JP2002520446A - Detergent tablets with high mechanical and dissolution properties - Google Patents

Abstract

  (57) [Summary] The present invention relates to a tablet formed by compressing a particulate material, the particulate material comprising a surfactant and a highly soluble compound, the highly soluble compound having an effect of adhering to the particulate material. In another aspect of the invention, there is provided a method of preparing an aqueous solution of a laundry detergent for use in a washing machine, wherein the aqueous solution of the laundry detergent dissolves a tablet formed by compressing particulate matter in water. The tablet contains a surfactant and a highly soluble compound, the highly soluble compound having an effect of adhering to the particulate material.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to detergent tablets, especially for use in cleaning.

[0002] A number of cleaning compositions in tablet form have been proposed, but they have virtually no success (except for personal soaps for personal cleaning), despite some of the benefits of the product in unit-dispense form. I don't. One of the reasons is that detergent tablets are usually less than the constituent powders from which they are made, simply because the constituent powders are intimately adhered in the tablet and there is relatively little opportunity for water to penetrate between them. Probably because it dissolves slowly. This causes problems, for example, that the tablet may dissolve slowly when it dissolves, as it is visible from the washing machine door during the washing cycle, adheres to the fabric at the end of the washing cycle, or both.

[0003] EP-A-0,711,827, published May 5, 1996, describes a laundry containing highly water-soluble substances which improves the disintegration of the whole tablet and the solubility of its soluble components. A detergent tablet is disclosed. However, especially in certain front loading washing machines,
There is the problem that tablet residues can be seen through the window of the washing machine.

It is an object of the present invention to provide a tablet formed by compressing a particulate material, wherein the particulate material contains a surfactant, and the tablet is stored, transported and handled without breakage It is easily and quickly dissolved in the washing solution, while releasing the active ingredient into the washing solution, and completely disintegrates and disperses in an alkaline or surfactant-rich solution such as the washing solution.

[0005]

[Summary of the Invention]

The object of the present invention is achieved by providing a tablet of the type described above, wherein the particulate material further comprises a highly soluble compound, the highly soluble compound having an effect of adhering to the particulate material. In another aspect of the invention, there is provided a method of preparing an aqueous solution of a laundry detergent for use in a washing machine, wherein the aqueous solution of the laundry detergent dissolves a tablet formed by compressing particulate matter in water. The tablet contains a surfactant and a highly soluble compound, the highly soluble compound having an effect of adhering to the particulate material.

[0006]

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to highly soluble compounds having an effect of adhering to particulate matter. Highly soluble compounds The present invention relates to highly soluble compounds. Such compounds may be formed from a mixture or a single compound. According to the present invention, a highly soluble compound is defined as follows. A solution containing deionized water and 20 g / L of a specific compound is prepared as follows.

[0007] 1-20 g of the specific compound is placed in a Sotax beaker. This beaker is placed in a thermostat set at 10 ° C. Put a stirrer equipped with a marine propeller in a beaker,
The bottom of the stirrer is 5 mm above the bottom of the Sotax beaker. 20 mixers
Set the rotation speed to 0 rotation / min. Put 2-980 g of deionized water into a Sotax beaker. 3- 10 seconds after the introduction of water, the conductivity of the solution is measured using a conductivity meter. 4-Step 3 is replaced with Step 2, 20, 30, 40, 50 seconds, 1, 2, 5 and 1
Repeat after 0 minutes. The measurement obtained after 5-10 minutes is used as plateau or maximum.

Certain compounds are highly soluble according to the present invention when the conductivity of the solution reaches 80% of its maximum within 10 seconds starting from the complete addition of deionized water to the compound. It is. In fact, when monitoring the conductivity in this way, the conductivity reaches a plateau after a certain time, and this plateau is considered the maximum. Such compounds preferably take the form of a flowable material composed of solid particles at temperatures of 10 to 80 ° C for ease of handling, but other forms such as pastes or liquids may be used. Examples of highly soluble compounds are sodium diisoalkylbenzenesulfonate or sodium toluenesulfonate.

Adhesion Effect For the purposes of the present invention, the adhesion effect of the detergent matrix to the particulate material is characterized by the force required to break tablets based on the test detergent matrix compressed under controlled compression conditions. Can be For a given compression force, a high tablet strength indicates that the granules adhere highly together when compressed, resulting in a strong adhesion effect. A means for assessing tablet strength (also called diameter breaking stress) is Pharmaceutical
utical dosage forms: tablets, volume 1, Ed.HALieberman et al, published i
n Seen in 1989.

The adhesion effect exhibited by the highly soluble compound compares the tablet strength of the base powder without the highly soluble compound with the tablet strength of a powder mix consisting of 97 parts of the base powder and 3 parts of the highly soluble compound. Thereby, it is measured according to the present invention.
Highly soluble compounds are added to the matrix in a substantially water-free form (less than 10% moisture (preferably less than 5%)). The addition temperature is 10 to 80C, more preferably 10 to 40C.

[0011] The highly soluble compounds, at a given compressive force of 3000 N, have a weight of 50 g of detergent granules and a tablet having a diameter of 55 mm, in the presence of 3% of highly soluble compounds having an adhesive effect on the base granules. When the tablet tensile strength is increased by more than 30% (preferably 60%, more preferably 100%), according to the present invention, it is defined as having an effect of adhering to the particulate matter. An example of a compound having an adhesive effect is sodium diisoalkylbenzenesulfonate.

According to the present invention, when a highly soluble compound having an effect of adhering to a particulate material is incorporated into a tablet formed by compressing a particulate material containing a surfactant, dissolution of the tablet in an aqueous solution Gender was found to increase significantly. In a preferred embodiment, at least 1% by weight of the tablet is formed from the highly soluble compound, more preferably at least 1% by weight, even more preferably at least 3%, most preferably at least 5% by weight of the tablet It is formed from highly soluble compounds that have an adhesion effect on A composition containing a highly soluble compound and a surfactant is EP-A-0,
It should be noted that the composition is a liquid composition disclosed in US Pat.

According to the present invention, the presence of highly soluble compounds that have an effect of adhering to particulate matter results in high tensile strength at a constant compressive force or lower compressive force when compared to traditional tablets. It has been found that tablets having equal tensile strength can be obtained. Typically, the tablet has a tensile strength of more than 5 kPa, preferably more than 10 kPa, more preferably more than 15 kPa, especially for laundering, even more preferably more than 30 kPa, most preferably more than 50 kPa, especially for dishwashing or automatic dishwashing. In; 300
less than kPa, preferably less than 200 kPa, more preferably less than 100 kPa,
Even more preferably, it has a tensile strength of less than 80 kPa, most preferably less than 60 kPa. In practice, for laundry, the tensile strength is preferably less than 30 kPa, since the tablets should not be as compressed as, for example, for automatic dishwashing, so dissolution occurs easily.

[0014] Thus, it is possible to produce a tablet that has a solidity and mechanical resistance comparable to that of traditional tablets, but does not make the tablet so compact and is therefore easily dissolved. Furthermore, because the compounds are highly soluble,
The dissolution of the tablets is further accelerated, providing a synergistic effect which facilitates the dissolution of the tablets according to the invention.

Tablet Preparation According to the present invention, it is possible to obtain tablets of lower compactness and lower density at a constant compression force when compared with traditional detergent tablets. The detergent tablets of the present invention can be manufactured simply by mixing the solid ingredients together and compressing the mixture in a traditional tablet press, for example, as used in the pharmaceutical industry. Preferably, the main component, especially the gelling surfactant, is used in particulate form. Any liquid component, for example a surfactant or a foam control agent, can be incorporated into the solid particulate component in a conventional manner. In particular, in the case of laundry tablets, components such as builders and surfactants may be spray dried in a conventional manner and then compressed at a suitable pressure. Preferably, a tablet according to the invention has a viscosity of less than 100,000 N, more preferably of less than 500
Compressed using a force of less than 00N, even more preferably less than 5000N, most preferably less than 3000N. In practice, the most preferred embodiment is a tablet suitable for washing compressed with a force of less than 2500 N, although tablets for automatic dishwashing are also conceivable, for example, such tablets for automatic dishwashing. Rather than compressed.

