ES2284164T3 - PAD OF DETERGENT COVERED AND PROCEDURE TO PRODUCE THE SAME. - Google Patents

Abstract

THE PRESENT INVENTION REFERS TO PILLS THAT UNDERSTAND A NUCLEUS AND A COATING, WHOSE NUCLEO IS FORMED BY COMPRESSING A MATERIAL IN PARTICLES, UNDERSTANDING THE MATERIAL IN PARTICLES A TENSIOACTIVE AND A BETTER DETERENDING THE UNDERSTANDING AGENTS PART OF THE DETEGRATING AGENT IN THE COATING. THE INVENTION ALSO REFERS TO PROCESSES FOR THE MANUFACTURE OF THE PADS.

Description

Coated detergent tablet and procedure to produce it.

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 tablets and loss of material active.

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

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 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

A disadvantage of the state descriptions of the technique is that a coating that is sufficiently thick and hard to resist abrasion, it also tends to Slowly dissolve or dissolve during use.

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 disperses completely, in particular in alkaline solutions or with a high content of surfactant as washing solutions.

Summary of the invention

The object of the present invention is achieved providing a tablet comprising a core and a coating, forming the core by compression of a material in the form of particles, the material comprising surfactant particles and detergency builder additive, characterized in that the coating material has a water solubility at 25 ° C of less than 20 g / l and is selected from C 2 -C 13 dicarboxylic acids and the coating comprises a disintegrant that will swell when placed on contact with water at a level such that the coating is broken in up to 30% by weight of the coating. It is preferred that the tablet also comprise an effervescent agent, for example, a source of soluble acid and an alkali metal carbonate.

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

(C)

let the coating material molten solidify; characterized in that the material of coating comprises a disintegrant, which will swell in contact with water at a level such that the coating breaks until 30% by weight, and where the coating material has a water solubility at 25 ° C of less than 20 g / l and is selected from C 2 -C 13 dicarboxylic acids.

Preferably, the coating materials they have a melting point in the range of 40 ° C to 200 ° C.

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), which typically results in low values of bulk density of 600 g / l or less. Fit materials of higher density particles can be prepared by granulation and densification in a high batch discontinuous mixer / granulator shear or by granulation and densification procedures continuous (for example, with Lodige® CB and / or Lodige® KM mixers). Other suitable procedures include bed procedures fluid and compaction processes (for example, compaction with roller), extrusion as well as any material in the form of particles prepared by any chemical process like flocculation or sintering by crystallization. The particles individual can also be any other type of particles, granules, spheres or grains.

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. Alternatively The mixing process can be carried out continuously dosing by weight and dispensing each component on a tape in movement and mixing the components in one or more drums or mixers A liquid spray can be performed on the mixture of particulate materials (for example, nonionic surfactants). Others can also be sprayed liquid ingredients on the mixture of materials in the form of particles, either separately or pre-mixed. For example, perfume and aqueous suspensions of optical brighteners After spraying the surfactant no ionic, a particle can be added to the particles finely divided fluidizer (dusting agent, such as zeolites, carbonates, silicas), preferably towards the end of process, in order to make the mixture 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 between 40 mm and 50 mm, and a weight between 25 and 60 g. The pressure of compaction used to prepare these pills should not exceed 5 MPa (5000 kN / m2), preferably should not exceed 3 MPa (3000 kN / m2), and most preferably should not exceed 1 MPa (1000 kN / m2).

According to the present invention, the tablets they can be coated with a coating such that the tablet do not absorb moisture, or absorb moisture only at a very high speed reduced The coating is also strong enough as for the moderate mechanical shocks to which they look subjected to the pills during handling, the 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 It is subjected to stronger mechanical shocks. It also turns out advantageous for the coating material to dissolve in alkaline conditions or that is easily emulsified by surfactants This prevents the deposition of particles or lumps of undissolved coating material in the wash load of clothes. This can be important when the coating material it is completely insoluble (for example, less than 1 g / l) in Water.

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

The coating materials are acidic C2-C13 dicarboxylic. Dicarboxylic acids Preferred are oxalic acid (C2), malonic acid (C3), acid succinic (C4), glutaric acid (C5), adipic acid (C6), acid pimelic (C7), subic acid (C8), azelaic acid (C9), acid sebacic (C10), undecanedioic acid (C11), dodecanedioic acid (C12) and tridecanedioic acid (C13).

