JP2001512784A - Tablet detergent - Google Patents

Abstract

(57) The present invention is directed to a tablet detergent comprising a core and a coating, wherein the core has a diametral fracture stress of less than 15 kPa and comprises a non-gelling binder. Wherein the coated tablet detergent has a diametral breaking stress of at least 20 kPa. In another aspect of the invention, a tablet detergent having a diametral breaking stress of at least 20 kPa, wherein three tablets weighing 60 g are placed on the bottom of a drum of a Miele ^R W831 washing machine, and a miscellaneous fabric Was placed on a tablet in a 2.5 kg drum in a stress test consisting of running the washing machine using a short cycle of “white cloth / colored product” at 30 ° C. and remaining at the end of the washing machine cycle. Is provided that yields less than 18 g.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a tablet detergent, particularly to a tablet detergent suitable for use in laundry.

[0002] Washing compositions in the form of tablets have often been proposed, but despite the product having several advantages in unit-dispensing form, any product (other than bar soap for body washing) has been proposed. He has never had substantial success. One reason for this may be that tablet detergents usually dissolve more slowly than the powders that make them up. This is simply because the component powders are compacted together under force into tablets, with relatively little opportunity for water to penetrate between them. This results in a slowly melting tablet
The problem is that residues which can be seen through the door of the washing machine during the washing cycle and / or residues which adhere to the fabric at the end of the washing cycle are produced.

[0003] European Patent Application No. A-0 716 1 published June 12, 1996
No. 44 discloses an acrylic / maleic copolymer, polyethylene glycol,
Disclosed are tablet laundry detergents having a water-soluble coating that may be PVPVA and organic polymers including sugars. This specification states that the diametral breaking stress of the tablets of the invention is preferably at least 5 kPa. The tablet disintegration rate is measured by a test using a wire mesh.

[0004] However, in some types of washing machines where laundry is loaded from the front, the problem of visible tablet residues still appearing in the washing machine windows is still seen.

[0005] It is an object of the present invention to provide a tablet having a core formed by compressing a particulate material comprising a surfactant and a detergent builder, which can be stored, transported and handled without breaking. To provide tablets suitable for

[0006] A further object of the present invention is to readily disintegrate and rapidly release the active ingredient into the cleaning solution, yet completely dissolve in alkaline or surfactant-rich solutions such as laundry liquors. To provide a tablet comprising a soft core which disintegrates and disperses into a tablet.

[0007]

[Summary of the Invention]

An object of the present invention is a tablet detergent comprising a core and a coating, wherein the core has a diametral fracture stress of less than 15 kPa and comprises a non-gelling binder. The crushing stress in the diameter direction of the tablet detergent is at least 20 k
It is achieved by providing what is Pa.

In a further aspect of the invention, the diametral fracture stress is at least 20 kPa
A tablet detergent, three tablets weighing 60 g, placed on the bottom of the drum of a Miele ^R W831 washing machine, 2.5 kg of miscellaneous fabric, placed on the tablets in the drum, at 30 ° C. In a stressed test consisting of running the washing machine using a short cycle of "white cloth / colored goods", a tablet detergent is provided which produces less than 18 g of residue at the end of the washing machine cycle.

In a further aspect of the present invention, there is provided a method of dispensing a tablet detergent from a dispensing drawer of a washing machine of the type which loads laundry from the front.

DETAILED DESCRIPTION OF THE INVENTION The tablet detergents of the present invention are made by simply mixing the solid components and compressing the mixture on a conventional tablet press, such as is used in the pharmaceutical industry. be able to. The main component, especially the gelling surfactant, is preferably used in the form of particles. Any liquid component, such as a surfactant or foam inhibitor, can be incorporated into the solid particulate component in a conventional manner.

Particularly for laundry tablets, components such as builders and surfactants can be spray-dried in a conventional manner and then compressed at a suitable pressure.

[0012] The tablet detergent may be made of any size and shape and, if desired, may be subjected to a surface treatment according to the present invention prior to coating. The tablet core includes a surfactant and a builder that generally defines a substantial portion of the tablet's detergency.
The term "builder" is used to ion-exchange, complex,
Any substance that tends to be removed, either by sequestration or by precipitation, is meant.

[0013] The granules used to make the tablets of the present invention can be made by any granulation method or granulation method. One example of such a method is spray drying (in a co-current or counter-current spray-drying tower), which typically results in a low bulk density of 600 g / l or less. Higher density particulate material is by granulation, densification in a high shear batch mixer / granulator, or (e.g. Lödige ^R CB mixer, and / or for using a Lödige ^R KM mixers) It can be made by continuous granulation / densification method. Other suitable methods include fluidized bed, compression (eg, roll compaction), extrusion, and any particulate material made by any chemical method such as coagulation, crystallization sintering, etc. Is included. The individual particles can be any other particles, granules, spheres, or coarse particles.

[0014] The particulate matter can be mixed by any conventional means.
For example, a batch is suitable for a concrete mixer, a noter mixer, a ribbon mixer and the like. Alternatively, the mixing process is weighed for each component and sent to a moving belt,
It may be done continuously by mixing them in one or more drums or mixers. A mixture of some or all of the particulate matter can be sprayed with a non-gelling binder. Other liquid components can also be sprayed separately or premixed onto the mixture of particulate matter. For example, a slurry of a fragrance or a fluorescent whitening agent can be sprayed. After spraying the binder, a fine flow aid (powder such as zeolite, carbonate, silica) can be added to the particulate material, preferably near the end of the process, to reduce the stickiness of the mixture. .

[0015] Tablets may be compressed using any compression method, such as tableting, blocking, or extruding.
And preferably by tableting. Suitable equipment includes standard
Single stroke press, or (Courtoy^R, Korch^R, Manesty ^R Or Bonals^RRotary press). According to the invention
The tablets prepared above preferably have a diameter of 40 to 60 mm and a weight of 25 to 100 g.
No. The ratio of thickness to diameter (or width) of the tablet is preferably greater than 1: 3,
: 2 is more preferable. The compression pressure used to make these tablets is 5
000kN / m²3,000 kN / m²Does not exceed
Most preferably 1000 kN / m²It is necessary not to exceed.

