MXPA96004261A - Enz granulates - Google Patents

Abstract

The present invention relates to granular components, comprising enzyme and polymeric binding material selected from the group consisting of: N-polyamine oxide, copolymers of N-polyvinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidone, polyvinylimidazole, polyaspartic acid and its salts; polymers and copolymers of maleic and acrylic acid and their salts, and mixtures thereof. Also disclosed is a process for the preparation of such granular compounds

Description

GRANULADOS DE ENZIMA The present invention relates to granular components comprising in? Anna and specified polyimepic bonding materials. The granular components are particularly suitable for use in compositions det gentes.

BACKGROUND OF THE INVENTION Encapsulates above that have enzymatic activity of approximately 4 KNPU / g that are commercially available today. As well as the active enzymes, the encapsulates which are available commercially contain a variety of fillers, binders and coating agents such as sodium chloride, sodium sulfate, methycellulose, yellow dextrin and kaolin clay. Representative of the prior art in this field is: EP206418, published on December 30, 1986, discloses granules above comprising fillers, binders, granulating agents, etc. The patent describes encapsulates which comprise enzymes at a concentration of 0.5% to 20%, preferably 5% by weight. The encapsulation also comprises (by weight) - 1. Fillers at 3% to 97.5%, preferably Four. Five%; 2. Cellulose from 2% to 40%, preferably 25%; 3. Binder from 0% to 0%; 4. Auxiliary granulation from 5% to 40%; However, the fillers and binders that are known in the art are mainly those which either have no active contribution to the process - detergent or those which have a weight or weight effectiveness in the detergent process. Such fillers and binders act simply as a "filler" in the washing process. The binders described in EP20S418 include polyvinyl pyrrolidone (PVP), dextpna, polyvinyl alcohol, hydroxypropyl cellulose, rnetyl cellulose and carboxy and cellulose (CMC). However, the detergent products of today, where high concentrations of active ingredients are required to achieve even more "compact" products, the presence of such fillers and binders is undesirable. It is a purpose of the present invention to provide * a granulate containing enzyme, which contains a high proportion of detergent active ingredients. It is a second purpose of the present invention to provide a process for the manufacture of such enzyme-containing granules. This has been achieved by the selection of highly efficient bonding materials, which are also active detergency ingredients. The binders of the present invention are more effective in weight as detergent ingredients than the binders proposed by the prior art, including PVP and CMC molecules.

BRIEF DESCRIPTION OF THE INVENTION The granular components of the present invention comprise an enzyme and a polya binding material selected from the group consisting of: N-oxido of polyamine; copolymers of N-vimlpyrrolidone and N-vmilirnidazole; polivimloxasili dona; polyvinylimidazole; poliaspar acid and its salts; polymers and copol ions of maleic acid and acrylic acid and their salts; and its mixtures. Preferably, the uni n? Ol? Rner material * Lco osta "present at a concentration of 0.1% to 25% by weight of the granular component (hereinafter referred to as the "granulate"), more preferably from 1% to 10%. The granulate may also consist of one or more fillers such as carbonate, bicarbonate, eitrate, alkali metal or alkalimetal metal phosphate salts.

Fl citric acid can also be used as the filler material. The granulate may also consist of waxy granulating agents having a melting point between 30 and < "00 ° C, as well as polyvinyl-1-pyrrolidone and carboxymethyl cellulose The process of the present invention comprises the steps of: (a) forming a powder from an enzyme solution and a particular filling material; ) granulate * ol powder with a granulation liquid to form a granulate; wherein the granulation liquid comprises a poly epic binding atheal, selected from the group consisting of: N-polyamide oxide; copolymers of N-vini lpyrrolidone and M ~ v? mlirnidazole; pol ivi ni loxasol idona, pol iv Lnilimidazole; polyaspartic acid and its salts; polymers and copolymers of acrylic and acrylic acid and their salts; and its mixtures. Preferably, the granulation liquid also comprises a nonionic surfactant or a mixture of nonionic surfactants. In a particularly preferred process, < The granulate is mixed with an auxiliary of the flow of finely divided particles, such as sodium aluinmosilicate, precipitated silica or silica vapor, or mixtures thereof.