However, detergent tablets are they prepare and, regardless of the way they are, they are coated then according to the present invention with a material of coating having a melting point preferably of 40 ° C at 200 ° C

The coating is applied by coating with a molten material The coating material is applied to a temperature above its melting point and solidifies in the tablet. The coating material can be applied to the tablet by, for example, spraying or immersion. Normally, when the molten material is sprayed on the tablet, it solidifies quickly forming a coating uniform. When the pads are submerged in the molten material and then removed, the rapid cooling again causes rapid solidification of the coating material. Obviously, virtually insoluble materials that have a melting point below 40 ° C are not solid enough at room temperature and it has been discovered that the materials that they have a melting point greater than about 200 ° C they cannot be used Preferably, the materials melt in the temperature 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 the present invention the fracture of the Washing coating is improved by adding a disintegrant to the covering. This disintegrant will swell on contact with the water and it will break the coating into small pieces. This It will favor the dissolution of the coating in the washing solution. The disintegrant is suspended in the coating melt at a level of up to 30%, preferably from 5% to 20% and with maximum 5% to 10% preference, by weight.

In the Handbook of Pharmaceutical Excipients (1986) possible disintegrants are described. Examples of disintegrants Suitable include starches (natural starch, modified or pregelatinized, sodium starch gluconate), gums (gum agar, guar gum, garrofín gum, karaya gum, pectin gum, rubber tragacanth), croscarmellose sodium, crospovidone, cellulose, carboxymethyl cellulose, alginic acid and its salts, such as alginate sodium, silicone dioxide, clay, polyvinylpyrrolidone, soy polysaccharides, ion exchange resins and mixtures of the 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.

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

= \ frac {2 \ F} {\ mu \ Dt}

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:

to)

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

-

  Place 2 tablets with a known DFS weight and tension in the analyzer drum

-

  Spin the drum 20 rotations.

-

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

-

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

-

  The higher the% of the product that passes through the sieve of 1.7 mm, the better the disintegration.

b)

 In a washing machine according to the following procedure

-

  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 the pads.

-

  Run a short cycle (program 4) at 30 ° C with water urban

-

  Stop the cycle after 5 minutes and check if the load There are pieces of undissolved tablet. Pick up 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 gaseous carbon,

100

\ Na_{3}C_{6}H_{5}O_{7} + 3CO_{2} \

101

\ + 3H_{2}Op. \ ex. \ C_ {6} H_ {O} {7} + 3NaHCO_ {3} \

100

\ Na_ {3} C6 {H} {5} {7} + 3CO_ {\}

101

\ + 3H_ {2} O

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 adition 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 useful surfactants in the present invention typically at levels of about 1% to about 55% by weight include the C 11 -C 18 alkylbenzenesulfonates Conventional ("LAS") and alkylsufatos ("AS") C_ {10} -C_ {20} branched chain primaries and randomized, C 10 -C 18 alkyl sulfates secondary (2,3) of formula CH 3 (CH 2) x (CHOSO_3- M +) CH 3 and CH 3 (CH2) y (CHOSO_3 M +) CH2CH3 where x e (y + 1) are integers of at least approximately 7, preferably at least about 9, and M is a cation Water soluble, especially sodium, unsaturated sulfates such as oleyl sulfate, alkylalkoxysulfates C_ {10} -C_ {18} ("AE_ {x} S"; especially ethoxy sulfates EO 1-7), alkylalkoxycarboxylates C_ {10} -C_ {18} (especially ethoxycarboxylates EO 1-5), glycerol ethers C 10-18, alkyl polyglycosides C_ {10} -C_ {18} and its corresponding sulfated polyglycosides and fatty acid esters C 12 -C 18 alpha-sulphonates. If desired, they can also be included in the general compositions conventional non-ionic and amphoteric surfactants such as C 12 -C 18 alkyl ethoxylates ("AE") including the so-called narrow-peak alkyl ethoxylates, and the C 6 -C 12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy / propoxy), betaines and sulfobetains ("sultaines") C 12 -C 18, amine oxides C 10 -C 18, and the like. Can also be use the N-alkyl polyhydroxyamides C 10 -C 18 of fatty acids. The examples Typical include N-methyl glucamides C_ {12} -C_ {18}. See WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy fatty acid polyhydroxyamides, such like C_ {10} -C_ {18} N- (3-methoxypropyl) glucamide. You can use the N-propyl to N-hexyl glucamides C_ {12} -C_ {18} to get a low formation of soaps. Conventional soaps can also be used C_ {10} -C_ {20}. If high training is desired soaps, branched chain soaps can be used C_ {10} -C_ {16}. Especially useful are mixtures of anionic and nonionic surfactants. Other surfactants Useful conventions are described in standard texts.