[0016] Suitable non-gelling binders include organic synthetic polymers such as polyethylene glycol, polyvinylpyrrolidone, polyacrylates, and water-soluble acrylate copolymers. The second edition of the Handbook of Pharmaceutical Excipients categorizes binders as follows: Acacia, alginic acid,
Carbomer, sodium carboxymethylcellulose, dextrin, ethylcellulose, gelatin, guar gum, hydrogenated vegetable oil type I, hydroxyethylcellulose, hydroxypropylmethylcellulose, liquid glucose, aluminum magnesium silicate, maltodextrin, methylcellulose, polymethacrylate, povidone, sodium alginate, starch, and Zein. The most preferred binders, such as cationic polymers such as ethoxylated hexamethylenediamine quaternary compounds and bishexamethylenetriamine, or others such as pentaamine, ethoxylated polyethyleneamine, and maleic acrylic polymers, are used during laundry washing. It also shows an effective cleaning action.

Preferably, the non-gelling binder material is sprayed on, so that it does not exceed 70 ° C., preferably 5 ° C., so as not to damage or degrade other active ingredients in the matrix.
It preferably has a suitable melting point of 0 ° C. or less. Most preferred are non-aqueous liquid binders (ie, not aqueous solutions) that can be sprayed in dissolved form
It is. However, the binder may also be a solid binder that binds in the tablet, which is incorporated into the matrix by dry addition.

The non-gelling bander material is preferably used in an amount of from 0.1 to 15%, more preferably not more than 5% of the composition, and especially if it is not a laundry effective material, a tablet Is preferably used in an amount of 2% by weight or less.

It is preferable that a gelling binder such as a nonionic surfactant should not be in a liquid form or in a dissolved form. Nonionic surfactants and other gelling binders are not excluded from the composition and it is preferred that they be processed into a tablet detergent rather than as a component of a particulate material and as a liquid.

In one embodiment of the invention, the tablet can then be coated so that the tablet does not absorb moisture or absorbs it only at a very slow rate. The coating is also robust, so that only moderate levels of mechanical impact on the tablet during handling, packaging, and transport disrupts or wears at very low levels. Finally, the coating is preferably brittle so that the tablet disintegrates when subjected to a stronger mechanical impact. It is further advantageous if the coating substance is soluble under alkaline conditions or is easily emulsified with a surfactant. This helps to avoid the problem of visible residue on the windows of washing machines of the front-loading type during the washing cycle and also coats the laundry on the washing machine. Prevents undissolved particles and lumps from adhering.

The degree of water solubility is determined by referring to “Standard Test Method for Measurements of Aqueous Solubil
measured according to the ASTM E1148-87 test protocol entitled "ity".

A suitable coating substance is a dicarboxylic acid. Particularly suitable dicarboxylic acids are oxalic acid,
It is selected from the group consisting of malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, tridecandioic acid, and mixtures thereof.

The coating material preferably has a melting point between 40 and 200 ° C. The coating can be applied in a number of ways. Two preferred coating methods are a) coating with a dissolved substance and b) coating with a solution of the substance.

In a), the coating substance is applied at a temperature above its melting point and solidifies on the tablet.
In b), the coating is applied as a solution and the solvent is dried, leaving a coherent coating. Substantially insoluble materials can be applied to tablets, for example, by spraying or dipping. When spraying the dissolved substance onto tablets, it usually solidifies rapidly, forming a coherent film. Also when the tablet is immersed in the melted material and then taken out, the rapid cooling causes a rapid solidification of the coating material. Apparently substantially insoluble substances with melting points below 40 ° C. are not sufficiently hard at ambient temperature. The melting point is about 20
It has been found that substances above 0 ° C. cannot be used in practice. The coating material is 60-1
It is preferably a substance that melts at 60 ° C, more preferably at 70 to 120 ° C.

“Melting point” means the temperature at which a slowly heating substance, for example in a capillary, becomes a clear liquid.

A coating of any desired thickness can be applied according to the present invention. For most purposes, the coating will comprise from 1 to 10% of the tablet weight, preferably from 1.5 to 5%.

The tablet coating of the present invention is very hard, providing additional strength to the tablet.

In a preferred embodiment of the invention, the destruction of the coating in the washing liquor is improved by adding a disintegrant to the coating. This disintegrant swells once in contact with water,
It breaks the coating into small pieces. This improves the solubility of the coating in the washing solution. The disintegrant is present in the coating melt in an amount of not more than 30% by weight, preferably 5% by weight.
Suspended at a level of -20% by weight, most preferably 5-10% by weight. Possible disintegrants are those described in "Handbook of Pharmaceutical Excipients" (1986). Examples of suitable disintegrants include: starch: natural starch, modified starch, pregelatinized starch, sodium gluconate starch; gum: agar gum, guar gum, locust bean gum, karaya gum, pectin gum, tragacanth gum; croscarmylose sodium , Crospovidone, cellulose, carboxymethylcellulose, alginic acid, and salts thereof including sodium alginate, silicon dioxide,
Includes clay, polyvinylpyrrolidone, soy polysaccharides, ion exchange resins, and mixtures thereof.

Depending on the composition of the starting materials and the shape of the tablets, the compression force used is adjusted so that the strength (diametral breaking stress) and the disintegration time in the washing machine are not affected. This method can be used to make homogeneous or layered tablets of any size or shape.

The diametral fracture stress (DFS) is one method of indicating tablet strength and is determined by the following equation: = 2F / μDt where F is the maximum force (Newtons) that causes tensile failure (fracture) as measured by a VK200 tablet hardness tester supplied by Van Kell Industries. D is the diameter of the tablet and t is the thickness of the tablet.

“Method Pharmaceutical Dosage Forms: Tablets”, Vol. 2, pp. 213-217. Tablets with a diametral breaking stress of less than 20 kPa are considered brittle, and it appears that some broken tablets will reach consumers. The fracture stress in the diameter direction is
It is preferably at least 25 kPa.

