CN110785481A - Granular detergent composition comprising perfume - Google Patents
Granular detergent composition comprising perfume Download PDFInfo
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- CN110785481A CN110785481A CN201880041299.1A CN201880041299A CN110785481A CN 110785481 A CN110785481 A CN 110785481A CN 201880041299 A CN201880041299 A CN 201880041299A CN 110785481 A CN110785481 A CN 110785481A
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- detergent
- perfume
- coating
- layer
- core
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/50—Perfumes
- C11D3/502—Protected perfumes
- C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay
Abstract
The present invention relates to detergent particles with perfume, and in particular to detergent particles with a coating applied around a surfactant core. It is an object of the present invention to provide a detergent particle having a core coated with a coating material and a perfume. The present inventors have found that perfume can be added to the coating of detergent particles, which reduces the losses encountered when adding perfume to extrudable materials prior to extrusion, while maintaining perfume delivery. It has also been found that the perfume added to the coating of the detergent particles of the present invention does not affect their free-flowing properties.
Description
Technical Field
The present invention relates to detergent particles with perfume, and in particular to detergent particles with a coating applied around a surfactant core.
Background
Perfumes are commonly incorporated into detergent compositions to deliver fragrance in the headspace of the package or to the clothes being laundered to produce a fresh, clean odor. The free oil and the perfume in granular or powder form are added to the detergent powder by spraying or other methods of incorporating the free oil. The fragrance added at this stage is held by capillary pressure in the pores present in the powder structure.
Detergent compositions may also be produced by extrusion processes in which perfume addition is with the extrudable mass. For a variety of reasons, flavors are added to the extrudable mass prior to the extrusion process. The addition of perfume prior to the extrusion process makes the product tacky and forms a readily extrudable mass, which is also more acceptable to consumers when extruded. The extrusion process eliminates the small capillary channels that normally hold perfume in powder detergent compositions, so pre-addition of perfume to the extrudable mass ensures better retention of perfume in the extruded particles.
WO2005/059083A1(Unilever) discloses a granular detergent composition with encapsulated perfume. The granular detergent product comprises a coated particle having a functional core and a coating having encapsulated perfume for improved dispersion of the dry encapsulated perfume throughout the detergent composition without the use of significant shear forces which can lead to significant perfume loss.
EP2627748B1(2014, Unilever) discloses a granular detergent composition having an extruded surfactant core with an inorganic coating. The detergent composition has perfume added to the core as a liquid or as encapsulated perfume particles.
However, adding perfume prior to extrusion has some undesirable effects. Adding the perfume together with the extrudable mass prior to the extrusion process exposes the perfume oil to temperatures and process conditions that can result in significant perfume loss. In addition, during extrusion, breakage was found in the perfume added to the extruder in encapsulated form.
The inventors have observed that perfume loss by evaporation is in the range of 10% -50% when exposed to the temperature conditions typically employed during extrusion. Furthermore, the exhaust gases carrying such fragrances affect the environment and surroundings, and therefore, the exhaust gases require further treatment before being released into the environment.
It is therefore an object of the present invention to provide a detergent particle having a core coated with a coating material and a perfume.
It is a further object of the present invention to provide free-flowing detergent particles with improved perfume delivery.
It is a further object of the present invention to minimize perfume loss while producing detergent granules.
Disclosure of Invention
We have now found that perfume can be added to the coating of detergent particles which reduces the losses encountered when perfume is added to an extrudable mass prior to extrusion, whilst maintaining perfume delivery. It has also been found that the perfume added to the coating of the detergent particles of the present invention does not affect their free flowing properties. In addition, incorporation of the fragrance late in the manufacturing process simplifies the conversion process from one product to another by late stage differentiation.
According to the present invention there is provided a detergent particle having a core and a coating surrounding the core, the detergent particle having orthogonal dimensions x, y and z, wherein x is from 0.2 to 2mm, y is from 2 to 8mm and z is from 2 to 8mm, and the particle comprising:
20-39 wt% of a surfactant;
ii.5-40 wt% of a coating material; and the combination of (a) and (b),
a perfume;
wherein the core comprises a total surfactant content of from 95 parts to 100 parts, and the coating comprises from 95 parts to 100 parts of the coating material and the perfume.
