ES2294784T3 - COVERED DETERGENT PAD. - Google Patents

Abstract

THE PRESENT INVENTION REFERS TO PADS THAT INCLUDE A NUCLEUS AND A COATING, WHOSE NUCLEO IS FORMED BY COMPRESSING A MATERIAL IN PARTICLES, UNDERSTANDING THE MATERIAL IN PARTICLES A TENSIOACTIVE AND A MATERIAL IMPROVEMENT, A MATERIAL DEVICE, A MATERIAL SUBSTANTIALLY INSOLUBLE IN WATER AT 25 (GRADES). THE INVENTION ALSO REFERS TO PROCESSES FOR THE MANUFACTURE OF THE PADS.

Description

Coated detergent tablet.

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The present invention relates to tablets of coated detergent, especially pads adapted for its use in washing machines, and processes to make the tablets of coated detergent.

Although compositions have often been proposed tablet-shaped cleaners, these have not yet reached a important success (except soap bars for grooming personal) despite the different advantages of products in a unit dispensing form. One of the reasons it may be that detergent tablets require a relatively complex manufacturing process. In particular, to it is often desirable to provide the tablet with a coating and This adds difficulties to manufacturing.

Although the uncoated tablets are fully effective in their use, they usually lack the hardness surface necessary to withstand the abrasion that is part of normal processing, packaging and handling. The result is that the uncoated tablets suffer abrasion during these processes, resulting in chipped pills and loss of active material.

Finally, it is often desirable to coat the pills for aesthetic reasons, to improve the appearance of the pill or to get some aesthetic effect particular.

Numerous methods have been proposed to coat pills and many of them have been suggested for pills detergents However, all these methods have some Disadvantages, as will be explained below.

The patent GB-A-0 989 683, published on 22 April 1965, describes a process for preparing a detergent in particle form from surfactants and inorganic salts, spray a water-soluble silicate and compress the particles of detergent in a solid pill that retains the shape. Finally, a water-soluble organic film forming polymer (for example, poly [vinyl alcohol]) provides a coating for make the detergent tablet abrasion resistant and to accidental breakage.

The patent EP-A-0 002 293, published on 13 June 1979, describes a coating of tablets comprising hydrated salt such as acetate, metaborate, orthophosphate, tartrate and sulfate.

The patent EP-A-0 716 144, published on 12 June 1996, also describes detergent tablets for laundry with water-soluble coatings that can be organic polymers that include acrylic / maleic copolymer, polyethylene glycol, PVPVA and sugar.

WO9518215, published July 6 from 1995, provides water-soluble coatings for tablets solid washings. The tablets are provided with coatings hydrophobes that include wax, fatty acid, fatty acid amides and polyethylene glycol

No state of the art describes the use of hydrophobic or virtually insoluble coating materials in water for pills that have a soft core prepared by compression of particulate materials.

The present invention provides a means whereby a hard and thin coating can be provided to pads with a core formed by compression of a material in the form of particles, the material comprising surfactant particles and detergency builder additive, of so that they can be stored, transported and handled, but that the coating breaks when the tablet is in the washing machine, exposing the soft core that breaks easily and quickly and releasing the active ingredients in the solution of washed.

The objective of the present invention is provide a tablet that disintegrates and disperse completely in alkaline or surfactant-rich solutions, such as the wash solution

Summary of the invention

The objective is achieved by providing a coating comprising adipic acid, acids C8-C13 dicarboxylic or mixtures thereof and it has a solubility in water at 25 ° C of less than 20 g / e. He coating is hydrophobic, which acts as a barrier to the moisture and provides better stability to ingredients such as bleach and enzymes.

In a further aspect of the invention, provides a process to make a tablet comprising the stages of:

(to)

form a nucleus compressing a particulate material, the material comprising of surfactant particles and additive reinforcing the detergency;

(b)

apply a coating material to the core, the coating material being in the form of dough cast

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(C)

let the coating material molten solidify;

where the material of coating comprises adipic acid, C8-C13 acids dicarboxylic or mixtures thereof and has a solubility in water at 25 ° C of less than 20 g / l. Preferably, the materials of coating have a melting point in the range of 40 ° C to 180 ° C

In an alternative to this embodiment of the invention is provided a process for making a tablet that It comprises the stages of:

(to)

form a nucleus compressing a particulate material, the material comprising of surfactant particles and additive reinforcing the detergency;

(b)

apply a coating material to the core, the coating material being dissolved in a solvent;

(C)

let the solvent evaporate;

where the material of coating comprises adipic acid, C8-C13 acids dicarboxylic or mixtures thereof and has a solubility in water at 25 ° C of less than 20 g / l

Detailed description of the invention

The pills to be coated with the The present invention can be prepared by simply mixing the solid ingredients with each other and compressing the mixture in a press of conventional tablets such as those used, for example, in the pharmaceutical industry. To solid ingredients in the form of particles can be added any liquid ingredient, by for example, the surfactant or suds suppressant, so  conventional. Preferably, the main ingredients are They use in the form of particles.