Detergency builders

The compositions of the present invention include can add detergency builders to facilitate Mineral hardness control. Reinforcing additives can be used of inorganic and also organic detergency. Additives detergency builders are typically used in laundry compositions to help remove stains 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 the "weak" detergency (compared to phosphates), such such as citrate, or in the so-called "infrastructure" situation which may occur when additives are used to strengthen the Zeolite or laminar silicate detergency.

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 US 4,664,839, granted on May 12, 1987 to H. P. Rieck. NaSKS-6 is the registered trademark of a silicate crystalline laminar marketed by Hoechst (hereinafter abbreviated like "SKS-6"). Unlike additives Zeolite-type detergency builders, the booster additive of Na SKS-6 silicate type detergency no contains aluminum The NaSKS-6 presents the delta-Na2 SiO5 morphology of silicate laminate. This can be prepared by methods such as described in DE-A-3,417,649 and DE-A-3,742,043. He SKS-6 is a very preferred laminar silicate, although so are other layered silicates, such as those with general formula NaMSi_ {x} O_ {2x + 1} \ cdotyH_ {2}, where M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0. Other layered silicates Hoechst's include NaSKS-5, NaSKS-7 and NaSKS-11, such as alpha, beta and gamma forms. How 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 intensive currently marketed and can also be a significant detergency builder additive for liquid detergent formulations. The reinforcing additives of the aluminosilicate type detergency include those that have the empirical formula:

M_ {z} (zAlO2) y} \ cdot xH_ {2} O

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 approximately 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. A method for produce aluminosilicate ion exchange materials se described in US 3,985,669, granted to Krummel et al. on October 12, 1976. The ion exchange materials preferred crystalline aluminosilicate useful herein are those marketed as Zeolita A, Zeolita P (B), Zeolita MAP and Zeolite X. In a particularly preferred embodiment, the material crystalline aluminosilicate ion exchanger has the formula:

Na 12 [(AlO 2) 12 (SiO 2) 12] \ cdot xH_ {2} O

where x is about 20 to about 30, especially about 27. This material is known as Zeolite A. They can also be used in the present invention dehydrated zeolites (x = 0-10). Preferably, the aluminosilicate has a particle size of approximately 0.1 to 10 micrometers of 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 salt form neutralized When used in the form of salt, salts are preferred of alkali metals, such as sodium, potassium and lithium, or of alkanolammonium

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Among detergency builders Different categories of polycarboxylate are included Useful materials An important category of reinforcing additives of the polycarboxylate type detergency encompasses the ether polycarboxylates, including oxidisuccinate, as described in US 3,128,287, granted to Berg on April 7, 1964, and in US-3,635,830, granted to Lamberti et al. on January 18, 1972. See also the reinforcing additives of the "TMS / TDS" type detergency of US 4,663,071, granted to Bush et al. May 5th from 1987. Suitable polycarboxylate ether also includes cyclic compounds, especially alicyclic compounds such as described in 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 and / or detergency builder additives laminar silicate. Oxydisuccinates are also especially useful in this type of compositions and combinations.

They are also suitable in the compositions detergents of the present invention the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and related compounds described in US 4,566,984, granted to Bush on January 28, 1986. Additives reinforcing acid detergency Useful succinic include alkyl and alkenyl acids C5 {C} {C20} succinic and salts of same. A particularly preferred compound of this type is the dodecenylsuccinic acid. Specific examples of additives Succinate type detergency builders 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 application EP-6200690.5 / 0.200.263, published on November 5 of 1986.

In US 4,144,226, granted to Crutchfield et al. on March 13, 1979, and in US 3,308,067, granted to Diehl on March 7, 1967, other suitable polycarboxylates are described. See also 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 will produce generally a decrease in soaps, which should have Consider 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, 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 invention may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators. When they are present, the bleaching agents will typically be at levels of about 1% to about 30%, more typically about 5% to about 20%, of the composition detergent, especially for washing fabrics. If they are present bleach activators, its quantity will be of form typically from about 0.1% to about 60%, more typical of about 0.5% to about 40% of the bleaching composition comprising the bleaching agent plus the bleach activator.