The disintegration rate of a tablet detergent can be measured by two methods.

A) Method in a “Wankel” crusher with a “Wankel-type” drum. -Weight and D.E. F. S. Put two tablets known to the crusher drum. -Rotate the drum 20 times; -Collect all of the disintegrated and remaining tablet pieces from the crusher drum and screen what remains on the 5 mm sieve and what passes through the 1.7 mm sieve. -What remains on the 5 mm sieve and what passes through the 1.7 mm sieve is expressed in%. The greater the percentage of material that passes through the 1.7 mm sieve, the better the disintegration.

B) A method in a washing machine according to the following method. Three tablets weighing nominally 60 grams are weighed and then placed on the bottom of the washing drum of a Miele ^R W831 washing machine of the type that loads laundry from the front. Thereafter, a 2.5 kg clean ballast consisting of eight terry towels, five T-shirts, and five kitchen towels is packed in a washing machine. Set the washing temperature of the washing machine to 30 ° C., set the water supplied to the washing machine to a hardness of 21 grains per gram, and set the washing cycle to “white cloth / colored goods, short cycle” in the washing program. .

At the end of the whole cycle, the residue is removed from the washing liquid and the residue adhering to the opening of the front window is collected and their total weight is measured. This procedure is repeated ten times to measure the level of the residue and the average level of the residue is calculated based on these ten measurements. In this stressed test, a residue of 18 g (ie, equivalent to 10% of the starting weight of the tablet) is considered a pass. Preferably, the residue is less than 10 g, more preferably less than 5 g.

In a more stress test, the washing machine is stopped after a 10 minute wash cycle, the residue is collected and weighed.

In another preferred embodiment of the present invention, the tablet further comprises an effervescent agent.

Foaming, as defined herein, refers to the generation of gas bubbles from a liquid as a result of the formation of carbon dioxide gas by a chemical reaction between a soluble acid source and an alkali metal salt of carbonic acid. Means That is,

Embedded image Further examples of acid sources, carbonate sources, and other foam systems are described in Pharmaceutical Dosage Form.
s: Tablets ", Vol. 1, pp. 287-291.

A foaming agent can be added to the tablet mixture in addition to the detergent component. The addition of this foaming agent to the tablet detergent improves the disintegration time of the tablet. The amount added is preferably 5 to 20% by weight of the tablet, most preferably 10 to 20% by weight. Preferably, the blowing agent should be added not as discrete particles, but as agglomerates of various particles or as a compact.

Due to the gas created by the effervescence of tablets, tablets have a higher D.D. F. S. And still exhibit the same disintegration time as non-effervescent tablets. D. of effervescent tablets F. S. Keeping the same as the non-effervescent tablet will accelerate the disintegration of the effervescent tablet.

[0041]Detergent surfactant Typically, levels from about 1 to about 55% by weight can be used in the present invention.
Non-limiting examples of surfactants include conventional C₁₁~ C₁₈Alkylbenzene sulfo
Nate ("LAS"), first branch and random C₁₀~ C₂₀Alkylsul
Fate ("AS"), formula CH₃(CH₂)_x(CHOSO_3-M⁺) CH₃And
CH₃(CH₂)_y(CHOSO_3-M⁺) CH₂CH₃(Where x and (y + 1
) Is an integer of at least about 7, preferably at least about 9, and M is water soluble
Cation, especially sodium)₁₀~ C₁₈2nd (2, 3)
Alkyl sulfate, unsaturated sulfate such as oleyl sulfate, C ₁₀ ~ C₁₈Alkylalkoxysulfate ("AExS"; especially EO1-7)
Ethoxy sulfate), C₁₀~ C₁₈Alkyl alkoxy carboxylates
(Especially ethoxycarboxylates of EO1-5), C₁₀~ C₁₈Glycerol
Ruether, C₁₀~ C₁₈Alkyl polyglycosides and the corresponding sulfur
Oxidized polyglycosides, and C₁₂~ C₁₈Alpha sulfonated fatty acid ester
Is included. If desired, a so-called narrow-peak alkyl ethoxylate or C₆ ~ C₁₂Alkylphenol alkoxylates (especially ethoxylates and mixed
C containing ethoxy / propoxy)₁₂~ C₁₈Alkyl ethoxylate ("AE
)), C₁₂~ C₁₈Betaine and sulfobetaine ("sultaine"), C₁₀ ~ C₁₈Conventional nonionic and amphoteric surfactants such as amine oxides
Agents can also be included in the overall composition. C₁₀~ C₁₈N-alkylpolyhydride
Roxy fatty acid amides can also be used. A typical example is C₁₂~ C₁₈ N-methylglucamide is included. International Patent Application No. WO 9,206,154
See the detailed book. Other sugar-derived surfactants include C₁₀~ C₁₈N- (3-me
N-alkoxy polyhydroxy fatty acids such as toxylpropyl) glucamide
Mids are included. For low foam, N-propyl to N-hexyl C₁₂~ C₁₈Guru
Camide can be used. C₁₀~ C₂₀Can also be used. High
If foaming is desired, the branched chain C₁₀~ C₁₆Soap may be used. Anion world
Mixtures of surfactants and nonionic surfactants are particularly useful. Other useful services
Native surfactants are those described in standard textbooks.

Builders The compositions of the present invention can optionally include detergent builders to help control the hardness of the inorganics. An organic builder can be used in addition to the inorganic builder. Builders are typically used in fabric laundering compositions to facilitate removal of particulate soil.

The level of the builder can vary greatly depending on the end use of the composition.