In the particular case of the tablets for laundry, ingredients such as the reinforcing additive of the detergency and the surfactant can be dried by spraying conventional form and then compact at a pressure adequate.

According to the present invention, the tablets of detergent can be prepared in any size or shape and, if you want, they can be treated superficially before applying the covering. The core of the tablet includes a surfactant and detergency builder additive that usually provides an important part of the cleaning capacity of the tablet. With the term "detergent booster additive" is intended include all products that have a tendency to eliminate the ion calcium solution by ion exchange, formation of complexes, kidnapping or precipitation.

The particulate material used for the production of the tablet of this invention it is possible to prepare by any particulate procedure or granulation. An example of such a process is drying by spray (in a spray-drying tower under current or countercurrent) that typically results in low values Bulk density of 600 g / l or less. The materials in higher density particle form can be prepared by granulation and densification in a batch mixer / granulator high shear or by granulation procedures and continuous densification (for example, with Lodige® CB mixers and / or Lodige® KM). Other suitable processes include bed processes fluid, compaction processes (eg roller compaction), extrusion, as well as any particulate material manufactured by any chemical process such as flocculation, crystallization sintering, etc. Individual particles they can also be any other type of particle, granule, sphere or grain

Particle-shaped materials can be mix with each other by any conventional means. The process batch mixing can be done properly, by example, with a horizontal mixer, a Nauta mixer, a belt mixer or any other mixer. Another alternative is carry out the mixing process continuously dosing in weight and dispensing each component on a moving belt and mixing the components in one or more drums or mixers. Be you can perform a liquid spray on the mixture of particulate materials (for example, non-surfactants ionic). Other liquid ingredients can also be sprayed on the mixture of particulate materials, either by separated or mixed previously. For example, they can be sprayed perfume and aqueous suspensions of optical brighteners. After of spraying the nonionic surfactant, it can be added to the particle-shaped materials a finely fluidizing divided (dusting agent, such as zeolites, carbonates, silicas), preferably towards the end of the process, so that the Mix be less sticky.

The tablets can be manufactured using any compaction process such as compression, briquetting or extrusion, preferably compression. The right equipment include a standard piston press or a rotary press (such as Courtoy®, Korch®, Manesty® or Bonals®). Pills prepared according to this invention preferably have a diameter from 40 mm to 50 mm and weighing 25 g to 60 g. The pressure of compaction used for the preparation of these pills not must exceed 5,000 kN / m2, preferably it must not exceed 3,000 kN / m2 and most preferably should not exceed 1,000 kN / m2.

According to the present invention, the tablets are then coated with a coating that is practically insoluble such that the tablet does not absorb moisture, or absorb moisture only in a very small proportion. The coating is also strong enough so that the moderate mechanical shocks to which the pads are subjected during handling, conditioning and transport only produce very low levels of breakage or wear. Finally, the coating is preferably brittle so that the tablet is broken when subjected to stronger mechanical shocks. Likewise, it is advantageous that the coating material is dissolved under alkaline conditions or that it is easily emulsified by the surfactants. This prevents the deposition of particles or lumps of undissolved coating material in the laundry load. This may be important when the coating material is completely insoluble (for example, less than
1 g / l) in water.

As defined herein, "basically insoluble" means that it has a solubility in very low water This should be understood as having a solubility. in water at 25 ° C of less than 20 g / l, preferably less than 5 g / l and more preferably less than 1 g / l. Water solubility is measured using the ASTM E1148-87 test protocol entitled "Standard test method for the determination of water solubility "

The coating materials used are adipic acid and C8-C13 dicarboxylic acids. The Preferred dicarboxylic acids are subic acid (C8), acid azelaic (C9), sebacic acid (C10), undecanedioic acid (C11), dodecanedioic acid (C12) and tricedanodioic acid (C13).

As the tablets and whatever their composition are prepared, they are then coated according to the present invention with a hydrophobic material having a melting point preferably of 40 ° C at
180 ° C

The coating can be applied in different shapes. Two preferred coating methods are a) coating  with a molten material and b) coating with a solution of material.

In a) the coating material is applied to a temperature higher than its melting point and solidifies on The pill. In b) the coating is applied as a solution and The solvent is dried to leave a uniform coating. He virtually insoluble material can be applied to the tablet, by example, by spraying or immersion. Normally when the molten material is sprayed on the tablet, it solidifies quickly forming a uniform coating. When the pills they are immersed in the molten material and then removed, the fast cooling again produces rapid solidification of the coating material. Obviously, the materials practically insoluble and having a melting point lower than 40 ° C are not solid enough at room temperature and will has observed that materials that have a melting point above 180 ° C cannot be used in the practice. Preferably, the materials melt in the range from 60 ° C to 160 ° C, more preferably from 70 ° C to 120 ° C.

"Melting point" means the temperature at which the material when heated slowly, by  example in a capillary tube, it becomes a liquid transparent.

According to the present invention, a coating with any desired thickness. For most of the For purposes, the coating represents 1% to 10%, preferably of 1.5% to 5%, of the weight of the tablet.

The tablet coatings of the present invention are very hard and provide additional resistance to The pill.