DETAILED DESCRIPTION OF THE INVENTION The pol-bonding materials of the present invention are chosen from the following: polyamine N-oxide; copol írneros of N- 'mi 1 p L roli ona and N-vim lirnidazol; polyvinyloxasolidone; pol i v ili idazol; polyaspartic acid and its salts; polymers and copolymers of maleic acid and acrylic acid and their salts; and mixtures thereof. a) Polymer N-oxide polymers The polyarylene N-oxide polymers suitable for use contain units having the following structural formula: P I (I) A R wherein P is a polishable unit, wherein the group R-N-0 may be attached to or in which the group R-M-0 forms part of the polishable unit or a combination of both. 0 0 0 A is NC, CO, C, -0-, - -, -N-; x is o o; R are aliphatic, aliphatic ethoxylated, het-cyclic or alicyclic groups or any combination thereof, in which the nitrogen of the group N-0 may be uni oo in which the nitrogen of the group N-0 is part of these groups The group N ~ 0 can be represented by the following general structures: O or (Rl) x - N - (R2) and ~ N- (Rl) x (R3) z wherein R 1, R 2 and R 3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof, X or / and y and / or Z is 0 or 1 and wherein the nitrogen of the group N ~ 0 may be attached or which is part of these groups to the nitrogen of group N-0. The group N-0 can be part of the polishable unit (P) or it can be attached to the polymeric backbone or a combination of both. Suitable polyamine N-oxides in which the N-0 group forms part of the polishable unit comprises polyamine N-oxides in which R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. A class of polyamine N-oxides comprises the group of polyalkyl N-oxides, in which the nitrogen of the group N-0 forms part of the group R. The preferred polyamine N-oxides and those in which R is a heterocyclic group, such as pipdin, pyrrole, imidazole, pi rrolidine, pipepdine, qumolm, acr *? d? na and their derivatives. Another class of polyamine N-oxides comprises the group of polyamine N-oxide, in which the nitrogen of the group N-0 is attached to the group R. Other suitable polyamine oxides are the polyamine oxides in which the group M-0 is attached to the polimepable unit.

