CN1425059A - Production process for detergent tablet - Google Patents

Abstract

The present invention relates to a process for making a detergent tablet, the process comprising a first step of providing a detergent composition, a second step of forming a particulate material comprising the detergent composition, and a third step of compressing the particulate material in a tablet form, the process being characterised in that it further comprises a step of cooling the detergent composition below ambient temperature between the first and the third step.

Description

Process for the preparation of detergent tablets

The present invention relates to a process for the preparation of detergent tablets.

Detergent tablets are now widely used in the automatic dishwashing field and are beginning to be used in the laundry field. These tablets are made by commercial processes which typically involve compressing a particulate material, typically made from a detergent composition, into tablets.

The present invention relates to a process for the preparation of a detergent tablet, the process comprising: a first step of providing a detergent composition, a second step of forming a granulate comprising the detergent composition, and a third step of pressing the granulate into tablets, is known from EP-a 2-0711828.

These methods have the advantage of being able to make relatively strong tablets based on traditional detergent powders, which reduces the mess caused by handling detergent compositions in a fluid state (powder, granule, liquid, gel or paste), while maintaining the tablets formed based on the already formed technology of handling granules. These tablets also produce additional dosage accuracy, which avoids overdosing or underdosing.

Although detergent tablets have these and other advantages, the detergent tablets obtained by such a process have disadvantages. For example, squeezing the granules can make it difficult to maintain their dissolution characteristics compared to detergent compositions in the fluid state.

It is an object of the present invention to provide a process for the preparation of detergent tablets of the above-mentioned type which produce detergent tablets having improved dissolution characteristics while maintaining the mechanical integrity of the tablets.

Summary of The Invention

According to the invention, the object of the invention is achieved by a process of the above-mentioned type further comprising the step of cooling the detergent composition to below ambient temperature between the first and third steps.

Detailed Description

The present invention relates to a process for the preparation of detergent tablets. The sheet should be understood to be a solid block that can be of various shapes and sizes. By a detergent tablet is understood a tablet containing detergent, i.e. generally containing surfactant. Such tablets are typically used for cleaning purposes.

The process of the present invention comprises a first step of providing a detergent composition. The detergent composition may be provided in various forms and may comprise a mixture of different materials. The process of the present invention further comprises a second step of forming a granulate comprising the detergent composition. The pellets may be formed by various methods, as will be exemplified later. It should be noted that these particulates comprising detergent compositions may also comprise other ingredients. The process of the present invention further comprises a third step of pressing the pellets into a sheet form. Also, various methods of obtaining tablets by pressing pellets will be described in the present application, but other methods may be used.

The process of the invention is characterized in that it further comprises a step of cooling the detergent composition to below ambient temperature between the first step and the third step. The ambient temperature is considered to be the ambient temperature of the production site in the tablet region. For example, the ambient temperature is the ambient temperature around the tablet press. It should be noted that in specific cases, for example in summer, the ambient temperature at the production site can reach higher temperatures, often exceeding 25 c and sometimes exceeding 30 c. The method of the present invention has been found to be particularly suitable for use in such high temperature environments. In fact, in a preferred embodiment, the ambient temperature is in excess of 18 ℃, even more preferably in excess of 20 ℃. Cooling to ambient temperature is understood to mean that the temperature of the detergent composition is brought to below ambient temperature at a time between the first and third steps. The cooling may be performed at any time between the first and third steps, for example in a silo, in a spray drum machine, in a Loedige KM machine, or as during storage between the second and third steps. In fact, in a preferred embodiment, the step of cooling the detergent composition is carried out by exposing the detergent composition to a portion of the space having a temperature below ambient temperature. However, other cooling methods may be used, such as reduced pressure. Even more preferably, such exposure is accomplished by placing the detergent composition in or through a portion of a space having a temperature below ambient for a period of time. This can be achieved, for example, by: placing the detergent composition in a silo having an internal temperature below ambient temperature, or passing the detergent composition through a cooling pipe at some stage of the processOr simply to provide a cooling air flow on the production line. Can be liquid nitrogen or solid CO₂The advantage of using such products for cooling is that they are chemically neutral materials because they do not normally react with detergent compositions and they evaporate quickly after release at ambient temperatures.

It should be noted that the process of the present invention has been found to be particularly useful for cooling detergent compositions which have a temperature above ambient temperature prior to the cooling step. Indeed, even if ambient temperature can lower the temperature of a detergent composition having a temperature above ambient temperature, the use of ambient temperature as described in the process of the present invention will allow for faster cooling of the detergent composition. This specificity is applicable to a wide range of ambient temperatures, i.e. ambient temperatures of at least 5 ℃, more preferably at least 10 ℃, even more preferably at least 15 ℃. It should be noted, moreover, that when cooling with a stream, the cooling step provided is even more efficient,the stream is formed by: mixing liquid (such as N)₂) Or gaseous (e.g. air) fluids or even solids such as CO₂Sprayed on the detergent composition or passed through such a fluid, or a combination of both fluids, in order to enhance heat transfer between the cooling gas or liquid fluid and the detergent composition.

The process of the invention is preferred when the difference between ambient temperature and the temperature below ambient temperature is at least 3 c, more preferably at least 5c, even more preferably at least 10 c.

In other preferred embodiments, the exposure time is proportional to the weight of detergent composition exposed divided by the difference between the ambient temperature and the temperature below ambient temperature during the cooling step. For example, in a process line where the detergent composition is handled at a rate of from 5 tonnes per hour to 100 tonnes per hour (preferably at least 10 tonnes per hour and less than 65 tonnes per hour), the detergent composition is preferably exposed to a stream of liquid nitrogen for 30 seconds, the liquid nitrogen stream being used at a rate of from 2 to 10 tonnes per hour.

In a preferred embodiment, the detergent composition comprises at least 10 wt% surfactant, more preferably at least 15 wt% surfactant, even more preferably more than 20 wt% surfactant, or at least 2 wt% binder, more preferably at least 3 wt% binder, even more preferably at least 5 wt% binder, most preferably at least 7 wt% binder. In fact, without wishing to be bound by theory, it is believed that: the improved disintegration of the tablets of the invention is due to a morphological change of one of these components due to a temperature difference.

In a most preferred embodiment, the temperature of the detergent composition after the cooling step and before the third step is below ambient temperature due to the cooling of the detergent composition. The temperature of the detergent composition is preferably at least 2 ℃, more preferably at least 5 ℃, most preferably at least 10 ℃ below ambient temperature.

It has been found that: the tablets obtained with the process of the invention are easier to dispense.

These tablets may include ingredients such as perfumes, surfactants, enzymes, detergents, and the like. The general composition of the tablets of the preferred embodiments of the invention is disclosed, for example, in pending european patent applications 96203471.6, 96203462.5, 96203473.2 and 96203464.1. The ingredients incorporated into detergent tablets or other forms of detergent compositions, such as liquids or granules, are described in detail in the following paragraphs. Highly soluble compounds

The detergent tablet may comprise highly soluble compounds. Such compounds may be formed from a mixture or a single compound. Highly soluble compounds are defined as follows:

the following solutions were prepared, including deionized water and 20 grams of the particular compound per liter:

1-20 g of a particular compound were placed in a Sotax beaker. The beaker was placed in a constant temperature bath set at 10 ℃. The stirrer with marine propeller was placed in the beaker with the stirrer bottom 5mm above the beaker bottom. The rotational speed of the mixer was set to 200 revolutions per minute.

2-980 grams of deionized water were added to a Sotax beaker.

3-deionized water was added for 10 seconds, and the conductivity of the solution was measured with a conductivity meter.