Detailed Description
Shape of detergent particles
The detergent particles disclosed have orthogonal dimensions x, y and z, wherein x is from 0.2 to 2mm, y is from 2 to 8mm and z is from 2 to 8 mm.
Preferably, in a detergent formulation having detergent particles according to the invention, at least 90 to 100% of the detergent particles are within a 20%, preferably 10%, variation in the x, y and z dimensions from the largest to the smallest detergent particles.
The detergent particles are larger and less spherical than conventional detergent powders. Preferably, the detergent particles are curved.
The detergent particle may be lenticular (shaped like a whole dried lentil), i.e. an oblate ellipsoid, where z and y are the equatorial diameters and x is the polar diameter; preferably y ═ z. The dimensions are such that y and z are at least 2mm, preferably at least 2.5mm, further preferably at least 3mm, more preferably at least 4mm, and x is in the range of 0.2-2mm, preferably in the range of 0.5-2 mm. More preferably 1-2mm, more preferably 0.6-1.6 mm.
A preferred range of y is from 3 to 8mm, more preferably from 4 to 6mm, still more preferably from 4.5mm to 5.5 mm. The preferred range of z is from 3 to 8mm, more preferably from 4 to 6mm, still more preferably from 4.5mm to 5.5 mm.
Preferably, the detergent particles may be disc-shaped. In a preferred embodiment, the detergent particle is an oblate spheroid. Preferably, the coated detergent particle has no pores; that is, the detergent particles do not have conduits penetrating between them through the core, i.e. the coated detergent particle has a topological genus of zero.
The porosity of the detergent particles of the invention having a coating surrounding the core is in the range of from 0 to 0.1 volume fraction, more preferably from 0.01 to 0.1, still more preferably from 0.04 to 0.1, most preferably from 0.05 to 0.1. It has surprisingly been found that detergent particles having an intra-particle porosity of from 0 to 0.1 volume fraction are able to retain perfume in the coating of the detergent particles of the present invention without altering the flowability of the detergent particles.
Preferably, the detergent particle of the present invention comprises an extruded core and the intra-particle porosity of the detergent particle having an extruded core and coated with the coating material is preferably in the range of from 0 to 0.1 volume fraction. The extruded granules have a lower intra-granular porosity than detergent granules prepared by a high shear mixing granulator. Typical values for intra-granular porosity of high shear mixer granulated detergent particles are in the range of 0.3 to 0.5 volume fraction. Without being bound by theory, it is believed that the high shear mixer granulated detergent particles are able to effectively retain liquids, such as perfume, added to the surface of the particles due to capillary pressure caused by intra-particle porosity. On the other hand, detergent particles having an extruded core and subsequently coated with a coating material preferably have lower intra-particle porosity and have a low ability to absorb liquid by capillary absorption.
And (3) porosity measurement:
the porosity of the detergent granules of the present invention was measured using a Quantachrom Helium Pycnometer, Model Ultrapycnometer 1000.
The intra-particle porosity E was calculated using the following equation
ρ。
BD＝U(1-E
ρ)(1-E
b)
Wherein;
bulk density of BD ═ solid (detergent particles)
U-absolute density of a solid measured in the helium pycnometer method (a measure of the volume of void space between pores and particles of the solid is excluded)
E
bBed porosity
E
ρSolid porosity
Preferably, the intra-granular porosity E of the detergent granule
ρCalculated as 0-0.2, more preferably 0-0.18, more preferably 0-0.1.
Composition of detergent granules
The disclosed detergent particles have a core and a coating applied to the core, the coating surrounding the core. If the core of the detergent particle is formed by extrusion, the appearance of the coated particle is pleasing. The core of the detergent particle comprises surfactant and the coating comprises a coating material and perfume. Preferably, the coating material forms a layer surrounding the core and the perfume forms a layer surrounding at least the outer surface of the coating material.
Preferably the ratio of core to coating of the detergent particle is from 3:1 to 20:1, most preferably from 5:1 to 15: 1; the optimum ratio of core to coating was 9: 1.
