ES2294628T3 - DETERGENT COMPOSITIONS IN THE FORM OF PILLS. - Google Patents

Abstract

A detergent composition in the form of a tablet, which includes a semi-solid region and a solid tablet body, in which the semi-solid region refers to compositions that are sufficiently solid to maintain their shape at room temperature but that do not they are completely solid, characterized in that a barrier layer formed of a hydrated polycarboxylate polymer is interposed between the semi-solid region and the solid tablet body.

Description

Detergent compositions in the form of pills

Field of the Invention

This invention relates to compositions of detergent in the form of shaped bodies, usually referred to as as pills, which are suitable for use in a dishwasher or laundry automatic, which are manufactured by a procedure that involves compaction of a particulate composition, and that includes a semi-solid zone

Background and prior art

The detergent compositions in the form of pills have advantages over powdered products since they don't require measurement and thus are easier to handle and dispense in The wash load.

The tablets of a cleaning composition are they usually manufacture by compressing or compacting an amount of the composition in the form of particles.

Pills have also been described which comprise Two or more regions. For example, WO 00/61717 describes a detergent tablet that is characterized because at least region of its outer surface is semi-solid. He WO 99/24549 describes a detergent tablet that it comprises a compressed solid body and a non-gelatinous portion tablet mounted on a mold of said body. WO document 99/37746 discloses a multilayer detergent tablet that it comprises: a) a core that has a first active agent Detergent; b) a first encapsulation layer surrounding said core, which has a second active detergent agent; cradle second encapsulation layer surrounding said first layer of encapsulation EP 1,239,029 A1 describes a tablet of cleaning or an area of a tablet made of a composition in compacted particles, which contains a substantial part of a plastically deformable material. US 6,313,080 B1 discloses a multiphase detergent tablet for fabric washing, which is compacted from one (s) composition (ones) of particulate detergent with an agent conditioning of fabrics present in an area of the tablet to a higher concentration than in another area. US 6,589,932 B1 describes a multiphase detergent tablet for use in a washing machine, comprising the tablet: a) a first phase in shape of a shaped body that has at least one mold in it; and b) a second phase in the form of a compressed particulate solid inside the mold Document DE 40 10 524 A1 discloses tablets of dishwashing machine detergent comprising silicate, nonionic surfactant, organic adjuvants, bleach and Water.

A problem with detergent tablets that include a semi-solid region in contact with a tablet body of, for example, particulate material solid compacted is the tendency of the semi-solid to Migrate to the body of the pill. In addition to being aesthetically little attractive, such migration can compromise the performance of the tablet causing chemically incompatible components to mix.

The present inventors have found that this problem can be solved by providing a barrier layer of water soluble polycarboxylate polymer forming a sheet between the semi-solid region and the body of the tablet.

The barrier layer according to the invention It has superior stability and appearance as well as good barrier properties

Summary of the invention

The invention provides a composition of detergent in the form of a pill, which includes a region semi-solid and a solid pill body, in the that the semi-solid region refers to compositions that are solid enough to retain its shape at temperature environment but that are not completely solid, characterized because a barrier layer formed from a polymer is interposed of hydrated polycarboxylate between the region semi-solid and solid body of the tablet.

Detailed description of the invention Semi-solid region

The semi-solid region of the tablet is preferably a separate layer of the tablet. Without However, the region could also have other forms, such as a core or insert.

