Die cross-sectional area-obtained by dividing
. Second phase (which terminology includes the possibility of multiple "second" phases, referred to herein as "
The granular solids (which may mean "any subsequent phase") are compressed by applying a compression pressure less than the pressure applied to the first phase, preferably at about 350 kg / c.
m ² less than the compression pressure, preferably about 40 kg / cm ² ~ about 300 kg / cm ² range, and more in preferably from about 70 to about 270 kg / cm ^2, preferably compressed in the mold. Such tablets are preferred in the present invention in terms of providing optimal tablet integrity and tablet strength (e.g., as measured by Child Bite Strength [CBS] test), and optimal product dissolution characteristics. The tablet of the present invention should have a minimum of about 6 kg of CBS, preferably about 8k
g, more preferably more than about 10 kg, particularly preferably about 12 k
Preferably, it has a CBS of greater than g, more preferably greater than about 14 kg, wherein the CBS is measured by the US Consumer Product Safety Commission inspection regulations. Also, the compression pressure on the first and second phases will generally be in a ratio of at least about 1.2: 1, preferably at least about 2: 1, more preferably at least about 4: 1. Thus, according to a further aspect of the invention, there is provided a multi-phase detergent tablet for use in a washing machine, comprising: a) the shape of a compressed compact having at least one mold therein. A first phase, wherein the compact is produced at a compaction pressure of at least about 350 kg / cm ² ; and b) a second phase in the form of compressed granular solids in the mold. There, about 350kg
The said second phase compressed at a pressure of less than / cm < ² >.

In another preferred embodiment, the second phase is in the form of a compact or compact contained within at least one mold of the first compact, for example by physical or chemical attachment. Preferably, the first and second phases are in a relatively large weight ratio on one side, such as at least about 6: 1, more preferably at least about 10: 1, and the tablet composition is predominantly concentrated in the second phase Contains one or more detergent actives (eg, enzymes, bleaches, bleach activators, bleach catalysts, surfactants, chelating agents, etc.), for example, at least about 50% by weight of the active ingredients, preferably at least about 60%. % By weight, especially about 80% by weight (based on the total weight of active ingredients in the tablet) is preferably present in the second phase of the tablet. Such compositions are also optimal for tablet strength, dissolution, cleaning, and pH control properties, for example, within 10, 5, 4 and even 3 minutes after the start of the washing process. At least 50%, preferably at least 60%, more preferably at least 8% by weight of the detergent active.
Provide a tablet composition capable of supplying 0% by weight.

Thus, according to another aspect of the present invention, there is provided a multi-phase detergent tablet for use in a washing machine, comprising: a) a molded article comprising at least one mold therein. B) a second phase in the form of a particulate solid compacted in said mold, wherein said tablet comprises at least one detergent active and at least 5 of said detergent active.
0%, preferably a minimum of 60%, more preferably a minimum of 80% by weight is supplied to the washing liquid within the first 10 minutes, preferably within the first 5 minutes, more preferably within 3 minutes of the washing process. It is blended as follows.

[0012] An additional advantage of the present invention is that different dissolutions from phase to phase, such that one phase of the tablet dissolves much faster before the other phase and almost completely dissolves before the other phase dissolves. Speed is to be gained. This is particularly important for the differential supply of detergent actives.

Thus, according to another aspect of the present invention, there is provided a multiphase detergent tablet comprising: a) a first phase in the form of a compact having at least one mold therein; and b. A) a second phase in the form of a compact included in the mold, wherein the tablet composition comprises one or more detergent actives predominantly concentrated in the second phase; The second phase additionally contains a disintegrant.

According to a further aspect of the present invention there is provided a multiphase detergent tablet comprising: a) a first phase in the form of a compact having at least one mold therein; and b) said mold. A second phase in the form of a compact contained within and contained therein, wherein the tablet composition comprises one or more detergent actives predominantly concentrated in the second phase;
And wherein the second phase additionally contains a binder.

[0015] Suitable one or more detergent active ingredients are selected from enzymes, bleaches, bleach activators, bleach catalysts, surfactants, chelating agents, crystal growth inhibitors and mixtures thereof; Is particularly preferred to increase the cleaning capacity during the very first cold water phase of the washing or cleaning operation. Highly preferred for use in the present invention are therefore enzymatic detergent active ingredients, especially enzymes and have enhanced or optimal activity in the pH range of 8-10, in the temperature range of 25 ° C. to 55 ° C. An enzyme mixture comprising one or more enzymes (eg, natalase).

Thus, according to yet another aspect of the present invention, there is provided a multiphase detergent tablet comprising: a) a first phase in the form of a compact having at least one mold therein; and b) a second phase in the form of a compact which is contained and contained in the mold, said second phase additionally comprising an enzyme.

[0017] Not only is resistant enough to firmly detailed description handling and transportation of the invention, at least a large part is rapidly dissolved in the washing water, detergent tablets which may also provide a detergent active ingredient rapidly It is an object of the present invention to provide It is preferred that 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 automatic dishwasher or washing machine washing cycle. Preferred washing machines are either automatic dishwashers or washing machines.
The time for the multiphase tablet or one phase thereof, or the detergent active to dissolve,
By DIN44990, determined using Bosch using dishwashing machine available from (Bosch), the standard 65 ° C. wash program called repeated a sufficient number of times to obtain a minimum of six or reliable reproducible water hardness 18 ^〇 H Can be

[0018] The multiphase detergent tablet of the present invention comprises a first phase, a second phase and optionally a subsequent phase. The first phase is in the form of a molded article of a detergent composition comprising one or more detergent components as described below. Suitable detergent ingredients include builders, bleach, enzymes and surfactants. The components of the detergent composition are mixed, for example, by mixing dry components or spraying liquid components. The components are then formed in the first phase using any suitable cutting equipment, but preferably by compression, for example, with a tablet compressor. Alternatively, the first phase can be manufactured by extrusion, casting and the like. Although the first phase can take a variety of geometric shapes, such as spherical, cubic, etc., preferred embodiments have a generally axially symmetric shape with a generally round, square or rectangular cross section.

[0019] The first phase is made to include at least one mold on the surface of the compact.
The mold or molds can also vary in size and shape, as well as their location, orientation and topography with respect to the first phase. For example, the one or more molds may be generally circular, square or oval in cross-section; they may form closed cavities or depressions therein, or they may be non-bonded areas of the surface of the compact. (E.g., axially opposed facing surfaces), which can form one or more topographical "holes" in the shaped body on the shaped body surface; They may be arranged symmetrically in other directions or may be arranged asymmetrically. In a preferred embodiment, the mold is made using a specially designed tablet press, wherein the punch surface in contact with the detergent composition is such that when it contacts and presses the detergent composition, Shaped to press one or more molds during the first phase of the multi-phase detergent tablet.
Preferably, the mold will have an inwardly concave or generally concave surface and will provide excellent adhesion to the second phase. Alternatively, the mold can be formed by compressing a pre-formed detergent composition placed annularly around a central die, whereby a cavity extending axially between opposing surfaces of the molded body. A compact having a shaped mold is formed.

The tablets of the present invention also include one or more additional phases made from one or more compositions that include one or more detergent ingredients as described below. At least one phase (referred to herein as a second phase) is compressed into / in one or more molds of the first phase of the detergent tablet, a granular solid (the term powder,
Preferably, it takes the form of granules, agglomerates and other particulate solids, for example mixtures thereof with liquid binders, meltable solids, sprays and the like, and the second phase itself takes the form of a compact. Optional other phases include one or more compositions in the form of a separate layer or layers. Suitable detergent components include builders, colorants, binders, surfactants, disintegrants and enzymes, especially amylase and protease enzymes. In another preferred aspect of the invention, the second phase and any subsequent phases include a disrupting agent selected from either disintegrants or blowing agents. Suitable disintegrants include agents that swell in contact with water or form channels in the detergent tablet to facilitate inflow and / or outflow of water. Any of the known disintegrants or foaming agents that can be suitably used for washing or dishwashing are recommended for use in the present invention. Suitable disintegrants include starch (eg, natural, modified, pregelatinized starch, such as those derived from corn, rice, and potato starch), U-Sperse (
Product name), Primojel (product name) and Explottab (Explot
ab) Starch derivatives such as (trade name), celluloses, microcrystalline cellulose, and Arbocel (trade name) and Vivapur (trade name) provided by Rettenmaier Cellulose derivatives, Nymcel (trade name), Avicel (trade name), Lattice NT (Lattice NT) (trade name) and Hanfloc (Hanfloc) provided by Metsa-serla Trade names), alginates, acetate trihydrate, burkeite, formula Na ₂ CO ₃ . Carbonic acid monohydrate with H ₂ O, content of phase I at least about 4
0% STPP hydrate, carboxymethylcellulose (CMC), CMC-
Base-polymers, including sodium acetate, aluminum oxide. Suitable blowing agents are those that generate gas upon contact with water. Suitable blowing agents may be oxygen, nitrogen dioxide or carbon dioxide generating species. Examples of suitable blowing agents are selected from the group consisting of perborate, percarbonate, carbonate, bicarbonate, and combinations with carboxylic acids or other acids such as citric acid, sulfamic acid, malic acid or maleic acid. it can.

The components of the detergent composition are mixed, for example, by mixing dry components and mixing or spraying liquid components. The components of the second phase and any subsequent phases are then fed to and retained in the mold made by the first phase.

A preferred embodiment of the present invention comprises two phases, a first and a second phase. The first phase usually contains one mold and the second phase usually consists of a single detergent active composition. However, it is contemplated that the first phase may comprise more than one mold and the second phase may be made from more than one detergent active composition. It is further contemplated that the second phase comprises more than one detergent active composition contained within one mold. It is also conceivable that several detergent active compositions are included in separate molds. In this way, potentially chemically sensitive detergent components can be separated to avoid reacting and performance degradation caused by components that may be inactivated or depleted.

In a preferred aspect of the invention, the first phase, the second phase and / or any subsequent phases can include a binder. At present, said binders are organic polymers such as polyethylene and / or polypropylene glycols, in particular with a molecular weight of 400
0, 6000 and 9000, paraffins, polyvinylpyrrolidone (P
VP), in particular PVP with a molecular weight of 90000, polyacrylates, sugars and sugar derivatives, starch and starch derivatives such as hydroxypropylmethylcellulose (HPMC) and carboxymethylcellulose (CMC); and inorganic polymers such as hexametaphosphate. Selected from the group. The binder is important both to maintain tablet integrity and to help obtain different dissolution of the first and second phases, as described below.

In a preferred aspect of the invention, the first phase is heavier than about 3 g, preferably more than about 4 g, more preferably more than about 5 g. More preferably, the first phase comprises from about 10 g to about 30 g, even more preferably from about 15 g to about 25 g, most preferably from about 18 g to about 18 g.
It weighs about 24 g. The second phase and any subsequent phases are less than 4 g. More preferably, the second phase and / or any subsequent phases are from about 0.1 g to about 3.
5 g, more preferably about 1 g to about 3.5 g, and most preferably about 1.3 g to about 1.3 g.
It is about 2.5 g.

In another embodiment of the present invention, the barrier layer comprising the barrier layer composition is provided between the first phase and the second phase and / or any subsequent phase, or indeed, the second phase. Located between a phase and any subsequent phases. The barrier layer composition includes at least one binder selected from the group described above. The advantage of the presence of the barrier layer is that the migration of components from one phase to another, such as from a first phase to a second phase and / or any subsequent phase, and vice versa, can be achieved. To prevent or reduce.

Preferably, the components of the second phase and any subsequent phases are compressed with a very low compression force compared to the compression forces normally used in tablet manufacture. An advantage of the present invention is therefore the use of low compressive forces, so that when heat-, force- or chemically-sensitive detergent components are inserted into a tablet, they do not suffer the necessary performance degradation normally encountered. The ability to insert such ingredients into detergent tablets. Alternatively, the second phase (one or more phases) can be compressed with the same or higher compression force as the first phase to obtain differential dissolution of the phases as described below.

Another advantage of the present invention is better protection of the second phase from damage caused, for example, by handling and transport. As noted above, multi-phase detergent tablets have been made by compressing the second layer with a smaller compression force than the first layer. However, although the dissolution rate is improved, the second layer of these tablets is susceptible to damage and tends to break or tear upon contact. However, the lightly compressed phase (one or more phases) of the detergent tablet of the present invention is protected in the mold provided by the first phase of the detergent tablet.

Another advantage of the present invention is that one can produce a multi-phase detergent tablet that can be designed to dissolve one phase before, and preferably obviously earlier, the other phase dissolves. In the present invention, the second phase and any subsequent phases (one or more phases) dissolve before the first phase. With the preferred weight ranges described above, the first phase dissolves in 5-20 minutes, more preferably 10-15 minutes, and the second phase and / or any optional phase in less than 5 minutes, more preferably 4. Dissolves in less than 5 minutes, most preferably in less than 4 minutes. Alternatively, if it is desired to provide a cleaning or rinsing effect, for example, at the end of the washing operation, the second phase can be dissolved after the first or other phases. The time for the first phase, the second phase and / or any subsequent phase to dissolve is independent of each other. Thus, in a particularly preferred aspect of the invention, differential dissolution of the phases is achieved. A particular advantage that allows for the differential dissolution of the multiphase detergent tablets of the present invention is that when one component is chemically inactivated by the presence of another component, the former component can be inserted into a different phase. That they can be separated. In this case, the components to be inactivated are preferably arranged in the second and subsequent optional phases (one or more phases).

Another advantage of the present invention is the excellent adhesion between the phases of the multiphase tablet of the present invention. This excellent adhesion can reduce the exposure of the second phase as compared to multi-phase tablets known to those skilled in the art, so that the tablet of the present invention suffers from breakage along the contact line between the phases. Hateful.

Process The multiphase detergent tablet of the present invention is manufactured using any suitable tablet press such as, for example, Courtoy R253. The tablet is preferably manufactured by compression on a tablet molding machine capable of manufacturing a tablet including a mold. In a particularly preferred embodiment of the invention, the first phase is prepared using a specially designed tablet press according to the following method. The punch of this tablet molding machine has been modified so that the punch surface in contact with the detergent composition has a convex surface.

The first detergent composition is supplied to a die of a tablet molding machine, and a punch is lowered,
The detergent composition is contacted and then compressed to form a first phase. The first detergent composition generally has a minimum of about 250 kg / cm ² , preferably about 350 to about 2000 k.
g / cm ^2, more preferably from about 500 to about 1500 kg / cm ^2, most preferably compressed with a pressure of about 600 to about 1200 kg / cm ^2. Thereafter, the punch is raised, exposing the first phase including the mold. The second phase and any optional detergent composition are then fed to the mold. The specially designed tablet machine punch is then lowered so that the second and optionally the next detergent composition is again lightly pressurized, and the second and any subsequent phases (single and multiple) are removed. Form.
In another embodiment of the present invention where there is an optional subsequent phase, the optional subsequent phase is made by an optional subsequent compression step, much like the second compression step described above. The second and optional detergent composition next to it is compressed preferably about 350 kg / cm ^2, more preferably from about 40 to about 300 kg / cm ^2, most preferably from about 70 to about 270 kg / cm ² of pressure . After compression of the second detergent composition, the punch rises again and the multiphase detergent tablet pops out of the tablet press.

Detergent Ingredients The first and second and / or optional subsequent phases of the multi-phase detergent tablets described herein are prepared by compression of one or more compositions containing detergent actives. . Suitably, the compositions used in any of these phases include builder compounds, surfactants, enzymes, bleaches, alkaline sources, colorants, fragrances, lime soap dispersants, polymerizable dye transfer inhibitors and the like. Various detergents such as organic polymer compounds, crystal growth inhibitors, heavy metal ion sequestering agents, metal ion salts, enzyme stabilizers, corrosion inhibitors, foam inhibitors, solvents, fabric softeners, optical brighteners and hydrotropes Components can be included.