The granulate used to make the tablets of the present invention may be prepared by any granulation or granulation process. An example of such a process is spray drying (in a co-current or counter-current spray drying tower), which results in a low bulk density, typically less than 600 g / L. Higher density particulate matter can be obtained by granulation and densification in a high shear batch mixer / granulator (granulator) or (
For example, it can be prepared by Lodige ^R CB and / or Lodige using ^R KM mixers) continuous granulation and densification process. Other suitable processes include fluidized bed processes, compaction processes (eg, roll compaction), extrusion, and chemical processes such as agglomeration, crystallization centering, etc., where particulate matter is made. The individual particles can be any other particles, granules, spheres or granules.

The components of the particulate material may be mixed together by any conventional means. Batch is
For example, a concrete mixer, a Nauta mixer, a ribbon mixer or any other suitable. The mixing process, on the other hand, weighs each component by weight, places it on a moving belt, and blends them with more than one drum or mixer,
It may be performed continuously. Non-gelling binders can also be sprayed on the mix of some or all of the components of the particulate material. Other liquid components may be separately sprayed or premixed into the mix of components. For example, a slurry of fragrance and optical brightener can be sprayed. Microflow aids (powder such as zeolite, carbonate, silica) can also be added to the particulate material after spraying the binder, preferably at the end of the process, to reduce the stickiness of the mix .

Tablets can be manufactured using any compression process, such as tableting, briquetting or extrusion, preferably tableting. Appropriate equipment includes
Standard single stroke or a rotary press (e.g., Courtoy ^R, Korch ^R, Ma
nesty ^R or Bonals ^R ). Tablets produced according to the invention preferably have a diameter of 20 to 60 mm, preferably at least 35 mm and within 55 mm, and a weight of 25 to 100 g. The height to diameter (or width) ratio of the tablet is
Preferably it is more than 1: 3, more preferably more than 1: 2. Compression force used to produce these tablets does not exceed 100000kN / m ^2, preferably 30
Not exceed 000kN / m ^2, more preferably not exceed 5000kN / m ^2, even more preferably not exceed 3000kN / m ^2, most preferably not exceed 1000 kN / m ^2.
In a preferred embodiment according to the present invention, the tablet is at least 0.9 g / cc, more preferably at least 1.0 g / cc, preferably at least less than 2.0 g / cc, more preferably at least 1.5 g / cc. Less than even more preferably at least less than 1.25 g / cc, most preferably at least less than 1.1 g / cc.

Hydrotrope Compounds In a preferred embodiment of the present invention, the highly soluble compounds having an adhering effect are specific compounds defined as being hydrotropes, hydrotrope compounds (SEFriberg and M. Chiu). , J.Dispersion Science and Technology, 9
(5 & 6), pages 443-457 (1988-1989)).

A solution consisting of 1.25% by weight of the specific compound and 75% by weight of water is prepared. 2. Octanoic acid is then added to the solution at 1.6 times the weight of the particular compound in the solution and the solution is brought to a temperature of 20 ° C. The solution is mixed in a Sotax beaker equipped with a stirrer equipped with a marine propeller, with the propeller placed about 5 mm above the bottom of the beaker and the mixer set at a rotation speed of 200 rpm. 3. If the octanoic acid is completely dissolved, that is, if the solution consists of only one phase and that phase is the liquid phase, the particular compound is a hydrotrope.

It should be noted that in a preferred embodiment of the present invention, the hydrotrope compound is a flowable substance composed of solid particles under operating conditions of 15-60 ° C. Hydrotrope compounds include the following compounds. A list of commercially available hydrotropes can be found in McCutcheon's Emulsifiers and Detergents, McCutcheon division of Manufac
Seen by the turing Confectioners Company. There are also less compounds of interest.

1. A nonionic hydrotrope having the following structure.

Embedded image In the above formula, R is a C ₈ -C ₁₀ alkyl chain, x is 1 to 15, and y is 3 to 10.

[0023] 2. Anionic hydrotropes such as alkali metal aryl sulfonates.
This includes benzoic acid, salicylic acid, benzenesulfonic acid and many of its derivatives,
There are alkali metal salts of naphthoic acid and various hydroaromatic acids. Examples of these are sodium, potassium and ammonium benzenesulfonates derived from toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, tetralinsulfonic acid, naphthalenesulfonic acid, methylnaphthalenesulfonic acid, dimethylnaphthalenesulfonic acid, trimethylnaphthalenesulfonic acid. Salt. Other examples include salts of dialkylbenzene sulfonic acids, such as diisopropylbenzene sulfonic acid,
Ethyl methylbenzene sulfonic acid salt, alkyl chain length of 3 to 10 (preferably 4 to
9) Alkyl benzene sulfonic acid, and linear or branched alkyl sulfonates having an alkyl chain length of 1 to 18 carbons.

[0024] 3. Solvent hydrotropes such as alkoxylated glycerin and alkoxylated glycerides, esters of alkoxylated glycerin, alkoxylated fatty acids, esters of glycerin, polyglycerol esters. Preferred alkoxylated glycerin has the following structure:

Embedded image In the above formula, l, m and n are each a number from 0 to about 20, and 1 + m + n = about 2 to about 6
0, preferably from about 10 to about 45, R represents H, a CH ₃ or _C 2 _{H 5.} Preferred alkoxylated glycerides have the following structure:

Embedded image In the above formula, R ₁ and R ₂ are each C _n COO or — (CH ₂ CHR ₃ O) ₁ —H
R ₃ = H, CH ₃ or C ₂ H ₅ , and l is a number from 1 to about 60;
n is a number from about 6 to about 24.

[0025] 4. Polymer hydrotropes as described in EP 636687.

Embedded image In the above formula, E is a hydrophilic functional group; R is H, a C ₁ -C ₁₀ alkyl group or a hydrophilic functional group; R ₁ is H, a lower alkyl group or an aromatic group; R ₂ is H , Cyclic alkyl or aromatic groups; the polymer typically has a molecular weight of about 1,000 to 1,000,000.

[0026] 5.5- carboxy-4-hydrotropic specific structures, such as hexyl-2-cyclohexene-1-Iruokutan acid (DIACID ^R)

The use of such a compound in the present invention will further improve the dissolution rate of the tablet, for example because the hydrotrope compound promotes the dissolution of the surfactant.
Such compounds can be formed from a mixture or a single compound.

Coating The solidity of the tablet according to the invention may be further improved by producing a coated tablet, the coating of which covers the uncoated tablet according to the invention to further increase the mechanical properties of the tablet. While improving, the solubility is maintained or further improved.

In one aspect of the invention, the tablets may be coated such that the tablets do not absorb moisture or absorb moisture at a very slow rate. The coating may be so strong that even a moderate mechanical shock to which the tablet is applied during handling, packaging and transport will result in only a very low level of breakage or attrition. Finally,
The coating is preferably brittle enough to break the tablet when subjected to a stronger mechanical shock. It is further advantageous if the coating substance is dissolved under alkaline conditions or is easily emulsified with a surfactant. This avoids the problem of visible residue on the windows of the front loading washing machine during the washing cycle,
Moreover, it helps to prevent the undissolved particles or the clumps of the coating substance from adhering to the laundry. Water solubility is "Standard Test Method for Measurements of Aqueous Solubilit
It is measured according to the test protocol of ASTM E1148-87 entitled "y".

A suitable coating material is a dicarboxylic acid. Particularly suitable dicarboxylic acids are
It is selected from the group consisting of oxalic acid, 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 several ways. Two preferred coating methods are a
A) coating with a molten 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 dried so that the solvent leaves the deposited coating. Substantially insoluble materials can be applied to tablets, for example, by spraying or dipping. Usually, when the molten substance is sprayed on tablets,
Rapidly solidifies to form an adherent coating. Rapid cooling also results in rapid solidification of the coating material when the tablet is dipped into the molten material and then removed. Obviously substantially insoluble materials having a melting point below 40 ° C have not been found to be completely solid at ambient temperature, and materials having a melting point above about 200 ° C have proven impractical. Preferably, the material melts in the range of 60-160C, more preferably 70-120C. By "melting point" is meant the temperature at which a substance becomes a transparent liquid when heated slowly, for example in a capillary tube.

[0032] A coating of any desired thickness may be applied according to the present invention. For most purposes, the coating will be 1-10% of the tablet weight, preferably 1.5-5%. The tablet coating of the present invention is very hard and provides additional strength to the tablet.