The semi-solid region is preferably a single discrete part of the tablet but also it can be a limited number (for example, say 1 to 5) of parts semi-solid discrete. Preferably, each of  these semi-solid parts is at least 1 gram, also preferably each of these parts semi-solid is substantially the same composition. If reference is made to the composition or weight of the semi-solid region is understood to refer to weight and total composition of these parts semi-solid

The expression "semi-solid" refers to compositions that are on the one hand sufficiently solid to maintain its shape at room temperature but not They are completely solid. A suitable test to check if a composition can be considered as semi-solid it describes and illustrates in WO 03/104380. In this essay, compress a cylindrical tablet of the composition to be tested with a diameter of 45 mm and a height of 20 mm, between the plates of a material testing machine until the fracture of the tablet. In the initial position, the plates are in contact with the tablet But they don't apply force. Force is applied to compress the pickup, the vertical speed of the upper plate being 25 mm / minute The test machine measures the applied force (F) and also the displacement (x) of the plates towards each other to As the tablet is compressed. Distance is also known (y) between the plates before the force is applied, which is the pill diameter In the fault, the tablet is broken and the force necessary to keep the displacement falls. The measurement stops when the applied force necessary to maintain the displacement has fallen 25% of its maximum value. Maximum force is the force in the fault (F_ {t}). The breaking energy is the area under the graph of force versus displacement, until the breaking point. This is given by the equation:

one

in which E_ {b} is the energy of rupture in mJoules, x is the displacement in meters and F is the force applied in Newtons to displacement x, and x_ {f} is the displacement in the failure.

Semi-solid compositions are characterized by a ratio F_ to E_ {b} of less than 1.0, more preferably from 0.1 to 0.9, most preferably from 0.2 to 0.6, while traditional tablets compacted particulate materials are generally characterized by a ratio of F_ {f} to E_ {b} of more than 1, more generally of more than 1.25 and even more than 1.5, for example 6.

Preferably, the region semi-solid comprises from 20 to 80% by weight of surfactant (based on the total weight of the region semi-solid), more preferably from 30 to 70% by weight, most preferably from 40 to 55% by weight.

Preferred surfactants for the region semi-solid include non-ionic surfactants, by example in a concentration of 30 to 50% by weight based on weight of the semi-solid region.

The semi-solid region can also preferably comprise soap, for example at a concentration of 0.1 to 10% by weight based on the weight of the region semi-solid

The region adequately Semi-solid tablet comprises materials diluents such as polyethylene glycol or (mono-) or (di-) propylene glycol. A preferred diluent material on di-propylene glycol. Preferably the concentration of these diluents is from 10 to 70% by weight, more preferably from 15 to 60% by weight, most preferably from 40 to 55% by weight based on the weight of the region semi-solid

Preferably the region semi-solid comprises little or no concentration of water. Preferably the water concentration is less than 20% in weight based on the weight of the semi-solid region, more preferably less than 15% by weight, most preferably from 2 Up to 10% by weight.

Preferably the total weight of the surfactants in the semi-solid region is from 0.01 up to 20 grams, more preferably from 0.1 to 10 grams, which more preferably from 0.5 to 2 grams.

Solid pickup body

The solid tablet body according to the invention is a solid that can, for example, be prepared by compression or melting. Preferably, the tablet body is a compacted particle composition.

The solid tablet body is preferably a unique discrete part of the tablet but it can also be composed of a limited number (for example 1 to 5) of parts solids, such as separate layers in the tablet. Preferably each of these solid parts has a weight of at least 10 grams of the same composition. If reference is made to the composition or Solid pill body weight is understood to refer to weight and total composition of these solid parts.

Preferably the solid tablet body It comprises nothing or few concentrations of surfactants. Preferably the concentration of surfactants in the body of tablet is less than 10% by weight (based on the total weight of the tablet body), more preferably from 0.1 to 5% by weight, most preferably from 0.5 to 2% by weight.

The solid tablet body comprises preferably tablet ingredients other than surfactants Examples of these ingredients are adjuvants, bleaching systems, enzymes. Preferably the adjuvants in the pill are predominantly present in the body of solid pill Preferably enzymes are present in predominant shape in the solid pill body. For him purpose of this invention the expression "present in a manner predominant "refers to a situation in which at least 90% by weight of an ingredient is present in the pill body solid, more preferably more than 95% by weight, most preferably more than 98% by weight.

Barrier layer

A barrier layer formed from a polymer of hydrated polycarboxylate interposes between the region semi-solid and solid pill body.