Highly preferred detergent components of the first phase are builder compounds, surfactants, enzymes and bleaches. Highly preferred detergent components of the second phase include builders, enzymes, crystal growth inhibitors, and disruptors and / or binders.

Builder Compounds Tablets of the present invention typically comprise from 1 to 80% by weight of the active detergent component composition,
It preferably comprises a builder compound present at a level of preferably 10-70% by weight, most preferably 20-60% by weight.

Water-soluble builder compounds Suitable water-soluble builder compounds include water-soluble monomeric polycarboxylates or homo- or copolymers of their acid forms, polycarboxylic acids or their salts (where these polycarboxylic acids are , Containing at least two carboxyl groups separated from each other by no more than two carbon atoms), carbonates, bicarbonates, borates, phosphates, and mixtures of the above compounds.

The carboxylate or polycarboxylate builder may be monomeric or oligomeric, but monomeric polycarboxylates are generally preferred from a price and performance standpoint.

Suitable carboxylates containing one carboxy group include lactic acid, glycolic acid and the water-soluble salts of their ether derivatives. Polycarboxylates containing two carboxy groups include water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetate, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, and ether carboxylate. And sulfinylcarboxylates. Polycarboxylates containing three carboxy groups include, among others, water-soluble citrates, aconitrates and citraconates, and British Patent No.
Succinic acid derivatives such as carboxymethyl oxysuccinates described in 1,379,241, lactoxy succinates described in British Patent No. 1,389,732, and aminosuccinates described in Netherlands Application No. 7205873; And 2-oxa-1,1,3-propane described in British Patent 1,387,447.
There are oxypolycarboxylate materials such as tricarboxylates.

[0038] Polycarboxylates containing four carboxy groups include GB 1,261,829.
Oxydisuccinates, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetra There are carboxylates. Polycarboxylates containing sulfo substituents include GB 1,398,421 and 1,398,42
No. 2 and U.S. Pat. No. 3,936,448, sulfosuccinate derivatives, and the sulfonated pyrolytic citrates described in GB 1,439,000.

Cycloaliphatic and heterocyclic polycarboxylates include cyclopentane-cis,
cis, cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran-cis, cis, c
is-tetracarboxylates, 2,5-tetrahydrofuran-cis-dicarboxylates, 2,2,5,5-tetrahydrofuran-tetracarboxylates, 1,2,3,4,5,6-hexane-hexa Carboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include British Patent 1,42
There are derivatives of melitic acid, pyromellitic acid and phthalic acid disclosed in 5,343.

Among the above, preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more preferably citrates.

The monomeric or oligomeric polycarboxylate chelating agent's parent acid or mixtures of these with salts thereof, such as citric acid or citrate / citric acid mixtures, are also considered useful builder components.

Borate (borate) builders can also be used, as well as builders that include borate-forming substances capable of forming borate during storage of the detergent or under washing conditions, but these include 50
Washing conditions of less than 0 ° C, especially less than 40 ° C are not preferred.

Examples of carbonate (carbonate) builders are alkaline earth and alkali metal carbonates, German Patent Application No. 2,321,00, published Nov. 15, 1973.
No. 1 include sodium carbonate and sesquicarbonate and mixtures thereof with ultrafine calcium carbonate.

Highly preferred builder compounds for use in the present invention are water-soluble phosphates (
(Phosphate) builders. Specific examples of water-soluble phosphate builders include alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphates, sodium and potassium orthophosphates, sodium polymeta / phosphate having a degree of polymerization in the range of 6-21, And phytic acid salts.

Specific examples of water-soluble phosphate builders include alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta / phosphorus having a degree of polymerization in the range of 6-21. Acid salts, and salts of phytic acid.

Partially Soluble or Insoluble Builder Compounds The tablets of the present invention can contain partially soluble or insoluble builder compounds. Partially soluble and insoluble builder compounds can be particularly suitably used in tablets manufactured for use in the washing machine cleaning process. Examples of partially water-soluble builders are the crystalline layered silicates disclosed, for example, in EP-A-0164514, DE-A-3417649, and DE-A-3740423. Preferred is a crystalline layered sodium silicate of the following general formula:

[0047]

[Formula 1] _{NaMSi x O 2 + 1 · yH} 2 O

In the above formula, M is sodium or hydrogen, x is a number from 1.9 to 4, and y is a number from 0 to 20. Crystalline layered sodium silicates of this type preferably have a two-dimensional "sheet" structure, such as, for example, a δ-layer structure, as described in EP 0 164 514 and EP 0 293 640. The preparation of crystalline layered silicates of this type is disclosed in DE-A-3417649 and DE-A-3742043. For the purposes of the present invention, x in the above general formula is a value of 2, 3 or 4, and 2
Is preferred.

The most preferred crystalline layered sodium silicate compound has δ-Na ₂ Si ₂ O ₅ and is known as NaSKS-6 (trade name) provided by Hoechst AG.

The crystalline layered sodium silicate material can be used as fine particles in PCT Patent Application WO 92/1
Preferably, it is present in the granular detergent composition intimately mixed with solid, water-soluble and ionizable substances as described in 8594. The solid, water-soluble, ionizable substance is selected from organic acids, organic and inorganic acid salts and mixtures thereof, with citric acid being preferred.

Examples of highly water-insoluble builders include sodium aluminosilicate. Suitable aluminosilicates, unit cell - expression _{Naz [(AlO 2) z (} SiO 2) y] ·
xH is aluminosilicate zeolites having ₂ O. Wherein z and y are at least 6; the molar ratio of z: y is from 1.0 to 0.5; x is at least 5;
Preferably it is 7.5-276, More preferably, it is 10-264. The aluminosilicate material is hydrated, comprising 10% to 28%, more preferably 18% to 22% water in bound form, and is preferably crystalline.

The aluminosilicate zeolite may be a naturally occurring material, but more preferably a synthetic one. Synthetic crystalline aluminosilicate ion-exchange materials include zeolite A (Zeolite A), zeolite B (Zeolite B), and zeolite P (Zeolite P).
, Zeolite X, Zeolite HS, and mixtures thereof.

A preferred synthesis of aluminosilicate zeolites is that described by Schoeman et al. (Zeolite (1994) 14 (2)
Vol., Pp. 110-116). In this description the author describes the preparation of colloidal aluminosilicate zeolites. The colloidal aluminosilicate zeolite particles should preferably have such that only 5% of said particles have a diameter of more than 1 μm and at most 5% of the particles have a diameter of less than 0.05 μm. . Preferably, the aluminosilicate zeolite particles have an average particle size of from 0.01 μm to 1 μm in diameter, more preferably from 0.05 μm to 0.9 μm in diameter, most preferably from 0.1 μm to 0.6 μm in diameter.

Zeolite A is represented by the following formula:

[0055]

Embedded image Na ₁₂ [AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] · xH ₂ O

In the above formula, x is from 20 to 30, especially 27. Zeolite X has the formula Na ₈₆ [(AlO_Two)₈₆(SiO_Two)₁₀₆] · 276H_TwoO. EP-B-384,070
The disclosed Zeolite MAP is preferred in the present invention.
It is a zeolite builder.

Preferred aluminosilicate zeolites are colloidal aluminosilicate zeolites. When used as a component of a detergent composition, colloidal aluminosilicate zeolites, particularly colloidal zeolite A, provide excellent builder performance in terms of improving soil removal. Excellent builder performance is also seen in terms of reducing fabric encrustation and improving retention of fabric whiteness.

A surprising finding is that a mixed aluminosilicate olite detergent composition comprising colloidal zeolite A and colloidal zeolite Y provides equivalent calcium sequestration performance as compared to an equal weight of commercially available zeolite A. That is. Another surprising finding is that the mixed aluminosilicate zeolite detergent composition described above provides superior magnesium ion sequestering performance over the same weight of commercially available zeolite A.

Surfactants Surfactants are preferred detergent actives of the compositions described herein.
Suitable surfactants are selected from anionic, cationic, nonionic, amphoteric and zwitterionic surfactants and mixtures thereof. Automatic dishwashers must be low foaming in nature. As such, the foaming of the surfactant system for use in dishwashing must be suppressed, or more preferably, should be low foaming, generally non-ionic in nature. Foaming caused by the surfactant system used in the washing method in the washing machine need not be suppressed to the same extent as required for dishwashing. The surfactants generally comprise from 0.2% to 30%, more preferably from 0.5% to 10%, and most preferably from 1% to 30%, by weight of the composition of the active detergent component.
It is present at a level of from 5% to 5% by weight.

A typical table of the classes and types of anionic, nonionic, amphoteric and zwitterionic of these surfactants can be found in Rollin, published December 30, 1975 (
Laughlin) and Heuring in US Patent No. 3,929,678. A list of suitable cationic surfactants is provided in Murphy, U.S. Pat. No. 4,259,217, issued Mar. 31, 1981. A table of surfactants commonly included in automatic dishwashing detergent compositions is found, for example, in EP-A-0414 549.
And WO 93/08876 and WO 93/08874.

Nonionic Surfactants Essentially any useful nonionic surfactant for detersive purposes can be included in the detergent tablet. Preferred (but not limiting) classes of useful nonionic surfactants are listed below.

Nonionic Ethoxylated Alcohol Surfactants Alkyl ethoxylate condensation products of aliphatic alcohols with 1 to 25 moles of ethylene oxide are suitably used in the present invention. The alkyl chain of the aliphatic alcohol may be either straight or branched, either first or second, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.

End-capped alkyl alkoxylate surfactants Suitable end-capped alkyl alkoxylate surfactants are epoxy-capped poly (oxyalkylated) alcohols of the formula:

[0064]

Embedded image

Wherein R ₁ is a straight or branched chain aliphatic hydrocarbon radical having 4 to 18 carbon atoms; R ₂ is a straight or branched chain aliphatic hydrocarbon radical having 2 to 26 carbon atoms. X is an integer having an average value of 0.5 to 1.5, more preferably 1; and y is an integer having a value of at least 15, more preferably at least 20.

It is preferred that at least 10 carbon atoms be present in the terminal epoxide unit [CH ₂ CH (OH) R ₂ ] in the surfactant of formula I. Suitable surfactants of the formula I according to the invention are described, for example, on October 13, 1994 by Olin Corpo.
Olyn Corporation POLY-TERGENT (trade name) SLF-18B non-ionic surfactants described in WO 94/22800, which is disclosed by J.A.

Ether- Capped Poly (oxyalkylated) Alcohols Suitable surfactants that can be used in the present invention include ether-capped poly (oxyalkylated) alcohols having the formula:

[0068]

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Where R ¹ and R ² are straight or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms; R ³ is H, A linear aliphatic hydrocarbon radical having 1 to 4 atoms; x has an average value of 1
When x is 2 or more, R ³ may be the same or different, k and j are integers having an average value of 1 to 12, and 1 to 5 are more preferable.

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

As noted above, in preferred embodiments, and when x is greater than 2, R ³ may be the same or different. That is, R ³ can vary to any of the alkyleneoxy units described above. For example, if x is 3, R ³ can be selected from ethyleneoxy (EO) or propyleneoxy (PO) and (EO) (P
O) (EO), (EO) (EO) (PO); (EO) (EO) (EO);
) (EO) (PO); (PO) (PO) (EO) and (PO) (PO) (PO)
). Of course, the integer 3 is chosen as an example, and the larger the integer value of x, the greater this variation will be, for example, a large number of (EO) units and a very small number of (PO) units. including.

Some of the above particularly preferred surfactants have a low cloud point below 20 ° C. These low cloud point surfactants exhibit excellent oil cleaning effects when used in combination with high cloud point surfactants, as described in detail below.

The most preferred ether-capped poly (oxyalkylated) alcohol surfactants are those in which k is 1 and j is 1, and thus have the following formula:

[0074]

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In the above formula, R ¹ , R ² and R ³ are defined as above, and x is an average value of 1 to 3
It is an integer of 0, preferably 1 to 20, and even more preferably 6 to 18. Most preferred is in the range of R ¹ and R ² 9-14, in R ³ is H, to form an ethyleneoxy, x is from a surfactant in the range of 6-15.

The ether-capped poly (oxyalkylated) alcohol surfactant is
It has three general components: linear or branched alcohols, alkylene oxides and alkyl ether endcaps. The alkyl ether end cap and the alcohol act as a hydrophobic, oil-soluble portion of the molecule, and the alkylene oxide group forms a hydrophilic, water-soluble portion of the molecule.

These surfactants, when used in combination with high cloud point surfactants, provide significant improvements in spotting and film forming properties, and removal of oily stains, as compared to common surfactants. Show.

Generally, the ether-capped poly (oxyalkylene) alcohol surfactants of the present invention react an aliphatic alcohol with an epoxide to form an ether, which then reacts with a base to form a secondary In the form of an epoxide. The second epoxide then reacts with the alkoxylated alcohol to form the novel compounds of the invention. An example of the preparation of an ether-capped poly (oxyalkylated) alcohol surfactant is described below:

Preparation of C _12/14 alkyl glycidyl ether C _12/14 fatty alcohol (100.00 g, 0.515 mol) and tin chloride (IV)
) (0.58 g, 2.23 mmol, available from Aldrich)
Are combined together into a 500 mL 3-neck round bottom flask equipped with a condenser (condenser), argon inlet, addition funnel, magnetic stirrer and internal temperature probe. Heat the mixture to 60 ° C. 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 treated with a 50% solution of sodium hydroxide (61.80 g, 0.773 mol, 50%) while mechanically stirring. After the addition is complete, the mixture is heated to 90 ° C. for 1.5 hours, cooled and filtered with the aid of ethanol. The filtrate was separated and the organic phase was washed with water (100 m
Wash with L), dry over MgSO ₄ , filter and concentrate. Add this oil to 100-12
Distillation at 0 ° C. (0.1 mmHg) gives the glycidyl ether as an oil.

Preparation of C _12/14 Alkyl-C _9/11 Ether Capped Alcohol Surfactant Neodol (trade name) 91-8 (20.60 g, 0.0393 mol)
Ethoxylated alcohol, available from Shell chemical Co.) and tin (IV) chloride (0.58 g, 2.23 mmol) were charged to a condenser (condenser), argon inlet, addition funnel, magnetic stirrer and Fit together into a 250 mL 3-neck round bottom flask equipped with an internal temperature probe. The mixture was heated to 60 ° C. and at this temperature C _12/14 alkyl glycidyl ether (11.00 g, 0.0
393 mol) is added dropwise over 15 minutes. After stirring at 60 ° C. for 18 hours,
Cool the mixture to room temperature and dissolve in an equal portion of dichloromethane. The solution is passed through a 1 inch pad of silica gel and eluted with dichloromethane. The filtrate was concentrated on a rotary evaporator and then Kugel tube oven (100 ° C., 0.5
mmHg), the surfactant is formed as an oil when stripped.

Nonionic ethoxylated / propoxylated fatty alcohol surfactants Ethoxylated C ₆ -C ₁₈ fatty alcohols and C ₆ -C ₁₈ mixed ethoxylated / propoxylated fatty alcohols are suitable for use in the present invention. Surfactant
This is especially true if it is water-soluble. Preferred ethoxylated fatty alcohols are
A C ₁₀ -C ₁₈ ethoxylated fatty alcohols degree of ethoxylation from 3 to 50, most preferred are C ₁₂ -C ₁₈ ethoxylated fatty alcohols degree of ethoxylation of 3 to 40. The preferred mixed ethoxylated / propoxylated fatty alcohol has an alkyl chain length of 10 to 18 carbon atoms, a degree of ethoxylation of 3 to 30, and a degree of propoxylation of 1 to 10.

Condensation products of ethylene oxide, a nonionic EO / PO condensate containing propylene glycol, and a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are suitable for use in the present invention. The hydrophobic portion of these compounds preferably has a molecular weight of 1500 to 1800 and is water-insoluble. Some examples of compounds of this type are commercially available Pluronic® surfactants sold by BASF.