Core
The detergent particle according to the invention has 20-39 wt% surfactant and the core of the detergent particle comprises a total surfactant content of 95 to 100 parts.
Preferably, the detergent particle comprises a total surfactant content of from 96 parts to 100 parts, more preferably from 97.5 parts to 100 parts, still more preferably from 98 parts to 100 parts.
Surface active agent
Generally, the nonionic and anionic surfactants of the surfactant system may be selected from "Surface active agents", Vol.1, Schwartz & Perry, Interscience 1949; volume 2, Schwartz, Perry & Berch, Interscience 1958; surfactants as described in the current version of "McCutcheon's emulsifiers and Detergents", published by Manufacturing conditioners Company, or "Tenside-Taschenbuch", H.Stache, 2 nd edition, Carl Hauser Verlag, 1981. Preferably, the surfactant used is saturated.
The detergent particles of the present invention comprise from 20 to 39 wt% surfactant, preferably from 25 to 39 wt%, and still preferably from 30 to 35 wt% surfactant. The surfactant is preferably selected from anionic surfactants, nonionic surfactants or mixtures thereof. Preferably, from 15 to 85 parts of the total surfactant content in the detergent particle is anionic surfactant and from 5 to 75 parts of the total surfactant content is nonionic surfactant.
Anionic surfactant:
suitable anionic detergent compounds which may be used are typically water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals. Suitable synthetic anionic washesExamples of detergent compounds are sodium and potassium alkyl sulfates, in particular higher C's produced by sulfation, for example from tallow or coconut oil
8To C
18Those obtained from alcohols; alkyl radical C
9To C
20Sodium and potassium benzene-sulphonates, especially linear secondary alkyl C
10To C
15Sodium benzenesulfonate; and sodium alkyl glyceryl ether sulfates, particularly those of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum. The most preferred anionic surfactant is Sodium Lauryl Ether Sulfate (SLES), particularly preferably having 1-3 ethoxy groups, C
10-C
15Sodium alkyl benzene sulfonate and C
12To C
18Sodium alkyl sulfate. Also suitable are surfactants such as those described in EP-A-328177(Unilever), which exhibit resistance to salting out, alkylpolyglycoside surfactants as described in EP-A-070074, and alkylmonoglycosides. The chain of the surfactant may be branched or straight.
Soaps may also be present. The fatty acid soaps used preferably contain from about 16 to about 22 carbon atoms, preferably in a straight chain configuration. The anionic contribution from the soap is preferably 0-30 wt% of the total anions.
Preferably, at least 50 wt% of the anionic surfactant is selected from: c
11-C
15Sodium alkyl benzene sulfonate; and C
12-C
18Sodium alkyl sulfate. Even more preferably, the anionic surfactant is C
11-C
15Sodium alkyl benzene sulfonate.
Nonionic surfactant:
suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, such as fatty alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide, alone or together with propylene oxide. Preferred nonionic detergent compounds are C
6-C
22Alkylphenol-ethylene oxide condensates, usually 5-25EO, i.e. 5-25 ethylene oxide units per molecule, and aliphatic C
8To C
18Condensation products of linear or branched primary or secondary alcohols with ethylene oxide, typically 5-50 EO. Preferably, the nonionic is 10-50EO, more preferably 20-35 EO. Alkyl ethoxylates are particularly preferred.
Preferably, all surfactants are mixed together prior to drying. Conventional mixing devices may be used. The surfactant core of the detergent particle may be formed by extrusion or roller compaction and then coated with the inorganic salt. Preferably, the core of the detergent particle is an extrudate.
Calcium tolerant surfactant system:
on the other hand, the surfactant system used is calcium tolerant, and this is a preferred aspect as it reduces the need for builders.
Surfactant mixtures are preferred which do not require the presence of builders for effective detergency in hard water. If such mixtures pass the tests described below, they are referred to as calcium tolerant surfactant mixtures. However, the invention can also be used for washing with soft water that is naturally occurring or made using water softeners. In this case, the calcium resistance is no longer important and mixtures other than calcium-resistant mixtures may be used.