Polycarboxylate polymers suitable for form the barrier layer should have a number of requirements functional, such as good water solubility, formation of coherent sheet and good adhesion to the region semi-solid to solid pill body.

A solubility of at least 10 g per desirable is desirable. 100 g of deionized water at 20 ° C. Solubilities are preferred larger, such as at least 20 g per 100 g.

A melt temperature is desirable or softened above the environment, conveniently above 35ºC, better at least 40ºC depending on where they are going to be sold and use the pills Preferably the melt temperature does not must exceed 80ºC, or even 70ºC, since a temperature of minor melt facilitates the fusion of polymer particles from polycarboxylate during compaction.

Polycarboxylate polymers suitable for forming the barrier layer according to the invention are preferably polymers of unsaturated monocarboxylic acids or unsaturated dicarboxylic acids. Monocarboxylic monomers Suitable include acrylic, methacrylic, vinylacetic acids, and protonic; suitable dicarboxylic monomers include acids maleic, fumaric, itaconic, mesaconic and citraconic and its anhydrides Polymers may also contain derived units. of non-carboxylic monomers, preferably in amounts minority

Polycarboxylate polymers suitable for form the barrier layer according to the invention have generally a weight average molecular weight from approximately 1,000 to approximately 400,000 Daltons.

Homopolymers are especially preferred. of acrylic acid and copolymers of acrylic and maleic acids. Commercially available examples of such materials are the BASF / acrylic copolymers available from BASF as the series Sokalan CP (trademark) and available polyacrylates from BASF such as Sokalan® CPS and preferably Sokalan® PA 25C1. Polymers They are available as powders and granules.

They may also be suitable to form the layer barrier according to the invention mixtures of any of the polycarboxylate polymers described above.

Hydration of the polycarboxylate polymer it is important to reduce or eliminate any tendency of the Polycarboxylate polymer to absorb water from medium surrounding the tablet. This can cause swelling, rupture and discoloration. which leads to an unacceptable pill appearance. This is a particular problem associated with polycarboxylate polymers that They have hygroscopic properties.

Hydration of the polycarboxylate polymer can be carried out by storing it in a highly humid medium before the formation of the tablet. However, the most preferred is that the hydration takes place in situ , so that the formation of the tablet can be carried out in a continuous process.

A particularly preferred way to achieve in situ hydration of the polycarboxylate polymer is to apply the polycarboxylate polymer to the tablet in admixture with a hydrated salt, followed by a pressure compaction step sufficient to cause a release of the salt crystallization water. hydrated The crystallization water thus released is consequently absorbed by the polycarboxylate polymer to provide a barrier layer formed from polycarboxylate polymer thus hydrated.

A barrier layer formed by the described method previously it will therefore comprise the polycarboxylate polymer hydrated and anhydrous salt derived from hydrated salt minus its water of crystallization.

The total weight of the barrier layer in a pill according to the invention will generally be in the range from 0.1 to 15% by weight, preferably from 2 to 10% in weight, more preferably from 5 to 8% by weight (of the total weight of the barrier layer based on the total weight of the tablet).

The appropriate weight ratio of polymer of hydrated salt polycarboxylate for the mixture to form the layer barrier according to the invention will depend in some way on the Crystallization water concentration in the molecular formula of Hydrated salt Generally, the polymer weight ratio of polycarboxylate to hydrated salt may be in the range from 5: 1 to 1: 5, preferably from 2: 1 to 1: 2, more preferably about 1: 1.

Hydrated salts suitable to form the barrier layer according to the invention are those that release its crystallization water when subjected to pressures of Typical compaction found in the manufacture of tablet detergent compositions. The pressure of compaction used to make machine pads dishwasher, bleaching tablets or other tablets that are not contain more than 7 to 8% by weight of surfactant is likely to is in a range from 30 to 250 Mpa (for example 30 to 200 kN applied to a cross section of the tablet from 8 to 10 cm2). The compaction pressure used to make pads for washing fabrics with a surfactant content above 7% in weight they are likely to be in a range from 4 to 40 Mpa (for example 6 to 60 kN applied to a cross section of approximately 15 cm 2 tablet).