In a preferred embodiment of the invention, the destructibility of the coating during cleaning is improved by adding a disintegrant to the coating. The disintegrant swells once in contact with water and then breaks the coating into smaller pieces. This also improves the solubility of the coating in the cleaning liquid. Disintegrants are suspended in the molten coating at a level of up to 30% by weight, preferably 5-20%, most preferably 5-10%. Possible disintegrants are described in the Handbook of Pharmaceutical Excipients (1986). Examples of suitable disintegrants are starch: natural, modified or pregelatinized starch, sodium starch gluconate; gums: agar gum, guar gum, locust bean gum, karaya gum, pectin gum, tragacanth gum; croscarmylose sodium, cloth Povidone, cellulose, carboxymethylcellulose, alginic acid and its salts such as sodium alginate, silicon dioxide, clay, polyvinylpyrrolidone, soy polysaccharide, ion exchange resins and mixtures thereof.

The tensile strength in accordance with the shape of the composition and tablets of the starting material, the compressive force used is adjusted so as not to affect the disintegration time in the tensile strength and the washing machine. This process may be used to produce uniform or laminated tablets of any size or shape.

In the case of a cylindrical tablet, the tensile strength corresponds to the diameter-rupture stress (DFS), which is a method for expressing the strength of the tablet and is determined by the following equation. = 2F / μDt In the above formula, F is the maximum force (Newton) that causes a tensile break (break), as measured by a VK200 tablet hardness tester supplied by Van Kell industries, Inc. D is the diameter of the tablet and t is the thickness of the tablet (Method Pharmaceutical dosage for
ms: tablets, volume 2, Page 213-217). Tablets having a diameter rupture stress of less than 20 kPa are considered brittle, and partially broken tablets can reach consumers. A diameter rupture stress of at least 25 kPa is preferred.

This also applies to non-cylindrical tablets in defining the tensile strength, where the cross-section perpendicular to the height of the tablet is not circular and the force is perpendicular and perpendicular to the height of the tablet. Applied in a direction perpendicular to the sides of the tablet, the sides being perpendicular to the non-circular cross section.

Tablet distribution properties The distribution rate of detergent tablets is determined by the following method. Weigh two tablets each 50 g, placed in the dispenser of Baucknecht ^R WA9850 washing machine. The water supply to the washing machine is set at a temperature of 20 ° C. and a hardness of 21 grains / gallon, and the dispenser water inlet flow rate is set at 8 L / min. The level of tablet residue left in the dispenser is checked by switching on washing on and setting the wash cycle to wash program 4 (white / color, short cycle). The distribution residual ratio is determined as follows. Partitioning ratio = residue weight / raw tablet weight × 100 The residue level is determined by repeating the operation ten times, and the average residue level is calculated based on each of the ten measurements. In this stress test, a residual of 40% of the starting tablet weight is considered acceptable. Preferably less than 30% remains, more preferably less than 25%. It should be noted that water altitude measurements are performed in traditional "grain / gallon" units, where 0.001 mol / L = 7.0 grains / gallon and the concentration of Ca2 ⁺ ions in solution Represents

[0038] In another preferred embodiment of the blowing agent present invention, the tablet is further containing a blowing agent. Foaming, as described herein, refers to the generation of gaseous bubbles from a liquid that result in carbon dioxide gas as a result of a chemical reaction between a soluble acid source and an alkali metal carbonate. That is, another example of C ₆ H ₈ O ₇ +3 NaHCO ₃ → Na ₃ C ₆ H ₅ O ₇ + 3CO ₂ ↑ + 3H ₂ O acid and carbonic acid sources and other foaming systems (Pharmaceutical Dosage Forms:
Tablets Volume 1, Page 287-291).

A foaming agent may also be added to the tablet mix in addition to the detergent ingredients. Addition of an effervescent agent to a detergent tablet improves the disintegration time of the tablet. The amount is preferably 5-20% by weight of the tablet
, Most preferably from 10 to 20%. Preferably, the blowing agent should be added as agglomerates of different particles, or as compact particles that are not separate. Thanks to the gas generated by effervescence in the tablet, the tablet can have a higher DFS but still have a disintegration time similar to a non-effervescent tablet. Effervescent tablet D
When the FS is kept the same as the tablet without it, the disintegration of the effervescent tablet is faster. In addition, dissolution aids may be provided by the use of compounds such as sodium acetate or urea. A list of suitable dissolution aids can be found in Pharmaceutical dosage forms: t
ablets, volume 1, Second edition, Edited by HALieberman et al, ISBN 0-8247
-8044-2 can also be seen.

[0040]Detergent surfactant Surfactants are contained in the tablets according to the invention. Highly soluble surfactants
It becomes better by adding a neutral compound. Non-limiting examples of surfactants useful herein, typically at a level of about 1 to about 55% by weight
Contains the conventional C₁₁-C₁₈Alkyl benzene sulfonate ("LAS"),
Primary, branched and random C₁₀-C₂₀Alkyl sulfate ("AS")
, The formula CH₃(CH₂)_x(CHOSO₃ ⁻M⁺) CH₃And CH₃(CH₂) _y (CHOSO₃ ⁻M⁺) CH₂CH₃C₁₀-C₁₈Secondary (2,3) Archi
Lusulfate (x and (y + 1) is at least about 7, preferably at least about 9
Where M is a water-soluble cation, especially sodium), unsaturated sulfate
For example, oleyl sulfate, C₁₀-C₁₈Alkyl alkoxy sulf
("AExS"; especially ethoxysulfate of EO1-7), C₁₀-C ₁₈ Alkyl alkoxy carboxylate (especially EO1-5 ethoxycarboxy)
Rate), C₁₀-C₁₈Glycerol ether, C₁₀-C₁₈Alkyl poly
Glycosides and their corresponding sulfated polyglycosides, and C₁₂-C₁₈α
-There are sulfonated fatty acid esters. If desired, conventional nonionic and
Amphoteric surfactants, including so-called narrow peak alkyl ethoxylates
C₁₂-C₁₈Alkyl ethoxylate ("AE"), C₆-C₁₂Alkyl
Phenol alkoxylates (especially ethoxylates and mixed ethoxy / propo
Kishi), C₁₂-C₁₈Betaine and sulfobetaine ("sultaine"), C ₁₀ -C₁₈Amine oxide and the like may also be included in the overall composition. C₁₀-
C₁₈N-alkyl polyhydroxy fatty acid amides can also be used. Typical example
Has C₁₂-C₁₈There is N-methylglucamide. See WO9,206,154
. Other sugar-derived surfactants include C₁₀-C₁₈N- (3-methoxypropyl) group
There are N-alkoxy polyhydroxy fatty acid amides such as lucamide. N-Pro
Pill to N-hexyl C₁₂-C₁₈Glucamide can be used for low foaming
Wear. C₁₀-C₂₀Conventional soaps may also be used. If high foaming is desired, branch
Chain C₁₀-C₁₆Soap may also be used. Of anionic and nonionic surfactants
Mixtures are particularly useful. Other conventional useful surfactants are listed in the standard text
Have been. In a preferred embodiment, the tablet comprises at least 5% by weight, more preferably
At least 15% by weight, even more preferably at least 25% by weight, most preferably 3% by weight.
Contains 5 to 45% by weight of surfactant.

Non-gelling binders Non-gelling binders can be incorporated into the tablet-forming particles to further facilitate dissolution. When non-gelling binders are used, suitable non-gelling binders include synthetic organic polymers such as polyethylene glycol, polyvinylpyrrolidone, polyacrylates and water-soluble acrylate copolymers. Pharmaceutical Excipients, se
The cond edition handbook has the following binder classifications. Gum arabic,
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. Most preferred binders, such as cationic polymers, i.e. ethoxylated hexamethylenediamine quaternary compound, bishexamethylenetriamine, or others such as pentaamine, ethoxylated polyethyleneamine, maleic acrylic acid polymers also have a laundry active cleaning function. are doing.

Since the non-gelling binder material is preferably sprayed, a suitable temperature below 90 ° C., preferably below 70 ° C., even more preferably below 50 ° C. so as not to damage or degrade other active ingredients in the matrix. Melting point. The most preferred are
A non-aqueous liquid binder (ie, not an aqueous solution) that is sprayed in molten form.
However, they may be solid binders incorporated into the matrix by dry addition, but should have binding properties in the tablet.

The non-gelling binder material is preferably in the range of 0.1 to 15% by weight of the composition, more preferably less than 5%, especially if it is a non-laundry active, 2% of the tablet Used in less than an amount. Gelling binders such as nonionic surfactants preferably avoid their liquid or molten form. Nonionic surfactants and other gelling agents are not excluded from the composition, but they are preferably incorporated into detergent tablets as a component of the particulate material rather than as a liquid.