The calcium resistance of the surfactant mixture was tested as follows:
the surfactant mixture in question is prepared in a concentration sufficient to give a French hardness of 40 (4X 10) per litre(s)
-3Molar Ca
2+) 0.7g of surfactant solids in water. Other hardness-free ionic electrolytes (e.g., sodium chloride, sodium sulfate, and sodium hydroxide) were added to the solution to adjust the ionic strength to 0.05M and the pH to 10. The absorption of light having a wavelength of 540nm through a 4mm sample was measured 15 minutes after sample preparation. Ten measurements were made and the average was calculated. Samples with absorption values less than 0.08 are considered calcium tolerant.
Examples of surfactant mixtures that meet the calcium resistance test described above include those that have a majority of LAS surfactant (which is not itself calcium resistance) mixed with one or more other surfactants (co-surfactants) that are calcium resistance to give sufficient calcium resistance to be used with little or no builder and to pass a given test. Suitable calcium tolerant co-surfactants include SLES 1-7EO, and alkyl ethoxylate nonionic surfactants, especially those having a melting point below 40 ℃.
The core is primarily a surfactant, which may also contain detersive additives such as shading dyes, enzymes, and polymers.
Coating layer
The detergent particles disclosed have a coating surrounding a core. The coating comprises a total coating material content and a total perfume content of from 95 parts to 100 parts of the detergent particle. The coating material forms a layer surrounding the core, and the fragrance forms a layer on the surface of the layer of coating material. It is preferred that the coating material forms a layer that surrounds at least a portion of the outer surface of the core, more preferably the coating material forms an outer surface that surrounds at least 50%, more preferably at least 60%, still more preferably at least 80%, and even more preferably completely surrounds the coating material.
Preferably, the coating comprises a total coating material content and a total perfume content of from 96 parts to 100 parts, more preferably from 98 parts to 100 parts, most preferably from 99 parts to 100 parts of the detergent particle.
The coating of the detergent particle comprises less than 5 wt%, even preferably less than 2.5 wt%, further preferably less than 1 wt%, yet preferably less than 0.5 wt% of a surfactant, more particularly a nonionic surfactant.
Coating material
Although the skilled person may assume that any known coating material may be used, for example organic coating materials including polymers, it has been found that the use of inorganic coating materials deposited by crystallization from aqueous solutions is particularly advantageous as this appears to give positive dissolution benefits and the coating gives good colour to the detergent particle even at lower coating levels.
The coating material is preferably applied to the surface of the surfactant core by deposition from an aqueous solution of the coating material. Alternatively, the layer of coating material is applied in the form of a slurry. It is highly preferred that the coating is carried out by spraying an aqueous solution of the coating material in a fluid bed dryer. The bed is typically fluidized with heated air to dry or partially dry the moisture from the spray coating at the time of application. Spraying is achieved by means of a nozzle which is capable of forming a fine or atomized spray of the coating mixture to achieve complete coverage of the particles. Typically, the droplet size from the atomizer is less than about 100 microns. This atomization can be achieved by means of conventional two-fluid nozzles with atomizing air, but also by means of conventional pressure nozzles. To achieve this type of atomization, the rheology of the solution or slurry is generally characterized by a viscosity of less than about 500 centipoise, preferably less than about 200 centipoise. For best results, the nozzle position is placed at or above the fluidization height of the particles in the fluidized bed. The fluidization height is typically determined by the weir or overflow gate height. The coating zone of the fluidized bed is then typically followed by a drying zone and a cooling zone. Of course, those skilled in the art will recognize that alternative arrangements to obtain the resulting coating on the detergent particles of the present invention are also possible.
An alternative embodiment uses a stirred fluidized bed which comprises mechanical and/or pneumatic mixing elements in addition to a conventional bed of fluidizing air passing through holes in the distributor plate. An advantage of an agitated bed is that it can be used to apply additional shear as a means of controlling particle shape and smoothness while the coating operation is being performed.
Inorganic materials and inorganic salts:
preferably, the coating material is an inorganic material. The inorganic material is preferably an inorganic salt, more preferably a water-soluble inorganic salt. The inorganic salt is preferably present on the detergent particle as a coating which is present as a surrounding core. The inorganic salts are preferably present at a level which reduces the stickiness of the detergent particles to the extent that the particles are free flowing.