A water solubility of at least 10 g per 100 g of deionized water at 20 ° C for hydrated salt. They are preferred higher solubilities, such as at least 20 g per 100 g.

Hydrated inorganic salts are preferred. Examples of hydrated salts include acetates, sulfates, carbonates, sesquicarbonates, phosphates, citrates, silicates, percarbonates and perborates of alkali metal, alkaline earth metal or ammonium and mixtures thereof.

Alkali metal acetates are preferred hydrated, sodium acetate being particularly preferred trihydrate

Product forms and proportions

The tablets according to the invention are particularly suitable for laundry or dishwashing automatic.

A laundry wash tablet will contain generally, in total, from 5% to 50% by weight of surfactant and from 5% to 80% by weight of detergency adjuvant which is a water softening agent. May be present particles that promote water soluble decay in a amount from 5% to 25% by weight of the composition.

Tablets for automatic dishwashing typically contain a high proportion of soluble salts in water, such as 50% to 95% by weight, at least some of which, exemplified by sodium tripolyphosphate, sodium citrate and Sodium silicate have water softening properties.

The materials that can be used in the pills of this invention will now be described in more detail.

Surfactant

Typically, a surfactant in an amount of 0.5 to 50% by weight, preferably 4 to 30 or 40% by weight of the total weight of the anionic surfactants based on the total weight of the composition may be present in the fabric washing tablets of the pill. It can be accompanied by a non-ionic surfactant in an amount from
3 to 20% by weight of the total weight of non-ionic surfactant based on the total weight of the tablet composition.

In a composition for automatic dishwashers, in general the surfactant is likely to constitute from 0.5 up to 8% by weight, most likely from 0.5 to 6% by weight of Total surfactant weight based on the total weight of the composition of the tablet, and is likely to consist of non-ionic surfactant, either alone or in admixture with surfactants anionic

Synthetic anionic surfactants (it is say, no soap) are well known to those skilled in the art. Preferred examples include alkylbenzenesulfonates, particularly linear sodium alkylbenzenesulfonates which they have an alkyl chain length C 8 -C 15; olefin sulfates; alkanesulfonates; dialkylsulfosuccinates; fatty acid esters sulfonates; Y primary alkyl sulfates having an alkyl chain length C_ {8} -C_ {18}.

It may also be desirable to include one or more fatty acid soaps. These are preferably soaps of sodium derived from naturally occurring fatty acids, for example, fatty acids of coconut oil, beef tallow, oil sunflower or hardened rapeseed.

Suitable non-ionic surfactant compounds which can be used include, in particular, the products of reaction of compounds that have a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkylphenols with alkylene oxides, especially ethylene oxide.

Specific non-ionic surfactant compounds are condensed from (C 8-22) alkyl phenol with oxide ethylene, condensation products aliphatic alcohols C_ {8-20} primary or secondary, linear or branched with ethylene oxide, and products manufactured by the condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine.

Especially preferred are the ethoxylates of primary and secondary alcohol, especially alcohols ethoxylated C_ {11-11} and C_ {15-15} primary and secondary with an average of between 5 and 20 moles of ethylene oxide per mole of alcohol.

Preferred non-ionic surfactants for EN use Dishwasher tablets are non-ionic surfactants of low or no foam formation containing oxide of ethylene and / or propylene oxide residues. Examples of alcohols linear chain ethoxylates, of low or no degree of formation of foam which are preferred non-ionic surfactants in the washing of machine tableware are the BASF Plurafac LF series, the series ICI Synperonic; the Lutensol® LF series, from BASF, and the series Triton® DF, by Rohm & Haas. Also of interest are the ethoxylated deactivated available as the SLF 18B series of Olin

Detergency adjuvants

Pills according to the invention or regions they may contain a so-called adjuvant that serves to remove or sequester calcium and / or magnesium ions in water.