Inorganic or phosphorus-containing detergent builders include alkali metal, ammonium, and alkanolammonium salts of polyphosphoric acid (eg, tripolyphosphate, pyrophosphate, and glassy polymeric metaphosphate), phosphonates Alkali metal, ammonium and alkanol ammonium salts of acids, alkali metal salts of phytic acid,
Ammonium salts and alkanol ammonium salts, alkali metal salts of silicic acid, ammonium salts and alkanol ammonium salts, alkali metal salts of carbonic acid (including bicarbonate and sesquicarbonate), ammonium salts and alkanol ammonium salts, sulfuric acid Includes but is not limited to alkali metal, ammonium and alkanol ammonium salts, and alkali metal, ammonium and alkanol ammonium salts of aluminosilicate. However, in certain areas, non-phosphate builders are required. The compositions of the present invention may be used in the presence of so-called "weak" builders, such as citrate (compared to phosphates), or the so-called "under-built," which may be caused by zeolite builders or layered silicate builders. The important point is that it works surprisingly well in these conditions.

Examples of silicate builders include alkali metal salts of silicic acid, especially those having a SiO ₂ : Na ₂ O ratio of 1.6: 1 to 3.2: 1, or H 2 on May 12, 1987. . P. R
a layered silicate such as the layered sodium silicate described in U.S. Pat. No. 4,664,839 issued to IECK. NaSKS-6 (commonly abbreviated herein as "SKS-6") is the trade name for crystalline layered silicate sold by Hoechst. Unlike zeolite builders, NaSKS-6 silicate builders do not contain aluminum. NaSKS-6 is one having the form of delta _-Na 2 SiO ₅ of the layered silicate. This can be made in a manner as described in German Patent Application No. A-3,417,649 and German Patent Application No. A-3,742,043. Although SKS-6 is a highly preferred layered silicate for use in the present invention, in the general formula _{NaMSi x O 2x +1 · yH 2} O ( wherein, M is sodium or hydrogen,, x is 1.9 to 4
Is preferably 2, and y is a number from 0 to 20, preferably 0.
Other layered silicates can be used in the present invention, such as Various other layered silicates of Hoechst include NaSKS-5, NaSKS-7, and NaSKS-11 as the alpha, beta, and gamma forms.
As described above, delta-Na ₂ SiO ₅ (NaSKS-
Type 6) is most preferred. Other silicates, such as magnesium silicate, may be useful. It serves as an agent for freezing the granular formulation, as a stabilizer for oxygen-based bleaches, and as a component of a foam control system.

Examples of carbonate builders are alkaline earth metal salts of carbonic acid and alkali, as disclosed in German Patent Application No. 2,321,001 published Nov. 15, 1973. It is a metal salt.

In the present invention, aluminosilicate builders are useful. Aluminosilicate builders are very important in most heavy granular detergent compositions currently marketed,
It is also an important builder component in liquid detergent formulations. Aluminosilicate builder has an empirical formula

Embedded image Are included. Wherein z and y are integers of at least 6, the molar ratio of z to y is 1.0 to about 0.5, and x is an integer of about 15 to about 264. Useful aluminosilicate ion exchange materials are commercially available. The structure of these aluminosilicates may be crystalline or amorphous, and may be naturally occurring aluminosilicate or may be obtained by synthesis. A method for producing an aluminosilicate ion exchange material is disclosed in U.S. Pat. No. 3,985,669 to Krummel et al., Issued Oct. 12, 1976.
Preferred synthetic crystalline aluminosilicate ion exchange materials useful in the present invention are available under the names zeolite A, zeolite P (B), zeolite MAP, and zeolite X. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula

Embedded image It has. Where x is from about 20 to about 30, especially about 27. This material is what is known as zeolite A. In the present invention, dehydrated zeolite (x = 0 to 10) can also be used. Aluminosilicate has a diameter of about 0
. It preferably has a particle size of 1 to 10 microns.

[0048] Suitable organic detergent builders for the purposes of the present invention include, but are not limited to, various polycarboxylate compounds. As used herein, "polycarboxylate" refers to a compound having a plurality of carboxylate groups, preferably at least three carboxylate groups. Polycarboxylate builder,
Generally, it can be added to the composition in the form of an acid, but it can also be added in the form of a neutralized salt. When utilized in the form of a salt, salts of alkali metals, such as sodium, potassium, and lithium, or alkanol ammonium salts are preferred.

Included in the polycarboxylate builders are various types of useful substances. One important class of polycarboxylate builders is April 7, 1964.
As disclosed in U.S. Pat. No. 3,128,287 issued to Berg et al. And U.S. Pat. No. 3,635,830 issued to Jan. 18, 1972 to Lamberti et al. And ether polycarboxylates including oxydisuccinate. See also the "TMS / TDS" builder described in U.S. Pat. No. 4,663,071 issued May 5, 1987 to Bush et al. Suitable ether polycarboxylates include cyclic compounds, especially US Pat. Nos. 3,923,679, 3,835,163, 4,158,63.
Alicyclic compounds such as those described in US Pat. No. 5,120,874 and 4,102,903 are also included.

Other useful detergency builders include ether hydroxy polycarboxylates, copolymers of maleic anhydride and ethylene or vinyl methyl ether,
1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid, and various alkali metal salts, ammonium salts of polyacetic acids such as carboxymethyloxysuccinic acid, ethylenediaminetetraacetic acid and nitrilotriacetic acid; and In addition to substituted ammonium salts, melitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1
And polycarboxylates such as 3,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and their soluble salts.

Citrate builders, such as citric acid, and their soluble salts (especially the sodium salt) can be obtained from renewable sources and are biodegradable, making them heavy liquids. It is a particularly important polycarboxylate builder for detergent formulations. Citrates can also be used in particulate compositions, especially in combination with zeolite builders and / or layered silicate builders. Oxydisuccinates are also particularly useful for use in such combinations in such compositions.

The detergent compositions of the present invention include 3,3-dicarboxy-4-oxa-1 disclosed in Bush, US Pat. No. 4,566,984, issued Jan. 28, 1986. , 6-Hexanediolate and related compounds are also suitable. Useful succinic acid builders, C ₅ -C ₂₀ alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenyl succinic acid.
Specific examples of succinate builders include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2
-Pentadecenyl succinate and the like. Lauryl succinate is a preferred builder of this group and is described in European Patent Application No. 86200600.5 / 0,200,263 published November 5, 1986.