4-repeat step 3 after 20 seconds, 30 seconds, 40 seconds, 50 seconds, 1 minute, 2 minutes, 5 minutes and 10 minutes after step 2.

The measured values at 5-10 minutes were used as plateau or maximum values.

The specific compounds according to the invention are highly soluble when the conductivity of the solution reaches 80% of its maximum value, measured in less than 10 seconds, starting from the time when deionized water is added to the compound in its entirety. In fact, when monitoring the conductivity in this way, the conductivity will reach a plateau value after a certain period of time, which plateau value is considered to be the maximum value. For ease of handling, such compounds are preferably flowable materials consisting of solid particles at a temperature of 10-80 ℃, however, other forms such as pastes or liquids may be used.

Examples of the highly soluble compound include sodium diisoalkylbenzene sulfonate (DIBS) or sodium toluene sulfonate. Bonding action

The tablet may include a compound which has a binding effect on the particulate material forming the detergent matrix of the tablet. The binding effect on the granules of the detergent matrix forming the layer of tablets or sheets is characterized by the force required to break the tablets or layers of the detergent matrix to be examined, which are based on pressing under controlled pressing conditions. For a given compression force, a high sheet or layer strength means that when the particles are compressed, they are highly bonded together, thus creating a strong bond. Pharmaceutical Dosage Forms: methods for evaluating sheet or layer strength (also known as radial rupture stress) are given in table ets, volume 1, h.a. lieberman et al, 1989. The cohesion is determined by comparing the strength of a sheet or layer of the original base powder, which does not contain the cohesion compound, with the strength of a sheet or layer of a powder mixture comprising 97 parts of the original base powder and 3 parts of the cohesion compound. The cementitious compound is preferably added to the matrix in a form substantially free of water (water content below 10% (preferably below 5%)). The addition temperature is 10-80 deg.C, more preferably 10-40 deg.C.

When 3% of the caking-effect compound is present in the base granule, the compound is defined as having a caking effect on the base granule when the increase in the sheet tensile strength of a sheet of detergent granules weighing 50g and having a diameter of 55mm exceeds 30% (preferably 60%, more preferably 100%) at a given compactibility of 3000N.

An example of a compound having a binding effect is sodium diisoalkylbenzene sulfonate.

When a compound which is both highly soluble and has a binding effect on the granules is used for a tablet or layer made by compacting the granules including a surfactant, the solubility of the tablet or layer in an aqueous solution is greatly improved. In a preferred embodiment at least 0.5 wt% of the tablets or layers are made of a highly soluble compound, more preferably at least 0.75 wt%, even more preferably at least 2 wt%, most preferably at least 4 wt% of the tablets or layers are made of a highly soluble compound having a binding effect on the granulate.

It should be noted that EP-A-0524075 discloses ｃA composition comprising ｃA highly soluble compound and ｃA surfactant, which composition is ｃA liquid composition.

Highly soluble compounds which bind to particulates can give tablets with higher tensile strength at constant compaction force or the same tensile strength at lower compaction force than conventional tablets. The tensile strength of the whole sheet is generally greater than 5kPa, preferably greater than 10kPa, especially for use in the laundry field, more preferably greater than 15kPa, even more preferably greater than 30kPa, most preferably greater than 50kPa, especially for use in the dishwashing or automatic dishwashing field; the tensile strength is less than 300kPa, preferably less than 200kPa, more preferably less than 100kPa, even more preferably less than 80kPa, most preferably less than 60 kPa. In fact, the tablets used in the laundry field are less stressed than tablets used in the field such as automatic dishwashing, such tablets are easily dissolved, and therefore the tensile strength of the tablets used in the laundry field is preferably less than 30 kPa.

This makes it possible to produce tablets or layers having a firmness and resistance comparable to those of conventional tablets, which are less dense and therefore more easily dissolvable. In addition, because the compound is highly soluble, it can also promote dissolution of the tablet or layer, and this synergistic effect results in the promotion of dissolution of the tablet of the present invention. Production of tablets

Such a sheet may comprise several layers. For the purpose of producing a single layer, the layer may be considered to be the sheet itself.

Detergent tablets may be prepared simply by mixing the solid ingredients together and then compressing the mixture in a conventional tabletting machine as used in the pharmaceutical industry. The main component, in particular the gelling surfactant, is preferably used in the form of granules. All liquid ingredients, such as surfactants or suds suppressors, can be added to the solid particulate ingredients in a conventional manner.

In particular for laundry tablets, the ingredients such as builders and surfactants are spray dried in a conventional manner and then compressed under suitable pressure. The pressure used when compressing the tablets of the invention is preferably less than 100000N, more preferably less than 50000N, even more preferably less than 5000N, most preferably less than 3000N. In fact, the most preferred embodiment is to compress tablets suitable for laundry with a pressure of less than 2500N, however, tablets for use in, for example, automatic dishwashing may additionally be considered, as automatic dishwashing tablets are generally more compact than compressed laundry tablets.

The granulate used for the preparation of the tablets can be produced by any granulation method or granulation method. An example of these processes is spray drying (in co-current or counter-current spray drying towers), in which generally bulk densities as low as 600g/l or less can be obtained. Higher density granulates can be prepared by granulation followed by densification in a high shear batch mixer/granulator or by continuous granulation and densification (e.g., using Lodige)^®CB and/or Lodige^®KM mixer). Other suitable processes include fluidized bed processes, compaction processes (e.g., roller compaction), extrusion processes, and granulates made by any of the chemical processes such as flocculation, crystallization delivery (sensing). The individual particles may also be any other particles, granules, pellets or grains.

The components of these pellets may be mixed together by any conventional method. Batch wise production in e.g. a concrete mixer, a Nauta mixer, a screw mixer or any other mixer is suitable. The mixing process may also be carried out continuously by metering the weight of each component on a conveyor belt and then mixing the components in one or more drums or mixers. The non-gel binder may be sprayed onto some or all of the components of the particulate. Other liquid ingredients may also be sprayed onto the mixture of these components, either alone or in a premix. For example, a slurry of perfume and optical brightener may be sprayed. After the binder is sprayed, preferably towards the end of the process, finely divided flow aids (release agents such as zeolites, carbonates, silicon dioxide) can be added to the granulate to reduce the viscosity of the mixture.

The tablets may be produced by any compression method, such as tabletting, molding or extrusion, preferably tabletting. Suitable equipment includes standard single stroke or rotary tablet presses (e.g., Courtoy)^®，Korch^®，Manesty^®Or Bonals^®). The tablets prepared according to the invention have a diameter of 20 to 60mm, preferably at least 35mm and a maximum of 55mm, and a weight of 25 to 100 g. The height to diameter (or width) ratio of the sheet is preferably greater than 1: 3, more preferably greater than 1: 2. In another preferred embodiment, the cross-section of the sheet is a square of 45mm by 45mm, the height of which is 25 mm. The pressure used to prepare these tablets must not be greater than 100000kN/m²Preferably not more than 30000kN/m²More preferably not more than 5000kN/m²And even more preferably not more than 3000kN/m²Most preferably not more than 1000kN/m². In a preferred embodiment according to the present invention, the tablet has a density of at least 0.9g/cc, more preferably at least 1.0g/cc, and preferably less than 2.0g/cc, more preferably less than 1.5g/cc, even more preferably less than 1.25g/cc, and most preferably less than 1.15 g/cc.