In a preferred embodiment of the present invention, fracture of the coating during washing is seen favored if a disintegrant is added to the coating. This disintegrant will swell on contact with water and break Coating in small pieces. This will favor dissolution. of the coating in the wash solution. The disintegrant is suspended in the coating melt at a level of up to 30%, preferably from 5% to 20% and most preferably from 5% to 10%, by weight.

Possible disintegrants are described in the Handbook of Pharmaceutical Excipients (1986). Examples of suitable disintegrants include starches (natural, modified or pregelatinized starch, sodium starch gluconate), gums (agar gum, guar gum, locust bean gum, karaya gum, pectin gum, tragacanth gum), croscarmellose sodium, crospovidone, cellulose, carboxymethyl cellulose, alginic acid and its salts, such as sodium alginate, silicone dioxide, clay, polyvinyl pyrrolidone, soy polysaccharides, ion exchange resins and mixtures of
same.

Depending on the composition of the material of starting and in the form of the pads, the force of compaction used so that it does not affect the resistance (tension of diametral fracture) or at the time of disintegration in the washing machine. This procedure can be used to prepare pills homogeneous or laminar of any size and shape.

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Diametral fracture tension (DFS) is a way of expressing the resistance of a pill and determining by the following equation:

one

where F is the maximum force (newtons) that produces traction failure (fracture) measured in a Van Kell VK 200 tablet hardness analyzer industries, Inc. D is the diameter of the tablet and t is the thickness of the pill. (Method Pharmaceutical Dosage Forms: Tablets, vol. 2, p. 213 a 217).

The disintegration rate of a pill of Detergent can be determined in two ways:

a) In a "VAN friability analyzer KEL "with drums" Vankel type ".

-

Place 2 pills with a weight and a Known DFS tension in the analyzer drum.

-

Do Turn the drum 20 rotations.

-

Collect all the product and the remains of drum pickup and pass through a 5 mm sieve and of 1.7 mm

-

Express as% of residue of a sieve 5 mm and 1.7 mm.

-

How much greater is the% of the product that passes through the 1.7 mm sieve, The better the disintegration.

b) In a washing machine according to the following process

-

Take two pills with a known fracture weight and tension and place the pills in the bottom of a clothes washer (for example, Bauknecht WA 950).

-

Place a mixed load of 3 kg on pills.

-

Run a short cycle (program 4) a 30ºC with urban water.

-

Stop the cycle after 5 minutes and check if in the wash load there are pieces of pill without dissolve. Collect and weigh the remains of pills and write down the percentage of waste remaining.

In another preferred embodiment of the present invention the tablets also contain an effervescent agent.

Effervescence, as defined herein memory, indicates the release of gas bubbles in a liquid as a result of a chemical reaction between an acid source soluble and an alkali metal carbonate, with dioxide production carbon gas,

2

Other examples of sources of acid and carbonate and Other effervescent systems can be found at: (Pharmaceutical Dosage Forms: Tablets, vol. 1, p. 287-291).

In addition to detergent components, the Pill mixture can be added an effervescent. The addition of this effervescent agent to the detergent tablet improves the time of disintegration of the tablet. The amount will be preferably from 5% to 20% and most preferably from 10% to 20% in weight of the pill Preferably the effervescent agent should be added in the form of agglomerate of the different particles or as a compact material and not in the form of separate particles.

Due to the gas produced by the effervescence in the pill, the pill can have a higher DFS and follow presenting the same disintegration time as a pill without effervescence. When the DFS of the effervescent tablet is keeps the same as a pill without effervescence, the Effervescent tablet disintegration will be faster.

Detersive Surfactants

Non-limiting examples of surfactants useful in the present invention typically at levels of about 1% to about 55% by weight include conventional C 11 -C 18 alkylbenzenesulfonates ("LAS") and alkyl sulfates ("AS" ) C 10 -C 20 branched and random primary, C 10 -C 18 secondary alkyl sulfates of formula CH 3 (CH 2) x (CHOSO 3 - M +) CH 3 and CH 3 (CH 2) y (CHOSO 3 - M +) CH_ {2} CH3 where xe (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-soluble cation, especially sodium, unsaturated sulfates such as oleyl sulfate, C_ alkylalkoxysulfates {10} -C_ {18} ("AE_ {S}"; especially EO 1-7 ethoxy sulfates), C 10 -C 18 alkoxycarboxylates (especially EO ethoxycarboxylates
1-5), C 10-18 glycerol ethers, C 10 -C 18 alkyl polyglycosides and their corresponding sulphated polyglucosides and C 12 -C 18 alpha-sulphonated fatty acid esters . If desired, conventional nonionic and amphoteric surfactants such as C 12 -C 18 alkyl ethoxylates ("AE") including so-called narrow-alkyl alkyl ethoxylates, and C_ alkyl may also be included in the general compositions. {6} -C 12 phenol alkoxylates (especially ethoxylates and mixed ethoxy / propoxy), betaines and sulfobetaines ("sultaines") C 12 -C 18, C 10 amine oxides - C 18, and the like. The C 10 -C 18 N-alkyl fatty acid polyhydroxyamides can also be used. Typical examples include the N-methyl C 12 -C 18 glucamides (see WO-9,206,154). Other sugar-derived surfactants include fatty acid N-alkoxy polyhydroxyamides such as N- (3-methoxypropyl) C 10 -C 18 glucamide. The glucamides of N-propyl to C12-C18-N-hexyl can be used to achieve low soaping. Conventional C 10 -C 20 soaps can also be used. If high soaping is desired, C 10 -C 16 branched chain soaps can be used. Mixtures of anionic and non-ionic surfactants are especially useful. Other useful conventional surfactants are described in the standard texts.