Other suitable polycarboxylates are described in US Pat. No. 4,144,226 to Crutchfield et al., Issued Mar. 13, 1979, and US Pat. No. 3,308,067. See also, Diehl U.S. Pat. No. 3,723,322.

Fatty acids, for example C ₁₂ -C ₁₈ monocarboxylic acids, alone or in combination with the abovementioned builders, in particular citrate builders and / or succinate builders, in the composition provide additional builder activity. Can be obtained. When fatty acids are used in this way, foaming properties are usually reduced. This is a point that the formulator must consider.

In situations where phosphorus-based builders can be used, and especially in the formulation of bars for use in manual laundry operations, the well known sodium tripolyphosphate, sodium pyrophosphate and ortho Various alkali metal salts of phosphoric acid, such as sodium phosphate, can be used. Ethane-1-hydroxy-1,1
Diphosphonates and other known phosphonates (eg, US Pat.
No. 59,581, No. 3,213,030, No. 3,422,021, No. 3,4
Phosphonate builders can also be used, such as 00,148, and 3,422,137).

Bleaching Agent The detergent composition of the present invention can optionally include a bleaching agent or a bleaching composition containing a bleaching agent and one or more bleaching activators. When present, the bleaching agent is typically about 1% to about 30% by weight of the detergent composition, especially for fabric laundering.
More typically at a level of about 5 to about 20% by weight. If present, the amount of bleach activator will typically be from about 0.1 to about 60%, more typically from about 0.5 to about 60%, of the bleach composition comprising the bleach plus the bleach activator. About 40%.

The bleach used in the present invention is a bleach useful in detergent compositions used for cleaning fabrics, for cleaning hard surfaces, or for other cleaning purposes now or to become known. Any of the agents may be used. These include oxygen bleaches, and other bleaches. In the present invention, a perborate bleach, for example, sodium perborate (for example, monohydrate or tetrahydrate) can be used.

Other types of bleaches that can be used without limitation include percarboxylic acid bleaches,
And their salts. Suitable examples of this type of bleach include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid, and diperoxide decane diacid. Such bleach is described in Hartma, published November 20, 1984.
U.S. Patent No. 4,483,781 to U.S. Patent Application No. 740,446 filed on June 3, 1985 by Burns et al .; European Patent Application published by Banks et al. on February 20, 1985. Nos. 0, 133, 354 and 1983
No. 4,412,934 issued to Chung et al. Highly preferred bleaches include B on January 6, 1987
Also included are 6-nonylamino-6-oxoperoxycaproic acid, as described in U.S. Patent No. 4,634,551 issued to Urns et al.

[0059] Peroxygen bleaches can also be used. Suitable peroxygen bleaching compounds include sodium carbonate hydrogen peroxide and its equivalent "percarbonate" bleach, sodium pyrophosphate hydrogen peroxide, urea hydrogen peroxide, and sodium peroxide .
Persulfate bleaches (eg, Oxone manufactured industrially by DuPont) can also be used.

Preferred percarbonate bleaches comprise dry particles having an average particle size of about 500 to about 1,000 micrometers, up to about 10% by weight of the particles being less than about 200 micrometers, and Less than about 10% by weight is greater than about 1,250 micrometers. The percarbonate can be optionally coated with a silicate, borate, or water-soluble surfactant. Percarbonates are available from various commercial sources, such as FMCC, Solvay, and Tokai Electrification.

Mixtures of bleaches can also be used.

A peroxygen bleach such as perborate or percarbonate is preferably combined with a bleach activator. A bleach activator is one that results in the in-situ production of the peroxyacid corresponding to the bleach activator in an aqueous solution (ie in a washing step). Various non-limiting examples of activators are described in U.S. Pat. No. 4 issued April 10, 1990 to Mao et al.
, 915,854, and U.S. Patent No. 4,412,934. Nonanoyloxybenzenesulfonate (NOBS) activators and tetraacetylethylenediamine (TAED) activators are typical, and mixtures thereof can also be used. See also U.S. Pat. No. 4,634,551 for other typical bleaches and activators useful in the present invention.

Highly preferred amide-derived bleach activators have the formula

Embedded image belongs to. Wherein R ¹ is an alkyl group having about 6 to about 12 carbon atoms, R ² is alkylene having 1 to about 6 carbon atoms, and R ⁵ is H or about 1 to about 10 carbon atoms. Is alkyl, aryl, or alkaryl, and L is any suitable leaving group. A leaving group is any group that leaves a bleach activator as a result of nucleophilic attack on the bleach activator by hydrogen peroxide decomposing anions. A preferred leaving group is phenylsulfonate.

Preferred examples of bleach activators of the above formula include (6-octanamido-caproyl) oxybenzenesulfonate, (6-nonanamide-) as described in US Pat. No. 4,634,551. Caproyl) oxybenzenesulfonate,
(6-decaneamido-caproyl) oxybenzenesulfonate, and mixtures thereof. This patent is incorporated herein by reference.

Another type of bleach activator is the Hodge, published October 30, 1990.
And benzoxazine-type activators disclosed in U.S. Patent No. 4,966,723. This patent is incorporated herein by reference. Very preferred activators of the benzoxazine type are

Embedded image It is.

Another class of preferred bleach activators includes acyllactam activators, especially acylcaprolactams of the formula: and acylvalerolactam.

Embedded image In the formula, R ⁶ is H or an alkyl group having 1 to about 12 carbon atoms, an aryl group, an alkoxyaryl group, or an alkaryl group. Highly preferred lactam activators include benzoylcaprolactam, octanoylcaprolactam, 3,5,5-
Trimethylhexanoylcaprolactam, nonanoylcaprolactam, decanoylcaprolactam, undecenoylcaprolactam, benzoylvalerolactam, octanoylvalerolactam, decanoylvalerolactam, undecenoylvalerolactam, nonanoylvalerolactam, 3,5,5-trimethyl Hexanoyl valerolactam, and mixtures thereof. S on October 8, 1985
See also U.S. Patent No. 4,545,784 issued to Anderson. This patent is incorporated herein by reference. This patent discloses acylcaprolactam, including benzoylcaprolactam, adsorbed on sodium perborate.