One skilled in the art will recognize that although multiple coatings of inorganic salts of the same or different inorganic salts may be applied, a single coating is preferred for ease of operation and to maximize the thickness of the coating.
The detergent particles disclosed comprise from 10 to 40 wt% of the coating material. When the coating material is an inorganic salt, it is preferably selected from sodium carbonate and/or sodium sulphate, wherein preferably at least 5 parts of the total inorganic salt is sodium carbonate.
Preferably, the inorganic salt forms a layer covering/encapsulating the core and the coating is applied to the surface of the surfactant core, preferably by deposition from an aqueous solution having 25-30 wt% of a water soluble inorganic salt. In the alternative, the coating may be performed using a slurry. The aqueous solution preferably comprises more than 150g/L, more preferably 300g/L of salt. It has been found that aqueous spraying of the coating solution in a fluidised bed gives good results and also produces a slight rounding of the detergent particles during fluidisation. Drying and/or cooling may be required to complete the process.
Perfume
In addition to the coating material, the coating of the detergent particle according to the invention comprises a perfume.
In the coating, the flavorant can be present within the layer of coating material, on the outer surface of the layer of coating material, or at least over a portion of the outer surface of the layer of coating material, or a combination thereof.
The fragrance forms a layer on the surface of the layer of coating material. Preferably, the perfume forms a layer that surrounds at least a portion of the outer surface of the coating material, more preferably completely surrounds the outer surface of the coating material.
The perfume is preferably sprayed onto detergent particles having a surfactant core pre-coated with a layer of coating material, preferably an inorganic salt, also preferably a water-soluble inorganic salt. As used herein, the term "pre-coated" refers to a detergent particle comprising a surfactant core which is encapsulated by a coating material but prior to coating with perfume. Preferably, the perfume forms a layer on the exposed outer surface of the layer of coating material. The fragrance layer covers a portion of the outer surface of the coating material layer or covers the entire outer surface of the coating material layer. It is believed that the presence of the perfume layer on the surface of the coating material layer improves perfume delivery and maintains the integrity of the encapsulated perfume. Preferably, the spray coating is in a mixer other than a fluid bed dryer.
Preferably, the perfume layer comprises free oil perfume, perfume in encapsulated form encapsulating the free oil, also referred to herein as encapsulated perfume, or mixtures thereof.
Preferably, when the flavor is a free oil flavor, the content of flavor molecules in the free oil is 90-100 wt% based on the weight of the free oil composition. The free oil may have a small amount of solvent in the composition, such solvent preferably being present in the range of 0-10 wt%, most preferably not more than 5 wt%.
Preferably, when the perfume is an encapsulated perfume, the encapsulated perfume is in the form of a slurry of encapsulated perfume droplets/particles suspended in a polar solvent, preferably the slurry is an aqueous slurry. Encapsulated perfume compositions of this form comprise from 30 to 60% by weight of moisture and from 30 to 50% by weight of perfume oil. Preferably, the encapsulated perfume composition comprises a polymeric structuring system to increase the viscosity of the aqueous phase. The inclusion of the polymeric structuring system ensures that the encapsulated perfume is uniformly dispersed in the composition without being separated from the mixture. Any commercially available encapsulated perfume can be used in the present invention. One preferred type of encapsulated perfume is a shear sensitive encapsulated perfume.
The preferred ratio of free oil to encapsulated perfume is present in the range of 5:1 to 1:5, more preferably 2:1 to 1:2, with an optimum ratio of 1: 1.
Preferably, the fragrance layer is multi-layered. The multi-layer fragrance comprises a fragrance layer in encapsulated form and a free oil layer. Preferably, the multi-layer perfume comprises a layer of perfume in encapsulated form encapsulating a layer of free oil. The layer of perfume in encapsulated form preferably covers a portion of the outer surface of the free oil layer, or more preferably covers the entire outer surface of the free oil layer. When the fragrance layer is multi-layered, it is preferred to first apply a layer of free oil and then deposit a layer of fragrance in encapsulated form. Thus, when the perfume layer is multi-layered, the free oil layer is proximal to the outer surface of the coating material layer of the detergent particle.