Detergent booster additives

The compositions of the present invention include they can add detergent booster additives to facilitate the mineral hardness control. Reinforcing additives of inorganic and also organic detergency. Additives detergency builders are typically used in clothes washing compositions to help eliminate spots in the form of particles.

The amount of additive reinforcing the detergency can vary widely depending on the end use of the composition.

Additives strengthening detergency inorganic or containing P include, but not limiting, alkali metal, ammonium and alkanolammonium salts of polyphosphates (illustrated by tripolyphosphates, pyrophosphates and vitreous polymeric metaphosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates and aluminosilicates. However, in certain cases it require phosphate-free detergency builder additives. Fits highlight that the present compositions act surprisingly well even in the presence of the so-called reinforcing additives of "weak" detergency (compared to phosphates), such as citrate or in the so-called situation "of infrastructure "that may occur when used zeolite or silicate detergency builder additives laminate.

Examples of reinforcing additives of the detergency alkali metal silicates, especially those that have a SiO 2: Na 2 O ratio in the range of 1.6: 1 to 3.2: 1, and laminar silicates such as silicates sodium laminar described in the patent US 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-6 is the trademark of a crystalline laminar silicate marketed by Hoechst (hereinafter abbreviated as "SKS-6"). Unlike the Zeolite-type detergency builder additives, the additive Na silicate detergency builder SKS-6 does not contain aluminum. He NaSKS-6 presents the morphology delta-Na2 SiO5 laminar silicate. May be prepared by methods such as those described in the patents DE-A-3,417,649 and DE-A-3,742,043. He SKS-6 is a very preferred laminar silicate for its use in the present invention, although others may also be used such laminar silicates such as laminar silicates that have the general formula NaMSi_ {O} {2x + 1} \ cdotyH2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, e y is a number from 0 to 20, preferably 0. Other layered silicates of Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 in its alpha, beta and gamma forms. How I know indicated above, the form delta-Na2 {SiO5 {(NaSKS-6) is most preferred for use in the present invention. Others silicates can also be useful as, for example, silicate magnesium, which can serve as a potentiating agent for friability in granulated formulations, as agent stabilizer for oxygen releasing bleach and as component of the regulating systems of the soaps.

They are examples of reinforcing agents of the carbonate type detergency metal carbonates alkaline earth metals and alkali metal carbonates described in Patent application DE-2,321,001, published on November 15, 1973.

Aluminosilicate-type reinforcing additives They are useful in the present invention. The reinforcing additives of the aluminosilicate type detergency are of great importance in the most granular cleaning detergent compositions currently intensive in the market and can also be a significant detergency builder ingredient for liquid detergent formulations. The reinforcing additives of the aluminosilicate type detergency include those that have the empirical formula:

3

where z and y are whole numbers of at least 6, the molar relationship between z and y is in the range of 1.0 to about 0.5 and x is an integer of about 15 to about 264

Ion exchange materials Useful aluminosilicate are in the market. These aluminosilicates can have a crystalline or amorphous structure and they can be natural or synthetic aluminosilicates. In the patent US 3,985,669, granted to Krummel et al. on 12 of October 1976, a method for producing materials is described aluminosilicate type ion exchangers. The materials crystalline aluminosilicate type ion exchangers and Synthetic preferred for use in the present invention are found available under the names of Zeolita A, Zeolita P (B), Zeolita MAP and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:

4

where x is from about 20 to about 30, especially about 27. This material is
known as Zeolite A. In the present invention, dehydrated zeolites can also be used (x = 0-10).
Preferably, the aluminosilicate has a particle size of about 0.1 to 10 micrometers in diameter.

Additives strengthening detergency organic ingredients suitable for the purposes of the present invention include, but not limited to, a wide variety of polycarboxylate compounds. Here the term "polycarboxylate" refers to compounds that have a plurality of carboxylate groups, preferably at least 3 carboxylates. The detergency reinforcing additive of type Polycarboxylate can generally be added to the composition in acid form, although it can also be added in the form of neutral salt. When used in salt form, metal salts are preferred alkaline such as sodium, potassium and lithium, or alkanolammonium.

Among detergency builders Different categories of polycarboxylate are included Useful materials An important category of reinforcing additives of the polycarboxylate type detergency are the ether polycarboxylates, including oxydisuccinate, as described in US Patent 3,128,287, granted to Berg on April 7, 1964 and the patent US 3,635,830, granted to Lamberti et al. on 18 of January 1972. See also the reinforcing additives of the Patent "TMS / TDS" detergency US 4,663,071, granted to Bush et al. May 5th 1987. Suitable ether polycarboxylates also they include cyclic compounds, especially alicyclic compounds, such as those described in the patents US 3,923,679, US 3,835,163, US 4,158,635, US 4,120,874 and US 4,102,903.