Multilayer tablets are generally formed by placing pellets in a rotary tablet press in each layer of a forced-feed flask, layer by layer. Because the process is continuous, the particulates are then laminated together in a pre-press and press stage to form a multilayer sheet. With some rotary tablet presses, it is also possible to compress the first feed layer prior to compressing the entire tablet. Hydrotrope compounds

Highly soluble compounds with binding properties can be incorporated into detergent tablets and therefore the compounds can also be hydrotrope compounds. Typically, such hydrotrope compounds are used to avoid gelling and thereby promote surfactant dissolution. Specific compounds defined as hydrotropes are as follows (see s.e. friberg and m.chiu, j.dispersion Science and technology, 9(5&6), page 443-:

1. a solution comprising 25 wt% of the specific compound and 75 wt% of water was prepared.

2. Octanoic acid was then added to the solution in an amount of 1.6 times the weight of the particular compound in the solution, the temperature of the solution being 20 ℃. The solution was stirred in a Sotax beaker with a stirrer with a marine propeller 5mm above the bottom of the beaker. The rotational speed of the mixer was set to 200 revolutions per minute.

3. This particular compound is a hydrotrope if the octanoic acid is completely dissolved, i.e. if the solution comprises only one phase and the phase is a liquid phase.

It should be noted that such hydrotrope compounds are flowable materials composed of solid particles under operating conditions of 15-60 ℃.

Hydrotrope compounds include the compounds listed below:

exemplary commercial hydrotropes may be found in McCutcheon's Emulsifiers and Detergents, published by the McCutcheon division of manufacturing conditioners Company. Related compounds also include:

1. a nonionic hydrotrope having the structure:wherein R is a C8-C10 alkyl chain, x is 1-15, and y is 3-10.

2. Anionic hydrotropes such as alkali metal aryl sulphonates. This includes alkali metal benzoic acid, salicylic acid, benzene sulfonates and many of their derivatives, naphthoic acid and salts of various hydrogenated aromatic acids. Examples of such salts are the benzene sulfonates of sodium, potassium and ammonium derived from toluene sulfonic acid, xylene sulfonic acid, cumene sulfonic acid, tetralin sulfonic acid, naphthalene sulfonic acid, methyl naphthalene sulfonic acid, dimethyl naphthalene sulfonic acid, trimethyl naphthalene sulfonic acid.

Other examples include dialkyl benzene sulfonates such as diisopropylbenzene sulfonic acid, ethylmethyl benzene sulfonic acid, alkyl benzene sulfonic acids having an alkyl chain length of 3 to 10 (preferably 4 to 9) carbons, salts of linear or branched alkyl benzene sulfonic acids having an alkyl chain of 1 to 18 carbons.

3. Solvent hydrotropes such as alkoxylated glycerols and alkoxylated glycerides, esters of alkoxylated glycerols, alkoxylated fatty acids, glycerides, polyglycerides. Preferred alkoxylated glycerols have the following structure:

wherein l, m and n are each a number from 0 to about 20, l + m + n is from about 2 to about 60, preferably from about 10 to about 45, and R represents H, CH₃Or C₂H₅。

Preferred alkoxylated glycerides have the following structure:

wherein R1 and R2 are both C_nCOO or- (CH)₂CHR₃-O)_l-H，R₃Is H, CH₃Or C₂H₅. l is a number from 1 to about 60 and n is a number from about 6 to about 24.

4. Polymeric hydrotropes such as those described in EP 636687:wherein E is a hydrophilic functional group, R is H or C1-C10 alkyl or a hydrophilic functional group; r1 is H or lower alkyl or aryl,r2 is H or cycloalkyl or aryl. The molecular weight of the polymer is generally from about 1000 to about 1000000.

5. Hydrotropes of unusual structure such as 5-carboxy-4-hexyl-2-cyclohexen-1-yl octanoic acid (Diacid)^®)。

The use of such compounds in the present invention will further increase the dissolution rate of the tablet, as the hydrotrope compound can facilitate dissolution of, for example, a surfactant. Such compounds may be formed from a mixture or a single compound. Tensile strength

To determine the tensile strength of a layer, the layer can be considered to be the sheet itself.

Depending on the raw material composition and shape of the tablet, the compression force used may be adjusted to not affect the tensile strength of the tablet and its disintegration time in a washing machine. Uniform or layered tablets of any size or shape can be prepared in this way.

For a cylindrical sheet, tensile strength corresponds to the radial fracture stress (DFS), a method of expressing the strength of the sheet or layer, determined by the following equation:

tensile strength 2F/pi Dt

Where F is the maximum force (in newtons) to cause tensile failure (fracture) as determined using a VK200 sheet hardness tester supplied by Van Kell industries, Inc. D is the diameter of the sheet or layer and t is the thickness of the sheet or layer. For a patch that is not circular, one can simply replace π D with the perimeter of the patch.

(Method Pharmaceutical Dosage Forms: Tablets Vol.2, page 213-217).

Tablets having a radial fracture stress of less than 20kPa, preferably at least 25kPa, are considered brittle, likely to cause some breakage in tablets distributed to consumers.

The definition of tensile strength applies equally to non-cylindrical sheets where the cross-section perpendicular to the height of the sheet is not circular and the direction of the applied force is in a direction perpendicular to the height of the sheet and perpendicular to the side of the sheet that is perpendicular to the non-circular cross-section. Dispensing of tablets

The dispensing rate of the detergent tablet was determined by the following method:

two tablets, both of which are nominal 50g, are weighed out and then placed in Baucknecht^®Dispenser for WA9850 washing machine. The temperature of the water supplied to the washer was 20 c, the hardness was 21 grains per gallon, and the flow rate at the water inlet of the dispenser was 8L/min. The wash switch is switched on and the wash cycle is set to wash program 4 (white/color, short cycle) to determine the remaining in the dispenserAmount of residue remaining. The percent distribution of residue was determined using the following equation:

percent partition ═ residue weight × 100/original tablet weight

The procedure was repeated 10 times, and the amount of residue was determined by calculating the average amount of residue based on the 10 measurements. In this stress test, a residue of 40% of the weight of the starting sheet was considered acceptable. Residues of less than 30% are preferred, and residues of less than 25% are more preferred.

It should be noted that the water hardness tested is given in the traditional "grains per gallon" unit, where: 0.001 moles per liter to 7.0 grains per gallon, which represents Ca in solution²⁺The ion concentration. Foaming agent (Effervescent)

The detergent tablet may also include a foaming agent.

Foaming, as defined in this application, means the escape of bubbles from a liquid, as a result of a chemical reaction between a soluble acid source and an alkali metal carbonate to form carbon dioxide gas,

that is to say that the first and second electrodes,

at the following stage: other examples of acid and carbonate sources and other foamer systems can be found in Pharmaceutical Dosage Forms: Tablets Vol.1, pp.287-291.

In addition to the detergent ingredients, a foaming agent may be added to the tablet mixture. The addition of such foaming agents to detergent tablets can improve the disintegration time of the tablets. The amount is preferably 5 to 20 wt%, most preferably 10 to 20 wt% of the weight of the tablet. A blowing agent. Preferably as agglomerates or compacts of different particles, rather than being added separately as individual particles.

Because the bubbling action causes gas generation in the tablet, the tablet has a higher d.f.s, which is still the same disintegration time as a tablet without bubbling action. When the d.f.s of the tablets with foaming action remains the same as that of the tablets without foaming action, the tablets with foaming action disintegrate more rapidly.

Cosolvents may also be provided by using compounds such as sodium acetate or urea. Pharmaceutical Dosage Forms: a list of suitable co-solvents may also be found in Tablets, volume 1, second edition, eds H.A. Lieberman et al, ISBN 0-8247-8044-2. Coating of

The robustness of the tablets can be improved by preparing coated tablets, the coating covering the uncoated tablets, thereby improving the mechanical properties of the tablets.