The non-ionic EO condensation products containing propylene oxide / ethylene diamine adducts The condensation products of ethylene oxide and the reaction product of propylene oxide and ethylene diamine are suitable for use in the present invention. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and excess propylene oxide and generally has a molecular weight of 2500-3000. Examples of non-ionic surfactants of this type include commercially available Tetronic (Tetronic sold by BASF)
tronic) (trade name).

Mixed Nonionic Surfactant System In a preferred embodiment of the present invention, the detergent tablet comprises at least one low cloud point nonionic surfactant and at least one high cloud point nonionic surfactant. A mixed nonionic surfactant system comprising:

As used herein, the “cloud point” is a well-known property of a nonionic surfactant, and is a property that appears as a result of the surfactant becoming less soluble as the temperature increases. The temperature at which the appearance of the second phase can be observed is referred to as the "cloud point" (see Kirk Osmer Encyclopedia of Chemical Engineering, 3rd Edition, Vol. 22, pages 360-379).

As used herein, a “low cloud point” nonionic surfactant is a nonionic surfactant having a cloud point below 30 ° C., preferably below 20 ° C., and most preferably below 10 ° C. Defined as activator-based component. Typical low cloud point nonionic surfactants include nonionic alkoxylated surfactants, especially ethoxylates derived from primary alcohols, and polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) reverse block polymers.
In addition, such low cloud point nonionic surfactants include, for example, ethoxylated
Propoxylated alcohol (eg, Olin Corporation's Poly-Tergent (trade name) SLF18), epoxy-
Capped poly (oxyalkylated) alcohols (eg,
Olyn Corporation's Poly-Tergent (trade name) S as described in WO 94/22800, disclosed by Olin Corporation on January 13,
LF18B nonionic surfactant series), and ether-capped poly (oxyalkylated) alcohol surfactants.

The nonionic surfactant can optionally include propylene oxide in an amount up to 15% by weight. Other preferred nonionic surfactants are described in September 1, 1980.
It can be made by the method described in US Pat. No. 4,223,163 to Builloty, issued on the 6th. This is incorporated herein by reference.

The low cloud point nonionic surfactants additionally include polyoxyethylene and polyoxypropylene block polymer compounds. Blocked polyoxyethylene-polyoxypropylene polymerized compounds include those based on ethylene glycol, propylene glycol, glycerol, trimethylolpropane, and ethylenediamine as initiator (initiator) reactive hydrogen compounds. BASF-Wyandotte Corp., Wyandotte, Michigan (BASF-Wyandotte Corp., Wyandotte,
Some of the block polymer surfactants called PLURONIC (trade name), REVERSED PLURONIC (trade name), and TETRONIC (trade name) by Michigan) are ADD compositions of the present invention. Suitable for. Preferred examples include REVERSED PLURONIC (trade name) 25R2 and TETRONIC (trade name) 702. Such surfactants are generally useful in the present invention as low cloud point nonionic surfactants.

As used herein, a “high cloud point” nonionic surfactant is a nonionic surfactant having a cloud point above 40 ° C., preferably above 50 ° C., and more preferably above 60 ° C. Defined as a drug system component. The nonionic surfactant system includes a monohydric alcohol or alkylphenol containing 8 to 20 carbon atoms,
On average there are ethoxylated surfactants derived from the reaction with 6 to 15 moles of ethylene oxide per mole of alcohol or alkylphenol. Examples of such a high cloud point nonionic surfactant include, for example, Tergitol
15S9 (supplied from Union Carbide), Rhodasurf TMD8.5 (supplied from Rhone Poulenc), and Neodol 91-8 (supplied from Shell). is there.

Also preferred for the purposes of the present invention are non-ionic surfactants with a high cloud point, further comprising a hydrophilic-liposoluble agent in the range from 9 to 15, preferably from 11 to 15. To have a balance ("HLB"; see Kirk Osmer, supra) value. Such materials include, for example, Tergitl 15S9 (supplied from Union Carbide), Rhodasurf TMD 8.5 (supplied from Rhone Poulin), and Neodol 91-8 (supplied from Shell).

Another preferred high cloud point nonionic surfactant is a linear or preferably branched chain containing 6 to 20 carbon atoms, or a secondary fatty alcohol (C ₆ -C ₂₀ alcohol) (secondary Alcohols and also branched primary alcohols). Preferred high cloud point nonionic surfactants average 6-15 mol, preferably 6-12 mol, and most preferably 6-9 mol per mol alcohol.
moles of branched or secondary alcohol ethoxylates condensed with ethylene oxide, more preferably mixed C9 / 11 or C11 / 15 branched chain alcohols
Ethoxylates. The ethoxylated nonionic surfactants thus derived preferably have a narrow ethoxylate distribution relative to the average.

Anionic surfactants Essentially any useful anionic surfactant for detersive purposes is suitable. These include salts of anionic sulfates, sulfonates, carboxylate and sarcosinate surfactants, including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and 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, and monosulfones of sulfosuccinates esters (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters), diesters of sulfosuccinate (especially saturated and unsaturated C ₆ -C ₁₄ diesters), there are N- acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, for example, rosin,
There are hydrogenated rosins, resin acids and hydrogenated resin acids are present in or derived from tallow oil.

Anionic Sulfate Surfactants Suitable anionic sulfate surfactants for use in the present invention include linear and branched, primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, C ₅ -C ₁₇ acyl -N- (C ₁ -C ₄ alkyl) and -N- (C ₁ -C ₂ hydroxyalkyl) glucamine sulfates, and alkyl There are sulfates of polysaccharides, such as sulfates of alkyl polyglucosides (nonionic, non-sulfated compounds are described herein).

The alkyl sulphate surfactants are preferably linear and branched primary C _10-
C ₁₈ is selected from alkyl sulfates, C ₁₁ -C ₁₅ branched chain alkyl sulfates and C ₁₂ -C ₁₄ straight chain alkyl sulfates are more preferred.

The alkyl ethoxy sulfate surfactant is used in an amount of 0.5 to 20 mo per molecule.
It is preferred to select from the group consisting of C ₁₀ -C ₁₈ alkyl sulfate ethoxylated with 1 ethylene oxide. More preferred alkyl ethoxy sulfate surfactants are C ₁₁ -C ₁₈ , more preferably C ₁₁ -C ₁₅ alkyl sulfates ethoxylated with 0.5 to 7, more preferably 1 to 5 mol of ethylene oxide per molecule. is there.

[0097] A particularly preferred aspect of the present invention is to use a mixture of the preferred alkyl sulfate and alkyl ethoxy sulfate surfactants. Such a mixture is disclosed in PCT Patent Application No. WO 93/18124.

[0098]Anionic sulfonate surfactant Anionic sulfonate surfactants that can be suitably used in the present invention include C_Five-C_{Two 0} Linear alkyl benzene sulfonate, alkyl ester sulfonate, C₆-C _{twenty two} Primary or secondary alkane sulfonate, C₆-C_{twenty four}Olefin sulfonate,
Sulfonated polycarboxylic acid, alkyl glycerol sulfonate, fatty acyl group
Lyserol sulfonate, salts of fatty oleyl glycerol sulfonate, and
And mixtures of these.

Anionic Carboxylate Surfactants Suitable anionic carboxylate surfactants include alkyl ethoxy carboxylates, alkyl polyethoxy polycarboxylate surfactants and soaps ("alkyl carboxyls"); In particular, there are some secondary soaps described herein.

Suitable alkylethoxycarboxylates include those of the formula RO (CH ₂ CH ₂ O) _x C
Some are represented by H ₂ COO ⁻ M ⁺ . Wherein R is a C ₆ -C ₁₈ alkyl group, x ranges from 0 to 10, and the ethoxylate distribution is such that the amount of material where x is 0 is less than 20% by weight. And M is a cation.
Suitable alkyl polyethoxy polycarboxylate surfactants include those of the formula RO- (
CHR ₁ —CHR ₂ —O) —R ₃ , wherein R is a C ₆ -C ₁₈ alkyl group, x is 1 to 25, R ₁ and R ₂ are hydrogen, methyl acid radical Succinate radical, hydroxysuccinate radical, and mixtures thereof, wherein R ₃ is hydrogen, a substituted or unsubstituted hydrocarbon having 1 to 8 carbon atoms,
And mixtures thereof.

Suitable soap surfactants include secondary soap surfactants that contain a carboxyl unit attached to a secondary carbon. Preferred secondary soap surfactants that can be suitably used in the present invention include 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, and 2-butyl-1-octane. A water-soluble member selected from the group consisting of acids and water-soluble salts of 2-pentyl-1-heptanoic acid. Some soaps are also included as suds suppressors.

Alkali metal sarcosinate surfactants and other suitable anionic surfactants are of the formula R-CON (R ¹ ) CH ₂ COOM
Alkali metal sarcosinates. In the above formula, R is a C ₅ -C ₁₇ linear or branched alkyl or alkenyl group, R ¹ is a C ₁ -C ₄ alkyl group,
And M are alkali metal ions. Preferred examples are myristyl and oleoylmethyl sarcosinate in the form of the sodium salt.

Amphoteric surfactants Amphoteric surfactants that can be suitably used in the present invention include amine oxide surfactants and alkyl amphocarboxylic acids.

Suitable amine oxides include compounds having the formula R ³ (OR ⁴ ) _x N ⁰ (R ⁵ ) ₂ . Wherein R ³ is selected from alkyl, hydroxyalkyl, acylamidopropyl and alkylphenyl groups containing from 8 to 26 carbon atoms, or mixtures thereof; R ⁴ is alkylene containing from 2 to 3 carbon atoms Or a hydroxyalkylene group, or a mixture thereof; x is 0-5, preferably 0-3; each R ⁵ is an alkyl or hydroxyalkyl group containing 1-3, or a poly containing ethylene oxide groups 1-3. It is an ethylene oxide group. C ₁₀ -C ₁₈ alkyl dimethyl amine oxides, and C _10-18 acylamido alkyl dimethylamine oxide.

Suitable examples of alkyl amphodicarboxylic acids are available from Milanor, Dayton, NJ (
Miranol, Inc. , Dayton, NJ), Milanol (trade name) C2M Conc. It is.

[0106] zwitterionic surfactants zwitterionic surfactants can also be incorporated in detergent compositions of the present invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are representative zwitterionic surfactants used in the present invention.

Suitable betaines are compounds having the formula R (R ′) ₂ N ⁺ R ² COO ⁻ . Herein, R is C ₆ -C ₁₈ hydrocarbyl group, each R ¹ is typically the C ₁ -C ₃ alkyl, and R ² is a C ₁ -C ₅ hydrocarbyl group. Preferred betaines, C _{12-18-dimethyl} - ammonio hexanoate and C _10-18 acylamido propane (
Or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants can also be suitably used in the present invention.

Cationic Surfactants The cationic ester surfactants used in the present invention preferably comprise at least one ester (ie, —COO—) bond and at least one cationically charged group. It is a water-dispersible compound having surfactant properties. Other suitable cationic ester surfactants, including choline ester surfactants, are described, for example, in US Pat.
Nos. 28042, 4239660 and 4260529.

Suitable cationic surfactants include mono C ₆ -C ₁₆ , preferably C ₆ -C ₁₀ N-
Quaternary ammonium surfactants selected from alkyl or alkenyl ammonium surfactants, wherein the remaining N positions are replaced by methyl, hydroxyethyl or hydroxypropyl groups. There is.

Enzymes Enzymes are preferred detergent components in the first phase and, in particular, in the second and / or optional subsequent phases. When the enzymes are present, cellulases, hemicellulases, peroxidases, proteases, glucoamylases, amylases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, Reductases, oxidases, phenol oxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidases, chondroitinase, laccase or mixtures thereof Selected from the group consisting of:

Preferred enzymes include proteases, amylases, lipases, peroxidases, cutinases and / or cellulases in combination with one or more plant cell wall degrading enzymes.

Cellulases that can be used in the present invention include both bacterial and fungal cellulases. It is preferred that they have an optimum pH of 5 to 12 and an activity above 50 CEVU (cellulose viscosity units). Suitable cellulases are described in US Pat. No. 4,435,307 to Barbesgoard et al., J61078384 and WO 96/02653.
Issue. These are Humicola insolens, Trichoderma, and Thi, respectively.
Fungal cellulases produced by elavia and Sporotrichum are disclosed. EP
739 982 describes cellulases isolated from a novel Bacillus species. Suitable cellulases are GB-A-2.075.028; GB-A-2.095.275; DE-O.
S-2.247832.32 and WO 95/26398 are also disclosed.

Examples of such cellulases are Humicola insolens (Humicola grisea var. Th.
ermoidea), especially cellulases produced by Humicola sp. DSM1800. Other suitable cellulases are those derived from Humicola insolens having a molecular weight of 50 KDa, an isoelectric point of 5.5 and containing 415 amino acids; Humic
ola insolens DSM 1800 derived cellulase activity 43k
D is an endoglucanase; a preferred endoglucanase component has the amino acid sequence disclosed in PCT Patent Application WO 91/17243. Suitable cellulases are also available from Genencor's W, published September 29, 1994.
EGIII cellulases from Trichoderma longibrachiatum described in O 94/21801. Particularly suitable cellulases are those having the advantage of color protection (care). Examples of such cellulases are the cellulases described in European Patent Application No. 91208799.2 (Novo), filed Nov. 6, 1991. Carezyme and Celluzyme (
Novo Nordisk (A / S) is particularly useful. WO 91/17244
See also WO 91/21801. Other cellulases suitable for fabric protection and / or cleaning properties are described in WO 96/34092, WO 96/17994 and WO 95/24471.

The cellulases are usually incorporated into detergent compositions at an active enzyme level of 0.0001% to 2% by weight of the detergent composition.

The peroxidase enzyme is used in combination with an oxygen source (source) such as percarbonate, perborate, persulfate, hydrogen peroxide and the like. They are used for "solution bleaching", i.e. to prevent dyes or pigments falling off the support during the washing operation from being transferred to another support of the washing solution. Peroxidase enzymes are known to those skilled in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidases such as chloro- and bromoperoxidase. Peroxidase-containing detergent compositions are described, for example, in PCT International Application WO 89/0998.
13, WO 89/09813 and European Patent Application E filed on November 6, 1991
P 91 202 882.6 and EP 99680013 filed on February 20, 1996.
. No. 8 is disclosed. Laccase enzymes are also suitable.

Preferred enhancers are substituted phenothiazines and phenoxazines 10-phenothiazinepropionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP) and 10-phenoxazine. Methylphenoxazine (described in WO 94/12621) and substituted syringates (C3-C5 substituted alkyl syringates) and phenols. Sodium percarbonate or sodium perborate is a preferred source of hydrogen peroxide.

The cellulases and / or peroxidases are usually incorporated into detergent compositions at an active enzyme level of 0.0001% to 2% by weight of the detergent composition.

Other preferred enzymes that can be included in the detergent compositions of the present invention include lipases. Lipase enzymes suitable for detergents include those produced by microorganisms of the genus Pseudomonas, such as Pseudomonas stutzeri ATCC 19.154 disclosed in GB 1,372,034. Suitable lipases include the microorganism Pseudomon
as fluorescent IAM1057 and those showing a positive immune cross-reactivity with a lipase antibody. This lipase is available from Amano Pharmaceutical (Nagoya, Japan) under the trade name Lipase P "Amano", hereinafter referred to as "Amano-P"("Amano-P"). . Other suitable commercially available lipases include Amano-CES, a lipase from Chromobacter viscosum, such as Chromobacter viscosum var. Sold by Toyo Brewery (Tagata, Japan). lipolyti
cun NRRLB 3673; Chromobacter viscosum lipase from Biochemicals USA (USA) and Disoynth (Netherlands), and Pseudomonas gl
There are lipases from adioli. A particularly suitable lipase is M1 lipase (M1 Li
pase) (trade name) and Lipomax (trade name) (Gist-Brocades) and Lipolase (trade name) and Lipolase Ultra (trade name) (Novo) There is something like that.
These have been found to be very effective when used in combination with the compositions of the present invention. EP258 068, WO 92/05249 and WO 95 / by Novo Nordisk
Lipolytic enzymes described in 22615 and WO 94/03578 by Unilever, WO 95/35381 and WO 96/00292 are also suitable.