Builder Detergent A builder may optionally be included in the composition to help control mineral hardness. Inorganic and organic builders can be used. Builders are typically used in fabric laundry compositions to help remove particulate soil. Builder levels vary widely depending on the end use of the composition.

For inorganic or P-containing detergent builders, polyphosphates (exemplified by tripolyphosphate, pyrophosphate and glassy polymer metaphosphate)
, Phosphonates, phytic acids, silicates, carbonates (including bicarbonates and sesquicarbonates), alkali metal, ammonium and alkanol ammonium salts of sulfates and aluminosilicates. However, phosphate-free builders are needed in some regions. Significantly, the composition may be citrate-like (compared to phosphate)
It works surprisingly well even in the presence of so-called "weak" builders, or in the so-called "under-built" situations that occur with zeolite or laminated silicate builders.

Examples of silicate builders are alkali metal silicates, in particular 1.6: 1-3.
Those having a SiO ₂ : Na ₂ O ratio in the 2: 1 range and laminated silicates such as the laminated sodium silicate described in US Pat. No. 4,664,839 issued to HP Rieck on May 12, 1987. NaSKS-6 is a trade name of a crystal-laminated silicate sold by Hoechst (generally referred to herein as "SKS-
6 "). Unlike zeolite builders, NaSKS-6 silicate builders do not contain aluminum. NaSKS-6 is a laminated silicate in the form of δ-Na ₂ SiO _5. It is German DE-A-3. 417,649 and DE-A-3,742,043.
Those Although KS-6 is used on highly preferred layered silicate herein, having other such layered silicates, such as the general formula _{NaMSi x O 2x + 1 · yH} 2 O (
M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2,
y is a number from 0 to 20, preferably 0) can also be used here. Various other stacked silicates by Hoechst include NaSKS-5, N as α, β and γ forms.
There are aSKS-7 and NaSKS-11. Δ-Na ₂ SiO ₅ (NaSKS-6 type) as described above is most preferred for use herein. Other silicates, such as magnesium silicates, which can function as crispening agents in granulation formulations, as stabilizers for oxygen bleaching, and as a component of a foam control system, are also useful.

Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application 2,321,001 published on Nov. 15, 1973.

Aluminosilicate builders are also useful in the present invention. Aluminosilicate building
Is a very important ingredient in most current heavy-duty granular detergent compositions, and
It is also an important builder component. Aluminosilicate builder has empirical formula: M _z (ZAlO₂)_y・ XH₂Some have O, where z and y are usually small.
An integer of at least 6, wherein the molar ratio of z to y ranges from 1.0 to about 0.5, and x is
It is an integer from about 15 to about 264.

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates may be crystalline or amorphous in structure, natural aluminosilicates or synthetically derived. A process for preparing aluminosilicate ion exchange materials is described in US Pat. No. 3,985, Krummel et al., Issued Oct. 12, 1976.
669. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are commercially 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: Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] xH ₂ O, wherein x is from about 20 to about 30, especially about 27. is there. This material is known as zeolite A. Dehydrated zeolites (x = 0 to 10) may also be used here. Preferably, the aluminosilicate has a particle size of about 0.1 to 10 microns in diameter.

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 multiple carboxylate groups, preferably at least three carboxylate groups. The polycarboxylate builder is usually added to the composition in the acid form, but may be added in the form of a neutralized salt. When utilized in salt form, alkali metal salts, such as sodium, potassium and lithium, or alkanolammonium salts are preferred.

[0051] Among the polycarboxylate builders, various categories of useful substances are included. One important category of polycarboxylate builders is 1964
Oxydisoxy, such as disclosed in Berg's US Pat. No. 3,128,287 issued Apr. 7, 1992, and Lamberti et al. US Pat. No. 3,635,830 issued Jan. 18, 1972. There are ether polycarboxylates, including nates. See also the "TMS / TDS" builder in US Pat. No. 4,663,071, issued May 5, 1987 to Bush et al. Suitable ether polycarboxylates include US Patents 3,923,679, 3,835,163, 4,158,635,4
, 120,874 and 4,102,903, especially cycloaliphatic compounds.

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

Citrate builders such as citric acid and its soluble salts (especially the sodium salt) are particularly important polycarboxylates in heavy liquid detergent formulations because of their availability from renewable sources and their biodegradability. Rate builder. Citrate may be used in the granular composition, especially in combination with zeolites and / or layered silicate builders. Oxydisuccinates are also particularly useful in such compositions and combinations.

In the detergent composition of the present invention, the 3,3-dicarboxy-4-oxa-1,6 disclosed in US Pat. No. 4,566,984, issued Jan. 28, 1986 to Bush, is used.
-Hexane diates and related compounds are also suitable. Useful succinic acid builders, C ₅ -C ₂₀ alkyl and alkenyl succinic acids, and their salts. 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 862 published November 5, 1986.
00690.5 / 0, 200, 263.

Another suitable polycarboxylate is Cr, issued March 13, 1979.
utchfield et al., US Pat. No. 4,144,226 and Diehl US Pat. No. 3,308,067, issued Mar. 7, 1967. See also Diehl US Patent 3,723,322. Fatty acids such as C ₁₂ -C ₁₈ monocarboxylic acids can also be incorporated into the compositions, alone or in combination with the aforementioned builders, especially citrate and / or succinate builders, to provide additional builder activity. This should be considered by the trader since such use of fatty acids usually results in reduced foaming.

Various alkali metal phosphates, such as the well-known sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate, are used in the context of the use of phosphorus-based builders, especially in bar formulations used in hand-washing operations. it can. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see, for example, US Pat.
159,581, 3,213,030, 3,422,021, 3,400,14
8 and 3,422,137) can also be used.

Bleach The detergent composition optionally contains a bleach or a bleach composition comprising a bleach and one or more bleach activators. When present, bleach is especially for fabric laundering, and is typically at a level of about 1 to about 30%, more typically about 5 to about 20% of the detergent composition. If present, the amount of bleach activator will typically be about 0. 1 of the bleaching composition of bleach activator.
1 to about 60%, more typically about 0.5 to about 40%.

The bleaches used herein may be any bleaches useful in detergent compositions for textile cleaning, hard surface cleaning or other cleaning purposes now or becoming known. . These include oxygen bleach and other bleaches. Perborate bleach, such as sodium perborate (eg, mono- or tetrahydrate), can be used here. Another category of bleach that may be used without limitation consists of percarboxylic acid bleach and its salts. Suitable examples of this type of agent include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of m-chloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid, and diperoxide decandioic acid. Such bleaching agents are described in US Pat. No. 4,483,781 to Hartman, issued Nov. 20, 1984; US Patent Application 740,446, Burns et al., Filed Jun. 3, 1985; Banks et al., European Patent Application 0,133,354, published on Jan. 20, and Chung et al., U.S. Pat.
It is disclosed in S Patent 4,412,934. Highly preferred bleaches include 19
There is also 6-nonylamino-6-oxoperoxycaproic acid as described in US Pat. No. 4,634,551, issued Jan. 6, 1987 to Burns et al.

[0059] Peroxygen bleaches can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate and the corresponding "percarbonate" bleach, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide. Persulfate bleach (for example,
OXONE, DuPont) may also be used.

A preferred percarbonate bleach consists of dry particles having an average particle size in the range of about 500 to about 1000 μm, of which less than about 10% by weight of about 200 μm
Smaller, less than about 10% by weight of the particles are greater than about 1250 μm. Optionally, the percarbonate may be coated with a silicate, borate or water-soluble surfactant. Percarbonates are available from various commercial sources such as FMC, Solvay and Tokai Denka. Mixtures of bleaches may also be used.

The peroxygen bleaches, perborates, percarbonates and the like are preferably combined with a bleach activator to produce the peroxyacid corresponding to the bleach activator in aqueous solution (ie, during the washing process). Various non-limiting examples of activators are disclosed in US Pat. No. 4,915,854 and US Pat. No. 4,412,934 issued to Mao et al. On Apr. 10, 1990. Nonanoyloxybenzenesulfonate (NOBS) and tetraacetylethylenediamine (TAED) activators are typical, and mixtures thereof can also be used. See also US Pat. No. 4,634,551 for other exemplary bleach and activators useful herein.