The preferred class of these polyamine N-oxides are the N-oxides of polyarnine having the general formula (I) in which R are aromatic, heterocyclic or alicyclic groups, in which the nitrogen of the functional group N -0 is part of the group R. Examples of these classes are pollamin oxides, in which R is a heterocyclic compound such as pyridine, pyrrole, irnidazole and its derivatives. Another preferred class of polyarynin N-oxides are polyarynin oxides having the general formula (T) in which R are aromatic, heterocyclic or alicyclic groups, in which the nitrogen of the functional group N-0 is attached to the groups R. Examples of these classes are polyamine oxides, in which the R groups can be aromatic such as femurs. Any polymer skeleton can be used as long as the amine oxide polymer formed is soluble in water. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, pollamide, poly unites, polyacrylates and mixtures thereof. The amine N-oxide polymers of the present invention typically have a ratio of amine to N-oi or amine 10: 1 to 1: 1,000,000. However, the amount of amine oxide groups present in the polyolefin oxide polymer can be varied by flake! appropriate absorption or by the appropriate degree of N-oxation. Preferably, the ratio of amine to N-oxide of amine is from 2: 3 to 1: 1,000,000. Of greater preference from 1: 4 to 1: 1,000,000, more preferably 1: 7 1: 1,000,000. The polymers of the present invention, actually encompass random copolymers or block copolymers where one type of monomer is an N-oxide of amine and the other +? Po of inonomer is either an N-oxide of amine or not. The amine oxide unit of the polyarynin N-oxides has a PKa < 10 preferably a PKa < 7, most preferred PKa < 6. Polya-oxides can be obtained in almost any degree of polymerization. The degree of polymerization is not critical on the condition that the material has the desired water solubility and strength to suspend the colorant. Typically, the average molecular weight is within the range of 500 to 1,000,000; preferably from 1000 to 50,000; more preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000. b) Copolymers of N-vmilpir rol i dona and N-vimlirnidazol. the polymers of N-vi or li idazole-N-vmylpyr rolidone used in the present invention have an average molecular weight in the range of 5,000-1,000,000; preferably from 20,000 to 200,000. Highly preferred polymers for use in the detergent compositions according to the present invention comprise a polymer selected from copolymers of N-vinylimidazole, N-vim lp rol i dona, wherein the polymer has an average molecular weight in the range of 5,000 to 50,000; of greater preference from 8,000 to 30,000, more preferably from 10,000 to 20,000. The rhodium molecular weight range was determined by light diffusion as described in áarth H.G and Mays 3.U. Chemical Analysis Vol. 113, "Modern Methods of Polymer Charactepzation. "Highly preferred Nv? N? L? Rn? Dazol-Nv? N? Lp? Rro-1 copolymers have an average molecular weight range in the range of 500 to 5,000; from 800 to 30,000; more preferably from 10,000 to 20,000. Copolymers of N-vimlimidazol-N-vini lpirro-lidona 'characterized by having an average molecular weight range that provides excellent properties that inhibit dye transfer, while not adversely affecting the cleaning efficiency of the detergent compositions formulated therewith. The copolunero of N ~ v? N? L? Rn? Dazol-N-v? nor lpirrol idona of the present invention, has a molar ratio of N-vini 1 ρruzole to N-vi or lpirroli ona from 1 to 0.2, more preferably from 0.8 to 0. 3, more preferably 0.6 0.4. c) Polyvinyl oxazolidone: The detergent compositions of the present invention can also use polyvinyl pyrrolidone ("PVP") having an average molecular weight of. The compositions of the present invention can also use polyvinyl oxazolidone as a binding agent. The polysaccharides oxazoli have an average molecular weight of about 2,500 to about 400,000, preferably approximately 100%. ,000 to about 200,000, most preferably from about 5,000 to about 50,000 and more preferably from about 5,000 to about 15,000. e) Other polymers Polymers which are particularly useful as binder components of the present invention, include polyaspartate (polyaspartic acid), polyacrylamides, polyacrylates and various copolymers such as those of aleic and acrylic acids. Molecular weights for such polymers vary widely, but most are in the range of 2,000 to 100,000. Polymethylcarboxylate builders are most preferred as set forth in U.S. Patent 3,308,067, to Diehl, issued March 7, 1967. Such materials include water soluble salts of homo- and copolymers of carboxylic acids. aliphatic, such as acne rnale co, itacomco acid, esacomco acid, furnapco acid, aconitic acid, citracomico acid and acid met i lenrnal or ni eo. Filler salts The filler salts are preferably chosen from those salts which are active detergent ingredients such as builders, such as carbonate, bicarbonate, citrate, alkali metal or alkaline earth metal phosphate salts. Citric acid in the form of particles can also be used as a salt of filler material in the present invention. Enzyme granulate and a procedure to make it. "1 enzyme granulate of the present invention, preferably has a particle size of 100 to 1,600 micrometers, more preferably 200 to 800 micrometers, more preferably 300-500 micrometers A preferred process for manufacturing enzyme granulates of this invention, comprises granulating in a drum an enzyme material, filler salts, a granulation binder, a liquid phase granulation agent and optionally finely divided cellulose fibers.The process for the production of the enzyme granules comprises, for example, introducing in a cylinder granulator from 0 to 40% cellulose in fibrous form, from 0.1 to 10% by weight of a binder as defined herein, from 0.5% to 20% enzyme or enzyme powder and from 3% to 97.5% filler salt material in an amount which generates the enzyme activity intended in the finished granulate, a liquid phase granulation agent consisting of a substance ia waxy, < As defined in the present and / or water, in an amount of 5% and 70% by weight, whereby the maximum amount of the waxy substance is 40% by weight and the maximum amount of water is 70% by weight, so that all percentages refer to the total amount of the dry substances, the sequence of introduction of the different materials is arbitrary, except that at least a main part of the granulating agent is introduced after at least a substantial part of the dry substances being introduced into the granulator, after which the granulation is necessary, it is dried in a conventional manner, preferably in a fluid bed. Cellulose in fibrous form can be sawdust, pure, fibrous cellulose, cotton or other forms of pure or impure fibrous cellulose. Several cellulose brands in fibrous form are on the market, for * example CEPO and ARBOCEL. In a publication of Svens a Tram olsfabpkerna AS "Cepo Cellulose Pouder", it is established that for cellulose Cepo S / 20 the approximate maximum fiber length is 500 micrometers, the approximate average fiber length is 150 micrometers, the width of approximate maximum fiber is 50 micrometers and the approximate average fiber width is 30 micrometers. Also, it is established that the cellulose S2 / 200 cellulose has a maximum fiber length of approximately 150 microns, an approximate average fiber length of 50 micrometers, a width of - approximate maximum fiber of 45 micrometers and an approximate average fiber width of 25 microns. Cellulose fibers with these dimensions are very suitable for the purpose of the invention. The binders used in the process of the present invention are the binders discussed in detail in the foregoing. Additionally, the binders conventionally used in the field of granulation with a high melting point or no melting point and of a non-waxy