Also suitable are cutinases, which are considered a special class of lipases [EC 3,1.1.50], ie lipases that do not require surface activation. Addition of cutinase to detergent compositions is described, for example, in WO-A-88 / 09367 (Genencor); WO 90/09446 (Plant Genetic System) and WO 94/14963.
And WO 94/14964 (Unilever).

The lipases and / or cutinases are usually incorporated into the detergent composition at an active enzyme level of from 0.0001% to 2% by weight of the detergent composition.

[0121] Suitable proteases are described in subtilis and B. licheniformis (subtilisin BPN and BPN '). One suitable protease is obtained from one Bacillus species, which has a maximum activity between a pH range of 8 and 12 and is available from Novo Industries A / S, Denmark (
Hereinafter referred to as “Novo”) and developed and sold as ESPERASE (trade name). Novo's GB 1,243,7
84. Other suitable proteases include KANNASE (trade name), ALCALASE (trade name), DURAZYM (trade name) and Savinase (trade name) available from Novo. Maxatase (MAXAT) sold by Gist-Brocades
ASE) (trade name), MAXACAL (trade name), Properase (PROPERAS)
E) (trade name) and MAXAPEM (trade name) (by Maxacal protein engineering). Proteolytic enzymes are modified bacterial serine proteases such as those described in European Patent Application No. 87 303761.8, filed April 28, 1987 (especially pages 17, 24 and 98), which It is referred to herein as "Protease B" and is described in Venegas European Patent Application No. 199,404 published October 29, 1986, which is incorporated herein by reference. It also includes what is called protease A ". What is referred to herein as "protease C" is also suitable. This is a variant of the alkaline serine protease from Bacillus, which replaces lysine and arginine at position 27, replaces tyrosine and valine at position 104, replaces serine and asparagine at position 123, and at position 274. Alanine and threonine have been replaced. Protease C is described in WO 91/066 published May 16, 1991.
EP 90915958: 4 corresponding to 37. In general, modified variants, particularly modified variants of protease C, are also included in the present invention.

A preferred protease, referred to as "Protease D", is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is numbered from the precursor carbonyl hydrolase to the subtilisin of Bacillus amyloliquefaciens. By replacing a plurality of amino acid residues with different amino acids at the position in the carbonyl hydrolase corresponding to position +76, more preferably in combination with +99, +101, +103, +1
04, 107, +123, +27, +105, +109, +126, +128,
+135, +156, +166, +195, +197, +204, +206, +
Induced by substituting a different amino acid at one or more amino acid residue positions corresponding to positions selected from the group consisting of 210, +216, +217, +218, +222, +260, +265, and / or +274. Is done. These are described in WO 95/10591 and in patent application US 08 / 322,677 to C. Ghosh et al., "Bleaching Compositions Containing Protease Enzymes," filed Oct. 13, 1994.

The proteases described in patent applications EP 251 446 and WO 91/06637, the protease BLAP (trade name) described in WO 91/02792 and those described in WO 95/23221 Mutants are also suitable for the present invention.

Bacillus sp. NCIMB4 described in WO 93 / 18140A given to Novo
See also the high pH protease obtained from 0338. Novo WO 92 /
03529A describes an enzyme detergent comprising a protease, one or more other enzymes, and a reversible protease inhibitor (inhibitor). If desired, proteases with low adsorptive and high hydrolytic properties can be obtained from Procter & Gamble (Proc.
ter & Gamble) WO 95/07791. Recombinant trypsin-like proteases for detergents suitable for the present invention are described in Novo WO 94/25583. Other suitable proteases are those described by Unilever in EP 516 2
00.

Other preferred protease enzymes include carbonyl hydrolase variants having an amino acid sequence not found in nature, wherein multiple amino acid residues of the precursor carbonyl hydrolase are substituted with different amino acids. The plurality of amino acid residues replaced in the precursor enzyme correspond to a combination of position +210 and one or more of the following residues:
33, +62, +67, +76, +100, +101, +103, +104, +
107, +128, +129, +130, +132, +135, +156, +1
58, +164, +166, +167, +170, +209, +215, +21
7, +218 and +222, where the above numbers are located in Bacillus amyloliq
Corresponds to a naturally occurring subtilisin from uefaciens or comparable amino acid residues in other carbonyl hydrolases or subtilisins (eg, Bacillus lentus subtilisin). Preferred enzymes of this type include those having positional changes of +210, +76, +103, +104, +156, and +166.

These proteolytic enzymes are present in the detergent composition of the present invention in an amount of 0.00
It is incorporated at a pure enzyme level of from 01% to 2%, preferably from 0.001% to 0.2%, more preferably from 0.005% to 0.1% by weight.

Amylases (α and / or β) can be included to remove carbohydrate-based soils. Novo Nordisk's WO 94/02597, published Feb. 3, 1994, describes a cleaning composition comprising a mutant amylase. In addition, Novo Nordisk's WO 95 published on April 20, 1995
See also / 10603. Other amylases known for use in cleaning compositions include both α- and β-amylases. α-amylases are known to those skilled in the art and are described in US Pat. No. 5,003,257; EP 252,666; WO / 91.
EP 285,123; EP 525,610; EP 368,341; and British Patent Specification No. 1,296,839 (Novo). Other suitable amylases are described in WO 94/18314 and 1 published Aug. 18, 1994.
Amylases with enhanced stability as described in Genencor's WO 96/05295 published February 22, 996, and from Novo Nordisk, disclosed in WO 95/10603 published April 1995. Amylase variants with additional modifications to the immediate parent. EP 277 216, WO 95/26397 and WO 96 /
Amylases described in 23873 (all by Novo Nordisk) are also suitable.

Examples of commercially available α-amylase products are Purafect Ox Am (trade name) from Genencor and Termamyl, all available from Novo Nordisk (Denmark). (Product name), van (
Ban) (trade name), Fungamyl (trade name) and Duramyl (Duram)
yl) (trade name) and Natalase (trade name). WO 95/26397 discloses other suitable amylases, namely, Phadebas (trade name) α
-At least 25% higher than the specific activity of Termamyl (trade name) in a temperature range of 25 ° C to 55 ° C and a pH range of 8 to 10, as measured by an amylase activity assay.
Α-amylases characterized by having a higher specific activity are described. WO
Mutants of the above enzymes described in 96/23873 (Novo Nordisk) are also suitable. Other amylolytic enzymes having improved properties with respect to activity levels and a combination of heat stability and higher activity levels are described in WO 95/35382.

Preferred amylase enzymes include WO 95/26397 and Novo Nordisk PCT
/ DK96 / 00056, and the like.

[0130] The amylolytic enzyme is added to the detergent composition of the present invention in an amount of 0.0001% by weight of the above composition.
It is incorporated at a pure enzyme level of 2% by weight, preferably 0.00018% to 0.06% by weight, more preferably 0.00024% to 0.048% by weight.

In a particularly preferred embodiment, the detergent tablets of the present invention comprise amylase enzymes, especially those described in co-pending applications by WO 95/26397 and Novo Nordisk PCT / DK96 / 00056 with supplemental amylase. Including combinations.

“Supplementary” means the addition of one or more amylases suitable for detergent purposes. Examples of supplemental amylase (α and / or β) are described below. WO 94/02597
And WO 95/10603 (Novo Nordisk) describe cleaning compositions incorporating mutant amylases. Other amylases known for use in cleaning compositions include both α- and β-amylases. α-amylases are known to those skilled in the art and are described in US Pat. No. 5,003,257; EP 252,666.
WO 91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341
And those disclosed in British Patent Specification No. 1,296,839 (Novo). Other suitable amylases are Genencor's WO 94/18314, and W
Highly stable amylases described in WO 96/05295, and WO 95/10603
Immediate parent available from Novo Nordisk disclosed in
Is a further modified amylase variant. Amylases described in EP 277 216 (Novo Nordisk) are also suitable. Examples of commercially available α-amylase products are Puractect Ox Am (trade name) from Genencor and Termamyl (trade name) available from Novo Nordisk, Denmark.
Van (trade name), Hungamil (trade name) and Duramill (trade name). W
O 95/26397 is another suitable amylase, namely Fadebas (trade name)
When measured by an α-amylase activity assay, the specific activity of termamyl (trade name) is at least 2 in the temperature range of 25 ° C. to 55 ° C. and the pH range of 8 to 10.
Α-amylases having a 5% higher specific activity are described. W
Also suitable are variants of the above enzymes described in O 96/23873 (Novo Nordisk). Other amylolytic enzymes having improved properties with respect to activity levels and a combination of heat stability and higher activity levels are described in WO 95/35382. A preferred supplementary amylase for the present invention is Purafect Ox Am (described in WO 94/18314, WO 96/05295, sold by Genencor).
Amylases (trade name); Termamyl (trade name), Hungamil (trade name), Van (trade name), Natalase (trade name) and Duramil (trade name), all available from Novo Nordisk -Maxamil (trade name) by Brocaise.

The supplemental amylase is added to the detergent composition of the present invention in an amount of 0.0001 of the above composition.
It is usually incorporated at a pure enzyme level of from 2% to 2% by weight, preferably from 0.00018% to 0.06% by weight, more preferably from 0.00024% to 0.048%. The weight ratio of the specific enzyme to the pure enzyme to the supplementary amylase is 9
: 1 to 1: 9, preferably 4: 1 to 1: 4, more preferably 2: 1 to 1: 2.

The enzymes mentioned above may be of any suitable source, such as from plants, animals, bacteria, fungi and yeast. The source is more mesophilic
ic) or extremophilic (extremophilic) (cryophilicity, psychotropic, thermophilic, barophilic, alkaliphilic, acidophilic, salty, etc.). Purified or unpurified forms of these enzymes can also be used. Also, by definition, mutants of the native enzyme are included. Mutants can be obtained by, for example, protein engineering and / or genetic engineering, chemical and / or physical modification of the native enzyme. Expression of the enzyme via the host microorganism, in which case the responsive genetic material for the production of the enzyme is cloned, is also commonly practiced.

The enzymes are generally incorporated into detergent compositions at an active enzyme level of from 0.0001% to 2% by weight of the detergent composition. The enzymes may be added as separate single components (eg, globules, granules, stabilizers, etc. containing one type of enzyme) or as a mixture of two or more enzymes (eg, composite granules, etc.).

Other suitable detergent ingredients that can be added are the enzymatic oxidation scavengers described in co-pending European Patent Application 928700188.6 filed Jan. 31, 1992. Examples of such enzymatic oxidation scavengers are ethoxylated tetraethylene polyamines.

The range of enzyme substances and the means for inserting them into detergent compositions are described in Genencor International's WO 9307263A and WO 9307260A, Novo's WO 89
08694A, and U.S. Patent No. 3,553,139, issued to McCarty et al. On January 5, 1971. Enzymes are also 1978
No. 4,101,457 to Place et al., Jul. 18, and U.S. Pat. No. 4,507,219 to Hughes, Mar. 26, 1985. Enzymatic substances useful for liquid detergent formulations and their insertion into such formulations are disclosed in Hora U.S. Pat. No. 4,261,868, Apr. 14, 1981. Enzymes used in detergents can be stabilized by various methods. Enzyme stabilization is described in US Pat. No. 3,600, Gedge et al., Aug. 17, 1971.
No. 319, Oct. 29, 1986, Venegas EP 199,405 and EP 200,586 and are specifically illustrated. Enzyme stabilizing systems are also described, for example, in US Pat. No. 3,519,570. Useful Bacillus sp. AC13 that provides proteases, xylanases and cellulases is described in Novo WO 9401532.

[0138] Highly preferred components of the bleach detergent ingredients composition is a bleaching agent. Suitable bleaching agents include
There are chlorine and oxygen releasing bleach.

In one preferred aspect, the oxygen releasing bleach comprises a hydrogen peroxide source and an organic peroxyacid bleach precursor compound. The production of organic peroxy acids occurs by an in situ reaction of the precursor with a source of hydrogen peroxide. Suitable sources of hydrogen peroxide include inorganic perhydrate bleach. In another preferred aspect, the preformed organic peroxyacid is inserted directly 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 contemplated.

The composition of the inorganic perhydrate bleach detergent component preferably contains a hydrogen peroxide source as an oxygen releasing bleach. Suitable hydrogen peroxide sources include inorganic perhydrate salts. Inorganic perhydrate salts, usually in the form of sodium salts, form 1% by weight of the composition.
40% by weight, more preferably 2% to 30% by weight, most preferably 5% by weight to
It is incorporated at a level of 25% by weight.

Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate, and persilicate. The inorganic perhydrate salt is usually an alkali metal salt. Inorganic perhydrate salts can also be included as crystalline solids without additional protection. However, for some perhydrate salts, a preferred implementation of such a granular composition utilizes a coated material to provide better storage stability to the perhydrate salt in the granular product.

The sodium perborate has the nominal structural formula NaBO_TwoH_TwoO_TwoMonohydrate or NaBO_TwoH _Two O_Two・ 3H_TwoIt is in the form of O tetrahydrate.

Alkali metal percarbonates, especially sodium percarbonate, are preferred perhydrates for insertion into the compositions according to the invention. Sodium percarbonate is 2Na ₂ C
O ₃ · 3H is an addition compound having ₂ O ₂ to the corresponding formula, and commercially available as a crystalline solid. Since sodium percarbonate is a hydrogen peroxide adduct, it tends to dissolve and release hydrogen peroxide very quickly, which may increase the tendency for local high bleach concentrations to occur. Most preferably, the percarbonate is inserted into such a composition in a coated form that provides stability in the product.

Suitable coating materials that provide product stability include mixed salts of water-soluble alkali metal sulfates and carbonates. Such coatings, as well as coating methods, are described in GB-1,466,799, already awarded to Interox on March 9, 1977. The weight ratio of mixed salt coating material to percarbonate ranges from 1: 200 to 1: 4, more preferably from 1:99 to 1: 9, and most preferably from 1:49 to 1:19. is there. The above mixed salt,
It is preferably a mixed salt of sodium sulfate and sodium carbonate having the general formula Na ₂ SO ₄ .n.Na ₂ CO ₃ . In the above formula, n is 0.1 to 3, preferably n is 0.3 to 1.0, and most preferably n is 0.2 to 0.5.

[0145] Another suitable coating material that provides product stability is SiO ₂ : N
There are sodium silicate and / or sodium metasilicate having an a ₂ O ratio of 1.8: 1 to 3.0: 1, preferably 1.8: 1 to 2.4: 1, and these are inorganic perhydrates. 2 wt% to 10 wt% of the salt (usually 3% to 5% by weight) SiO ₂
It is preferably applied at the level of The coating may also include magnesium silicate. Coatings comprising silicates and borates or boric acid or other inorganic substances are also suitable.

Other coatings, including waxes, oils, fatty soaps, can also be used to advantage within the scope of the present invention.

[0147] Potassium peroxymonopersulfate is another inorganic perhydrate salt that can be used in the compositions of the present invention.

Peroxy Acid Bleach Precursor A peroxy acid bleach precursor is a compound which reacts with hydrogen peroxide in a perhydrolysis reaction to produce peroxy acid. Generally, the peroxyacid bleach precursor can be represented by the following formula:

[0149]

Embedded image

In the above formula, L is a leaving group, X is essentially any functional group, and the structure of the peroxyacid generated in the perhydrolysis is as follows.

[0151]

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Preferably, the peroxyacid bleach precursor compound is inserted at a level of 0.5% to 20% by weight of the composition, more preferably 1% to 10% by weight of the composition
, Most preferably 1.5% to 5% by weight.

Suitable peroxyacid bleach precursor compounds are usually one or more N- or O-
Contains an acyl group. These precursors can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides, lactams, and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A-1586789. Suitable esters are GB-A
-836988, 864798, 1147871, 2143231 and EP-A-0170386.