This method is very advantageous for application on multilayer sheets, the mechanical properties of the more elastic layer being transmitted to the other layers of the sheet by the coating, and it therefore combines the advantages of the coating with those of the more elastic layer. In fact, the mechanical constraint is transmitted through the coating, which improves the mechanical integrity of the sheet. In one embodiment of the invention, the sheet is subsequently coated so that it does not absorb moisture, or absorbs moisture only at a very low rate. The coating is also strong so that the sheet is not damaged or abraded to more than a very low degree by moderate mechanical shock during handling, packaging and shipping. Finally, the coating is preferably brittle, allowing the sheet to crack rapidly when subjected to stronger mechanical vibrations. In addition, it is advantageous if the coating material is soluble under alkaline conditions or is easily emulsified by surfactants. This helps to avoid the problem of visible residues in the window of a front-loading washing machine during the wash cycle and also helps to avoid particles or lumps of undissolved coating material being deposited on the wash.

Water solubility is determined according to ASTM E1148-87, Test Method entitled "Standard Test Method for measuring Water solubility" Test Method for aqueous solubility. The melting point of the coating material is preferably 40-200 ℃.

Coating can be carried out in a variety of ways. Two preferred coating methods are a) coating with molten material and b) coating with a solution of the material.

In a), the coating is carried out at a temperature above its melting point and is then cured on the sheet. In b), the coating is carried out with the solution, leaving a bond coat after the solvent has dried. The substantially insoluble material may be applied to the sheet by, for example, spraying or dipping. Typically, the molten material will solidify rapidly to form a bond coat when sprayed onto the sheet. Rapid cooling can also cause rapid solidification of the coating material when the sheet is immersed in the molten material and then removed. During the curing process, the coating is subjected to certain internal stresses (e.g., shrinkage upon cooling) and external stresses (e.g., sheet relaxation). If the coating material is too brittle to withstand these mechanical stresses, some cracks such as edge cracks may be caused in the structure of the sheet, which often occurs when the coating is made of components that are solid at only 25 ℃. In fact, the coating preferably comprises a component that is liquid at 25 ℃. It can be considered that: this liquid component enables the coating to better withstand and absorb mechanical stresses by making the coating structure more elastic. The amount of the component added to the coating material that is liquid at 25 ℃ is preferably less than 10%, more preferably less than 5%, most preferably less than 3% by weight of the coating. The amount of the component added to the coating material that is liquid at 25 ℃ is preferably greater than 0.1%, more preferably greater than 0.3%, and most preferably greater than 0.5% by weight of the coating. In order to further strengthen the structure, it is also preferred to add reinforcing fibers to the coating.

The coating preferably comprises a crystalline structure. Crystalline is to be understood as meaning a coating comprising a material which is solid at ambient temperature (25 ℃) and has a certain ordered structure. This is typically detectable on the material itself by using common crystallographic techniques such as X-ray analysis. In a more preferred embodiment, the material forming the crystalline structure does not co-crystallize or only partially co-crystallize with the optional components described above that are liquid at 25 ℃. In fact, it is preferred that the optional components in the detection of the crystal structure remain in the liquid state at 25 ℃ in order to make the structure elastic and resistant to mechanical stress. In another embodiment, optional ingredients that are liquid at 25℃ that have a function such as silicone oils or fragrance oils that provide suds suppression benefits are advantageous in laundry.

The coating material may also include other optional components. Suitable coating materials are, for example, dicarboxylic acids. Particularly suitable dicarboxylic acids are selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid and mixtures thereof. Most preferred is adipic acid.

Apparently substantially insoluble materials with melting points below 40 ℃ are often not true solids at ambient temperatures and have been found to: materials with melting points above about 200 c cannot be practically used. Preference is given to using acids having a melting point of greater than 90 ℃ such as azelaic acid, sebacic acid and dodecanedioic acid. Even more preferably, an acid having a melting point above 145 deg.C, such as adipic acid, is used.

"melting point" refers to the temperature at which the material is slowly heated in a capillary to become a transparent liquid.

Any desired thickness of the coating may be used in accordance with the present invention. For most purposes, the coating is formed in an amount of 1 to 10%, preferably 1.5 to 5% by weight of the tablet.

The coating of the tablet is very hard, giving the tablet additional strength.

Examples of optional components that are liquid at 25 ℃ include polyethylene glycol, heat transfer oil, silicone oil, dicarboxylic acid ester, monocarboxylic acid, paraffin, triacetin, perfume or alkaline solution. The structure of the component that is liquid at 25 c is preferably close to the structure of the material forming the crystalline structure so that the structure of the sheet is not excessively fractured. In a most preferred embodiment, adipic acid forms a crystalline structure, commercially available from Chemoxy International under the name Coasol^TMThe component (b) which is liquid at 25 ℃ is a mixture of diisobutyl esters of glutaric, succinic and adipic acids. The advantage of using this component is that good dispersibility in adipic acid makes the tablet elastic. It should be noted that Coasol^TMThe adipate contained in (A) can further improve the disintegration of adipic acid.

The addition of a disintegrant to the coating improves the disintegration of the coating upon washing. The disintegrant swells upon contact with water, breaking the coating into small pieces. This will improve the solubility of the coating in the wash liquor. The amount of disintegrant suspended in the coating melt can be up to 30 wt%, preferably 5 wt% to 20 wt%, most preferably 5 wt% to 10 wt%. Disintegrants are available as described in Handbook of pharmaceutical Excipients (1986). Examples of suitable disintegrants include starch: natural, modified or pregelatinized starch, sodium starch gluconate; gum: agar gum, guar gum, locust bean gum, karaya gum, pectin gum, tragacanth gum; croscarmylose sodium, crospovidone, cellulose, carboxymethylcellulose, alginic acid and its salts including sodium alginate, silica, clays, polyvinylpyrrolidone, soybean polysaccharides, ion exchange resins, polymers containing cationic groups (such as quaternary ammonium salts), amine-substituted polyacrylates, polymeric cationic amino acids such as L-polylysine, polyallylamine hydrochloride and mixtures thereof.

The coating preferably comprises an acid having a melting point of at least 145 ℃, such as adipic acid, and a clay, such as bentonite, which acts here as a disintegrant and makes the adipic acid structure more water-permeable, thus improving the dispersibility of the adipic acid in an aqueous medium. The particle size of the clay is preferably less than 75 μm, more preferably less than 53 μm, in order to produce the desired effect on the structure of the acid. Bentonite is preferred. In fact, the melting point of the acid is such that conventional cellulose disintegrants undergo thermal decomposition during the coating process, but the clay has been found to be more heat stable. In addition, the following findings are provided: conventional cellulose disintegrants such as Nymcel^TMIt will turn brown at these temperatures.

In another preferred embodiment, the coating further comprises reinforcing fibers. These fibers have been found to further improve the resistance of the coating to mechanical stresses and to minimize the possibility of cracking defects. For structural reinforcement, the length of these fibers is preferably at least 100 μm, more preferably at least 200 μm, most preferably at least 250 μm. In order not to affect the dispersibility of the coating in an aqueous medium, the length of these fibers is preferably less than 500. mu.m, more preferably less than 400. mu.m, most preferably less than 350. mu.m. Materials that can be used for these fibers include viscose rayon, natural nylon, synthetic nylon (polyamides of types 6 and 6, 6), acrylic, polyester, cotton and cellulose derivatives such as CMC. Most preferably from Fibers Sales&Development is commercially available under the trademark Solka-Floc^TMThe cellulosic material of (a). It should be noted that: these fibers typically do not need to be pre-compressed in order to reinforce the coating structure. These fibers are preferably added in an amount of less than 5%, more preferably less than 3% by weight of the coating. These fibers are preferably added in an amount greater than 0.5%, more preferably greater than 1% by weight of the coating. Detergent surfactant

Surfactants are typically included in the detergent compositions. The addition of a highly soluble compound can facilitate the dissolution of the surfactant.