The bleaching agents herein invention used can be any of the agents bleaching agents useful for cleaning detergent compositions of fabrics, cleaning of rigid surfaces or other purposes of cleaning that are already known or become known. These they can be oxygen bleaching or other agents whitening In the present invention they can be used perborate type 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 magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloroperbenzoic acid, the acid 4-nonylamino-4-oxoperoxybutyric and diperoxidedecanedioic acid. Such bleaching agents are described in US 4,483,781, granted to Hartman on 20 November 1984, US-740,446, granted to Burns et al. and filed on June 3, 1985, EP-0.133.354, granted to Banks et al. and published on February 20, 1985, and US-4,412,934, granted to Chung et al. on November 1, 1983. Bleaching agents very preferred also include the acid 6-nonylamino-6-oxoperoxicaproproic as described in US-4,634,551, granted on 6 January 1987 to Burns et al.

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Bleach can also be used peroxygenated Among peroxygenated bleaching compounds suitable are sodium carbonate peroxyhydrate and bleaches of equivalent "percarbonate" type, 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. whitening

Peroxygen bleach, perborates, percarbonates, etc. they are preferably combined with bleach activators, which result in the in situ production of the peroxyacid corresponding to the bleach activator in aqueous solution (ie, during the washing process). Several non-limiting examples of activators are described in US 4,915,854, issued to Mao et al. on April 10, 1990, and US-4,412,934. Nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylenediamine (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:

\hskip0.5cm

o

\hskip0.5cm

R^{1}C(O)N(R^{5})R^{2}C(O)LR 1 N (R 5) C (O) R 2 C (O) L

 \ hskip0.5cm 

or

 \ hskip0.5cm 

R 1 C (O) N (R 5) R 2 C (O) L

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 group outgoing is any group that is displaced from the activator of the bleach as a result of the nucleophilic attack of the anion of perhydrolysis on the bleach activator. An outgoing group preferred is the phenylsulfonate.

Preferred examples of activators of bleach of the above formulas include (6-octanamido-caproyl) oxybenzenesulfonate, (6-nonanamido-caproyl) oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzenesulfonate and mixtures thereof, as described in the US-4,634,551., Incorporated by reference in the present memory

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

one

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

2

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 oxygen releasing bleaches are also known for the technique and can be used in the present invention. A kind of oxygen bleaching agent not of special interest are photoactivated bleaching agents such as phthalocyanines of sulfonated zinc and / or aluminum. See US 4,033,718, granted on July 5, 1977 to Holcombe et al. If the detergent compositions, these will typically contain about 0.025% to about 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 US 5,246,621, US 5,244,594; US 5,194,416; US-5,114,606 and in 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 bleach catalysts based in metal include those described in US-4,430,243 and US 5,114,611. The use of manganese with various complex ligands to reinforce bleaching also described in 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 of most typical form of about 0.01 mg to about 3 mg, of active enzyme per gram of the composition. In other words, the compositions in the present invention will comprise typical 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 to remove 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 of International Bio-Synthetics, Inc. and TERMAMYL de Novo Industries

Cellulases that can be used in the present invention include both bacterial and fungal cellulases. Preferably, they will have an optimum pH between 5 and 9.5. Suitable cellulases are described in US 4,435,307, issued to Barbesgoard et al. on March 6, 1984, which describes the fungal cellulase produced from Humicola insolens and the strain of Humicola DSM1800 or a 212 cellulase-producing fungus belonging to the genus Aeromonas, and the cellulase extracted from the hepatopancreas of a marine mollusc ( Dolabella Solander headset). 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 use in detergents 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 JP-53.20487, filed for public inspection on February 24, 1978. This lipase is marketed by 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 Chromobacter viscosum lipases from US Biochemical Corp., USA, and Disoynth Co., The Netherlands, and Pseudomonas gladioli lipases. The Lipolase enzyme 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. In 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 the PCT international application WO 89/099813, granted on October 19 from 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 are also described in US-3,553,139, granted on 5 from January 1971 to McCarty et al. Other enzymes are also described. in US 4,101,457, granted to Place et al. on 18 of July 1978, and in US-4,507,219, granted to Hughes on March 26, 1985. Enzymatic materials useful for liquid detergent formulations and their incorporation in said Formulations are described in US 4,261,868, granted to Hora et al. on April 14, 1981. Enzymes for use in detergents they can be stabilized by various techniques. The Enzymatic stabilization techniques are described and illustrated in 3,600,319, issued August 17, 1971 to Gedge, et al., And application EP-0,199,405, the application EP-86200586.5, published on October 29 of 1986, granted to Venegas. Stabilization systems enzymatic are also described, for example, in 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