nature for example polyvinylpyrrole idone, dextrin, olivinyl alcohol and cellulose derivatives, including, for example, hydroxypropyl ulose, rneti 1 cellulose or CMC The term "enzymes" as used herein means the enzyme of raw material unless otherwise indicated.The term "enzyme powder" means the enzyme of raw material mixed with inorganic salts such as NaCl, carbonate, bicarbonate, citrate, phosphate and CaC12 All enzymes can be granulated by the process Preferably, the ailas and protemases are granulated according to the invention. a proteinase of Bacillus licheniformis), FSPERASER and SAVTNASCR (microbial alkaline proteins produced according to British patent number 1, 243, 784) and TERflAMYLR (an amylase from Bacillus licheni forrní s). The enzyme can be introduced into the granulator as a ground powder, pre-dried or as a solution, for example a concentrated enzyme solution prepared by filtration, reverse osmosis or evaporation. The granulating agent is water and / or a waxy substance. The granulation agent is always used as a liquid phase in the granulation process; the substance if present, therefore is either dissolved or dispersed in the water or melted. By a "waxy substance" is meant a "wax" which has all of the following characteristics: (1) the melting point is between 30 ° C and 100 ° C, preferably between 40 ° C and 60 ° C (2) ) the substance is hard and non-brittle in nature and (3) the substance possesses substantial plasticity at ambient temperature. Both the water and the waxy substance are granulation agents, that is to say, both are active during the formation of the granulate; the waxy substance remains as a constituent in the finished grain, while most of the water is removed during drying. In this way, to refer to all the quantities for finishing, dry granulation, all percentages are calculated based on the total dry granulate unless otherwise specified, which means that water, one of the agents of granulation, which is added to the other constituents when the percentage of water is calculated, while the waxy substance, the other granulating agent, is to be added to the other dry constituents when the percentage of the waxy substance is calculated. Examples of waxy substances are polyglycolics, fatty alcohols, ethoxylated fatty alcohols, higher fatty acids, •• mono-, di- and tnglicerolesters of superabsorbent fatty acids, for example a glycerol stearate, alkylamino ethoxylate, coconut nonoethanol amide, polyhydroxy fatty acid amide. An illustrative summary of a process used to prepare an enzyme granulate is: 1. provide dry enzyme powder, cellulose fillers, filler salt materials and binders. 2. Mix the dry powders of the granulate. 3. Moisten the powder mixture with the granulation agent, eg water or molten wax 4. Process the wet, powdery mixture from stage 3 into a granulation apparatus (rotating knife) until the granulate has the desired size distribution An FM 103 DI7 cylindrical type Loedige mixer (US Pat. No. 3,027,102) can be used in the process for this step.The mixer is equipped with both plug-shaped mixers mounted on a rotating shaft ( axial) and a granulation device, consisting of one or more transverse blades mounted on an ee introduced into the mixer through the cylindrical wall in a direction perpendicular to the horizontal rotary axis mentioned above (ie, radial (ii) To dry in a fluidized bed the granulate from stage 4 to dryness, which satisfies both of the requirements of - Enzyme stabilization and the requirements of free-flowing properties and mechanical strength. Usually this corresponds to a water content of less than 10%, preferably less than 3% and more preferably dry bone. In the examples, where the granulation agent is exclusively or mainly a waxy substance, only cooling may be required. 6. Optionally coat the enzyme granulate with a coating of alkaline buffer salt, a wax and some other compatible substance. Calcium present in the granulate and coating The enzyme granulate of this invention can be improved if it contains from 40 to 3,000 ppm of calcium calculated as calcium chloride. Calcium can be added to the granulate as calcium chloride or calcium sulphate powder in the granulation process or by the use of water containing a calcium content of 100-500 ppm, preferably 170-300 ppm, calculated as chloride of calcium in the water used in the granulation and / or coating process. Optional Waxy Coating Material The non-ionic waxy material can be applied over the enzyme granulate or over the enzyme granulate coated with the alkaline buffer salt. Practical concentrations of the optional waxy coating material is up to 57% by weight of the composition, preferably 5-30%. Examples of such waxy coatings are polyethylene glycols, fatty alcohols, fatty alcohols ** - Ethoxides, higher fatty acids, mono-, di- and t-glycols esters of fatty acids, for example glycerol monostearate, alkylatoxylates and coconut nonoethanol amide. Preferred non-lone waxy substances are TAE22 (bait alcohol condensed with 22 moles of ethylene oxide per * mole of alcohol), PEG 1500-8000 (polyethylene glycol of molecular weight 1500-B000) and palic acid. Another waxy coating having a melting point of at least 38 ° C, preferably of at least 50 ° C, can also be used, for example, this waxy coating is melted (50-70 ° C) and " It is sprayed onto the granulate in a fluidized bed where cold air (15-30 ° C) is applied to solidify the waxy coating A preferred final processing step is the coating of the enzyme granulate with a flow aid. Typically the flow aid is finely divided particulate material, especially sodium aluminosilicate, and particularly preferred flow aids include Zeolite A, Zeolite E, Zeolite X and Zeolite MAP. EXAMPLES »: Exercise 1 An enzyme powder is produced by spray drying (ie an enzyme suspension and milling) The enzyme powder is then granulated in a mixer with the following materials:% By weight Powder of enzyme 10 Fibers of cellulose 10 Na2C03 30 Copolymer (as a 40% solution) 30 Zeolite A (80% active) 15 Cellulose fibers and sodium carbonate act as fillers. The Zeolite acts as an auxiliary flow or auxiliary agglomeration and the copolymer (which is an enerminator of rnaleic acid and acrylic acid) acts as a "glutinant." The granulation process can be carried out in batches or with only one LoedigeR KM mixer or a similar type mixer The operation can be carried out in one or several stages.The enzyme granules then pass to a fluid bed dryer, where the moisture content is reduced to 3%. They are sieved and passed to a two-stage coating process.The coating is required since the first stage enzyme granulates are usually colored * brown.The coating step requires the use of a finely divided white powder and a binder. This is sprayed with 4% nonionic surfactant TAE50 (ethoxylated bait alcohol with an average of 50 moles of EO) is sprayed onto the granules in a LoedigeR KM followed by sprinkling n 5% Zeolite A. The procedure is repeated in the second KM LoedigeR. A final coating of PFG 4,000 to 5% and carboxymethylcellulose is added in a final dusting / drying step in a fluidized bed. The composition (% by weight) of the final granulate was: Enzyme powder 10 Cellulose fibers 10 Na2CO 30 copolymer 1 (anhydrous) 1 Zeoite A (anhydrous) 12 Humidity 3 Enzyme coating: Zeolite A 10 TAE50 8 Peg 4000 / CMC 5 The resulting granule contains 87% of the detergent ingredients . Fjernplo 2 The following enzyme granulate composition was prepared * "using the same procedure as in Example 1, this time using a 15% solution of poly (N-oxide of 4- vini lpipdin) as the binder Enzyme granulation% by weight Enzyme powder 15 Cellulose fibers 5 Na2C03 25 Ci treatment of Na 10 - PVNO 5 Hum dd 2 Zeolite MAP 15 Coating: Zeoli e MAP 5 Titanium dioxide 5 TAE50 n PEG 4000 5 The resulting granulate had 88% detergent ingredients.