Bleaches other than oxygen bleaches are known in the art and can be used in the present invention. One type of non-oxygen bleach that is of particular interest is:
Photoactive bleaches such as sulfonated zinc and / or aluminum phthalocyanine are included. See U.S. Pat. No. 4,033,718 issued to Holcombe et al. On July 5, 1977. If used, compositions typically contain from about 0.025 to about 1.25% by weight of such bleaches, especially zinc phthalocyanine sulfonate.

If desired, the manganese compound can catalyze the bleaching compound.
Wear. Such compounds are well known in the art and include, for example,
U.S. Pat. No. 5,246,621; U.S. Pat. No. 5,244,594;
No. 5,194,416; U.S. Pat. No. 5,114,606;
Patent Application Publication Nos. 549,271A1, 549,272A1, and 544
No. 440A2 and No. 544,490 A1.
Gun based catalysts are included. Preferred examples of these catalysts include Mn^IV ₂ (U-O)₃(1,4,7-trimethyl-1,4,7-triazacyclononane
)₂(PF₆)₂, Mn^III ₂(U-O)₁(U-OAc)₂(1,4,7-
Trimethyl-1,4,7-triazacyclononane)₂(ClO₄)₂, Mn^IV ₄ (U-O)₆(1,4,7-triazacyclononane)₄(ClO₄)₄, Mn ^III Mn^IV ₄(U-O)₁(U-OAc)₂(1,4,7-trimethyl-1
, 4,7-Triazacyclononane)₂(ClO₄)₃, Mn^IV(1,4,7-
Trimethyl-1,4,7-triazacyclononane)-(OCH₃)₃(PF₆)
, And mixtures thereof. Other metal-based bleach catalysts
U.S. Patent Nos. 4,430,243 and 5,114,611.
Includes those disclosed in the specification. Various manganese to improve bleaching
Use with complex ligands is also described in U.S. Pat. Nos. 4,728,455 and 5,2.
Nos. 84,944, 5,246,612, 5,256,779, and 5,2
Nos. 80,117, 5,274,147, 5,153,161, and 5
, 227,084.

As a practical matter, and not by way of limitation, the compositions and methods of the present invention provide an effective bleach catalyst species in aqueous laundry liquors of approximately 1 / 10,000,000,000,000.
Parts and more than about 0.1 to about 0.1% of the catalyst species in the washing liquid.
Preferably, it provides about 700 ppm, more preferably about 1 to about 500 ppm.

For various washing purposes of the fabric, including the removal of soils based on enzymes such as proteins, carbohydrates or triglycerides, and to prevent the migration of fallen dyes, Enzymes can also be included in the formulations of the present invention for fabric recovery. The enzymes to be incorporated include protease, amylase, lipase, cellulase, and peroxidase, and mixtures thereof. Other types of enzymes can also be included. They may be obtained from any suitable source, such as from plants, animals, bacteria, fungi, and yeasts.
However, their choice depends on several factors, such as optimal pH activity and / or stability, thermal stability, stability versus active ingredient, builder, and the like. In this regard, bacterial and fungal enzymes such as bacterial amylase and protease and fungal cellulase are preferred.

[0071] Enzymes are usually formulated at a level sufficient to provide no more than about 5 mg, more typically about 0.01 to about 3 mg, of the active enzyme per gram of the composition. Unless otherwise noted, the compositions of the present invention typically contain about 0.001 to about 5%, preferably 0.01 to 1%, by weight of a commercially available enzyme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide an activity of 0.005 to 0.1 Anson units (AU) per gram of composition.

A suitable example of a protease is subtilisin obtained from a particular strain such as B. subtilis or B. licheniforms. Another suitable protease is obtained from one strain of the genus Bacillus that exhibits maximum activity in the pH range of 8 to 12, and is developed and sold by Novo Industries under the registered trade name Esperase. Things. The preparation of this and similar enzymes is described in Novo GB 1,243,784. Commercially available proteolytic enzymes suitable for removing protein-based soils include the trade names Alcalase and Savinase from Novo Industries (Denmark) and Maxatase from International BioSynthetics (Netherlands). Includes those sold under the trade name. Other proteases include Protease A (see European Patent Application No. 130,756 published January 9, 1985) and Protease B (see European Patent Application filed April 28, 1987). No. 8733761.8 and European Patent Application No. 130,756 to Bott et al., Published Jan. 9, 1985).

Amylases include, for example, α-amylases described in GB 1,296,839 (Novo), rapidase from International Biosynthetics, and Termamyl from Novo Industries. .

Cellulases that can be used in the present invention include both bacterial and fungal cellulases. Their optimum pH is preferably between 5 and 9.5. Suitable cellulases are described in Barbesgo, published March 6, 1984.
No. 4,435,307 to Ard et al. This patent specification discloses fungal cellulases produced by Humicola insolens or Humicola strain DSM1800, or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulases extracted from the hepatopancreas of marine molluscs (Dolabella Auricula Solander). Is disclosed. Suitable cellulases are described in British Patent Application No. A-2.
No. 075.028, British Patent Application No. A-2.095.275 and German Patent Application No. 2.247.832. Kalezyme (
Novo) is particularly useful.

Suitable lipase enzymes for detergent applications include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154 disclosed in GB 1,372,034. included. See also the lipase described in Japanese Patent Application No. 53/20487 published Feb. 24, 1978. This lipase is available from Amano Pharmaceutical Co., Ltd. in Nagoya, Japan, under the trade name Lipase P "Amano" (hereinafter referred to as "Amano P"). Other commercially available lipases include Amino CES, a lipase obtained from Chromobacter viscosum such as Chromobacter viscosum var.lipolyticum NRRLB3673, marketed by Toyo Brewing Co., Ltd. in Tagata, Japan; Chemical and other Chromobacter viscosum lipases from Disoins of the Netherlands and lipases from Pseudomonas gladioli. Humicola lanug
The lipolase enzyme obtained from inosa and marketed by Novo (see also EP 341 947) is a preferred lipase for use in the present invention.