A highly preferred amide-derived bleach activator is of the formula: R ¹ N (R ⁵ ) C (O) R ² C (O) L or R ¹ C (O) N (R ⁵ ) R ² C (O) L wherein R ¹ is from about 6 to about 12 carbon atoms An alkyl group having an atom, and R ² is 1 to
Alkylene having from about 6 carbon atoms, R ⁵ is alkyl, aryl or alkaryl having a H or from about 1 to about 10 carbon atoms,, L is any suitable leaving group. A leaving group is a group that leaves a bleach activator as a result of a nucleophilic attack on the bleach activator by a perhydrolysis anion. A preferred leaving group is phenylsulfonate. Preferred examples of bleach activators of the above formula include (6-octanamidocaproyl) oxybenzenesulfonate, (6) as described in US Pat. No. 4,634,551, which is incorporated herein by reference. -Nonanamidocaproyl) oxybenzenesulfonate, (6-decanamidocaproyl) oxybenzenesulfonate and mixtures thereof.

Another type of bleach activator is US Pat. No. 4,966,7 of Hodge et al., Issued Oct. 30, 1990, which is incorporated herein by reference.
Consisting of the benzoxazine type activator disclosed in No. 23. There are less highly preferred activators of the benzoxazine type.

Embedded image

Yet another type of preferred bleach activator is an acyllactam activator, especially acylcaprolactam and acylvalerolactam of the formula:

Embedded image Wherein R ⁶ is H or an alkyl, aryl, alkoxyaryl or alkaryl group having 1 to about 12 carbon atoms. Highly preferred lactam activators include benzoylcaprolactam, octanoylcaprolactam,
3,5,5-trimethylhexanoylcaprolactam, nonanoylcaprolactam, decanoylcaprolactam, undecenoylcaprolactam, benzoylvalerolactam, octanoylvalerolactam, decanoylvalerolactam, undecenoylvalerolactam, nonanoylvalerolactam, 3 , 5,5-trimethylhexanoylvalerolactam and mixtures thereof. The disclosure of acylcaprolactam, including benzoylcaprolactam adsorbed in sodium perborate, is incorporated herein by reference on Oct. 8, 1985.
See also US Patent No. 4,545,784 issued to nderson.

Bleaches other than oxygen bleaches are known in the art and may be utilized herein. One type of non-oxygen bleach that is of particular interest is a light-activated bleach such as sulfonated zinc and / or aluminum phthalocyanine. See US Pat. No. 4,033,718 issued to Holcombe et al. On Jul. 5, 1977. If used, detergent compositions contain such bleaching, especially sulfonated zinc phthalocyanine, typically at about 0.025 to about 1.25% by weight.

If desired, the bleaching compound can be catalyzed by a manganese compound. This kind of
Compounds are well known in the art, for example, US Pat. No. 5,246,621, US Pat.
244,594, US Patent 5,194,416, US Patent 5,114,606,
European Patent Application Publication 549,271A1, 549,272A1, 544,440A
2 and 544,490 A1. These touches
Preferred examples of the medium include Mn^IV ₂(UO)₃(1,4,7-trimethyl-1,4
, 7-Triazacyclononane)₂(PF₆)₂, Mn^III ₂(UO)₁(U-
OAc)₂(1,4,7-trimethyl-1,4,7-triazacyclononane)₂ (ClO₄)₂, Mn^IV ₄(UO)₆(1,4,7-triazacyclononane) ₄ (ClO₄)₄, Mn^IIIMn^IV ₄(UO)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
No. 4,430,243 and US Pat. No. 5,114,611.
There is something. Combination of manganese and various complex ligands to enhance bleachability is also listed below
Reported in US patent specification. 4,728,455; 5,284,944;
5,246,612; 5,256,779; 5,280,117; 5,274.
147; 5,153,161 and 5,227,084

As a practical matter, without limitation, the compositions and processes can be adjusted to provide at least about 0.1 ppm of active bleach catalyst species in an aqueous wash liquor, and preferably from about 0.1 to about 0.1 ppm in a wash liquor. About 700 ppm, more preferably about 1 to about 500 pp
m of the catalyst species.

[0068] enzymes enzymes are, for example, protein-based, removal of carbohydrate-based, or triglyceride-based stains, to prevent the free dye transfer, and including fabric regeneration, for a variety of fabric laundering purposes, contained in the formulation Can be done. Enzymes that can be combined include
There are proteases, amylases, lipases, cellulases, peroxidases and mixtures thereof. Other types of enzymes may also be included. They may be of any suitable origin, such as of plant, animal, bacterial, fungal and yeast origin.
However, their choice is dictated by several factors, such as pH activity and / or optimal stability, thermal stability, and stability to active detergents, builders, and the like. In this regard, bacterial or fungal enzymes such as bacterial amylase and protease, and fungal cellulase are preferred.

[0069] The enzyme may be present in an amount of up to about 5 mg per gram of the composition, more typically from about 0.01 to
It is usually formulated at a level sufficient to provide about 3 mg of active enzyme. In other words, the composition will typically contain from about 0.001 to about 5% by weight, preferably from 0.01 to 1%.
Including commercially available enzyme products. The protease enzyme is present in an amount of from 0.005 to 0 per gram of the composition.
. It is usually present in such products at a level sufficient to provide one Anson unit (AU) of activity.

A suitable example of a protease is subtilisin obtained from certain strains of B. subtilis and B. licheniformis. Another suitable protease is obtained from a strain of Bacillus, has maximum activity in the pH range of 8-12, has been developed by Novo Industries A / S, and is sold under the registered trademark ESPERASE. Products of this and similar enzymes are described in Novo UK Patent Specification 1,243,784. Commercially available proteolytic enzymes suitable for removing protein-based stains include the trade names ALCALASE and SAVINASE, Int from Novo Industries A / S (Denmark).
Some are sold at MAXATASE by ernational Bio-Synthetics, Inc. (Netherlands). Other proteases include Protease A (see European Patent Application 130,756, published Jan. 9, 1985) and Protease B (European Patent Application 8737301.8, filed April 28, 1987, and 1985). See European Patent Application 130,756 to Bott et al.

Amylases include, for example, α-amylase, RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo Industries as described in British Patent Specification No. 1,296,839 (Novo).

Cellulases that can be used in the present invention include both bacterial and fungal cellulases.
Preferably, they have an optimal pH between 5 and 9.5. Suitable cellulases are described in US Pat. No. 4,435,3, Barbesgoard et al., Issued on Mar. 6, 1984.
07, where Humicola insolens and Humicola strain DSM1 are disclosed.
No. 800 or fungal cellulases produced from cellulase 212-producing fungi belonging to the genus Aeromonas, and cellulases extracted from the hepatopancreas of marine molluscs (Dolabella Auricula Solander). A suitable cellulase is GB-A
-2,075,028, GB-A-2,095,275 and DE-OS-2
247, 832. CAREZYME (Novo) is particularly useful.

[0073] Suitable lipase enzymes for detergents include those produced by microorganisms of the genus Pseudomonas, such as Pseudomonas stutzeri ATCC 19.154, disclosed in British Patent 1,372,034. See also the lipase of Japanese Patent Application 53/20487 published February 24, 1978. This lipase is available under the trade name Lipase P "Am
“ano” is commercially available from Amano Pharmaceutical Co. Ltd. of Nagoya, Japan, and is referred to as “amano-P”. Other commercially available lipases include Amano-CES, Chromob
acter viscosum, for example, Chromobact commercially available from Toyo Brewing Co., Ltd.
lipase from er viscosum var. lipolyticum NRRLB 3673; USBioche from USA
Chromobacter viscosum lipase from Mical Corp. and Disoiynth Co. of the Netherlands; lipase from Pseudomonas gladioli. LIPOLASE enzyme commercially available from Novo, derived from Humicola lanuginosa (see also EPO 341,947)
Is a preferred lipase for use herein.

The peroxidase enzyme is a source of oxygen such as percarbonate, perborate,
Used in combination with persulfate, hydrogen peroxide and the like. They are used for "solution bleaching", i.e. to prevent dyes or pigments that have fallen off the substrate during the washing operation from being transferred to another substrate in the washing liquor. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidases such as chloro and bromoperoxidase. Peroxidase-containing detergent compositions are described, for example, by O. Kirk, January 1989.
It is disclosed in PCT International Application WO 89/099813, published on January 19, and assigned to Novo Industries A / S.