[0154] (a thereafter L groups) leaving the leaving group, the optimum time frame (e.g., the wash cycle) perhydrolysis (perhydrolysis) reaction must be sufficiently reactive to occur within. However, if the reactivity of L is too great, the activator is difficult to stabilize for use in bleaching compositions.

Preferred L groups are those selected from the group consisting of:

[0156]

Embedded image

And mixtures thereof. In the above formula, R ¹ is an alkyl, aryl, or alkaryl group containing 1 to 14 carbon atoms, R ³ is an alkyl chain containing 1 to 8 carbon atoms, and R ⁴ is H or R ³ R ⁵ is an alkenyl chain containing 1 to 8 carbon atoms, and Y is H or a solubilizing group. Any of R ¹ , R ³ and R ⁴ can be replaced by virtually any functional group including, for example, alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammonium groups.

Preferred solubilizing groups are -SO_Three ^-M⁺, -CO_Two ^-M⁺, -SO_Four ^-M⁺, -N⁺(R^Three)_FourX ^- And O <-N (R^Three)_ThreeAnd most preferably -SO_Three ^-M⁺, And -C
O_Two ^-M⁺It is. In the above formula, R^ThreeIs an alkyl chain containing 1-4 carbon atoms;
Is a cation that confers solubility to the bleach activator, and X is
It is an anion that gives solubility. M is an alkali metal, ammonium or substituted
Preferably a monium cation, most preferably sodium and potassium
And X is a halide, hydroxide, methyl sulfate or acetate
Is on.

[0159] perbenzoic acid precursors perbenzoic acid precursor compounds undergo perhydrolysis (perhydrolysis) provide perbenzoic acid. Suitable O-acylated perbenzoic acid precursor compounds include, for example, benzoyl,
There are substituted and unsubstituted benzoyloxybenzene sulfonates including oxybenzene sulfonates:

[0160]

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

[0162]

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The imide-type perbenzoic acid precursor compounds include N-benzoylsuccinimide, tetrabenzoylethylenediamine and N-benzoyl-substituted-ureas. Suitable imidazole-type perbenzoic acid precursors include N-benzoylimidazole and N-benzoylbenzimidazole, and other useful N-acyl group-containing perbenzoic acid precursors include N-benzoylpyrrolidone, dibenzoyltaurine And benzoyl pyroglutamic acid.

Other perbenzoic acid precursors include benzoyl diacyl peroxides, benzoyl tetraacyl peroxides, and compounds having the formula:

[0165]

Embedded image

[0166] Phthalic anhydride is another suitable perbenzoic acid precursor compound in the present invention:

[0167]

Embedded image

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

[0169]

Embedded image

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

[0171] perbenzoic acid derivative precursors perbenzoic acid derivative precursors provide substituted perbenzoic acids undergo perhydrolysis (perhydrolysis).

Suitable substituted perbenzoic acid derivative precursors are those wherein the benzoyl group is substantially positively uncharged (ie, non-ionic, including, for example, alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, and amide groups, etc.). ) Include any of the perbenzoic acid precursors disclosed herein, substituted by a functional group.

A preferred class of substituted perbenzoic acid precursor compounds are amide substituted compounds of the general formula:

[0174]

Embedded image

In the above formula, R ¹ is an aryl or alkaryl group having 1 to 14 carbon atoms, R ² is an arylene or alkaryl group containing 1 to 14 carbon atoms,
And R ⁵ is alkyl, aryl, or alkaryl group containing from 1 to 10 H or a carbon atom, L is may be virtually any leaving group. R ¹ is a carbon atom 6-1
It is preferred to include two. R ² preferably contains from 4 to 8 carbon atoms. R ¹ can be aryl, substituted aryl or alkylaryl with branched substituents, or both, and can be initiated from either synthetic sources or natural sources including, for example, tallow butter. A similar structural change is possible with R ² . Substituents 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 total carbon atoms. Amide-substituted bleach activating compounds of this type are described in EP-A-0170386.

Cationic Peroxy Acid Precursor The cationic peroxy acid precursor compound undergoes perhydrolysis (perhydrolysis) to give a cationic peroxy acid.

In general, the cationic peroxyacid precursor is a group in which the peroxyacid moiety of the appropriate peroxyacid precursor compound is a positively charged functional group, such as an ammonium or alkylammonium group, preferably an ethyl or methylammonium group. It is formed by substituting with The cationic peroxyacid precursor is generally present in the composition as a salt with a suitable anion, such as, for example, a halide ion or a methyl sulfate ion.

The peroxyacid precursor compound thus cationically substituted may be perbenzoic acid, a substituted derivative thereof, or a precursor compound as described above. Alternatively, the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxy acid precursor as described below.

The cationic peroxyacid precursors are disclosed in US 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; EP 475,512; 458,396;
284,292; and JP 87-318,332.

Suitable cationic peroxyacid precursors include ammonium or alkyl ammonium substituted alkyl or benzoyloxybenzene sulfonates, N-acylated caprolactams, and monobenzoyl tetraacetylglucose benzoyl peroxides.

A preferred cationic substituted benzoyloxybenzenesulfonate is a 4- (trimethylammonium) methyl derivative of benzoyloxybenzenesulfonate:

[0182]

Embedded image

Preferred cationically substituted alkyloxybenzene sulfonates have the formula:

[0184]

Embedded image

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

[0186]

Embedded image

Other preferred cationic peroxyacid precursors of the N-acylated caprolactam class include trialkyl ammonium methylene alkyl caprolactams:

[0188]

Embedded image

In the above formula, n is 0 to 12, especially 1 to 5.

Another preferred cationic peroxyacid precursor is 2- (N, N, N,-
Trimethylammonium) ethyl 4-sulfophenyl carbonate carbonate.

Alkyl percarboxylic acid bleach precursor The alkyl percarboxylic bleach precursor undergoes perhydrolysis to form percarboxylic acid. Preferred precursors of this type undergo perhydrolysis to give peracetic acid.

Preferred alkyl peroxycarboxylic acid precursor compounds of the imide type include N, N, N ¹ N ¹ tetraacetylated alkylenediamines in which the alkylene group contains 1 to 6 carbon atoms, in particular, when the alkylene group has 1 There are the above compounds containing 2 and 6 carbon atoms. Tetraacetylethylenediamine (TAED) is particularly preferred.

Other preferred alkylpercarboxylic acid precursors include 3,5,5-trimethylhexanoyloxybenzenesulfonate (iso-NOBS), sodium nonanoyloxybenzenesulfonate (NOBS), sodium acetoxybenzenesulfonate ( ABS) and pentaacetylglucose.

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

[0195]

Embedded image

In the above formula, R¹Is an alkyl group having 1 to 14 carbon atoms;^TwoIs a carbon atom 1
An alkylene group containing 14 and R^FiveIs H or 1 to 10 carbon atoms
And L can be virtually any leaving group. R¹Is 6
It preferably contains １２12 carbon atoms. R^TwoContains from 4 to 8 carbon atoms
preferable. R¹Is straight-chain alkyl, or branched, containing branched, substituted or both
It can be an alkyl, either a synthetic source or a natural source containing, for example, tallow fat
Can also be started. R^TwoHowever, similar structural changes are possible. The substituent is alkyl,
There are halogens, nitrogen, sulfur and other typical substituents or organic compounds. R ^Five Is preferably H or methyl. R¹And R^FiveIs a total of more than 18 carbon atoms
Should not be included. This type of amide-substituted bleach activating compound is described in EP-A-01
70386.

Benzoxazine organic peroxyacid precursors Also suitable are precursor compounds of the benzoxazine type disclosed, for example, in EP-A-332,294 and EP-A-482,807, especially those having the formula:

[0198]

Embedded image

These also include substituted benzoxazines of the type

[0200]

Embedded image

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, amino, alkylamino, CO
It may be the same or a different substituent selected from OR ₆ (where R ₆ is H or an alkyl group) and a carbonyl function. Particularly preferred benzoxazine-type precursors are:

[0202]

Embedded image

Preformed Organic Peroxy Acids The organic peroxy acid bleaching system can be used in addition to, or instead of, the organic peroxy acid bleach precursor compound to provide a preformed organic peroxy acid to the above composition. 0.5 to 25% by weight, more preferably 1 to 10% by weight.

A preferred class of organic peroxyacid compounds are amide substituted compounds of the general formula:

[0205]

Embedded image

In the above formula, R ¹ is an alkyl, aryl or alkaryl group having 1 to 14 carbon atoms, R ² is an alkylene, arylene and alkarylene group containing 1 to 14 carbon atoms, and ⁵ is H or an alkyl, aryl or alkaryl group containing 1 to 10 carbon atoms. R ¹ preferably contains 6 to 12 carbon atoms. R ² preferably contains from 4 to 8 carbon atoms. R ¹ can be straight or branched alkyl, substituted aryl, or alkylaryl containing branched, substituted, or both, and can be initiated from either synthetic sources or natural sources including, for example, tallow butter. A similar structural change is possible with R ² . Substituents can be alkyl, aryl, halogen, nitrogen, sulfur and other common 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 described in EP-A-0 170 386.

Other organic peroxyacids include diacyl and tetraacyl peroxides, especially diperoxidedecandionic acid, diperoxytetradecandionic acid, and diperoxyhexadecandionic acid. Dibenzoyl peroxide is
Preferred organic peroxy acids of the present invention. Mono- and diperazelaic acid,
Mono- and diperbracyl acids, and N-phthaloylaminoperoxycaproic acid are also suitable in the present invention.

A controlled release rate- means is provided for controlling the release rate of the bleach, especially the oxygen bleach, into the washing solution.

[0209] Means for controlling the release rate of the bleach may be provided for controlled release of the peroxide species into the laundry solution. Such measures may include, for example, controlling the release of any inorganic perhydrate salts that act as a source of hydrogen peroxide into the washing solution, and the like.

Another mechanism for controlling the release rate of the bleach is to coat the bleach with a coating designed to control the release. Thus, the coating comprises, for example, a substance that is sparingly soluble in water, or the coating is sufficiently thick to dissolve the kinetics of the thick coating.
tics) to provide a controlled release rate.

[0211] The coating materials are applied using a variety of methods. Any coating material may have a weight ratio of coating material to bleach, typically from 1:99 to 1: 2.
, Preferably from 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. is there.

[0213] Other suitable coating materials include alkali and alkaline earth metal sulfates, silicates and carbonates, such as calcium carbonate and silica.

Preferred coating materials, especially for inorganic perhydrate salt bleach sources
Preferred coating materials are 1.8: 1 to 3.0: 1, preferably 1.8:
1-2.4: 1 SiO_Two: Na_TwoSodium silicate with O ratio and / or preferred
Or 2 to 10% by weight (usually 3 to 5% by weight) of inorganic perhydrate salt _Two Comprising sodium metasilicate applied in an amount of. Magnesium silicate also
It can be included in the coating.

[0215] Any of the inorganic salt coating materials can be combined with an organic binder material to provide a composite inorganic salt / organic binder coating. Suitable binders, there are C ₁₀ -C ₂₀ alcohol ethoxylates containing ethylene oxide 5-100 moles per mole of alcohol, and the alcohol per mole 20-100
C ₁₅ -C ₂₀ primary alcohol ethoxylates containing moles of ethylene oxide are more preferable.

Other preferred binders include some polymeric substances. Average molecular weight 12,
Polyvinylpyrrolidones having a molecular weight of from 000 to 700,000 and an average molecular weight of 60
0-5 × 10 ⁶ , more preferably 1000-400,000, most preferably 1
Polyethylene glycols (PEG) having 000 to 10,000 are examples of such polymeric materials. In a copolymer of maleic anhydride and ethylene, methyl vinyl ether or methacrylic acid, maleic anhydride is at least 20% of the above polymer.
The above copolymers that make up the mole percent are other examples of polymeric materials useful as binders. It These polymeric materials may be used as it is, or water may be used in combination with C ₁₀ -C ₂₀ alcohol ethoxylate solvent comprising propylene glycol and of 5-100 mol per 1 mol of the ethylene oxide. Other examples of binding agents, C ₁₀ -C ₂₀ mono - there and also diglycerol ethers and C ₁₀ -C ₂₀ fatty acids.

Cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or co-polymerized polycarboxylic acids or their salts are other examples of binders that can be suitably used in the present invention.

One means of applying a coating substance is agglomeration. A preferred aggregation process is
Including the use of any of the organic binder materials described above. Any conventional agglomerator / mixer may be used, including, but not limited to, pans, rotating drums and vertical blender types. The melt coating composition can also be applied by pouring over the bleach or spraying it on a moving bed of bleach.

Other means of achieving the required release control include mechanical means of altering the physical properties of the bleach to control its solubility and release rate. Suitable protocols include compression, mechanical injection, manual injection, and adjusting the solubility of the bleach compound by selecting the particle size of some particulate components.

The choice of particle size is dependent on the composition of the particulate component as well as the desired controlled release kinetics.
Depending on the requirements of cs), it is desirable for the particle size to be greater than 500 micrometers, more preferably to have an average particle diameter of 800 to 1200 micrometers.

An additional protocol that provides a controlled means is that when the composition is placed in a wash liquor, the resulting ionic strength environment will provide the required controlled kinetics. Including appropriately selecting any other ingredients of the detergent composition.

Metal-Containing Bleaching Catalysts The compositions described in the present invention that include a bleaching agent as a detergent component can further include a metal-containing bleaching catalyst as a suitable component. The metal-containing bleaching catalyst is preferably a transition metal-containing bleaching catalyst, and more preferably a manganese or cobalt-containing bleaching catalyst.

Suitable types of bleaching catalysts are heavy metal cations with defined bleaching catalytic activity, such as copper, iron cations, auxiliary metal cations having little or no bleaching catalytic activity, such as zinc or aluminum cations. And sequestering agents with defined and defined stability for the above catalysts and auxiliary metal cations, especially catalysts comprising ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) and its water-soluble salts. . Such catalysts are disclosed in U.S. Pat.
No. 243.

[0224] Preferred types of bleaching catalysts include US Pat. No. 5,246,621 and US Pat.
Manganese-based complexes disclosed in US Pat. Advantages of these catalysts
A good example is Mn^IV _Two(U-O)_Three(1,4,7-trimethyl-1,4,7-to
Riazacyclononane)_Two− (PF₆)_Two, Mn^III _Two(U-O)₁(U-OAc)_Two(
1,4,7-trimethyl-1,4,7-triazacyclononane)_Two− (ClO_Four) _Two , Mn^IV _Four(U-O)₆(1,4,7-triazacyclononane)_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)_Three, And their mixtures
is there. Others are described in European Patent Application Publication No. 549,272. Suitable for the present invention
Other ligands that can be used readily include 1,5,9-trimethyl-1,5,9-
Triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2
-Methyl-1,4,7-triazacyclononane, 1,2,4,7-tetramethyl
-1,4,7-Triazacyclononane, and mixtures thereof.

[0225] Bleaching catalysts useful in the compositions of the present invention can also be selected to be suitable for the present invention. For examples of suitable bleaching catalysts, see U.S. Patent Nos. 4,246,612 and 5,227,0
See No. 84. Further, Mn _{(1,4,7-trimethyl-1,4,7-triazacyclononane) (OCH 3) 3 - (} PF 6) mononuclear manganese (IV) United States patents that teach the complexes such as See also 5,194,416.

Another type of bleaching catalyst, such as that disclosed in US Pat. No. 5,114,606, comprises manganese (III) and / or (IV) and a non-blend having at least three consecutive C-OH groups. It is a water-soluble complex with a ligand that is a carboxylate polyhydroxy compound. Preferred ligands include sorbitol, iditol, dulcitol, mannitol, xylitol, arabitol, adonitol, meso-erythritol,
There are meso-inositol, lactose, and mixtures thereof.