The peroxidase enzyme is a source of oxygen such as percarbonate, perborate, persulfate,
Used in combination with hydrogen peroxide and the like. They are used for "solution bleaching", i.e. to prevent the transfer of dyes or pigments that have fallen off the substrate during the washing operation to other substrates in the washing liquor. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidases such as chloroperoxidase and bromoperoxidase. The peroxidase-containing detergent composition is described in, for example, O.D., published October 19, 1989, and assigned to Novo Industries, Inc. PCT International Patent Application No. WO89 / by Kirk
No. 099813.

Various enzyme substances and various means for incorporating them into synthetic detergent compositions include:
U.S. Pat. No. 3,55, issued to McCarty et al. On January 5, 1971.
No. 3,139 is also disclosed. Enzymes are further described in US Pat. No. 4,101,457 to Place et al., Issued Jul. 18, 1978;
Hughes, U.S. Pat. No. 4,507,219, issued Aug. 26, is incorporated herein by reference. For useful enzyme substances in liquid detergent formulations and their incorporation into such formulations, see Hor, published April 14, 1981.
a, et al., U.S. Pat. No. 4,261,868. Enzymes used in detergents can be stabilized by various techniques. Enzyme stabilization technology is 197
U.S. Pat. No. 3,600,31 issued to Gege et al.
No. 9 and Venegas published European Patent Application No. 0 199 405 published Oct. 29, 1986 (Application No. 86200586.5). Enzyme stabilization systems are described, for example, in US Pat.
No. 19,570.

Other components commonly used in detergent compositions and which can be incorporated into the tablet detergents of the present invention include chelating agents, soil release agents, soil redeposition inhibitors,
Includes dispersants, brighteners, foam inhibitors, fabric softeners, dye transfer inhibitors, and fragrances.

Putting the tablet laundry detergent together with the laundry into the laundry drum means
Are known. However, this method has a tendency to produce considerable visible residue on the windows, especially in certain washing machines designed to work with low water. In extreme cases, at the end of the washing cycle, visible residue may also remain on the fabric.

The present invention also relates to a washing method which avoids this problem significantly. This new method consists of preparing an aqueous laundry detergent solution for use in a washing machine of the type that puts laundry in from the front side having a drawer for dispensing and a drum for washing, in which a tablet detergent is dissolved in water. In the method of making an aqueous laundry detergent solution, a tablet-type detergent is placed in a dispensing drawer, and water is passed through the dispensing drawer so that the tablets are dispensed as an aqueous solution of the laundry detergent. It is characterized by being passed through a washing drum.

Although any tablet detergent may be used in the method of the present invention, the tablets described herein may be used to remove the residue from the dispensing drawer without leaving a residue in the dispensing drawer. It turned out to be the most completely dispensed. Tablet density is 0.9-1.1 g / cc
And more preferably 0.95 to 1.05 g / cc.

Example Composition 1 Composition 2 Composition 3 Anionic surfactant aggregate 28.69 28.99 34.80 Nonionic surfactant aggregate 5.93 5.93-Cationic surfactant aggregate--5.51 Bleach activator aggregate 6.10 6.10 4.53 Sulfonic acid Zinc phthalocyanine inclusion 0.03 0.03 0.03 Foam inhibitor 3.46 3.46 1.89 Dry zeolite 6.75 6.75-Layered silicate 14.67 14.67 10.68 Migrant anti-migration 0.14 0.14-Perfume inclusion 0.25 0.25-AE7 / PEG4000 spray 5.82 5.82-PEG200-1.20 -Diamine quat 1.50-1.08 Optical brightener 0.28 0.28 0.183 Sodium carbonate 5.02 5.02 13.96 Sodium perborate monohydrate 17.80 17.80-Sodium percarbonate--14.33 Sodium HEDP 0.85 0.85 0.74 Soil release polymer 0.19 0.19 0.33 Fragrance 0.35 0.35 0.46 Protease 0.92 0.92 0.89 Cellulase 0.27 0.27 0.21 Lipase 0.23 0.23 0.275 Amylase 0.75 0.75 1.04 Citric acid-- 7.16 Soap--1.90 Total 100.00 100.00 100.00

The anionic surfactant agglomerates were 38% anionic surfactant and 22% zeolite
, And 40% carbonate. Nonionic surfactant aggregates consist of 26% nonionic surfactant and 48% zeolite.
, And 26% of carbonate. Cationic surfactant agglomerates consist of 24% cationic surfactant (alkylhydroxyethyl dimethyl ammonium chloride), 64% zeolite, and 12% sulfate.
%. The bleach activator agglomerates consist of 81% TAED, 17% acrylic / maleic copolymer (in acid form), and 2% water. The active ingredient in the zinc sulphonate phthalocyanine fill is 10%. Foam suppressants were 11.5% silicone oil (Dow Corning) and starch 88.
. It consists of 5%. The layered silicate is composed of Hoechst SKS-6 78% and citric acid 22%. The migration inhibitor agglomerates consist of 21% PVNO / PVPVI, 61% zeolite, and 18% carbonate. The perfume fill consists of 50% perfume and 50% starch. The AE7 / PEG4000 propellant comprises 83% of C12-C15 AE7 (alcohol having an average of 7 ethoxy groups per molecule) and 17% of polyethylene glycol having an average molecular weight of 4000. PEG 200 is a polyethylene glycol having an average molecular weight of 200. Diamine quat is an ethoxylated hexamethylene diamine quaternary compound.

Example 1 A detergent base powder of Composition 1 is prepared by the following steps.

A mixture of nonionic surfactant and AE7 / PEG4000 is sprayed onto sodium perborate in a mixing drum. After spraying, the perborate containing the nonionic surfactant is dusted with a zeolite to eliminate the possibility of binding with other powders; ethoxylated hexamethylenediamine quaternary compound (non- The gelling binder) is sprayed onto the layered silicate, bleach activator agglomerate, and carbonate; then the contents of these two mixing drums are mixed with the remaining particulate material of Composition 1 to form a homogeneous Form particles.