The various enzymatic substances and their means of incorporation into synthetic detergent compositions are also described in 1971
No. 3,553,139 issued to McCarty et al. The enzyme is disclosed in Place et al., US Pat.
Hughes U.S. Pat. No. 4,101,457 and issued Mar. 26, 1985.
, 507, 219. Enzymatic substances useful in liquid detergent formulations and their incorporation into such formulations are disclosed in Hora et al., US Pat. No. 4,261,868, issued Apr. 14, 1981. Enzymes useful in detergents can be stabilized by various techniques. Enzyme stabilization techniques are described in US Pat. Nos. 3,600,319 and 1986 issued to Gedge et al. On Aug. 17, 1971.
It is disclosed and exemplified in Venegas European Patent Application Publication 199,405, application 86200586.5, published October 29, 1998. Enzyme stabilization systems are also described, for example, in US Pat. No. 3,519,570.

Other components commonly used in detergent compositions and which can be incorporated into the detergent tablets of the present invention include chelating agents, soil release agents, soil redeposition preventive agents, dispersants, brighteners, foam control. Agents, fabric softeners, dye transfer inhibitors and perfumes.

Cleaning Method It is known to put traditional laundry detergent tablets into the washing drum along with the laundry. However, this method tends to produce unpleasant residues visible through the windows, especially in certain types of washing machines designed to operate with low water consumption. In extreme cases, visible residues may remain on clothing at the end of a wash cycle due to incomplete dissolution.

The present invention also relates to a cleaning method that significantly avoids this problem. A novel method is to prepare an aqueous solution of laundry detergent for use in a washing machine. The aqueous solution of laundry detergent is formed by dissolving a tablet formed by compressing particulate matter into water, and the tablet is made up of a surfactant and a high-performance detergent. It contains soluble compounds, the highly soluble compounds having the effect of adhering to particulate matter.

In a preferred embodiment according to the present invention, the method is more particularly described in which the front-loading washing machine has a dispensing drawer and a washing drum and an aqueous solution of laundry detergent is formed by dissolving the detergent tablets in water. Concerning the preparation of an aqueous solution of laundry detergent for use in a front-loading washing machine, the detergent tablets are placed in a dispensing drawer and the water is passed through the dispensing drawer, resulting in the tablets being dispensed as an aqueous solution of laundry detergent. And the aqueous solution is passed through a washing drum.

【Example】

Example Base Particulate Material Composition: Composition A (wt%) Anionic Aggregate 1 21.45 Anionic Aggregate 2 13.00 Cationic Aggregate 5.45 Stacked Silicate 10.8 Sodium Percarbonate 14. 19 Bleach activator aggregates 5.49 Sodium carbonate 13.82 EDDS / sulfate particles 0.47 Tetrasodium salt of hydroxyethanediphosphonic acid 0.73 Soil release polymer 0.33 Fluorescent agent 0.18 Zinc phthalocyanine sulfonate inclusion 0 0.025 Soap Powder 1.40 Foam Inhibitor 1.87 Citric Acid 7.10 Protease 0.79 Lipase 0.28 Cellulase 0.22 Amylase 1.08 Binder Spray-On System 1.325 Total 100.0

Anionic aggregate 1 consists of 40% anionic surfactant, 27% zeolite and 33% carbonate. Anionic aggregate 2 consists of 40% anionic surfactant, 28% zeolite and 32% carbonate. Cationic aggregates consist of 20% cationic surfactant, 56% zeolite and 2%
Consists of 4% sulfate. The stacked silicate consists of 95% SKS6 and 5% silicate. The bleach activator aggregate consists of 81% TAED, 17% acrylic / maleic acid copolymer (acid form) and 2% water. Ethylenediamine N, N-disuccinate sodium salt / sulfate particles
Consists of 8% ethylenediamine N, N-disuccinic acid sodium salt, 23% sulfate and 19% water. The zinc phthalocyanine sulfonate inclusion is 10% active. The suds suppressor consisted of 11.5% silicone oil (ex. Dow Corning), 59% zeolite and 29.5% water. The binder spray-on-system consists of 50% Lutensit K-HD 96 and 50% PEG (polyethylene glycol).

Example 1 (Contains Highly Soluble Compound with Adhesive Effect to Particulate Matter) i) A detergent base powder of composition A (see table above) was prepared as follows. All the particulates of Base Composition A were mixed together in a mixing drum to form a uniform particulate mixture. Spray-on was performed during this mixing. ii) 97 parts of the base powder of composition A were mixed in a mixing drum with 3 parts of sodium diisoalkylbenzenesulfonate (a highly soluble compound having an effect of adhering to particulate matter). iii) The tablets were then manufactured as follows. 50 g of the mixture were introduced into a 5.5 cm diameter circular mold and compressed to give a tablet tensile strength (or diameter breaking stress) of 15 kPa. The force required to obtain a tablet tensile strength of 15 kPa was 2400N.
The tablet height was 1.94 cm. iv) The level of residue in the washing machine dispenser is " Tablet Dispensin
g Test ". Two wash tablets are placed in a Baucknecht WA9850 dispenser. The water supply to the washing machine is set to a temperature of 20 ° C and a hardness of 21 grains / gallon, and the dispenser water inlet flow rate is set to 8 L / min. The level of tablet residue remaining in the dispenser is checked by switching on washing on and setting the wash cycle to wash program 4 (white / color, short cycle). Percentage = residue weight / raw tablet weight × 100 The percentage distribution is given in the table “dispensing Residues”.

Example 2 (Highly soluble compound) i) A similar composition A was prepared according to a similar process as in Example 1. ii) 97 parts of the base powder of composition A were mixed with 3 parts of sodium toluenesulfonate (highly soluble compound) in a mixing drum. iii) Tablets were then prepared according to the same procedure as described in Example 1. 15k
The force required to obtain a tablet tensile strength of Pa was 3100N. Tablet height is 1
. It was 88 cm. iv) The level of residue in the washing machine dispenser was evaluated according to the same procedure as described in Example 1. The distribution percentages are shown in the table "dispensing Residues".

Example 3 (Highly soluble compound) i) A similar composition A was prepared according to a similar process as in Example 1. ii) 97 parts of the base powder of composition A were mixed with 3 parts of sorbitol (highly soluble compound) in a mixing drum. iii) Tablets were then prepared according to the same procedure as described in Example 1. 15k
The force required to obtain a tablet tensile strength of Pa was 3500N. Tablet height is 1
. It was 83 cm. iv) The level of residue in the washing machine dispenser was evaluated according to the same procedure as described in Example 1. The distribution percentages are shown in Table 3.

Example 4 (Compound having an effect of adhering to particulate matter) i) A similar composition A was prepared according to the same process as in Example 1. ii) 97 parts of the base powder of composition A was prepared by adding sodium dodecylbenzenesulfonate (
(Highly soluble compound) in a mixing drum. iii) Tablets were then prepared according to the same procedure as described in Example 1. 15k
The force required to obtain a tablet tensile strength of Pa was 2600N. Tablet height is 1
. It was 95 cm. iv) The level of residue in the washing machine dispenser was evaluated according to the same procedure as described in Example 1. The distribution percentages are shown in Table 3.

Example 5 (Base particulate composition) i) A similar composition A was prepared according to the same process as in Example 1. ii) Tablets were then prepared according to a procedure similar to that described in Example 1. 15k
The force required to obtain a tablet tensile strength of Pa was 3200N. Tablet height is 1
. 82 cm. iii) The level of residue in the washing machine dispenser was evaluated according to the same procedure as described in Example 1. The distribution percentages are shown in Table 3.

Results: Distribution residue table: Example: 1 2 3 4 5 Compressive force (N) 2400 3100 3500 2600 3200 Tablet height (cm) 1.94 1.88 1.83 1.95 1.82 Distribution residue (%) 24.2 98.8 71.5 68.8 100

[0088] Conductivity tables for compounds added to Composition A to obtain tablets of Examples 1-4. Example Compound: Conductivity (%) reached in 12 3 4 10 seconds 95 100 100 64

Another base particulate composition. Composition B (% by weight) Anionic aggregate 1 21.45 Anionic aggregate 2 13.00 Cationic aggregate 5.45 Stacked silicate 10.8 Sodium percarbonate 14.19 Bleach activator aggregate 5.49 Carbonate Sodium 12.645 EDDS / sulfate particles 0.47 Tetrasodium salt of hydroxyethanediphosphonic acid 0.73 Soil release polymer 0.33 Fluorescent agent 0.18 Zinc phthalocyanide sulfonate inclusion 0.025 Soap powder 1.40 Foam Inhibitor 1.87 Citric Acid 7.10 Protease 0.79 Lipase 0.28 Cellulase 0.22 Amylase 1.08 Binder Spray-On System 2.5 Total 100.00

Anionic aggregate 1 consists of 40% anionic surfactant, 27% zeolite and 33% carbonate. Anionic aggregate 2 consists of 40% anionic surfactant, 28% zeolite and 32% carbonate. Cationic aggregates consist of 20% cationic surfactant, 56% zeolite and 2%
Consists of 4% sulfate. The stacked silicate consists of 95% SKS6 and 5% silicate. The bleach activator aggregate consists of 81% TAED, 17% acrylic / maleic acid copolymer (acid form) and 2% water. Ethylenediamine N, N-disuccinate sodium salt / sulfate particles
Consists of 8% ethylenediamine N, N-disuccinic acid sodium salt, 23% sulfate and 19% water. The zinc phthalocyanine sulfonate inclusion is 10% active. The suds suppressor consisted of 11.5% silicone oil (ex. Dow Corning), 59% zeolite and 29.5% water. Binder spray-on system is 50% Lutensit K-HD 96 and 50% PEG
(Polyethylene glycol).