The amount of surfactant suitable for use in the present invention is generally from about 1 wt% to about 55 wt%, non-limiting examples of which include conventional C₁₁-C₁₈Alkyl benzene sulfonates ("LAS") and primary branched and random C₁₀-C₂₀Alkyl sulfate ("AS"), formula CH₃(CH₂)_X(CHOSO_3-M⁺)CH₃AndCH₃(CH₂)_Y(CHOSO_3-M⁺)CH₂CH₃c of (A)₁₀-C₁₈Secondary (2, 3) alkyl sulfates wherein X and Y +1 are integers of at least about 7, preferably at least about 9, M is a water-soluble cation, particularly sodium, an unsaturated sulfate such as oleyl sulfate, C₁₀-C₁₈Alkyl alkoxy sulfates (' AE)_XS "; in particular EO1-7 ethoxy sulfate), C₁₀-C₁₈Alkyl alkoxy carboxylates (especially EO1-5 ethoxy carboxylates), C₁₀-C₁₈Glycerol ethers, C₁₀-C₁₈Alkyl polyglycosides and their corresponding sulfated polyglycosides, and C₁₂-C₁₈α -sulfonated fatty acid esters if desired, conventional nonionic and amphoteric surfactants such as C may also be included in the overall composition₁₂-C₁₈Alkyl ethoxylates ("AE"), which include so-called narrow peak alkyl ethoxylates and C₆-C₁₂Alkylphenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy). C₁₂-C₁₈Betaines and thiobetaines ("sulfobetaines"), C₁₀-C₁₈Amine oxides, and the like. Also usable are C₁₀-C₁₈N-alkyl polyhydroxy fatty acid amides. See WO 9206154. Other saccharide-derived surfactants include N-alkoxy polyhydroxy fatty acid amides such as C₁₀-C₁₈N- (3-methoxypropyl) glucamide. N-propyl to N-hexyl C₁₂-C₁₈Glucamides are useful for reducing foaming. Also can use C₁₀-C₂₀Conventional soaps are used. If high foaming is desired, a branched chain C may be used₁₀-C₁₆A soap is provided. Mixtures of anionic and nonionic surfactants are particularly useful. Other traditionally useful surfactants are listed in standard texts. In a preferred embodiment, the tablet comprises at least 5 wt% surfactant, more preferablyPreferably at least 15 wt%, even more preferably at least 25 wt%, most preferably from 35 wt% to 45 wt% of surfactant. Non-gel adhesive

To further promote dissolution, a non-gelling binder may be added to the detergent composition.

If a non-gelling binder is used, suitable non-gelling binders include synthetic organic polymers such as polyethylene glycol, polyvinylpyrrolidone, polyacrylates and water-soluble acrylate copolymers. The second edition of the handbook of pharmaceutical excipients consists of the following classes of binders: acacia, alginic acid, acrylic acid polymers, sodium carboxymethylcellulose, dextrin, ethylcellulose, gelatin, guar gum, type I hydrogenated vegetable oil, hydroxyethyl cellulose, hydroxypropyl methylcellulose, liquid glucose, magnesium aluminum silicate, maltodextrin, methylcellulose, polymethacrylates, povidone, sodium alginate, starch and zein. Most preferred binders also have an active cleaning action in the wash, such as cationic polymers, i.e., ethoxylated hexamethylene diamine quaternaries, bis hexamethylene triamine, or other materials such as pentamine, ethoxylated polyethylene amine, maleic acrylic polymers.

The non-gelling binder material is preferably sprayed onto the tablets and should therefore have a suitable melting point, which is below 90 c, preferably below 70 c, even more preferably below 50c, in order not to damage or decompose other active ingredients in the matrix. Most preferably, an anhydrous liquid binder that can be sprayed in the molten state (i.e., not in an aqueous solution) is used. However, it is also possible to add to the matrix a solid binder which is added in the dry state but which is adhesive in the sheet.

The amount of non-gelling binder material in the composition is preferably from 0.1 to 15% by weight of the tablet, more preferably less than 5%, especially when the material is a non-detergent active material, more preferably less than 4%.

The use of gel binders such as nonionic surfactants in liquid or molten form is preferably avoided. The use of nonionic surfactants and other gel binders is not excluded from the composition, but is preferably processed into detergent tablets as a particulate component rather than added in liquid form. Builder

Detergent builders may optionally be included in the compositions of the present invention to assist in controlling mineral hardness. Inorganic and organic builders can be used. Builders are commonly used in fabric washing compositions to aid in the removal of particulate soils.

The amount of builder used can vary over a very wide range depending on the end use of the composition.

Inorganic or phosphorus-containing detergent builders include, but are not limited to: alkali metal, ammonium and alkanolammonium polyphosphates (such as tripolyphosphates, pyrophosphates and glassy polymeric metaphosphates), phosphates, phytates, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates and aluminosilicates. Importantly, the compositions of the present invention are surprisingly good even in the presence of so-called "weak" builders such as citrate or in the case of "under-built" conditions which may occur when zeolite or layered silicate builders are used.

Examples of silicate builders are alkali metal silicates, in particular SiO₂∶Na₂Those alkali metal silicates and layered silicates in which O is 1.6: 1 to 3.2: 1, such as the layered sodium silicate described in us patent 4664839 to h.p. rieck, 1987.5.12. NaSKS-6 is the trade name for crystalline layered silicates sold by Hoechst (generally abbreviated herein as "SKS-6"). Unlike zeolite builders, the NaSKS-6 silicate builder does not contain aluminum. NaSKS-6. delta. -Na with layered silicate₂SiO₅The type is shown. These can be prepared by the processes described in DE-A-3417649 and DE-A-3742043. SKS-6 is a highly preferred layered silicate for use in the present invention, however, other such layered silicates, such as those of the formula NaMSi, can be used in the present invention_XO_2X+1.YH₂O, wherein M is sodium or hydrogen, X is a number between 1.9 and 4, preferably 2, Y is a number between 0 and 20, preferably 0 various other layered silicates commercially available from Hoechst can be used, including α, β and NaSKS-5, NaSKS-7 and NaSKS-11 in the gamma formδ-Na₂SiO₅(NaSKS-6 type). Other silicates such as magnesium silicate are also useful as crispening agents (crispening agents) in granular formulations, as stabilizers for oxygen bleaches, and as a component of foam control systems.

An example of a carbonate builder is the alkaline earth and alkali metal carbonates disclosed in german patent application 2321001, published at 1973.11.15.

Aluminosilicate builders can be used in the present invention. Aluminosilicate builders are of great importance in most of the heavy duty granular detergent compositions currently marketed. Aluminosilicate builders include those of the empirical formula:

M_z(zAlO₂)_y]·xH₂o wherein z and y are integers of at least 6, the molar ratio of z to y is from 1.0 to about 0.5, and x is an integer from 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 natural or synthetic. 1976.10.12 to Krummel et al, U.S. patent 3985669 discloses a process for the preparation of aluminosilicate ion exchange materials. Synthetic crystalline aluminosilicate ion exchange materials useful in the present invention are commercially available under the designations zeolite a, zeolite p (b), zeolite MAP and zeolite X. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:

Na₁₂[(AlO₂)₁₂(SiO₂)₁₂]·xH₂o wherein x is from about 20 to about 30, especially about 27. This material is known as zeolite a. Dehydrated zeolites (x ═ 0 to 10) can also be used in the present invention. The particle size of the aluminosilicate is preferably about 0.1 to 10 μm.