US Pat. No. 5,114,611 teaches a bleach catalyst comprising a complex of a transition metal, including Mn, Co, Fe, or Cu, with a non- (macro) -cyclic ligand.
The ligands are represented by the following formula:

[0228]

Embedded image

In the above formula, R ¹ , R ² , R ³ and R ⁴ are each H, and each of R ¹ —N 、 C—R ² and R ³ —C = N—R ⁴ is derived from a substituted alkyl and aryl group. It is selected to form a 5- or 6-membered ring. The ring may be further substituted. B is O, S, CR ⁵ R ⁶ ,
A bridging group selected from NR ⁷ and C ＝ O, wherein R ⁵ , R ⁶ and R ⁷ are each an H, alkyl, or aryl group (including a substituted or unsubstituted group). Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings. Optionally, the ring may be substituted with substituents such as alkyl, aryl, alkoxy, halide, and nitro. Particularly preferred is the ligand 2,2'bispyridylamine. Preferred bleaching catalysts include Co, Cu, Mn, Fe, -bispyridylmethane and -bispyridylamine complexes. Highly preferred catalysts include Co (2,2′-bispyridylamine) Cl ₂ , di (isothiocyanate) bispyridylamine-cobalt (II), trisdipyridylamine-cobalt (II) perchlorate, Co ( 2,2-
Bispyridylamine) ₂ O ₂ ClO ₄ , bis- (2,2′-bispyridylamine)
Copper (II) perchlorate, tris (di-2-pyridylamine) iron (II) perchlorate,
And mixtures thereof.

Preferred examples include binuclear Mn complexes with tetra-N-dentate and bi-N-dentate ligands, which are N ₄ Mn ^III (uO) ₂ Mn ^IV N ₄ ) ⁺ and ^{_{[bipy 2 Mn III (u-}} O) 2 Mn IV bipy 2] - comprising the (ClO _{4) 3.}

Although the structures of the bleaching catalyst manganese complexes of the present invention have not been elucidated, they include chelates or other hydrated coordination complexes formed by the interaction of manganese ions with the carboxyl and nitrogen atoms of the ligand. It is thought that it becomes. Similarly, the oxidation state of the manganese cation during the catalytic process is not known with certainty, probably in the (+ II), (+ III), (+ IV) or (+ V) valence state. Since there may be six points where the ligand binds to the manganese cation, it is reasonably possible that polynuclear and / or "cage" structures are present in the aqueous bleach solution. Whatever the form of the active Mn-ligand species actually present, it clearly functions in catalytic behavior and improves the bleaching effect on stubborn soils such as tea, ketchup, coffee, wine, juice and the like.

Other bleaching catalysts are, for example, EP 408,131 (cobalt complex catalysts), EP 384,503 and 306,089 (metal-porphyrin catalysts), US Pat. No. 4,728,455 (manganese / multiple). Ligand catalyst), US Patent No. 4,711
U.S. Patent No. 4,748,748 and European Patent Application Publication No. 224,952 (manganese catalyst absorbed on aluminosilicate), U.S. Patent No. 4,601,845 (aluminosilicate support bearing manganese and zinc or magnesium salts), U.S. Patent No. 4,626,373 ( Manganese / ligand catalyst), US Pat. No. 4,119,557 (ferric complex catalyst), German Patent Specification 2,054,
019 (Cobalt-chelate catalyst) Canada No. 866,191 (transition metal containing salt), US Pat. No. 4,430,243 (chelate of manganese cation and non-catalytic metal cation), and US Pat. No. 4,728,455 (manganese gluconate catalyst) Has been described.

Another preferred example is a cobalt (III) catalyst having the formula:

[0234]

Embedded image

In the above formula, cobalt is in the +3 oxidation state; n is an integer from 0 to 5 (
M ′ is a monodentate ligand; m is 0 or 4 is preferred; 5 is most preferred);
B 'is a bidentate ligand; b is an integer from 0 to 2; T' is a tridentate ligand Is;
t is 0 or 1; Q is a tetradentate ligand; q is 0 or 1; P is a pentadentate ligand; p is 0 or 1; and n + m + 2b + 3t + 4q + 5
p = 6; Y is one or more appropriately selected counter anions present in the number of y, where y is an integer from 1 to 3 to obtain a charge balanced salt (
2-3 are preferred; 2 is most preferred when Y is a -1 valent anion); suitable Y is chloride, nitrate, nitrite, sulfate, citrate, acetate, carbonate, and the like. Selected from the group consisting of combinations; and under the conditions of use of an automatic dishwasher, at least one of the coordination sites that binds to cobalt is unstable, and the remaining coordination sites are as described above under automatic dishwasher conditions. The cobalt is stabilized so that the reduction potential of cobalt (III) to cobalt (II) under alkaline conditions is less than 0.4 volts (preferably less than 0.2 volts) relative to a regular hydrogen electrode. Preferred cobalt catalysts of this type have the formula:

[0236]

Embedded image

In the above formula, n is an integer from 3 to 5 (preferably 4 or 5; most preferably 5); M ′ is an unstable coordination moiety, preferably chlorine, bromine, hydroxyl And m is an integer from 1 to 3 (preferably 1 or 2; most preferably 1); m + n = 6 And Y is a suitably selected counter anion present by y numbers, and y is an integer from 1 to 3 that can provide a charge-balanced salt (
Preferably 2-3; when Y is a monovalent anion, it is most preferably 2).

Preferred cobalt catalysts of this type useful in the present invention are of the formula [Co (NH ₃ ) ₅ C
l)] Cobalt pentaamine chloride salt with Yy, especially [Co (NH ₃ ) ₅ Cl)] Cl ₂ .

More preferred are compositions of the present invention using a cobalt (III) bleach catalyst having the formula:

[0240]

Embedded image

In the above formula, cobalt is in the +3 oxidation state; n is 4 or 5 (preferably 5); M is one or more ligands that coordinate cobalt at one position; m is 0, 1 or 2 (preferably 1); B is a ligand coordinating the cobalt at two positions; b is 0 or 1 (preferably 0), and b = 0. Sometimes m + n = 6, and when b = 1, m = 0 and n = 4; and T is one or more appropriately selected counter anions present in y numbers, where y is the charge An integer from which a balanced salt can be obtained (y is preferably 1 to 3,
Most preferably, T is 2 when T is a -1 valent anion);
The catalyst has a base hydrolysis rate constant of less than 0.23 M ⁻¹ s ⁻¹ (25 ° C.).

Preferred T are chloride, iodide, I ₃ ⁻ , formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide, PF ₆ ⁻ , BF ₄ ⁻ , B (Ph
) ₄ ^-, phosphate, phosphite, silicate, chosen tosylate, methanesulfonate, and combinations thereof. If more than one anionic group is present in T, for example HPO ₄ ²⁻ , HCO ₃ ⁻ , H ₂ PO ₄ ⁻ etc. T can optionally be protonated. In addition, T may be an anionic surfactant (eg, linear alkyl benzene sulfonates (LAS), alkyl sulfates (AS), alkyl ethoxy sulfonates (AES), etc.), and / or an anionic polymer (eg, polyacrylates). , Polymethacrylates, etc.) may be selected from the group consisting of non-traditional inorganic anions.

[0243] The M moieties include, without limitation, for example _{^{F -, SO 4 -2, NCS}} -, SCN -, S 2 O 3 -2, NH 3, PO 4 3-, and carboxylates (mono - Carboxylates are preferred, but more than one carboxylate may be present in that moiety, as long as the attachment to cobalt is effected by only one carboxylate per moiety, in which case the other of the M moiety The carboxylate is protonated or in its salt form). If M has more than one anionic group (eg, HPO ₄ ²⁻ , HCO ₃ ⁻ , H ₂ PO ₄ ⁻ , HOC (O) CH ₂ C (
O) O-, etc.) and optionally M can be protonated. Preferred M moieties are substituted and unsubstituted C ₁ -C ₃₀ carboxylic acids having the formula:

[0244]

Embedded image RC (O) O-

In the above formula, R is hydrogen and C ₁ -C ₃₀ (preferably C ₁ -C ₁₈ ) unsubstituted and substituted alkyl, C ₆ -C ₃₀ (preferably C ₆ -C ₁₈ ) unsubstituted and substituted aryl , and C ₃ -C ₃₀ (preferably C ₅ -C ₁₈₎ is preferably selected from the group consisting of unsubstituted and substituted heteroaryl, where the substituents ^{_{NR '3, -NR' 4 +}} , -C
(O) OR ', - OR ', - C (O) ' is selected from the group consisting of _2, this time R' NR is selected from the group consisting of hydrogen and C ₁ -C ₆ moieties. Therefore thus substituted R is moiety - (CH _{2) n} OH and - (CH _{2) n} NR 'includes a ₄ ^+, wherein n is an integer from 1 to 16, preferably from 2 to 10, And most preferably an integer from 2 to 5.

Most preferred M has the formula above, wherein R is a carboxylic acid selected from the group consisting of hydrogen, methyl, ethyl, propyl, straight or branched chain C ₄ -C ₁₂ alkyl, and benzyl. It is. Most preferred R is methyl. Preferred carboxylic acid M moieties include formic acid, benzoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, malonic acid, maleic acid, succinic acid, adipic acid, phthalic acid, 2-ethylhexanoic acid, naphthenic acid, oleic acid Acid, palmitic acid, triflate, tartrate,
There are stearic, butyric, citric, acrylic, aspartic, fumaric, lauric, linolenic, lactic, malic, and especially acetic acids.

Part B includes carbonates, di- and higher carboxylates (eg oxalates,
Malonate, malate, succinate, maleate), picolinic acid, and alpha and beta amino acids (e.g., glycine, alanine, beta-alanine,
Phenylalanine).

Cobalt bleaching catalysts useful in the present invention are known and include, for example, ML Tobe
), "Base hydrolysis of transition metal complexes", Adv. Inorg. Bioinorg. Mech. (198
3) Volume 2, pages 1-94, along with their base hydrolysis rates.
You. For example, Table 1 on page 17 shows that oxalate (^kOH = 2.5 × 10^-FourM^-1s^-1(
25 ° C)), NCS^-(^kOH = 5.0 × 10^-FourM^-1s^-1(25 ° C.)), formate ( ^k OH = 5.8 × 10^-FourM^-1s^-1(25 ° C.)) and acetate (^kOH = 9.6 ×
10^-FourM^-1s^-1(25 ° C.)) and base hydration of a cobalt pentaamine catalyst complexed with
Decomposition rate (here, K_OHIs described). Most useful in the present invention
A preferred cobalt catalyst is of the formula [Co (NH_Three)_FiveOAc] Cobalt pen with Ty
Taamine acetate (where OAc represents the acetate moiety), and especially
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)_Two;
And [Co (NH_Three)_FiveOAc] (NO_Three)_Two(Here, “PAC”).

These cobalt catalysts can be prepared by known methods, for example, using the previously mentioned Tobe literature and references cited therein, Diakun (March 7, 1989).
U.S. Patent No. 4,810,410, J. Diakun) et al. Chem. Ed. (1989), 66 (12
), 1043-45; Synthesis and Characterization of Inorganic Compounds, Jolly (W.
. L. Jolly) (Prentice-Hall; 1970), pp. 461-3; Inorg. Chem.
18, pp. 1497-1502 (1979); Inorg. Chem. 21 volumes, 28
81-2885 (1982); Inorg. Chem. 18, 2023-2025 (1979); Inorg. Synthesis. 173-176 (1960); and Journal of Physical Chemistry, Vol. 56, 22-25 (1952); and readily prepared by the synthetic examples described below.

Cobalt catalysts suitable for incorporation into the detergent tablets of the present invention are described in US Pat.
It can be prepared by the synthetic routes disclosed in 5,559,261, 5,581,005 and 5,597,936. This disclosure is incorporated herein by reference.

These catalysts may be used, if desired for the aesthetic appearance of the product, with auxiliary materials to reduce the effect on color, or as contained in the enzyme-containing particles, as explained in more detail below. It may be used together with. Alternatively, the above composition is treated with a catalyst "spot (sp
eckles) ".

Organic Polymer Compounds Organic polymer compounds can be added according to the invention as preferred components of detergent tablets. By organic polymeric compound is meant substantially all polymeric organic compounds commonly found in detergent compositions having dispersants, anti-redeposition agents, soil release agents or other detergent properties.

The organic polymer compound is generally present in the detergent composition of the present invention in an amount of 0% of the above composition.
. It is present at a level of from 1% to 30%, preferably from 0.5% to 15%, most preferably from 1% to 10% by weight.

Examples of the organic polymer compound include a water-soluble organic homopolymer or copolymer polycarboxylic acid, a modified polycarboxylate or a salt thereof. Here, a polycarboxylic acid contains at least two carboxyl groups separated from each other by no more than two carbon atoms. Polymers of the latter type are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates of molecular weight 2000-10000, and modified acrylic acid, fumaric acid, maleic acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, and methylenemalonic acid or their Copolymers with other suitable monomers, including salts, maleic anhydride, acrylamide, alkylene, vinyl methyl ether, styrene and any mixture thereof. Copolymers of acrylic acid and maleic anhydride having a molecular weight of 20,000 to 100,000 are preferred.

Preferred commercially available acrylic acid-containing polymers having a molecular weight of less than 15,000 are sold by BASF GmbH under the trade names Sokalan PA30, PA20, PA15, PA10 and Sokalan CP10. Some are sold by Rohm & Haas under the trade name Acusol 45N, 480N, 460N.

Preferred acrylic acid-containing copolymers include as monomer units: a) 90-1
0% by weight, preferably 80 to 20% by weight of acrylic acid or salts thereof and b)
10-90 wt%, preferably a 20 to 80% by weight of substituted acrylic monomer or its salts, they have the general formula _{- [CR 2 -CR 1 (CO} -O-R 3)] - is represented by the formula Wherein 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,
R ₁ or R ₂ may be hydrogen, and R ₃ includes hydrogen or the above substituted acrylic monomer or a salt thereof, which is an alkali metal salt. Most preferably, R ₁
Is methyl and R ₂ is hydrogen (ie, a methacrylic acid monomer). The most preferred copolymer of this type has a molecular weight of 3500
And comprises 60-80% by weight of acrylic acid and 40-20% by weight of methacrylic acid.

Polyamines and modified polyamine compounds are useful herein and are described in EP-A-
305282, EP-A-305283 and those derived from aspartic acid as disclosed in EP-A-351629 and the like.

Other optional polymers include modified or unmodified polyvinyl alcohols and acetates, cellulosic and modified cellulosic materials, polyoxyethylenes, polyoxypropylenes, and copolymers thereof (modified ones). Terephthalate esters of ethylene or propylene glycol or mixtures thereof with polyoxyalkylene units.

Suitable examples are disclosed in US Pat. Nos. 5,591,703, 5,597,789, and 4,490,271.

Soil Release Agents Suitable polymerizable soil release agents include those soil release agents, including:
a) one or more nonionic hydrophilic components, substantially (i) a polyoxyethylene segment having a degree of polymerization of at least 2, or (ii) oxypropylene or a polyoxy having a degree of polymerization of 2 to 10. A propylene segment (in which case the hydrophilic segment does not contain any oxypropylene units unless the oxypropylene units are linked to the adjacent portions of each end by an ether bond), or (iii) oxyethylene and 1 to 30 oxypropylene units The hydrophilic segment preferably comprises at least 25% of oxyethylene units, especially at least 50% for components having 20 to 30 oxypropylene units.
Or more preferably (b) one or more hydrophobic components comprising: (i) C ₃ oxyalkylene terephthalate segments, wherein said hydrophobic component is oxyethylene terephthalate The ratio of oxyethylene terephthalate: C ₃ oxyalkylene terephthalate units is 2: 1 or less; (ii) C ₄ -C ₆ alkylene or oxy C ₄ -C ₆ alkylene segments, or Mixtures, (iii) poly (vinyl ester) segments, preferably polyvinyl acetate having a degree of polymerization of at least 2, or (iv) C ₁ -C ₄ alkyl ether or C ₄ hydroxyalkyl ether substituents, or mixtures thereof. ; forms or C ₄ ratio of the time said substituents C ₁ -C ₄ alkyl ether Combination of, or (a) and (b); the form of b carboxyalkyl ether cellulose derivatives, or as a mixture thereof.