3

4

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

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 inhibitor of dye transfer comprises 21% PVNO / PVPVI, 61% of 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 of mixed 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 in 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.

The adipic acid was heated in a bath thermostatic up to 170 ° C gently stirring until melted. He disintegrating agent, Nymcel ZSB-16®, was added to then continuously stirring until adipic acid formed a suspension Pills prepared as described previously they were then added to the liquid to form the final coated tablet, where this tablet had a total weight of 41.1 g and a tensile strength of 12.6 kPa.

A second series of pills was prepared with a compaction force of 1 kN or about 65 N / cm2 to provide pills approximately 2.0 cm high, a density of approximately 1.2 g / cc and a tensile strength of 9.0 kPa.

After coating with adipic acid, the tablets had a weight of 41.2 g and tensile strength It was 21.2 kPa.

A third series of pills with a compaction force of 1.5 kN or approximately 95 N / cm2, to provide tablets of approximately 1.9 cm of height, a density of approximately 1.3 g / cc and a resistance to the traction of 12.9 kPa. After coating with adipic acid, the pills had a weight of 41.1 g and resistance to traction was 31.5 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.

The manufacture of the pills and the coating was carried out according to the method described in the Example one.

A first series of tablets 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 adipic acid the pills had a weight of 41.1 g and tensile strength It was 14.4 kPa.

A second series of pills was made with a compaction force of 1.5 kN or about 95 N / cm2 to provide pills approximately 2.2 cm high, a density of approximately 1.2 g / cc and a tensile strength of 8.5 kPa.

After coating with adipic acid the pills had a weight of 41.1 g and tensile strength It was 22.2 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.

After coating with adipic acid the pills had a weight of 41.1 g and tensile strength increased to 31 kPa.

In Comparative Example 3, the process of example 1 but without disintegrant. Resistance to Final traction of the three series of pads was 6.5 kPa, 15.5 kPa and 19.5 kPa, respectively.

In Comparative Example 4, the process of example 4 but without disintegrant. Resistance to Final traction of the three series of pads was 10.4 kPa, 14.5 kPa and 21.3 kPa, respectively.

Claims (6)

1. A tablet comprising a core and a coating, the core being formed by compressing a particulate material, the particulate material comprising surfactant and detergency builder additive, characterized in that the coating material has a water solubility at 25 ° C of less than 20 g / l and is selected from C 2 -C 13 dicarboxylic acids and the coating comprises a disintegrant, which will swell once it comes into contact with water at a level to break the coating up to 30% by weight of the coating. 2. The tablet according to claim 1, which it comprises a disintegrant selected from the group consisting of natural starch, modified starch, pregelatinized starch, sodium starch gluconate, croscarmellose sodium, crospovidone, cellulose, carboxymethyl cellulose, alginic acid, sodium alginate, silicone dioxide, clay, agar rubber, guar rubber, garrofín rubber, Karaya gum, pectin gum, tragacanth gum, polyvinylpyrrolidone, soy polysaccharides, ion exchange resins and mixtures of the same. 3. The tablet according to claim 1 or the claim 2, further comprising an effervescent agent. 4. The tablet according to claim 3, in where the effervescent agent is a source of soluble acid and a alkali metal carbonate. 5. A process to make 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 in the form of dough cast

(C)

let the coating material molten solidify;

characterized in that the coating material comprises a disintegrant which will swell in contact with water at a level to break the coating up to 30% by weight and where the coating material has a water solubility at 25 ° C of less than 20 g / l and is selected from C 2 -C 13 dicarboxylic acids. 6. A process according to claim 5, in where the material, or the mixture of materials, of coating they have a melting point of 40 ° C to 200 ° C.