When an adjuvant of the water softening detergency, its amount usually ranges from 5 to 80% by weight, more likely from 15 to 80% by weight, of the total weight of detergency adjuvant based on the Total weight of the tablet composition.

Water softening adjuvants, soluble in Water, without phosphorus, can be organic or inorganic. products Inorganic that may be present include zeolites, silicates stratified, alkali metal carbonate (usually sodium); while inorganic products include polymers of polycarboxylate, such as polyacrylates, copolymers acrylic / maleic, and acrylic phosphonates, polycarboxylates monomers such as citrates, gluconates, oxidisuccinates, mono-, di- and triglycerolsuccinates, carboxymethyloxysuccinates, carboxymethylximalonates, dipicolinates, nitrilotriacetates e hydroxyethyliminodiacetates.

Pill compositions include preferably polycarboxylate polymers, more especially polyacrylate and acrylic / maleic copolymers that have some functions as water softening agents and also inhibit unwanted deposition on the fabric of a laundry wash liquor or in glass of an automatic dishwashing liquor.

The category of inorganic adjuvants that contain phosphorus, water soluble, includes orthophosphates, metaphosphates, pyrophosphates and alkali metal polyphosphates. Specific examples of inorganic detergency builders of phosphate include tripolyphosphates, orthophosphates and hexametaphosphates of sodium and potassium Sodium tripolyphosphate is an adjuvant preferred containing phosphorus for dishwasher tablets automatic This exists in hydrated form, anhydrous or partially hydrated, and mixtures of these forms can be used to regulate the speed of dissolution and disintegration of the tablet.

Additional Optional Ingredients Bleaching activators

The tablets according to the invention can contain bleach activators, also known as bleaching precursors. Preferred examples include precursors of peracetic acid, for example, tetraacetylethylenediamine (TAED), and perbenzoic acid precursors. Also of interest are phosphonium and quaternary ammonium bleach activators disclosed in documents US4751015 and US4818426 (Lever Brothers Company). Another type of bleach activator that can be used, but which it is not a bleaching precursor, it is a metal catalyst of transition as disclosed in the documents EP-A-458397, EP-A-458398 and EP-A-549272. A stabilizer of bleaching (heavy metal sequestrant) may also be present such as ethylenediaminetetramethylene phosphonate and diethylenetriaminepentamethylene phosphonate.

Enzymes

The tablets according to the invention can contain one of the well-known detergency enzymes in the matter for its ability to degrade and assist in the elimination of the various dirt and stains. Enzymes suitable for tissues include various proteases, cellulases, lipases, amylases, and mixtures thereof, which are designed to eliminate a variety of dirt and fabric stains. Examples of Suitable proteases are Maxatase (trademark), supplied by Genencor, and Alcalase (trademark), and Savinase (brand commercial), supplied by Novo Industri A / S, Copenhagen, Denmark.

The enzymes for washing dishes are lipases, Amylases and proteases. The most commonly used enzymes in compositions for machine dishwashing are enzymes amylolytic Preferably the composition also contains a proteolytic enzyme

Detergency enzymes are used commonly in the form of granules or marumes, optionally with a protective layer, in an amount that generally ranges from 0.1 up to 5.0% by weight, of the total weight of the enzyme based on weight Total composition of the tablet.

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Chelating agent

A metal ion chelating agent (often called metal ion sequestrant) may be present in the composition. If present, it is preferred that the concentration of chelating agent is 0.5 to 3% by weight of total agent weight chelator based on the total weight of the tablet composition. It can work to stabilize the bleach of the premature decomposition catalyzed by transition metals and / or to inhibit the scale formation of calcium carbonate.

Preferred chelating agents include organic phosphonates, aminocarboxylates, compounds polyfunctionally substituted, and mixtures thereof.