Other useful additives are the ether-hydroxypolycarboxylates, the copolymers of maleic anhydride with ethylene or vinyl methyl ether, the acid 1,3,5-trihydroxybenzene-2,4,6-trisulfonic and carboxymethyloxysuccinic acid, the various metal salts alkali, ammonium and substituted ammonium of polyacetic acids such such as ethylenediaminetetraacetic acid and acid nitrilotriacetic, as well as polycarboxylates such as acid  melitic, succinic acid, oxidisuccinic acid, acid polyimaleic acid benzene-1,3,5-tricarboxylic acid, the carboxymethyloxysuccinic acid and soluble salts thereof.

Citrate additives, for example, acid citric and soluble salts thereof (especially salt sodium), they are additive builders of type detergency polycarboxylate of particular importance for formulations liquid detergents for intensive cleaning due to their availability to from renewable resources and their biodegradability. Can be used also citrates in granulated compositions, especially together with zeolite-type detergency builders and / or laminar silicate. Oxydisuccinates are also especially useful in this type of compositions and combinations.

In the detergent compositions herein invention are also suitable 3,3-dicarboxy-4-oxa-1,6-hexanedioates  and related compounds described in the patent US 4,566,984, granted to Bush on January 28, 1986. Additives reinforcing acid detergency Useful succinic include alkyl and alkenyl acids C 5 -C 20 succinic and salts thereof. A particularly preferred compound of this type is acid. dodecenyls succinic. Specific examples of reinforcing additives of Succinate type detergency include: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate and the like. The lauryl succinates are detergency builders preferred from this group and are described in the patent EP-6200690.5 / 0.200.263, published on November 5 of 1986.

Other suitable polycarboxylates are described in US 4,144,226, granted to Crutchfield et al. he March 13, 1979, and in US-3,308,067, granted to Diehl on March 7, 1967. See also the US-3,723,322 granted to Diehl.

They can also be incorporated into the compositions fatty acids, for example, monocarboxylic acids C_ {12} -C_ {18}, alone or together with the above detergency builder additives, especially citrate and / or reinforcing additives of succinate type, to obtain a additional reinforcing activity. Said use of fatty acids It will generally reduce the formation of soaps, which should be taken into account by the formulator.

When additives based on phosphorus, and especially in the formulation of washing tablets by hand of the laundry, the various phosphates of alkali metals, such as the well known tripolyphosphates sodium, sodium pyrophosphate and sodium orthophosphate. Can be used also phosphonate-type detergency builders, such as the ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see, for example, patents US-3,159,581, US-3,213,030, US-3422,021, US-3,400,148 and US 3,422,137).

Bleach

The detergent compositions herein may optionally contain bleaching agents or compositions bleaching and one or more activators of the bleaching effect. When are present, bleaching agents will typically be at levels of about 1% to about 30%, more typical of about 5% to about 20%, of the detergent composition, especially for washing fabrics. Yes bleach activators are present, their quantity will be typically from about 0.1% to about 60%, of more typically about 0.5% to about 40%, of the bleaching composition comprising the bleaching agent plus the bleach activator.

Bleaching agents herein invention used can be any of the agents useful bleaching agents for detergent compositions for tissue cleaning, cleaning of rigid surfaces or others cleaning purposes that are already known or become known. These may be oxygen releasing bleach or other bleaching agents In the present invention they can use perborate bleaches, such as perborate sodium (for example, monohydrate or tetrahydrate).

Another category of bleaching agent that can used without restriction are acid bleaching agents percarboxylic and salts thereof. Among the appropriate examples of this class of agents is monoperoxyphthalate magnesium hexahydrate, the magnesium salt of acid metachloroperbenzoic acid 4-nonylamino-4-oxoperoxybutyric  and diperoxidedecanedioic acid. Such bleaching agents are described in patents US-4,483,781, granted to Hartman on November 20, 1984; US-740,446, granted to Burns et al. on June 3, 1985; EP-0.133.354, granted to Banks et al. on 20 of February 1985, and US-4,412,934, granted to Chung and cabbage. on November 1, 1983. Among the bleaching agents very preferred also include acid 6-nonylamino-6-oxoperoxicaproic,  as described in US Patent 4,634,551, issued on January 6, 1987 to Burns et al.

Bleaching agents can also be used peroxygenated Among peroxygenated bleaching compounds suitable are sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, the sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide A bleach of the type can also be used persulfate (for example, OXONE, marketed by DuPont).

A preferred percarbonate bleach It comprises dry particles with an average particle size between 500 micrometers and 1,000 micrometers; at most approximately 10% by weight of said particles are less than 200 micrometers and at most approximately 10% by weight of said particles are larger than 1,250 micrometers. Optionally the percarbonate can be coated with silicate, borate or agents water soluble surfactants. Percarbonate is marketed by various companies such as FMC, Solvay or Tokai Denka.