Typically, the polyoxyethylene segments of (a) (i) have a degree of polymerization up to 200 (although higher degrees of polymerization can be used), preferably from 3 to 150, more preferably from 6 to 100 It has a degree of polymerization. Suitable oxy C ₄ -C ₆ alkylene hydrophobic segment, Gosurinku, issued Jan. 26, 1988 (Gosselink) U.S. Patent disclosed in No. _{4,721,580 MO 3 S (CH 2)} n OCH 2 end of CH ₂ O- polymerizable soil release agents such as - sodium caps (wherein M is and n
Is an integer of 4-6), but is not limited thereto.

[0262] Polymerizable soil release agents useful in the present invention also include cellulose derivatives such as hydroxyether cellulose polymers, copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and include hydroxyethers of cellulose such as METHOCEL (DOW). Cellulosic soil release agents useful in the present invention include C _1-
Also included are those selected from the group consisting of C ₄ alkyl and C ₄ hydroxyalkyl cellulose; see US Pat. No. 4,000,093 to Nicol et al., Issued Dec. 28, 1976.

Soil release agents featuring poly (vinyl ester) hydrophobic segments include graft copolymers of poly (vinyl ester), for example, C _1- grafted to a polyalkylene oxide backbone such as a polyethylene oxide backbone. C ₆ vinyl ester,
Preferably, poly (vinyl acetate) or the like is used. See European Patent Application No. 0 219 048 to Kud et al., Published April 22, 1987.

Another suitable soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight of the polymerizable soil release agent is in the range of 25,000 to 55,000. Heys U.S. Pat. No. 3,959,230, issued May 25, 1976.
No. 3 and Basadur US Patent No. 3 issued July 8, 1975.
No., 893,929.

Another suitable polymerizable soil release agent is a polyester having repeating units of ethylene terephthalate units, from 10-15% by weight of ethylene terephthalate units and polyoxyethylene glycol having an average molecular weight of 300-5000. With 90-80% by weight of the derived polyoxyethylene terephthalate units.

Another suitable polymerizable soil release agent is a substantially linear ester oligomer comprising an oligomer ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and a terminal moiety covalently bonded to the backbone. Is a sulfonated product of
These stain release agents are described in JJ Scheib published November 6, 1990.
el) and EP Gosselink, US Pat. No. 4,968,451. Other suitable polymerizable soil release agents include Goslink et al., U.S. Pat. No. 4,711,730, issued Dec. 8, 1987, and Goslink U.S. Pat. No. 4,721,580, issued Jan. 26, 1988. Anionic end-capped oligomeric esters, and Oct. 27, 1987
There is a block polyester oligomer compound of Goslink US Pat. No. 4,702,857 issued to Sun. Other polymerizable soil release agents also include those of Maldonado et al., Issued October 31, 1989; which discloses anionic, especially sulfoallyl, end-capped terephthalate esters.

Another soil release agent is an oligomer having repeating units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1,2-propylene units. The repeating unit forms the backbone of the oligomer and preferably ends with a modified isethionate end-cap. A particularly preferred soil release agent of this type comprises 1, sulfoisophthaloyl units, 5, terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio from 1.7 to 1.8, sodium 2 -End-cap unit 2 of-(2-hydroxyethoxy) -ethanesulfonate.

Heavy Metal Sequestering Agent The tablets of the present invention preferably contain a heavy metal ion sequestering agent as an optional ingredient. Heavy metal ion sequestering agents, as used herein, are components that act to sequester (chelate) heavy metal ions. These components also have the ability to form calcium and magnesium chelates, but exhibit selectivity for preferential binding to heavy metal ions such as iron, manganese and copper.

Heavy sequestering agents 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. And most preferably from 0.5% to 5% by weight.

Heavy sequestering agents are acidic in nature, for example with phosphonic acid- or carboxylic acid functionality, etc., and are also in their acid form or with suitable counter cations, such as alkali or alkali metal ions, ammonium, or substituted ammonium. ion,
Alternatively, it can also be present as a complex / salt with these mixtures. Preferably, any salts / complexes are water-soluble. Preferably, the molar ratio of said counter cation to heavy sequestering agent is at least 1: 1.

Suitable heavy metal sequestering agents for use in the present invention include organic alkylates such as aminoalkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxydiphosphonates and nitrilotrimethylene phosphonates. Among the above types, diethylene triamine penta (methylene phosphonate),
Preferred are ethylenediamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1-diphosphonate.

Other suitable heavy sequestering agents for use in the present invention include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetraacetic acid, ethylenetriaminepentaacetic acid, ethylenediaminedisuccinic acid, ethylenediaminediglutaric acid,
There are 2-hydroxypropylenediamine disuccinic acid or salts thereof.

Particularly preferred is ethylenediamine-N, N′-disuccinic acid (EDDS) or an alkali metal, alkaline earth metal, ammonium, or substituted ammonium salt thereof, or a mixture thereof. Preferred EDDS compounds are the free acid form and its sodium or magnesium salt or complex.

Crystal Growth Inhibiting Component The detergent tablet of the present invention preferably contains a crystal growth inhibiting component, preferably an organic diphosphonic acid component. It preferably comprises from 0.01% to 5% by weight of the composition, more preferably from 0.1% to 2% by weight.

By organic diphosphonic acid is meant here organic diphosphonic acid which does not contain nitrogen as part of its chemical structure. This definition excludes organic aminophosphonates, which may be included in the compositions of the present invention as heavy metal sequestrant components.

The organic diphosphonic acid is preferably a C ₁ -C ₄ diphosphonic acid, more preferably a C ₂ diphosphonic acid such as ethylene diphosphonic acid, or most preferably ethane 1
-Hydroxy-1,1-diphosphonic acid (HEDP), which may be present in partially or fully ionized form, in particular as a salt or complex.

Water Soluble Sulfate The detergent tablets of the present invention optionally include a water soluble sulfate. When present, the water-soluble sulfate comprises from 0.1% to 40%, more preferably 1% by weight of the composition.
-30% by weight, most preferably at a level of 5-25% by weight.

The water-soluble sulfate can be virtually any salt of a sulfate with any counter cation. Preferred salts are selected from alkali and alkaline earth metal sulfates,
Particularly, sodium sulfate is preferable.

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 to 3.0, preferably 1.8 to 3.0.
Sodium silicate with 2.4, most preferably 2.0. Sodium silicate is less than 20 wt%, preferably from 1% to 15%, most preferably to exist SiO ₂ of 3 wt% to 12 wt% level. The alkali metal silicate can be in either anhydrous or hydrated form.

The alkali metal silicate may be present as a component of the alkaline system. Alkaline system preferably comprises also sodium metasilicate levels of minimum 0.4 wt% SiO _2. Sodium metasilicate has a nominal SiO ₂ : Na ₂ O ratio of 1.0.
It is. The weight ratio of said sodium silicate to said sodium metasilicate measured as SiO ₂ is preferably from 50: 1 to 5: 4, more preferably 15: 5.
It is from 1 to 2: 1, most preferably from 10: 1 to 5: 2.

Colorant As used herein, the term "colorant" refers to any substance that absorbs a particular wavelength of light from the visible light spectrum. Such coloring agents, when added to the detergent composition, have the effect of changing the visible color, and thus changing 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 into which it is inserted. For example, the colorant in a high pH composition is preferably alkali stable, and the colorant in a low pH composition is
It is preferably acid-stable.

The first phase and / or the second phase and / or any other phase comprises a colorant, a mixture of colorants, a colored particle or a mixture of colored particles, wherein the various phases have different visual appearances It can also have. Preferably, any one of the first or second phases contains a colorant. If the first and second phases and / or subsequent phases include a colorant, it is preferred that the colorant have a different visual appearance.

Examples of suitable dyes include reactive dyes, direct dyes, azo dyes. Preferred dyes include phthalocyanine dyes, anthraquinone dyes, quinoline dyes, monoazo, disazo and polyazo. More preferred dyes include anthraquinone, quinoline and monoazo dyes. More preferred dyes include Clariant
) (UK) all available from SANDOLAN E-HRL 180% (trade name), SANDOLAN MILLING BLUE (trade name), TURQUAOIS
E ACID BLUE (trade name) and SANDOLAN BRILLIANT
H available from GREEN (trade name), Pointing (UK)
EXACOL QUINOLIN YELLOW (trade name) and HEXACOL
BRILLIANT BLUE (trade name), ULTRA MARINE BLUE (trade name) available from Holliday or Bayer (U
There is LEVAFIX TURQUISE BLUE EBA (trade name) available from SA).

The colorants may be inserted into these phases in any suitable way. Suitable methods include mixing the colorant with all or selected detergent components in a drum, or spraying the colorant with all or selected detergent components in a rotating drum.

When present as a component of the first phase, the colorant is 0.001% to 1.5%, preferably 0.01% to 1.0%, most preferably 0.1% to 0.1%. Present at 3% level. When present as a component of the second phase and / or optionally other phases, the colorant is generally 0.001% to 0.1%, more preferably 0.005% to 0%.
. It is present at a level of 0.05%, most preferably 0.007% to 0.02%.

Corrosion Inhibiting Compounds Tablets of the present invention suitable for use in the dishwashing process are preferably organic silver coatings, especially paraffin, nitrogen coating corrosion inhibiting compounds and Mn (II
C) compounds, especially corrosion inhibitors selected from Mn (II) salts of organic ligands.

Organic silver coatings are described in PCT Publication No. WO 94/16047 and co-pending European Application EP-A-690122. Nitrogen-containing corrosion inhibiting compounds are described in co-pending European application EP-A-634,478. Mn (II) compounds for use in corrosion inhibitors are described in co-pending European application EP-A-672 749.

The organic silver coating is present at a level of from 0.05% to 10%, preferably from 0.1% to 5% by weight of the total composition.

The functional role of the silver coating agent is to form a "in use" protective coating layer on any silverware component of any dishwashing dish using the composition of the present invention.
As such, the silver coating must have a high affinity to adhere to the solid silver surface, especially when it is present as a component of the wash and bleach aqueous solutions used to treat the solid silver surface.

Suitable organic silver coating agents of the present invention include fatty acid esters of mono- or polyhydric alcohols having from 1 to 40 carbon atoms in the hydrocarbon chain.

The fatty acid part of the fatty ester can be obtained from mono- or polycarboxylic acids having 1 to 40 carbon atoms in the hydrocarbon chain. Suitable examples of monocarboxylic acid fatty acids include behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid, lauric acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid,
There are lactic acid, glycolic acid, and β, β′-dihydroxyisobutyric acid. Examples of suitable polycarboxylic acids include n-butyl-malonic acid, isocitric acid, citric acid, maleic acid, malic acid and succinic acid.

The fatty alcohol radical in the fatty ester can be represented by a mono- or polyhydric alcohol having 1 to 40 carbon atoms in the hydride chain. Examples of suitable fatty alcohols include behenyl, arachidyl, cocoyl, oleyl, and lauryl alcohol, ethylene glycol, glycerol, ethanol, isopropanol, vinyl alcohol, diglycerol, xylitol, sucrose, erythritol, pentaerythritol, sorbitol or sorbitan .

The fatty acid and / or fatty alcohol group of the fatty ester addition substance preferably has 1 to 24 carbon atoms in the alkyl chain.

The preferred fatty esters of the present invention are ethylene glycol, glycerol and sorbitan esters, where the fatty acid portion of the ester is usually selected from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid. Including types.

Glycerol esters are also very preferred. These are mono-, di- or tri-esters of glycerol and fatty acids as described above.

Specific examples of the fatty alcohol esters used in the present invention include: stearyl acetate, palmityl di-lactate, cocoyl isobutyrate, oleyl maleate, oleyl dimaleate, and talloyl proprionate. Fatty acid esters useful in the present invention include: xylitol monopalmitate, pentaerythritol monostearate, sucrose monostearate, glycerol monostearate, ethylene glycol monostearate, sorbitan esters. Suitable sorbitan esters include sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan monomyristate, sorbitan monobehenate, sorbitan monooleate, sorbitan dilaurate, sorbitan distearate, sorbitan dibehenate, sorbitan Dioleate,
And also mixed tallow alkyl sorbitan mono- and di-esters.

Glycerol monostearate, glycerol mono-oleate, glycerol monopalmitate, glycerol monobehenate, and glycerol distearate are preferred glycerol esters in the present invention.

Suitable organic silver coatings include triglycerides, mono- or diglycerides, and all or partially hydrogenated derivatives thereof, and mixtures thereof. Suitable sources of fatty acid esters include vegetable and fish oils and animal fats. Suitable vegetable oils include soybean oil, cottonseed oil, castor oil, olive oil, peanut oil, safflower oil, sunflower oil, rapeseed oil, grape seed oil, palm oil and corn oil.

Waxes, including microcrystalline waxes, are suitable organic silver coating agents in the present invention. Suitable waxes have a melting point in the range of 35 ° C to 110 ° C, and
Includes ~ 70 carbon atoms. Preferred are petroleum waxes of the paraffin and microcrystalline type. These consist of long chain saturated hydrocarbon compounds.

Alginate and gelatin are suitable organic silver coatings in the present invention. Dialkylamino oxides such as C ₁₂ -C ₂₀ methylamine oxide, and C ₁₂ -C ₂₀ dialkyl quaternary ammonium compounds and salts, such as ammonium halides are also suitable.

[0301] Other suitable organic silver coatings include several polymeric 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, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, And cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose are examples of such polymeric substances.

Some perfume materials, especially those that exhibit a high degree of direct adhesion to metal surfaces, are also useful as organic silver coatings in the present invention. Polymerizable soil release agents can also be used as the organic silver coating.

Preferred organic silver coating agents are paraffin oils, generally having 2 carbon atoms.
Preferred are paraffin oils having a ratio of cyclic to acyclic hydrocarbons of from 1:10 to 2: 1, preferably from 1: 5 to 1:
1 is selected from the broadly branched C _25-45 species. Paraffin oils having a cyclic to acyclic hydrocarbon ratio of 32:68 and meeting the above characteristics are intended to be used in winters.
tershall) (Salzbergen, Germany) under the trade name WINOG70.

Nitrogen-Containing Corrosion Inhibiting Compounds Suitable nitrogen-containing corrosion inhibiting compounds include imidazole and its derivatives such as benzimidazole, 2-heptadecyl imidazole and their imidazole derivatives. These are Czech patent 139,279 and British patent GB-A-1,1.
37,741 and also discloses a process for preparing imidazole compounds.

Also suitable as nitrogen-containing corrosion inhibiting compounds are pyrazole compounds and their derivatives, especially those in which the pyrazole is substituted at any of the 1, 3, 4 or 5 positions with substituents R ₁ , R ₃ , R ₄ and R _{5 wherein} R ₁ is H, CH ₂ OH, CO
NH ₃ , or COCH ₃ , R ₃ and R ₅ are either C ₁ -C ₂₀ alkyl or hydroxyl, and R ₄ is H, NH ₂ or NO ₂ .

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

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

Mn (II) Corrosion Inhibiting Compound The detergent tablets of the present invention can include a Mn (II) corrosion inhibiting compound.
The Mn (II) compound is preferably present at a level of from 0.005% to 5%, more preferably from 0.01% to 1%, most preferably from 0.02% to 0.4% by weight of the composition. Included in. Preferably, the Mn (II) compound is present in any bleaching solution at a level that provides from 0.1 ppm to 250 ppm, more preferably from 0.5 ppm to 50 ppm, most preferably from 1 ppm to 20 ppm of Mn (II) ions. .

The Mn (II) compound may be an anhydrous salt or any hydrated 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 complex of an organic fatty acid, such as manganese acetate or manganese stearate.

The Mn (II) compound may be a salt or a complex of an organic ligand. In one preferred aspect, the organic ligand is a heavy metal ion sequestering agent. In another preferred aspect, the organic ligand is a crystal growth inhibitor.