Organic detergent builders that may be suitable for the purposes of the present invention include, but are not limited to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to compounds having multiple carboxylate groups, preferably at least 3 carboxylate groups. Polycarboxylate builders can generally be added to the compositions in either the acid or neutral salt form. When salt forms are used, alkali metal salts such as sodium, potassium and lithium or alkanolammonium salts are preferred.

Various useful materials are included in polycarboxylate builders. One important class of polycarboxylate builders comprises the ether polycarboxylates, including oxydisuccinates, disclosed in 1964.4.7, U.S. Pat. Nos. 3128287 and 1972.1.18 to Berg, U.S. Pat. No. 3635830 to Lamberti et al. See also 1987.5.5 for "TMS/TDS" builders in U.S. Pat. No. 4663071 to Bush et al. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, as disclosed in U.S. patent nos. 3923679; 3835163, respectively; 4158635, respectively; 4120874 and 4102903.

Other useful detergent builders include ether hydroxypolycarboxylates, copolymers of maleic anhydride and ethylene or vinyl methyl ether, 1, 3, 5-trihydroxybenzene-2, 4, 6-trisulfonic acid, and carboxymethyloxysuccinic acid, salts of various alkali metals, ammonium and ammonium-substituted polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, and polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1, 3, 5-tricarboxylic acid, esters of carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate builders, such as citric acid and its soluble salts (especially sodium salts), are particularly important polycarboxylate builders for heavy duty liquid detergent compositions because they are available from renewable resources and are biodegradable. Citrate salts may also be used in granular formulations, particularly in combination with zeolite and/or layered silicate builders. Oxosuccinates are also particularly useful in such compositions and combinations.

Also suitable for use in the present invention are the 3, 3-dicarboxy-4-oxa-1, 6-adipates and related compounds disclosed in U.S. Pat. No. 4566984 issued to Bush, 1986.1.28. Useful succinic acid builders include C₅-C₂₀Alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this class is dodecenylsuccinic acid. Specific examples of succinates include: lauryl succinate, myristyl succinate, palmityl succinate2-dodecenyl succinate (preferred), 2-pentadecenyl succinate and the like. Lauryl succinate is a preferred builder from this group and is disclosed in European patent application 86200690.5/0200263 published at 1986.11.5.

1979.3.13 U.S. Pat. Nos. 4144226 and 1967.3.7 to Crutchfield et al, U.S. Pat. No. 3308067 to Diehl, disclose other suitable polycarboxylates. See also U.S. patent 3723322 to Diehl.

Fatty acids such as C₁₂-C₁₈The monocarboxylic acids of (a) may also be incorporated into the composition, either alone or in combination with the above-mentioned builders, especially citrate and/or succinate builders, to produce additional builder activity. Such use of fatty acids generally reduces foaming, which the formulator should take into account.

In the case of phosphorus-based builders, particularly in bar formulations for hand washing operations, various alkali metal phosphates such as the well-known sodium tripolyphosphates, pyrophosphates and orthophosphates may be used. Phosphate builders such as ethane-1-hydroxy-1, 1-diphosphate and other known phosphates may also be used (see, for example, U.S. Pat. Nos. 3159581; 3213030; 3422021; 3400148 and 3422137). Bleaching agent

The detergent compositions of the present invention may optionally contain a bleaching agent or a bleaching composition comprising a bleaching agent and one or more bleach activators. When present, especially for fabric laundering, the bleaching agent is typically present in an amount of from about 1% to about 30%, more typically from about 5% to about 20% of the detergent composition. If present, the amount of bleach activator is typically from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the bleaching composition comprising the bleach and the bleach activator.

The bleaching agent used in the present invention may be any bleaching agent suitable for use in detergent compositions for known or future fabric cleaning, hard surface cleaning or other cleaning applications. These bleaching agents include oxygen bleaching agents and other bleaching agents. Perborates such as sodium perborate (e.g., sodium perborate mono or tetrahydrate) may be used in the present invention.

Another class of bleaching agents that may be used without limitation includes percarboxylic acid bleaching agents and salts thereof. Examples of such bleaching agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of chloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. These bleaching agents are disclosed in U.S. patent 4483781 to Hartman at 1984.11.20, U.S. patent application 740446 to Burns et al 1985.6.3, european patent applications 0133354 and 1983.11.1 to Banks et al at 1985.2.20, U.S. patent 4412934 to Chung et al. Highly preferred bleaching agents also include 1987.1.6 6-nonylamino-6-oxoperoxyhexanoic acid described in U.S. Pat. No. 4634551 to Burns et al.

Peroxygen bleaches may also be used. Suitable peroxygen bleach compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide. Persulfate bleach (e.g., OXONE, commercially produced by DuPont) can also be used.

Preferred dried particles of percarbonate bleach have an average particle size of from about 500 μm to about 1000 μm, no more than 10% by weight of said particles being less than about 200 μm and no more than 10% by weight of said particles being greater than about 1250 μm. The percarbonate may optionally be coated with silicate, borate or water soluble surfactants. Percarbonate is commercially available from various commercial sources such as FMC, Solvay and Tokai Denka.

Mixtures of bleaching agents may also be used.

Peroxygen bleaches, perborates, percarbonates, and the like are preferably used in combination with bleach activators which are capable of producing an aqueous solution of the peroxyacid corresponding to the bleach activator in situ (i.e., during the wash). 1990.4.10 to Mao et al, U.S. Pat. No. 4915854 and U.S. Pat. No. 4412934 disclose various non-limiting examples of active agents. Typically, nonanoyl phenolsulfonate (NOBS) and Tetraacetylethylenediamine (TAED) actives are used, or mixtures thereof may be used. Other general bleaching agents and activators useful in the present invention can also be found in US 4634551.

Highly preferred amido-derived bleach activators are those of the formula:

R¹N(R⁵)C(O)R²c (O) L or R¹C(O)N(R⁵)R²C (O) L wherein R¹Is an alkyl group having from about 6 to about 12 carbon atoms, R²Is alkenyl of 1 to about 6 carbon atoms, R⁵Is H or an alkyl, aryl or alkaryl group containing from about 1 to about 10 carbon atoms. L is any suitable leaving group. The leaving group is any group that is displaced from the bleach activator by nucleophilic attack by the perhydrolytic anion. A preferred leaving group is phenylsulfonate.

Preferred examples of bleach activators having the above formula include (6-octanamido-hexanoyl) phenolsulfonate, (6-nonanamido-hexanoyl) phenolsulfonate, (6-decanamido-hexanoyl) phenolsulfonate and mixtures thereof, as described in U.S. patent 4634551, which is incorporated herein by reference.

Another class of bleach activators includes 1990.10.30, which is incorporated herein by reference, which is a benzoxazine-type activator disclosed in U.S. Pat. No. 4966723 to Hodge et al. Highly preferred benzoxazine-type active agents are:

another preferred class of bleach activators comprises acyl lactams, particularly those having the following moleculesAcyl caprolactams and acyl valerolactams of formula (la):

wherein R is⁶Is H or an alkyl, aryl, alkoxyaryl or alkylaryl group containing from 1 to about 12 carbon atoms. Highly preferred lactam actives include benzoyl caprolactam, octanoyl caprolactam, 3, 5, 5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecanoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecanoyl valerolactam, nonanoyl valerolactam, 3, 5, 5-trimethylhexanoyl valerolactam and mixtures thereof. See also 1985.10.8 U.S. Pat. No. 4545784 to Sanderson, which is incorporated herein by referenceFor reference, the patent discloses acyl caprolactams including benzoyl caprolactam absorbed into sodium perborate.