Organic chelating agents particularly Preferred are organic phosphonates such as α-hydroxy-2-phenylethyldiphosphonate, ethylenediphosphonate, hydroxy-1,1-hexylidene, vinylidene-1,1-diphosphonate, 1,2-dihydroxyethane-1,1-diphosphonate and hydroxy-ethylene-1,1-diphosphonate. The most preferred is acid hydroxy-ethylene-1,1-diphosphonate, 2-phosphono-1,2,4-butanetricarboxylic or you leave it.

Additional ingredients that optionally can be employees include agents anti-fogging for dishwashing, bleach casting optics, antifoaming granules, additives disintegration of pills such as swelling particles or salts highly soluble in water, perfumes, dyes or specks of color. Fabric washing tablets may include agents softeners and / or anti-redeposition such as linear sodium carboxymethylcellulose, poly (pyrrolidone from vinyl) linear chain and cellulose ethers, such as methylcellulose and ethylhydroxyethylcellulose.

Tablets for machine dishwashing may include polymers to inhibit scale formation and polymers to inhibit staining glass.

Manufacturing method

In another aspect, this invention provides a method of manufacturing a detergent composition in the form of pill, (i.e. body-shaped), in which the pill includes a semi-solid region and a body of solid tablet, characterized in that a barrier layer formed by a hydrated polycarkoxylate polymer is interposed between the semi-solid region and the pill body solid.

The tablets according to the invention are preferably manufactured by a process comprising the steps from:

(a) insert a particulate composition into a pill mold,

(b) insert a mixture of a polymer of polycarboxylate and a hydrated salt in the tablet mold,

(c) co-compress the composition to form a solid tablet body of the composition in compacted particles and a polymer barrier layer of hydrated polycarboxylate, and

(d) prepare a region semi-solid and apply it to the composition so that the barrier layer is interposed between the region semi-solid and solid pill body.

Stages (a) and (b) can be in any order, although preferably the particulate composition is first enter the pill mold, followed by placement of the mixture of polycarboxylate polymer and hydrated salt in the mold.

Preferably the particle composition is flattened or pre-compressed before introducing the Polycarboxylate polymer mixture and hydrated salt (step (b)). The more preferably the particulate composition is pre-compressed at a force of 0.01 to 5 kN / cm2 before the introduction of the polycarboxylate polymer mixture and hydrated salt

Preferably co-compression in step (c), a force of from 0.1 to 20 takes place kN / cm2. Especially if the particle composition has been pre-compressed co-compression in step (c), can be advantageously at a force of 0.01 to 10 kN / cm2, more preferably 2 to 8 kN / cm2.

The semi-solid region in the step (d) can be prepared by mixing its ingredients constitutive The pressure to prepare the region semi-solid can vary from 0 to 5 kN / cm2, preferably from 0.01 to 5 kN / cm2.

The application of the region semi-solid in stage (d) can take place by spraying or under the application of a force of co-compression That co-compression it can take place properly at a force of from 0.1 to 20 kN / cm2.

The pickup machine capable of carrying The manufacturing of the tablets of the invention is known, for example suitable tablet presses are available in Carver and in Korsch.

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The size of a pill will vary appropriately from 10 to 160 grams, preferably from 15 g to 60 g, depending on the intended conditions of use.

The pills can be any way. Without However, to facilitate the packaging are preferably blocks of substantially uniform cross section, such as cylinders or cuboid.

The overall density of a pill for the fabric washing is preferably in a range from 1040 or 1050 g / l, preferably at least 1100 g / l, up to 1400 g / l. The density of the tablet can also be found in a range up to no more than 1350 or even 1250 g / l.

The overall density of a washing tablet machine dishes or as a bleaching additive, may vary up to 1700 g / l and will often be in a range of 1300 to 1550 g / l.

The invention will now be illustrated in the following non-limiting example, in which all percentages are parts in weight based on total weight unless specified contrary.