Example 5 (Base Particulate Material Composition) i) Composition B was prepared according to a process similar to that of Example 1. ii) Tablets were then prepared according to a procedure similar to that described in Example 1. The applied force was 2000N. The tablet tensile strength was 10.9 kPa.

Example 7 (PEG) i) A similar composition B was prepared according to a similar process to Example 1. ii) 97 parts of the base powder of composition A were mixed with 3 parts of PEG (binding compound) in a mixing drum. iii) Tablets were then prepared according to the same procedure as described in Example 1. The applied force was 2000N. The tablet tensile strength was 12.8 kPa.

Example 8 (Sodium diisoalkylbenzenesulfonate) i) A similar composition B was prepared according to a similar process to Example 1. ii) 97 parts of the base powder of composition A were mixed with 3 parts of sodium diisoalkylbenzenesulfonate in a mixing drum. iii) Tablets were then prepared according to the same procedure as described in Example 1. The applied force was 2000N. The tablet tensile strength was 17.8 kPa.

Example 9 of a Tablet According to the Invention : i) A detergent base powder of composition C was prepared as follows. All the particulate material of Base Composition C was mixed together in a mixing drum to form a uniform particulate mixture. Spray-on was performed during this mixing. After spray-on, sodium diisoalkylbenzenesulfonate (= DIBS) was added to the rest of the matrix. ii) Tablets were then manufactured as follows. 43 g of the mixture were introduced into a 5.5 cm diameter circular mold and compressed to give a tablet tensile strength (or diameter breaking stress) of 15 kPa. iii) The distribution residual ratio of the 43 g tablet was less than 15%.

Composition C (%) Anionic aggregate 1 9.1 Anionic aggregate 2 22.5 Nonionic aggregate 9.1 Cationic aggregate 4.6 Laminated silicate 9.7 Sodium percarbonate 12.2 Bleach activator aggregates 6.1 Sodium carbonate 7.27 EDDS / sulfate particles 0.5 Tetrasodium salt of hydroxyethanediphosphonic acid 0.6 Soil release polymer 0.3 Fluorescent agent 0.2 Zinc phthalocyanine sulfonate inclusion 03 Soap powder 1.2 Foam inhibitor 2.8 Citric acid 5.5 Protease 1 Lipase 0.35 Cellulase 0.2 Amylase 1.1 Binder spray-on system 3.05 Fragrance spray-on 0.5 DIBS 2.1

[0096] Anionic aggregate 1 consists of 40% anionic surfactant, 27% zeolite and 33% carbonate. Anionic aggregate 2 consists of 40% anionic surfactant, 28% zeolite and 32% carbonate. Nonionic aggregates consist of 26% nonionic surfactant, 6% Lutensit K-HD 96,
Consists of 40% anhydrous sodium acetate, 20% carbonate and 8% zeolite. Cationic aggregates consist of 20% cationic surfactant, 56% zeolite and 2%
Consists of 4% sulfate. The stacked silicate consists of 95% SKS6 and 5% silicate. The bleach activator aggregate consists of 81% TAED, 17% acrylic / maleic acid copolymer (acid form) and 2% water. Ethylenediamine N, N-disuccinate sodium salt / sulfate particles
Consists of 8% ethylenediamine N, N-disuccinic acid sodium salt, 23% sulfate and 19% water. The zinc phthalocyanine sulfonate inclusion is 10% active. The suds suppressor consisted of 11.5% silicone oil (ex. Dow Corning), 59% zeolite and 29.5% water. The binder spray-on system is 0.5 parts Lutensit K-HD 96 and 2.5 parts PE
Consists of G.

The following experiments were also performed to determine the solubility of non-tablet granular material to a highly soluble compound, ie, DIBS
Was tested with and without. A detergent of composition D was prepared as follows. All the particulate matter except the dried zeolite was mixed together in a mixing drum to form a uniform particulate mixture. Spray-on was performed during this mixing. After spray-on, spraying was performed with dry zeolite.

Table 1: Detergent Base Powder Composition Composition D (%) Anionic Aggregate 1 32 Cationic Aggregate 5 Laminated Silicate 11.5 Sodium Percarbonate 16.2 Bleach Activator Aggregate 4.7 Sodium Carbonate 3 .76 sodium bicarbonate 2.0 sodium sulfate 2.4 EDDS / sulfate particles 0.5 tetrasodium salt of hydroxyethanediphosphonic acid 0.8 soil release polymer 0.3 fluorescent agent 0.1 zinc phthalocyanine sulfonate inclusion 02 Foaming Inhibitor 2.1 Citric Acid 2 Protease 0.7 Lipase 0.2 Cellulase 0.2 Amylase 0.6 Perfume Inclusion 0.2 Polymer Particles 3 Perfume Spray On 0.35 Nonionic Spray On System 5.17 Zeolite 6.2

Anionic aggregate 1 consists of 40% anionic surfactant, 27% zeolite and 33% carbonate. Cationic aggregates consist of 20% cationic surfactant, 56% zeolite and 2%
Consists of 4% sulfate. The stacked silicate consists of 95% SKS6 and 5% silicate. The bleach activator aggregate consists of 81% TAED, 17% acrylic / maleic acid copolymer (acid form) and 2% water. Ethylenediamine N, N-disuccinate sodium salt / sulfate particles
Consists of 8% ethylenediamine N, N-disuccinic acid sodium salt, 23% sulfate and 19% water. The zinc phthalocyanine sulfonate inclusion is 10% active. The suds suppressor consisted of 11.5% silicone oil (ex. Dow Corning), 59% zeolite and 29.5% water. The perfume fill consists of 50% perfume and 50% starch. The polymer particles consist of 36%, 54% zeolite and 10% water. The nonionic spray-on system consists of 67% C ₁₂ -C ₁₅ AE5 (alcohol with an average of 5 ethoxy groups per molecule), 24% N-methylglucose amide and 9% water.

150 g of this granular detergent of composition D were introduced into the dispensing drawer of a “Hotpoint” washing machine. The water supply of the washing machine was set at a flow rate of 2 L / min at a temperature of 20 ° C. and a hardness of 21 grains / gallon. After 2 minutes, 38 g of detergent composition D remained undissolved in the distribution drawer.

145 g of this granule detergent of composition D were mixed with 5 g of DIBS. This granule mixture was introduced into the dispensing drawer of a "Hotpoint" washing machine. The water supply of the washing machine is 2L / min
At a flow rate of 20 ° C. and a hardness of 21 grains / gallon. After 2 minutes, 30 g of detergent composition D remained undissolved in the distribution drawer.

In another preferred embodiment according to the following example, the addition of the highly soluble compound (the highly soluble compound is preferably a hydrotropic compound) to the particulate material, together with a mixture of at least two polymers, comprises dissolving It has further been found that this synergistic effect has been found to occur particularly with mixtures of polymers such as PEG (polyethylene glycol), but more particularly with PEG having a molecular weight of 200-9000, preferably with a molecular weight of 1000-4000. Mixtures of PEG having the following have proven advantageous. Such PEGs are described, for example, in EP-A-0,522,766.
Other polymers include cationic polymers such as Lutensit KHD96. Thus, the molecular weight is regarded as an average molecular weight having a predetermined molecular weight distribution.