Bleaching agents other than oxygen bleaching agents are also well known in the art and may be used in the present invention. One particularly useful class of non-oxygen bleaching agents includes photosensitizing bleaching agents such as sulfonated zinc and/or aluminum phthalocyanine salts. See 1977.7.5 U.S. Pat. No. 4033718 to Holcomb et al. If used, detergent compositions typically contain such bleaching agents, particularly sulfonated zinc phthalocyanines, in amounts of about 0.025 wt% to about 1.25 wt%.

If desired, the bleach compound may be catalyzed by a manganese compound. Such compounds are well known in the art, for example, manganese-based catalysts are disclosed in U.S. patent nos. 5246621; 5244594, respectively; 5194416, respectively; 5114606, respectively; and european published patent application 549271a 1; 549272A 1; 544440A2 and 544490A1, 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^IIIMn^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 include those disclosed in U.S. patent 4430243 and U.S. patent 5114611. The following U.S. patents also report the use of manganese with various complexing ligands to enhance bleaching: 4728455, respectively; 5284944, respectively; 5246612, respectively; 5256779, respectively; 5280117, respectively; 5274147, respectively; 5153161And 5227084.

As a practical matter, and not by way of limitation, the compositions and methods of the present invention may be adjusted to provide concentrations of active bleach catalyst material in the aqueous wash liquor of at least one million parts per million, with the concentration of the catalyst material in the wash liquor being from about 0.1ppm to about 700ppm, more preferably from about 1ppm to about 500 ppm. Enzyme

Enzymes may be included in the compositions of the present invention for a wide range of fabric laundering purposes, such as those involving removal of protein-, carbohydrate-or triglyceride-based soils, for the prevention of bleed dye transfer, for the refreshment of fabrics. Enzymes that may be added include 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 vegetable, animal, bacterial, fungal and yeast origin. However, their selection is limited by several factors, such as optimum pH activity and/or stability, thermal stability, stability towards active detergents, builders, etc. Bacterial or fungal enzymes, such as bacterial amylases and proteases, and fungal cellulases are preferred in this regard.

Typically, the enzyme is added in an amount sufficient to produce up to about 5 mg, more typically about 0.01 mg to about 3 mg, of active enzyme per gram of composition. It is further noted that the compositions of the present invention generally comprise from about 0.001 wt% to about 5 wt%, preferably from 0.01 wt% to 1 wt%, of the commercial enzyme preparation. The protease enzyme is typically present in such commercial enzyme preparations in an amount sufficient to produce 0.005-0.1Anson Units (AU) of active enzyme per gram of composition.

Examples of suitable proteases are subtilisins derived from Bacillus subtilis and Bacillus licheniformis of a particular strain. Another suitable protease is obtained from a strain of Bacillus having maximum activity in the pH range 8-12, cultivated and sold by Novo IndustriesA/S, registered under the trade name ESPERASE. This enzyme preparation and isoenzymes are described in the specification of British patent 1243784 to Novo. Commercially available proteolytic enzymes suitable for removing protein-based soils include those sold under the trade names ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthesis, Inc. (the Netherlands). Other proteases include protease A (see European patent application 130756 published by 1985.1.9) and protease B (see European patent application 87303761.8 published by 1987.4.28 and European patent application 130756 published by 1985.1.9).

Amylases include α -amylase as described in the specification of UK patent 1296839(Novo), RAPIDASE from International Bio-Synthesis, Inc., and TERMAMYL from Novo industries.

Cellulases usable in the present invention include bacterial cellulases or fungal cellulases. Their optimum pH range is preferably 5-9.5. 1984.3.6 issued to Barbesgord et al, U.S. Pat. No. 4435307 discloses suitable cellulases, which discloses fungal cellulases produced by Humicola insolens and Humicola strain DSM1800 or cellulases 212 produced by a fungus belonging to the genus Aeromonas, and cellulases extracted from the hepatopancreas of marine mollusks (Dolabella Auricula Solander). GB-A-2075028; suitable cellulases are also disclosed in GB-A-2095275 and DE-OS-2247832. CAREZYME (Novo) is particularly useful.

Suitable lipases for use in the wash include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154 as disclosed in British patent 1372034. See also 1978.2.24, published Japanese patent application 5320487 for lipases. This enzyme is commercially available from Amano Pharmaceutical co.ltd., japan under the trademark lipase P "Amano", hereinafter referred to as "Amano-P". Other commercial lipases include Amano-CES, a lipase from Chromobacterium viscosum (Chromobacterium viscosum), such as the Lipofeum viscosum variant NRRLB 3673 commercially available from Toyo Jozo Co., Tagata, Japan; lipases obtainable additionally from U.S. biochemical corp., usa and Disoynth co., chromobacterium viscosum lipase commercially available in the netherlands, and Pseudomonas gladioli. The LIPOLASE enzyme derived from humicola lanuginosa and commercially available from Novo (see also EPO 341947) is a preferred lipase in the present invention.

Peroxidase enzymes are used in combination with oxygen sources such as percarbonates, perborates, persulfates, hydrogen peroxide, and the like. They are used for "solution bleaching", i.e. to prevent the transfer of dyes or pigments removed from a substrate during washing to other substrates in the wash liquor. Peroxidases are known in the art and include, for example, horseradish peroxidase, ligninase and haloperoxidase such as chloro-and bromo-peroxidase. For example, PCT International application WO89/099813, published by O.Kirk, assigned to Novo Industries A/S, 1989.10.19, discloses peroxidase-containing detergent compositions.

1971.1.5 U.S. patent 3553139 to McCarty et al also discloses a wide range of enzymatic materials and methods of incorporating them into synthetic detergent compositions. Enzymes are also disclosed in 1978.7.18, U.S. Pat. Nos. 4101457 and 1985.3.26 to Place et al, U.S. Pat. No. 4507219 to Hughes. 1981.4.14 to Hora et al, U.S. Pat. No. 4261868, discloses enzymes for use in liquid detergent compositions and methods of adding them to the compositions. Enzyme stabilization in detergents can be used with various techniques. For example, 1971.8.17 discloses enzyme stabilization techniques in U.S. Pat. No. 3600319 to Gedge et al and European patent application No. 0199405 to Venegas, 1986.10.29 published as 86200586.5. For example, an enzyme stabilization system is described in U.S. Pat. No. 3519570.

Other components which may be used in detergent compositions in general and which may be incorporated into detergent tablets include sequestrants, soil release agents, soil redeposition agents, dispersants, suds suppressors, fabric softeners, dye transfer inhibitors and perfumes.

It is advantageous that the compounds for use in products disclosed above are packaged in a packaging system.

The packaging system may be made from a sheet of flexible material. Materials suitable for use as the flexible sheet include single layer, coextruded or laminated films. Such films may include various components such as polyethylene, polypropylene, polystyrene, polyethylene terephthalate. The packaging system is preferably formed from MVTR less than 5g/day/m²Is made of a co-extruded film of polyethylene and bi-directional polypropylene. The MVTR of the packaging system is preferably less than 10g/day/m²More preferably less than 5g/day/m². The film (2) may have various thicknesses. The thickness should generally be from 10 to 150. mu.m, preferably from 15 to 120. mu.m, more preferably from 20 to 100. mu.m, even more preferablyPreferably 25-80 μm, most preferably 30-40 μm.

The packaging material preferably includes a barrier layer made of a conventional packaging material having a low oxygen transmission rate, the barrier layer having an oxygen transmission rate of less than 300cm³/m²Day, preferably less than 150cm³/m²Day, more preferably less than 100cm³/m²Day, even more preferably less than 50cm³/m²/day, most preferably less than 10cm³/m²And/day. Materials having such barrier properties typically include biaxially oriented polypropylene, polyethylene terephthalate, nylon, poly (ethylene vinyl alcohol), or include one of these materials and SiO_X(silicon oxide), or a metal foil such as aluminum foil. Such packaging materials have a beneficial effect on the stability of the product, e.g. during storage.