Agent mixtures can also be used. whiteners

Peroxygen bleaching agents, perborates, percarbonates, etc. they are preferably combined with bleach activators, which lead to the in situ production of the peroxyacid corresponding to the bleach activator in aqueous solution (ie, during the washing process). In US Patent 4,915,854, issued April 10, 1990 to Mao et al., And US 4,412,934 several non-limiting examples of activators are described. Nonanoyloxybenzenesulfonate (NOBS) and tetracetylethylene diamine (TAED) activators are typical, and mixtures thereof can also be used. See also US-4,634,551 for other typical bleach and activators useful in the present invention.

Bleach activators amidoderivatives very Preferred are those of the following formulas:

5

where R 1 is a group alkyl containing from about 6 to about 12 carbon atoms, R2 is an alkylene containing from 1 to about 6 carbon atoms, R 5 is H or alkyl, aryl or alkaryl containing from about 1 to about 10 carbon atoms and L is any suitable leaving group. A outgoing group is any group that is displaced from the trigger bleach as a result of nucleophilic anion attack of perhydrolysis on the bleach activator. A group preferred outbound is the phenylsulfonate.

Preferred examples of activators of bleach of the above formulas include (6-octanamido-caproyl) oxybenzenesulfonate,  (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzenesulfonate and mixtures thereof, as described in the patent 4,634,551.

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Other class of bleach activators comprises the benzoxazine type activators described by Hodge and cabbage. in US-4,966,723, issued on 30 October 1990, and incorporated herein by reference memory. A highly preferred activator of the benzoxazine type is:

6

Another class of bleach activators preferred are type activators acyl lactam, especially acylcaprolactams and the acilvalerolactamas of the formulas:

7

where R 6 is H or a group alkyl, aryl, alkoxyaryl or alkaryl containing from 1 to approximately 12 carbon atoms. Lactamic activators Very preferred include benzoyl caprolactam, octanoyl caprolactam,  3,5,5-trimethylhexanoyl caprolactam, nonanoil caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoil valerolactam, octanoil valerolactam, decanoil valerolactam, undecenoil valerolactama, nonanoil valerolactama, 3,5,5-tri-methylhexanoyl valerolactam and mixtures thereof. See also the patent US 4,545,784, granted to Sanderson on October 8 1985, which describes acylcaprolactams, including benzoylcaprolactam, adsorbed in perborate sodium

Bleaching agents other than agents Oxygenated bleaches are also known in the art and They can be used in the present invention. A type of agent Non-oxygen bleach of special interest are the photoactivated bleaching agents such as phthalocyanines from sulfonated zinc and / or aluminum. See the patent US 4,033,718, issued July 5, 1977 to Holcombe et al. If detergent compositions are used, these they will typically contain approximately 0.025% at approximately 1.25%, by weight, of these bleaches, especially sulfonated zinc phthalocyanide.

If desired, bleaching compounds may be catalyzed by a manganese compound. Sayings Compounds are well known in the art and include, for example, the manganese-based catalysts described in the patents 5,246,621, 5,244,594, US 5,194,416 and US 5,114,606; and the European patent applications pub. no. EP-549.271A1, EP-549.272A1, EP-544.440A2 and EP-544.490A1. Preferred examples of these catalysts include Mn IV 2 (u-O) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (PF 6) 2, Mn III 2 (uO) 1 (u-OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 - (ClO 2) 4) 2, Mn IV 4 (u-O) 6 (1,4,7-triazacyclononane) 4 (ClO 4) 4, Mn III Mn IV 4 (uO) 1 (u-OAc) 2 - (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (ClO 4) 3, Mn IV (1,4,7-trimethyl-1,4,7-triazacyclononane) - (OCH 3) 3 (PF 6) and mixtures thereof. Other metal-based bleaching catalysts are the described in US Pat. Nos. 4,430,243 and US 5,114,611. The use of manganese with various complex ligands to improve bleaching is also described in the following patents: US-4,728,455, 5,284,944, 5,246,612, US 5,256,779, US 5,280,117, US 5,274,147, US 5,153,161 and 5,227,084.

As a practical matter, and not by way of limitation, the compositions and processes of the present invention can be adjusted to obtain at least one part of the order ten million of the active bleaching catalyst species in the aqueous wash solution, which will preferably involve about 0.1 ppm to about 700 ppm, more preferably from about 1 ppm to about 500 ppm, of the catalytic species in the laundry solution.

Enzymes

In the formulations of the present invention, They can include enzymes for different laundry purposes such as for example, the removal of protein stains, hydrates carbon or triglycerides or to avoid dye transfers or to restore tissue. The enzymes that can be incorporated are proteases, amylases, lipases, cellulases and peroxidases, as well as mixtures thereof. Other types of enzymes These may be of any appropriate origin such as, e.g. eg, vegetable, animal, bacterial, fungal and yeast. Without However, your choice is governed by several factors such as pH activity and / or optimum stability, thermostability, stability against active detergents, reinforcing additives the detergency, etc. Enzymes are preferred in this regard. bacterial or fungal, such as amylases and proteases Bacterial and fungal cellulases.

Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, more typically from about 0.01 mg to about 3 mg, of active enzyme per gram of the composition. Said of another Thus, the compositions in the present invention will comprise typical form of about 0.001% to about 5%, preferably 0.01% -1% by weight of a commercial preparation of enzyme. Protease enzymes are normally present in these commercial preparations at sufficient levels to provide 0.005 to 0.1 Anson units (AU; from English, Anson unit) of activity per gram of composition.

Suitable examples of proteases are subtilisins that are obtained from special strains of B. subtilis and B. licheniformis . Another suitable protease is that obtained from a strain of Bacillus and having a maximum activity in the range of pH 8-12, developed and sold by Novo Industries A / S under the trademark of ESPERASE. The preparation of this enzyme and analogous enzymes is described in patent GB-1,243,784 to Novo. Suitable proteolytic enzymes for removing commercially available protein stains are those that are marketed under the ALCALASE and SAVINASE brands of Novo Industries A / S (Denmark) and MAXATASE of International Bio-Synthetics, Inc. (Netherlands). Other proteases include Protease A (see application EP-130,756, published on January 9, 1985) and Protease B (see application EP-87303761.8, filed on April 28, 1987, and application EP-130,756, Bott et al., published January 9, 1985).

Amylases include, for example, α-amylases described in the patent GB-1,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo Industries

Cellulases that can be used in the present invention include both bacterial and fungal cellulases. Preferably, they will have an optimum pH of 5 to 9.5. Suitable cellulases are described in US Pat. No. 4,435,307, issued to Barbesgoard et al. on March 6, 1984, which describes the fungal cellulose produced by Humicola insolens and the strain of Humicola DSM1800 or cellulase 212, produced by a fungus belonging to the genus Aeromonas and the cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricula Solander) . Other suitable cellulases are also described in GB-A-2,075,028, GB-A-2,095,275 and DE-OS-2,247,832. CAREZYME (Novo) is especially useful.

Lipase enzymes suitable for detergent use include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19,154, as described in GB-1,372,034. See also lipases in patent application JP-53.20487, filed on February 24, 1978. This lipase can be purchased from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the name Lipasa P "Amano", hereinafter referred to as "Amano-P". Other commercial lipases are Amano-CES, Chromobacter viscosum lipases, p. eg, Chromobacter viscosum var. NRRLB 3673 lipoliticum, marketed by Toyo Jozo Co., Tagata, Japan; and other lipases from Chromobacter viscosum from US Biochemical Corp., USA, and Disoynth Co., The Netherlands, and lipases from Pseudomonas gladioli . The enzyme lipolase derived from Humicola lanuginosa and marketed by Novo (see also EP O 341,947) is a preferred lipase for use in the present invention.

Peroxidases enzymes are used together with sources of oxygen, for example, percarbonate, perborate, persulfate, hydrogen peroxide, etc. These are used to "bleach the solution", that is, to prevent transfer  of dyes or pigments released from the substrates during washing operations to other substrates of the washing solution. Peroxidase enzymes are known in the art and include, for example, Horseradish peroxidase, ligninase and haloperoxidase such as chloro- and bromo-peroxidase. The compositions of detergent containing peroxidase are described, for example, in PCT international application WO 89/099813, granted on 19 October 1989 to O. Kirk and assigned to Novo Industries A / S.

A wide range of enzymatic products and of means for incorporation into synthetic detergent compositions They are also described in US Patent 3,553,139, granted on January 5, 1971 to McCarty et al. Other enzymes They are also described in US Patent 4,101,457, granted to Place et al. on July 18, 1978, and in the patent US 4,507,219, granted to Hughes on March 26, 1985. Enzymatic materials useful for formulations liquid detergents and their incorporation into said formulations are described in US Patent 4,261,868, issued to Hora et al. on April 14, 1981. Enzymes use in Detergents can be stabilized by different techniques. The Enzymatic stabilization techniques are described and illustrated in the US-3,600,319, issued August 17, 1971 to Gedge, et al., And application EP-0,199,405, application EP-86200586.5, published on 29 October 1986, granted to Venegas. Stabilization systems enzymatic are also described, for example, in the patent US 3,519,570.

Other components that are commonly used in detergent compositions and which can be incorporated into detergent tablets of the present invention include agents chelators, agents to release dirt, inhibitors of redeposition of stains, dispersing agents, brighteners, suds suppressors, fabric softeners, agents inhibitors of the transfer of dyes and perfumes.

Examples that are not according to the invention

8

Anionic agglomerates comprise 38% of anionic surfactant, 22% zeolite and 40% carbonate.

Non-ionic agglomerates comprise 26% of nonionic surfactant, 48% zeolite and 26% carbonate.

The effect activator agglomerates bleach comprise 81% TAED, 17% copolymer acrylic / maleic (acid form) and 2% water.

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Zinc phthalocyanine encapsulates Sulfonated have an activity of 10%.

The suds suppressor comprises a 11.5% silicone oil (eg Dow Corning) and 88.5% of starch.

The laminar silicate comprises 78% of SKS-6 from Hoechst and 22% citric acid.