Other corrosion inhibiting compounds Other suitable additional corrosion inhibiting compounds include mercaptans and diols, especially mercaptans containing from 4 to 20 carbon atoms, such as lauryl mercaptan, thiophenol, thionaphthol, thionalide and And thioanthranol. Further, saturated or unsaturated C ₁₀ -C ₂₀ fatty acids or their salts, in particular aluminum tristearate also suitable. C ₁₂ -C ₂₀ hydroxy fatty acids, or their salts, are also suitable. Also suitable are phosphonated octadecane and other antioxidants such as betahydroxytoluene (BHT).

Copolymers of butadiene and maleic acid, in particular Polysciences (Polysc
iences Inc. as trade reference no. 07787 has been found to be particularly useful as a corrosion inhibiting compound.

Hydrocarbon Oils Other suitable detergent components for use in the present invention are hydrocarbon oils, usually predominantly long chain aliphatic hydrocarbons having from 20 to 50 carbon atoms; and/
Or preferably it is branched; preferred hydrocarbon oils, the ratio of cyclic to non cyclic hydrocarbon is 1: 10 to 2: 1, more preferably 1: 5 to 1: 1 is, C ₂₅ was widely branched -C Select from ₄₅ types. The preferred hydrocarbon oil is paraffin. A paraffinic oil having a ratio of cyclic to acyclic hydrocarbons of 32:68, meeting the characteristics outlined above, is available from WINTERG (Salzbergen, Germany).
It is sold under 70 trade names.

Water-Soluble Bismuth Compound The detergent tablet of the present invention, which can be suitably used in the dish washing method, can contain a water-soluble bismuth compound. It preferably comprises 0.005% to 20%, more preferably 0.01% to 5%, most preferably 0.1% by weight of the composition.
Present at １1% by weight level.

The water-soluble bismuth compound may be substantially any salt or complex of bismuth and substantially any inorganic or organic counter anion. Preferred inorganic bismuth salts are selected from bismuth trihalides, bismuth nitrate and bismuth phosphate. Bismuth acetate and bismuth citrate are preferred salts with organic counter anions.

Enzyme Stabilizing System Suitable enzymes contained in the compositions of the present invention comprise from 0.001% to 10%, more preferably from 0.005% to 8%, most preferably 0.01% by weight. ~ 6
% By weight of the enzyme stable system. The enzyme stable system can be any stable system that is compatible with the detergent enzyme. Such stable systems can include calcium ions, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, chlorine bleach scavengers and mixtures thereof. Such a stable system can also include a reversible enzyme inhibitor, such as a reversible protease inhibitor.

Lime Soap Dispersant Compound The tablets of the present invention may contain a lime soap dispersant compound, preferably from 0.1% to 40%, more preferably from 1% to 20%, by weight of the composition. ,
Most preferably it is present at a level of 2% to 10% by weight.

Lime soap dispersants are substances that prevent the precipitation of alkali metal, ammonium or amine salts of fatty acids by calcium or magnesium ions. Preferred lime soap dispersant compounds are disclosed in PCT Application No. WO 93/08877.

Foam Suppressing System When the detergent tablet of the present invention is formulated for use in a machine with a cleaning composition, the foam suppressing system is used in an amount of 0.01% to 15% by weight of the above composition, preferably 0.0
Preferably it is present at a level of 5% to 10%, most preferably 0.1% to 5% by weight.

Suitable foam control systems for use in the present invention include virtually any known antifoaming compounds, such as silicone antifoaming compounds, 2-alkyl and alkanol antifoaming compounds, and the like. . Preferred foam control systems and antifoaming compounds are disclosed in PCT applications WO 93/08876 and EP-A-705 324.

Polymerizable Dye Transfer Inhibitor The detergent tablet of the present invention comprises 0.01% by weight to 10% by weight, preferably 0.0% by weight.
5% to 0.5% by weight of a polymerizable dye transfer inhibitor can also be included.

The polymerizable dye transfer inhibitor is preferably a polyamine N-oxide polymer, N
-Selected from copolymers of vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or combinations thereof.

Detergent tablets that can be suitably used in the method of washing optical brightener selection, as described herein, include:
Optionally, from 0.005% to 5% by weight of any type of hydrophilic optical brightener can also be included.

Useful hydrophilic optical brighteners herein include those having the following structural formula:

[0325]

Embedded image

In the above formula, R ₁ is anilino, N-2-bis-hydroxyethyl and NH-2
- is selected from hydroxyethyl; R ₂ is N-2- bis - hydroxyethyl, N
Selected from -2-hydroxyethyl-N-methylamino, morphino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.

Where R ₁ is anilino, R ₂ is N-2-bis-hydroxyethyl, and M is a cation such as sodium, the brightener is 4,4
'-Bis [(4-anilino-6- (N-2-bis-hydroxyethyl) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid and disodium salt. This particular type of brightener is available from Chiba-Geigy
Corporation under the trade name 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, R ₁ is anilino, and R ₂ is N-2-hydroxyethyl-N-2-
When methylamino and M is a cation such as sodium, the brightener is 4,4'-bis [(4-anilino-6- (N-2-hydroxyethyl-
N-methylamino) -s-triazin-2-yl) amino] 2,2'-stilbene disulfonate disodium salt. This particular type of brightener is commercially available from Ciba Geigy under the trade name Tinopal 5BM-GX.

Where R ₁ is anilino, R ₂ is morpholino, and M is a cation such as sodium, the brightener is 4,4′-bis [(4-anilino- 6-morpholino-s-triazin-2-yl) amino] 2,2′-stilbene disulfonic acid, sodium salt. This particular type of brightener is commercially available from Ciba Geigy under the trade name Tinopal AMS-GX.

Detergent tablets suitable for use in the clay softening laundry cleaning method can include a clay softener comprising a clay mineral compound and optionally a clay flocculant.

The clay mineral compound is preferably a smectite clay compound. Smectite clays are disclosed in U.S. Pat. Nos. 3,862,058, 3,948,790, 3,954,632, and 4,062,647. European patent applications EP-A-299,575 and EP-A-313,146 in the name of the Procter & Gamble Company describe suitable organic polymerizable clay flocculants.

Cationic fabric softeners Cationic fabric softeners can also be incorporated into the compositions according to the invention, which can be suitably used for cleaning and washing methods. Suitable cationic fabric softeners include GB-A-1 514 27
There are water-insoluble tertiary amines or dilong chain amide materials disclosed in US Pat.

The cationic fabric softener generally comprises from 0.5% to 15%, usually 1% by weight.
-5% by weight.

Other Optional Ingredients Other optional ingredients that may be suitably included in the compositions of the present invention include perfume and filler (filler) salts, with sodium sulfate being the preferred filler (filler) salt.

Composition pH The detergent tablets of the present invention are not preferably formulated to have an unduly high pH, having a pH of from 8.0 to 12.5, measured as a 1% solution in distilled water. Is preferred, 9.0 to 11.8 is more preferred, and 9.5 to 11.5 is most preferred.

Dishwasher Method Suitable methods for mechanically cleaning or cleaning soiled dishes are contemplated. A preferred dishwasher method involves dissolving or dissolving an effective amount of a detergent tablet according to the present invention with a dirty dish selected from porcelain, glassware, silverware, metalware, table knife, fork and spoon, and combinations thereof. Treating with the partitioned aqueous solution. An effective amount of a detergent tablet is an amount of 8 g to 60 g of the above product dissolved or dispersed in a 3 to 10 liter wash solution, which is a typical product dosage commonly used in conventional dishwashers. And washing liquid capacity. The detergent tablet preferably weighs from 15 to 40 g, more preferably from 20 to 35 g.

Laundry Washing Method The washing method using a washing machine generally involves washing dirty laundry using a washing solution in which an effective amount of the detergent tablet composition for a washing machine according to the present invention is dissolved or distributed. Includes in-flight processing. An effective amount of a detergent tablet composition is 40 g to 300 g of the product dissolved or dispersed in a 5-65 liter wash solution, which is a typical product commonly used in conventional washing machine washing methods. Mean dose and wash volume.

In a preferred use aspect, a dispensing device is used in the washing method. The dispensing device is loaded with a detergent product and the product is inserted directly into the drum of the washing machine using the dispensing device before the start of the washing cycle. The volume of the dispensing device must be able to contain sufficient detergent products commonly used in the above washing methods.

As soon as the laundry is loaded into the washing machine, the dispensing device containing the detergent product is placed in a drum. At the beginning of the washing cycle of the washing machine, water is introduced into the drum and the drum rotates periodically. The design of the dispensing device can include a dry detergent product, but by vibrating the device during rotation of the drum during subsequent washing cycles and as a result of contact of the device with the wash water. , The product must be released.

The device can have a number of holes through which the product can pass so that the detergent product can be released during washing. Alternatively, the device can be made of a material that is permeable to liquids but impermeable to solid products. This allows the release of dissolved product. Preferably, the detergent product is released quickly at the beginning of the washing cycle, thereby resulting in a temporary high concentration of the product locally in the washing machine drum at this stage of the washing cycle.

The preferred dispensing device is reusable and is designed to maintain container integrity during dry conditions and washing cycles.

Alternatively, the dispensing device may be a flexible container such as a bag or pouch. The bag may be of a fibrous structure coated with a water impermeable material to retain the contents, as disclosed in European Patent Application No. 0018678. Alternatively, European Patent Applications 0011500, 0011501, 0011
As disclosed in 502 and 0011968, the ends may be formed from a water-insoluble synthetic polymer material that is sealed or closed, and may be adapted to break in aqueous solution. A common form of water-sensitive closure involves applying a water-soluble adhesive along one end of a pouch formed from a water-impermeable polymeric film such as polyethylene or polypropylene and sealing it.

[0343]

EXAMPLES Abbreviations Used in the Examples In the detergent composition of the present invention, the abbreviations of the components have the following meanings: STPP: sodium tripolyphosphate Bicarbonate (bicarbonate): sodium bicarbonate Citric Acid (citric acid) : Citric anhydride Carbonate: Sodium carbonate anhydrous Silicate: Amorphous sodium silicate (SiO ₂ : Na ₂ O ratio = 2.0) SKS-6: Formula δ-Na ₂ Si ₂ O ₅ the crystalline layered silicate PB1: anhydrous sodium perborate monohydrate nonionic (non-ionic): C ₁₃ -C ₁₅ mixed ethoxylated with an average degree of ethoxylation of 3.8 and an average propoxylated Le degree 4.5 / Propoxylated fatty alcohol; sold by BASF under the trade name Plurafac. TAED: tetraacetylethylenediamine HEDP: ethane 1-hydroxy-1,1-diphosphonic acid PAAC: pentaamine cobalt acetate (III) salt Paraffin: sold under the trade name Winog 70 from Wintershall Paraffin oil Protease: Protease Amylase: Starch degrading enzyme BTA: Benzotriazole Sulphate: Anhydrous sodium sulfate PEG3000: Polyethylene glycol with a molecular weight of about 3000 available from Hoechst PEG6000: From Hoechst Available polyethylene glycol of molecular weight approx. 6000 pH: measured as a 1% solution in distilled water at 20 ° C. In the following examples all levels are given as parts by weight:

Examples I-IV The following table shows examples of detergent tablets of the present invention that are suitably used in dishwashers.

[0345]

[Table 1]

A multi-layer tablet composition is prepared as follows. The first phase detergent active composition is prepared by mixing the granular and liquid ingredients and then passing through a conventional rotary press die. The press includes a punch in a form suitable for forming a mold. The cross section of the die is about 30 × 38 mm. The composition is then 940
When a compressive force of kg / cm ² is applied to raise the punch, the first phase of the tablet including the mold is exposed on the upper surface. A second phase detergent active composition is similarly prepared and passed through a die. The granular active composition is then subjected to a compressive force of 170 kg / cm ² and the punch is raised, causing the multilayer tablet to pop out of the tablet press. The resulting tablet dissolves or disintegrates within 12 minutes as described above, and the second phase of the tablet dissolves within 5 minutes. The tablets provide excellent dissolution and cleaning properties with good tablet integrity and tablet strength.

──────────────────────────────────────────────────続 き Continuation of front page (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, FI, 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) CINCINNATI, OHIO, UNITED STATES OF AMERICA (72) Inventor Benny, Brenda Francis United Kingdom, Northern Barland, NNY 23, 9Fs, Cramlington, Dela Mia, Crescent 34A (72) Inventor Binder, Christopher James UK Country, Newcastle, Upon, Tyne, NE2, 2D, Jesmond, Saint, Georges, Terrace 116 F-term (reference) 4H003 AC08 AC23 BA03 BA17 CA08 DA01 DA19 EA06 EA09 EA12 EA15 EA16 EA19 EA20 EB02 EB08 EB20 EB24 EB26 EB36 EB41 EC01 EC02 EE05 FA32 FA43

Claims (18)

[Claims] 1. A multi-phase detergent tablet for use in a washing machine, comprising: a) a first phase in the form of a compact having at least one mold; and b) a particulate solid compacted in said mold. A tablet comprising a second phase of a shape. 2. The multi-phase detergent tablet of claim 1, wherein the second phase is compressed at a pressure of less than about 350 kg / cm ² . 3. A multi-phase detergent tablet for use in a washing machine, comprising: a) in a first phase in the form of a compression molding having at least one mold, said molding comprising at least about 350 kg / cm ² . Said first phase produced under compaction pressure; b) a second phase in the form of a granular solid compacted in said mold, comprising about 350 kg
/ Said second phase compressed at a pressure of less than / cm ² . 4. The multiphase detergent tablet according to claim 1, wherein the second phase dissolves faster than the first phase. 5. The multi-phase detergent tablet according to claim 1, wherein the second phase dissolves in the dishwasher within 5 minutes. 6. A multi-phase detergent tablet for use in a washing machine, comprising: a) a first phase in the form of a compact having at least one mold; b) a granular solid compacted in said mold. Wherein the tablet comprises at least one detergent active, wherein at least 50%, preferably at least 60%, more preferably at least 80% by weight of the detergent active is 10%.
Said multi-phase detergent tablet being formulated to be supplied to the wash water within minutes, preferably within 5 minutes, more preferably within 3 minutes. 7. A multi-phase detergent tablet for use in a washing machine, said tablet comprising: a) a first phase in the form of a compact having at least one mold; b) compressed in said mold. Wherein the tablet composition comprises enzymes, bleaches, bleach activators, bleach catalysts, surfactants, chelating agents, crystal growth inhibitors and mixtures thereof. The multi-phase detergent tablet comprising one or more selected detergent actives. 8. The multiphase detergent tablet according to claim 1, wherein the second phase additionally comprises a breaking agent. 9. The multiphase detergent tablet according to claim 1, wherein the second phase contains an enzyme. 10. A multiphase detergent tablet for use in a washing machine, said tablet comprising: a) a first phase in the form of a compact having at least one mold; b) compressed in said mold. Said multiphase detergent tablet comprising a second phase in the form of a granular solid. 11. Multi-phase detergent tablet according to claim 1, wherein the first and / or second phase comprises a binder. 12. The multiphase detergent tablet according to claim 11, wherein the binder is selected from the group consisting of sugar and sugar derivatives, starch and starch derivatives, inorganic and organic polymers. 13. The method of claim 1, further comprising a barrier phase between the first and second phases.
13. The multi-phase detergent tablet according to any one of claims 12 to 12. 14. The multiphase detergent tablet of claim 13, wherein said barrier layer comprises a binder provided in liquid form. 15. A composition comprising: a) compressing a first detergent active composition to form a first phase comprising a mold; b) feeding a second detergent active composition in particulate form to said mold; c) said granular detergent. A method of making a multi-phase detergent tablet comprising the steps of compressing a composition into said mold. 16. The method of claim 15, wherein said second detergent composition is compressed at a pressure of less than 350 kg / cm ² . 17. A method of washing with a washing machine, comprising inserting one or more multi-phase detergent tablets according to any one of claims 1 to 14 into the washing machine. 18. The method of claim 17, wherein the multiphase detergent tablet dissolves or disintegrates in a dishwasher in less than 15 minutes according to the dissolution test method of the present invention.