The packaging method used is generally the packaging method disclosed in WO92/20593, including flow wrapping and over wrapping. When such a method is used, a longitudinal seal, either a fin seal or an overlap seal, is created, and then the first end of the packaging system is sealed with a first end seal, followed by sealing the second end of the packaging system with a second end seal. The packaging system may comprise a reclosing device as described in WO 92/20593. In particular, the use of twisted threads, cold seals or adhesives is particularly suitable. In fact, the cold-seal or adhesive tape may be applied to the surface of the packaging system at a location adjacent the second end of the packaging system, and thus, such tape may initially seal and register the packaging system. In this case, the adhesive tape or cold seal tape may correspond to an area having an adhesive surface, that is, a surface which can be adhered only to another adhesive surface. The registration device may also include a Spacer layer (Spacer) to prevent unwanted bonding. 1995.5.18 discloses WO95/13225 which describes such a separating layer (Spacer). There may also be a plurality of Spacer layers (spacers) and a plurality of strips of adhesive material. The main requirement is that the communication between the outside and the inside of the package should be minimized even after the first opening of the packaging system. Cold seals, particularly cold seal grids, may be used, with which the packaging system may be conveniently opened.

Examples

Example 1

i) 25kg of detergent base powder composition a was prepared as follows: the granules of the basic composition are mixed together in a mixing drum to form a homogeneous mixture of granules. Spraying is carried out during the mixing process. After preparation, the substrate was placed in a sealed plastic bag and stored in a storage room set at 23 ℃ for 24 hours.

ii) then making into tablets by the following method: 50g of the matrix was taken and put in a circular mold having a diameter of 5.5cm, and the tensile strength (or radial rupture stress) of the pressed tablet was 10 kPa. The temperature of the matrix during tabletting was 23-27 ℃.

iii) the tablets were then impregnated at 140 ℃ with a solution comprising 90 parts by weight of sebacic acid and 10 parts by weight of Nymcel-ZSB16 from Metsa Serla^TMIn the bath liquid of (1). The immersion time of the tablets in the heated bath was adjusted so that 4g of the bath mixture could be applied. The sheet was then allowed to cool at ambient temperature of 25 ℃ for 24 hours. The tensile strength of the coated sheet increased to 30 kPa.

iv) the amount of residue in the drawer dispenser of the washing machine was determined with the following "Tablet dispensing test" (Tablet dispensing test): the two sheets were placed in the dispensing drawer of the BaucknechtWA9850 washing machine. The temperature of the water supplied to the washing machine was 8 ℃, the hardness was 21 grains per gallon, and the flow rate was 4L/min. The amount of tablet residue remaining in the dispenser was checked 78 seconds after the water flow switch was turned on. The percent distribution of residue was determined using the following equation:

partition% (weight of residue) × 100/(weight of two original sheets)

	Composition A
			(wt％)
Anionic agglomerates 1	21.5
		Anionic agglomerates 2	13.0
Cationic agglomerates	5.5
		Layered silicate	10.8
Sodium percarbonate	14.2
		Bleach activator agglomerates	5.5
Sodium carbonate	10.98
		EDDS/sulfate particles	0.5
Hydroxy ethane diphosphate tetrasodium salt	0.8
		Soil release polymers	0.3
Fluorescent agent	0.2
		Phthalocyanine sulfonic acid zinc salt	0.02
Soap powder	1.4
		Suds suppressor	1.9
Citric acid	7.1
		Protease enzyme	0.8
Lipase enzyme	0.3
		Cellulase enzymes	0.2
Amylase	1.0
		Binder spraying system	4

The anionic agglomerate 1 comprises 40% anionic surfactant, 27% zeolite and 33% carbonate.

The anionic agglomerate 2 comprises 40% anionic surfactant, 28% zeolite and 32% carbonate.

The cationic agglomerates comprise 20% cationic surfactant, 56% zeolite and 24% sulfate.

The layered silicate comprises 95% SKS 6 and 5% silicate. The bleach activator agglomerate comprises 81% TAED, 17% acrylic acid/maleic acid copolymer (acid form) and 2% water. The ethylenediamine N, N-disuccinate/sulfate granules included 58% ethylenediamine N, N-disuccinate, 23% sulfate and 19% water. The zinc phthalocyanine sulfonate capsule has 10% of activity. The suds suppressor comprises 11.5% silicone oil (from Dow Corning), 59% zeolite and 29.5% water. The binder spray system comprised 25% Lutensit K-HD 96 and 75% PEG (polyethylene glycol). All percentages in the above compositions are by weight.

Example 2

i) 25kg of detergent base powder composition a was prepared as follows: all of the granules of the basic composition are mixed together in a mixing (rotating) drum to form a homogeneous mixture of granules.

Spraying is carried out during the mixing process. After preparation, the substrate was placed in a sealed plastic bag and stored in a storage room set at 10 ℃ for 24 hours.

ii) then making into tablets by the following method: 50g of the matrix was taken and put in a circular mold having a diameter of 5.5cm, and the tensile strength (or radial rupture stress) of the pressed tablet was 10 kPa. The temperature of the matrix during tabletting was 10-20 ℃.

iii) the tablets were then impregnated at 140 ℃ with a solution comprising 90 parts by weight of sebacic acid and 10 parts by weight of Nymcel-ZSB from Metsa Serla^TMIn the bath liquid of (1). The immersion time of the tablets in the heated bath was adjusted so that 4g of the bath mixture could be applied. The sheet was then allowed to cool at ambient temperature of 25 ℃ for 24 hours. The tensile strength of the coated sheet increased to 30 kPa.

iv) the amount of residue in the drawer dispenser of the washing machine was determined with the following "sheet dispensing test": the two sheets were placed in the dispensing drawer of the Baucknecht WA9850 washing machine. The temperature of the water supplied to the washing machine was 8 ℃, the hardness was 21 grains per gallon, and the flow rate was 4L/min. The amount of tablet residue remaining in the dispenser was checked 78 seconds after the water flow switch was turned on. The percent distribution of residue was determined using the following equation:

partition% (residue weight) × 100/(two original sheet weights) results:

the% partitioning of the tablets of example 1 was 50% and the% partitioning of the tablets of example 2 was 8%.

Claims (10)

1. A process for the preparation of a detergent tablet, the process comprising: a first step of providing a detergent composition, a second step of forming a granulate comprising the detergent composition, and a third step of compressing the granulate into a tablet form, the process being characterized in that it further comprises a step of cooling the detergent composition to below ambient temperature between the first and third steps.

2. The method of claim 1 wherein the ambient temperature is greater than 18 ℃.

3. A process according to any of claims 1 or 2, wherein the step of cooling the detergent composition is carried out by exposing the detergent composition to a space having a temperature below ambient temperature.

4. A method according to claim 3, wherein the exposing is accomplished by placing the detergent composition in or through a portion of the space having a temperature below ambient temperature for a period of time.

5. A method according to any one of claims 3, 4 or 5 wherein the difference between the ambient temperature and the temperature below ambient temperature is at least 3 ℃.

6. A method according to claims 4 and 5 wherein the exposure time is proportional to the weight of detergent composition exposed divided by the temperature differential.

7. A process according to any preceding claim, wherein the detergent composition comprises at least 10 wt% surfactant.

8. A process according to any preceding claim, wherein the detergent composition comprises at least 2 wt% binder.

9. A process according to any preceding claim, wherein the temperature of the detergent composition after the cooling step and before the third step is below ambient temperature.

10. A tablet obtainable by the process of any preceding claim.