Example A (Formulation Used in Modified National Wave 1) i) A detergent base powder of Composition E (see below) was prepared as follows. All the particulate material of the base composition E was mixed together in a mixing drum to form a uniform particulate mixture. Spray-on was performed during this mixing. After spray-on, sodium diisoalkylbenzene sulfonate (sticky hydrotrope) was added to the rest of the matrix. ii) Tablets were then manufactured as follows. 43 g of the mixture were introduced into a 5.5 cm diameter circular mold and compressed to give a tablet tensile strength (or diameter breaking stress) of 15 kPa. iii) The tablets were then immersed at 140 ° C. in a bath in which 80 parts of sebacic acid were mixed with 20 parts of Nymcel zsb16. The time for immersing the tablets in the heating bath was adjusted so that 3 g of the mixture could be applied to it. The tablets were then allowed to cool at room temperature of 25 ° C. for 24 hours. iv) The level of residue in the washing machine dispenser was evaluated by the "stress tablet distribution test". Put two laundry tablets into Baucknecht WA9850 dispenser. The water supply to the washing machine is set at a temperature of 8 ° C. and a hardness of 21 grains / gallon, and the dispenser water inlet flow rate is set at 4 L / min. The level of tablet residue remaining in the dispenser is checked by flushing the dispenser with water for 78 seconds. The distribution residual ratio is determined as follows. % Distribution = Residue weight / raw tablet weight x 100 The distribution% is given in the table below.

Example B The procedure of making the tablet of Example A was repeated with the powder of Composition F. The polymer sprayed on the matrix contains 0.67 parts PEG 4000 and 0.33 parts P
It consisted of EG1000. The use of a mix of two PEG polymers resulted in better distribution results than the use of one PEG.

Detergent Base Powder Compositions E and F Example A (%) Example B (%) Anionic Aggregate 1 9.1 9.1 Anionic Aggregate 2 22.5 22.5 Nonionic Aggregate 9.1 9.1 Cationic aggregates 4.6 4.6 Stacked silicate 9.7 9.7 Sodium percarbonate 12.2 12.2 Bleach activator aggregates 6.1 6.1 Sodium carbonate 8.42 8.42 EDDS / Sulfate particles 0.5 0.5 Tetrasodium salt of hydroxyethanediphosphonic acid 0.6 0.6 Soil release polymer 0.3 0.3 Fluorescent agent 0.2 0.2 Zinc phthalocyanine sulfonate inclusion 0.030 .03 Soap powder 1.2 1.2 Foaming inhibitor 2.8 2.8 Citric acid 5.5 5.5 Protease 11 Lipase 0.35 0.35 Cellulase 0.2 0.2 Amirror 1.1 1.1 Binder Spray-On System PEG4000 1 0.67 PEG1000 0.33 Perfume Spray-On 0.5 0.5 DIBS 3 3 Tablet Stress Distribution (%) Resulting from Compression by Pressing 146 2000N 15. 6 16.6 Tablet tensile strength kPa

Anionic aggregate 1 consists of 40% anionic surfactant, 27% zeolite and 33% carbonate. Anionic aggregate 2 consists of 40% anionic surfactant, 28% zeolite and 32% carbonate. Nonionic aggregates consist of 26% nonionic surfactant, 6% Lutensit K-HD 96,
Consists of 40% anhydrous sodium acetate, 20% carbonate and 8% zeolite. Cationic aggregates consist of 20% cationic surfactant, 56% zeolite and 2%
Consists of 4% sulfate. The stacked silicate consists of 95% SKS6 and 5% silicate. The bleach activator aggregate consists of 81% TAED, 17% acrylic / maleic acid copolymer (acid form) and 2% water. Ethylenediamine N, N-disuccinate sodium salt / sulfate particles
Consists of 8% ethylenediamine N, N-disuccinic acid sodium salt, 23% sulfate and 19% water. The zinc phthalocyanine sulfonate inclusion is 10% active. The suds suppressor consisted of 11.5% silicone oil (ex. Dow Corning), 59% zeolite and 29.5% water. The binder spray-on system is 0.5 parts Lutensit K-HD 96 and 2.5 parts PE
Consists of G.

Examples CD The procedure for making the tablets of Example A was repeated with the powder of composition GH. The tablet tensile strength before coating with sebacic acid and Nymcel mix was 12 kPa. The use of a mix of three polymers gave better distribution results than the use of two polymers.

Detergent base powder compositions G and H Example C (%) Example D (%) Anionic aggregate 1 9.1 9.1 Anionic aggregate 2 22.5 22.5 Nonionic aggregate 9.1 9.1 Cationic aggregates 4.6 4.6 Stacked silicates 9.7 9.7 Sodium percarbonate 12.2 12.2 Bleach activator aggregates 6.1 6.1 Sodium carbonate 8.32 8.32 EDDS / Sulfate particles 0.5 0.5 Tetrasodium salt of hydroxyethanediphosphonic acid 0.6 0.6 Soil release polymer 0.3 0.3 Fluorescent agent 0.2 0.2 Zinc phthalocyanine sulfonate inclusion 0.030 .03 Soap powder 1.2 1.2 Foaming inhibitor 2.8 2.8 Citric acid 5.5 5.5 Protease 11 Lipase 0.35 0.35 Cellulase 0.2 0.2 Amirror 1.1 1.1 binder spray-on system Lutensit KHD 96 0.3 0.4 PEG4000 1.7 0.75 PEG1000 0.85 Perfume spray-on 0.5 0.5 DIBS 2.1 2.1 Tablet stress dispensing (%) 53 9

Anionic aggregate 1 consists of 40% anionic surfactant, 27% zeolite and 33% carbonate. Anionic aggregate 2 consists of 40% anionic surfactant, 28% zeolite and 32% carbonate. Nonionic aggregates consist of 26% nonionic surfactant, 6% Lutensit K-HD 96,
Consists of 40% anhydrous sodium acetate, 20% carbonate and 8% zeolite. Cationic aggregates consist of 20% cationic surfactant, 56% zeolite and 2%
Consists of 4% sulfate. The stacked silicate consists of 95% SKS6 and 5% silicate. The bleach activator aggregate consists of 81% TAED, 17% acrylic / maleic acid copolymer (acid form) and 2% water. Ethylenediamine N, N-disuccinate sodium salt / sulfate particles
Consists of 8% ethylenediamine N, N-disuccinic acid sodium salt, 23% sulfate and 19% water. The zinc phthalocyanine sulfonate inclusion is 10% active. The suds suppressor consisted of 11.5% silicone oil (ex. Dow Corning), 59% zeolite and 29.5% water. The binder spray-on system is 0.5 parts Lutensit K-HD 96 and 2.5 parts PE
Consists of G.

──────────────────────────────────────────────────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) Applicant ONE PROCTER & GANBLE PLAZA, CINCINNATI, OHIO, UNITED STATES OF AMERICA (72) Inventors Jose, Lewis, Vega Be-1853, Strombeek-Beaver, Bremendal-Larn, 47 (72) Inventors Jean, Webers Be--1840, Steen, Belgium Heufer, Heide, 17F term (reference) 4H003 AB18 BA17 DA01 EA12 EA15 EA16 EA24 EA28 EB12 EB13 EB22 EB26 EB32 EB36 EB37 ED02 FA32

Claims (11)

[Claims] 1. A tablet formed by compressing a particulate material, wherein the particulate material comprises a surfactant and a highly soluble compound, the highly soluble compound having an effect of adhering to the particulate material. A tablet. 2. A tablet according to claim 1, wherein at least 1% by weight, preferably at least 2% by weight of the tablet is formed from a highly soluble compound. 3. The highly soluble compound comprises sodium diisoalkylbenzenesulfonate,
The tablet according to claim 1. 4. The tablet has a tensile strength of more than 5 kPa, preferably less than 300 kPa.
The tablet according to claim 1. 5. The tablet according to claim 1, wherein the tablet has been compressed using a force of less than 100,000 N. 6. The tablet according to claim 1, wherein the tablet contains at least 5% by weight of a surfactant. 7. The tablet according to claim 1, wherein the highly soluble compound is a hydrotrope compound. 8. The uncoated tablet is as described in any one of claims 1 to 7,
Coated tablets. 9. A tablet according to claim 1, wherein the particulate material comprises a mixture of at least two polymers. 10. A method for preparing a laundry detergent aqueous solution for use in a washing machine, wherein the laundry detergent aqueous solution is formed by dissolving a tablet formed by compressing a granular substance in water. The method wherein the particulate material comprises a surfactant and a highly soluble compound, and wherein the highly soluble compound has an effect of adhering to the particulate material. 11. The method according to claim 9, wherein the tablets have a density of at least 0.9 g / cc, preferably less than 2 g / cc.