Then, in a mixing drum, 80 parts of composition 1, 15 parts of sodium acetate, and 5 parts of an effervescent mixture of 54.5% sodium bicarbonate and 45.5% citric acid are mixed.

Then, 55 g of this mixture is introduced into a circular mold (diameter 54 mm) and compressed to obtain a tablet having a thickness of 21 mm and a density of 1.1 g / cc, thereby producing a tablet.
The breaking stress in the diameter direction is 6 kPa.

The tablets are then immersed in a coating bath heated to 140 ° C., containing 90 parts of dodecanediacid mixed with 10 parts of Nimcell z6b16. The tablets are left in the bath long enough to apply 5 g of coating, after which the tablets are removed and
Cool at 24 ° C. for 24 hours. This coating increases the fracture stress in the diametrical direction,
It becomes larger than Pa.

Example 2 A detergent base powder of Composition 2 is prepared by the following steps.

A mixture of nonionic surfactant and AE7 / PEG4000 is sprayed onto sodium perborate in a mixing drum. After spraying, the perborate, which has absorbed a nonionic surfactant, is ground with a zeolite in order to eliminate the possibility of binding with other powders; PEG 200 (non-gelling binder) is coated with layered silica Spray salt, bleach activator agglomerate, and carbonate; and then compress 45 g of this composition to a thickness of 23 mm, density 1.1 g /
The method of Example 1 is repeated except that the tablet is 45 cc in diameter and 45 mm in diameter.

The puncture stress in the diameter direction of the uncoated tablet is 10.2 kPa.

A tablet detergent having the following properties is obtained. Example 1 Example 2 Diameter (mm) 55 45 Diameter breaking stress 24 kPa 30 kPa Residue after 10 minutes (g) 177 Residue at end of washing machine cycle (g) 7 2

[0093] In Example 1, and Example 2, three tablets, put together with the laundry drum Miele ^R W831 washing machine, used to wash the laundry.

Example 3 i) Detergent composition 3 is prepared as follows. All of the particulate matter of Base Composition 3, except diamine quat and fragrance, were mixed in a mixing drum to form a homogeneous particle mixture. During this mixing, the diamine quat and the fragrance were sprayed. ii) The tablets were then made as follows. 45 g of the mixture are 4.5
cm and a tablet having a thickness of 2.3 cm and a density of 1.0 g / cc. The tensile stress (or diametral breaking stress) of this tablet is 10.2k
Pa.

In Examples 4, 5 and 6, tablets similar to Examples 1, 2 and 3 were made. However, in Examples 4, 5 and 6, the tablet density is 1 g / cc. These tablets were placed in the drawer for dispensing the Miele ^R W831 washing machine, put the laundry into the drum, to perform a cycle of the washing machine.

──────────────────────────────────────────────────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, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GE, GH, GM, HU, ID, IL, 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, ZW (71) Applicant ONE PROCTER & GANBLE PLAZA, CINCINNATI, OHIO, UNITED STATES OF AMERICA (72) Invention Person Stephen, Reine, Ongena Be-9170, Belgium, Sint-Jili-Worth, Newstraat, 9F term (reference) 4H003 AC08 BA09 DA01 EA15 EA16 EA28 EB07 EB08 EB16 EB36 EE05 FA32

Claims (11)

[Claims] Claims: 1. A tablet detergent comprising a core and a coating, wherein the core has a diametral fracture stress of less than 15 kPa and comprises a non-gelling binder. A tablet detergent characterized by having a breaking stress in the diameter direction of the tablet detergent of at least 20 kPa. 2. The tablet detergent according to claim 1, wherein the diametral stress of the detergent core is less than 10 kPa, preferably less than 5 kPa. 3. A tablet detergent having a diametral breaking stress of at least 20 kPa, wherein three tablets weighing 60 g are placed on the bottom of a drum of a Miele ^R W831 washing machine and 2.5 kg of miscellaneous cloth is placed. Put less than 18 g of residue at the end of the machine cycle in a stress test consisting of placing the tablet in a drum and running the machine using a short cycle of "white cloth / color" at 30 ° C. The resulting tablet detergent. 4. The tablet detergent according to claim 3, wherein the breaking stress in the diameter direction of the tablet is at least 25 kPa. 5. The residue in the stressing test is less than 10 g, preferably less than 5 g.
The tablet detergent according to claim 3. 6. A tablet detergent comprising a core and a coating, wherein the core has a diametral fracture stress of less than 15 kPa and comprises a non-gelling binder. The tablet detergent is characterized in that the breaking stress in the diametric direction is at least 20 kPa, and three tablets weighing 60 g are placed at the bottom of the drum of the Miele ^R W831 washing machine, and 2.5 kg of miscellaneous fabrics are placed. Place on the tablets in the drum,
A tablet detergent that produces less than 18 g of residue at the end of the washing machine cycle in a stressed test consisting of running the washing machine using a "white cloth / color" short cycle. 7. A method for preparing a laundry detergent aqueous solution for use in a washing machine of a type in which laundry is put in from the front side having a drawer for dispensing and a drum for washing, comprising: In a method of dissolving to form the aqueous laundry detergent solution, the tablet detergent is placed in a dispensing drawer, and water is passed through the dispensing drawer such that the tablet is dispensed as an aqueous solution of the laundry detergent. And a method of passing the aqueous solution through a washing drum. 8. The method according to claim 7, wherein the tablet detergent is the coated tablet detergent according to claim 1 or 2. 9. The method according to claim 8, wherein said coated tablet detergent comprises a water-insoluble coating. 10. The method according to claim 8, wherein the coated tablet detergent comprises a coating, and the coating comprises a dicarboxylic acid. 11. The method according to claim 7, wherein the density of the tablet is 0.9 g / cc to 1.1 g / cc.