Example

A powder composition with the ingredients as shown in table 1 below, it was prepared and pre-compressed at a pressure of 0.25 kN / cm2 in a Carver laboratory press, to form 18.5 tablets grams

TABLE 1

2

In a peer comparison trial, it they added the following ingredients to the pills of the Following way:

Pickup 1:

0.75 grams of sodium acetate trihydrate and 0.75 grams of Sokalan® PA 25Cl (from BASF)

Pickup 2:

0.75 g of anhydrous sodium acetate and 0.75 grams of Sokalan® PA 25Cl.

The resulting products were pressed to 5 kN / cm2 in the Carver press and the products were stored under moderate conditions (i.e., 20 ° C and 65 HR).

After two weeks of storage, the layer made of anhydrous sodium acetate (tablet 2) had swollen, causing cracks in the pill.

On the contrary, the layer made with acetate of sodium trihydrate (tablet 1) had not swollen. Had one attractive and shiny surface and under the pill did not show fissures

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A semi-solid composition with the ingredients shown in Table 2 below was prepared by mixing, heating the mixture at 80 ° C and molding in molds

TABLE 2

3

In a peer comparison test, 2 ml of the semi-solid composition was sprayed on the part top of each of tablets 1 and 2, as described higher.

After two weeks of storage in normal ambient conditions (i.e., 20ºC and 65 HR), the product according to the invention (i.e. using sodium acetate trihydrate so the polymer is hydrated) was maintained Stable, not swollen and attractive appearance. On the contrary, the comparative product (i.e. using anhydrous sodium acetate for what the polymer is not hydrated) had a little appearance attractive. The polymer layer was swollen, distorting the overall shape of the pill, and lots of brown coloring points Reddish were evident throughout the solid part of the tablet.

Claims (9)

1. A detergent composition in the form of a tablet, which includes a semi-solid region and a solid tablet body, in which the semi-solid region refers to compositions that are sufficiently solid to maintain their shape at room temperature but which are not completely solid, characterized in that a barrier layer formed of a hydrated polycarboxylate polymer is interposed between the semi-solid region and the solid tablet body. 2. A composition according to claim 1, in which the semi-solid region comprises from 20 to 80% by weight of surfactants (based on the total weight of the region semi-solid). 3. A composition according to claim 1 or claim 2, wherein the solid tablet body is a compacted particle composition. 4. A composition according to claim 1, in which the polycarboxylate polymer is selected from homopolymers of acrylic acid, copolymers of acrylic and maleic acids, and mixtures thereof. 5. A method of manufacturing a detergent composition in the form of a tablet, wherein the tablet includes a semi-solid region and a solid tablet body, wherein the semi-solid region refers to compositions that are sufficiently solid to maintain its shape at room temperature but which are not completely solid, characterized in that a barrier layer formed of a hydrated polycarboxylate polymer is interposed between the semi-solid region and the solid tablet body. 6. A method according to claim 5, in the that the polycarboxylate polymer is applied to the tablet in mixture with a hydrated salt, followed by a stage of compaction to sufficient pressure to cause a release of water from crystallization of hydrated salt, so that water from crystallization thus released is absorbed by the polymer of polycarboxylate to provide a barrier layer formed from of the polycarboxylate polymer hydrated in this way. 7. A method according to claim 6, in the that the hydrated salt is selected acetates, sulfates, carbonates, sesquicarbonates, phosphates, citrates, silicates, percarbonates and perborates of alkali metals, alkaline earth metals or ammonium, and mixtures thereof. 8. A method according to claim 7, in the that hydrated salt is a hydrated alkali metal acetate, preferably sodium acetate trihydrate. 9. A method according to any of the claims 6 to 9, comprising the steps of: (a) insert a particulate composition into a pill mold, (b) insert a mixture of a polymer of polycarboxylate and a hydrated salt in the tablet mold, (c) co-compress the composition to form a solid tablet body of the composition in compacted particles and a polymer barrier layer of hydrated polycarboxylate, and (d) prepare a region semi-solid and apply it to the composition so that the barrier layer is interposed between the region semi-solid and solid pill body.