Example 3 The following enzyme granulation composition was prepared in a similar process using polyaspartate solution (30%) as a binder: Enzyme granulation% by weight Enzyme powder 15 Cellulose fibers 10 Na2CO3 30 Polysaccharide 10 Moisture 2.5 Zeoli e X 13 Coating: Zeoli e X 8 Silica 0.5 Base GS / AE5 6 PEG 4000 5.

Claims (9)

NOVELTY OF THE INVENTION CLAIMS

1. A granular component characterized in that it comprises an enzyme and a polypnepic binding material selected from the group consisting of: N-polyarnine oxide; copolymers of N-VLmlp? rrol? dona and N-vinylirnidazole; polyvinyl loxazolidone; polyvinyl lyrni dazol; asparatic acid and its salts; polymers and copolymers of rnaleic acid and acrylic acid and their salts; and its mixtures.

2. The granular component according to claim 1, characterized in that it also comprises carbonate, bicarbonate, citrate, alkali metal or alkaline earth metal phosphate salts or mixtures thereof.

3. The granular component according to claim 1, further characterized in that it comprises waxy granulating agents having a melting point of between 30 and 100 ° C.

4. The granular component according to claim 1, further characterized in that it comprises polyvinylpyrrolidone, carboxymethylcellulose or mixtures thereof.

5. A process for manufacturing a granular component *, which comprises the steps of: (a) forming a powder from an enzyme solution and a particulate filler; (b) granulating the powder with a granulating liquid to form a granulate; characterized in that the granulation liquid comprises a binding material of the group consisting of: N-polyoxine oxide; copolymers of N-vinylpyrroli dona and N-vinylnidazole, polyvinyl loxazolidone; polyvinyl irnidazole; polyaspartic acid its salts; polymers and copol ions of maleic acid and acrylic acid and their salts; and its mixtures.

6. The process according to claim 5, characterized in that the particulate filler material is citric acid. The process according to claim 5, characterized in that the granulation liquid also comprises a nonionic surfactant or a mixture of nonionic surfactants. 8. The process according to claim 5, further characterized by the step of (c) mixing the granulate with a particularly finely divided flow aid. The process according to claim 8, characterized in that the finely divided particulate flow aid is selected from the group consisting of sodium alumina, precipitated or steam silica or mixtures thereof.