Agglomerates of the dye inhibitor they comprise 21% PVNO / PVPVI, 61% zeolite and 18% carbonate.

Perfume encapsulates comprise 50% of perfume and 50% starch.

The spray of non-ionic paste comprises a 67% of AE5 C12-C15 (alcohol with an average of 5 ethoxy groups per molecule), 24% of N-methylglucosamide and 9% water.

The effervescence compact comprises 54.5% sodium bicarbonate and 45.5% citric acid.

All particulate materials of the Example 1, except the dried zeolite, was mixed in a drum mixing to form a homogeneous mixture in the form of particles; during this mixing the sprays were carried out. After spraying, lubrication was performed with The dried zeolite.

A first series of tablets of the as follows: approximately 37.5 g of the mixture was introduced of a circular shaped mold with a diameter of 4.5 cm and compressed with a force of 0.5 kN or approximately 30 Newton / cm2, to obtain approximately 2.2 cm tablets of height and a density of approximately 1.1 g / cc. Resistance to The traction of the tablet was 3.5 kPa.

Lauric acid was heated in a thermostatic bath at 60 ° C stirring gently until casting. The product Molten was a clear liquid. Then they submerged the tablets prepared as indicated in the liquid for get the final coated tablet; this pill had a weight total of 38.5 g and a tensile strength of 10.1 kPa.

A second series of pills was made with a compaction force of 1 kN, or about 63 N / cm2,  to provide pills approximately 2.0 cm tall, a density of approximately 1.2 g / cc and a resistance to tensile of 9.0 kPa.

After coating with lauric acid the These tablets had a weight of 38.5 g and resistance to traction was 21 kPa.

A third series of pills with a compaction force of 1.5 kN or approximately 95 N / cm2, to provide approximately 1.9 cm tablets high, a density of approximately 1.3 g / cc and a tensile strength of 12.9 kPa.

After coating the tablets with acid lauric these had a weight of 38.5 g and resistance to traction was 23.4 kPa.

Example 2

Mixing was performed according to the described method. in example 1 and, after lubrication, the granules were added of effervescence to the mixing drum for mixing final.

Compaction was carried out and the coating according to the method described in example 1.

A first series of pads with a compaction force of 1 kN or approximately 63 Newton /
cm2, to provide pads approximately 2.2 cm high, a density of approximately 1.1 g / cc and a tensile strength of 4.5 kPa.

After coating with lauric acid, the pills had a weight of 38.5 g and tensile strength It was 13.1 kPa.

A second series of pills was made with a compaction force of 1.5 kN or approximately 95 N / cm2, to provide tablets of approximately 2.1 cm of height, a density of approximately 1.2 g / cc and a resistance to the tensile of 8.5 kPa.

After coating with lauric acid, the pads had a weight of 38.5 g and a tensile strength of 15.8 kPa.

A third series of pills with a compaction force of 2.5 kN or approximately 160 N / cm2, to provide tablets of approximately 2.0 cm of height, a density of approximately 1.2 g / cc and a resistance to the traction of 15.7 kPa.

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After coating with lauric acid, the pills had a weight of 38.5 g and tensile strength increased to 24.1 kPa.

Example 1 was repeated replacing the acid lauric by hexadecanol. Hexadecanol was heated in a bath thermostatic at 80ºC gently stirring until casting. The final tensile strength of the three series of pads was 14.1 kPa, 21 kPa and 23.4 kPa, respectively.

Example 2 was repeated replacing the acid lauric by hexadecanol. Hexadecanol was heated in a bath thermostatic at 80ºC gently stirring until casting. The final tensile strength of the three series of pads was 12.1 kPa, 13.6 kPa and 22.1 kPa, respectively.

Claims (5)

1. A tablet comprising a core and a coating, the core being formed by compression of a particulate material, the particulate material comprising surfactant and detergency builder additive, characterized in that the coating comprises adipic acid, acids C8-C13 dicarboxylic or mixtures thereof and has a solubility in water at 25 ° C of less than 20 g / l. 2. A tablet according to claim 1, which It comprises a coating of practically insoluble materials in water that have a melting point in the range from 40 ° C to 180 ° C 3. A process to make a pill that It comprises the stages of:

(to)

form a nucleus compressing a particulate material, the material comprising of surfactant particles and additive reinforcing the detergency;

(b)

apply a coating material to the core, the coating material being in the form of dough cast

(C)

let the coating material molten solidify;

characterized in that the coating material comprises adipic acid, C8-C13 dicarboxylic acids or mixtures thereof and has a solubility in water at 25 ° C of less than 20 g / l. 4. A process according to claim 3, in the that the material or mixture of coating materials have a melting point of 40 ° C to 180 ° C. 5. A process to make a pill that It comprises the stages of:

(to)

form a nucleus compressing a particulate material, the material comprising of surfactant particles and additive reinforcing the detergency;

(b)

apply a coating material to the core, the coating material being dissolved in a solvent;

(C)

let the solvent evaporate;

characterized in that the coating material comprises adipic acid, C8-C13 dicarboxylic acids or mixtures thereof and has a solubility in water at 25 ° C of less than 20 g / l.