Preferably, after coating the core of the detergent particle with a coating material, preferably an inorganic salt layer, the particle is then treated to provide a perfume layer on the coating material layer. The perfume layer is preferably provided by spraying perfume oil or perfume in encapsulated form onto the pre-coated detergent particles in a coating mixer. The coating mixer can be any of a number of mixers, including low speed mixers and drum mixers.
The detergent particle comprises perfume, preferably in the range of 0.001 to 3 wt%, most preferably in the range of 0.1 to 2 wt%. Many suitable examples of fragrances are provided in CTFA (Cosmetic, Toiletry and fragrance Association)1992International layers Guide, published by CFTApublications, and OPD1993Chemicals layers Directory 80th annular Edition, published by Schnell Publishing Co.
It is common for multiple perfume components to be present in a formulation. In the compositions of the present invention, it is envisaged that four or more, preferably five or more, more preferably six or more, or even seven or more different perfume components will be present.
Preferably, the fragrance may be in the form of a solid liquid solution with an organic solvent, or in the form of a slurry with a polar solvent.
In the perfume mixture, preferably 15-25% by weight is top notes. Top notes are defined by Poucher (Journal of the society of Cosmetic Chemists 6(2):80[1955 ]). Preferred top notes are selected from citrus oil, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol.
Preferably, the detergent particles are free of peroxygen bleach, such as sodium percarbonate, sodium perborate and peracids.
Water content
The detergent particles preferably comprise from 0 to 15 wt% water, more preferably from 0 to 10 wt%, most preferably from 1 to 5 wt% water at 293K and 50% relative humidity. This promotes the storage stability of the detergent particles and their mechanical properties.
Other ingredients
The detergent particle according to the invention may comprise further ingredients as described below, which may be present in the coating layer or core of the particle, or in both the core and coating layer.
Fluorescent agent
The detergent particles preferably comprise a fluorescer (optical brightener). Fluorescent agents are well known, and many such fluorescent agents are commercially available. Typically, these fluorescent agents are provided and used in the form of their alkali metal salts, e.g., sodium salts. The total amount of fluorescer or fluorescers used in the composition is typically from 0.005 to 2 wt%, more preferably from 0.01 to 0.1 wt%. Suitable fluorescers for use in the present invention are described in Chapter 7 of Industrial Dyes, 2003, Wiley-VCH ISBN 3-527-30426-6, edited by K.Hunger.
Preferred fluorescent agents are selected from the following classes: distyryl biphenyls, triazinylaminodistyrenes, bis (1,2, 3-triazol-2-yl) diphenyls, bis (benzo [ b ] furan-2-yl) biphenyls, 1, 3-diphenyl-2-pyrazolines and coumarins. The fluorescer is preferably sulphonated.
A preferred class of fluorescent agents is: distyrylbiphenyl compounds such as Tinopal (trademark) CBS-X; diamine stilbene disulfonic acid compounds, such as Tinopal DMS pure Xtra and Blankophor (trade Mark) HRH, and pyrazoline compounds, such as Blankophor SN. Preferred fluorescent agents are: sodium 2- (4-styryl-3-sulfophenyl) -2H-naphtho (napthol) [1,2-d ] triazole, disodium 4,4' -bis { [ (4-anilino-6- (N-methyl-N-2-hydroxyethyl) amino-1, 3, 5-triazin-2-yl) ] amino } stilbene-2-2 ' -disulfonate, disodium 4,4' -bis { [ (4-anilino-6-morpholinyl-1, 3, 5-triazin-2-yl) ] amino } stilbene-2-2 ' -disulfonate, and disodium 4,4' -bis (2-sulfostyryl) biphenyl.
Polymer and method of making same
The detergent particles may preferably comprise one or more polymers. Examples are carboxymethylcellulose, poly (ethylene glycol), poly (vinyl alcohol), polyethyleneimine, ethoxylated polyethyleneimine, water-soluble polyester polymers polycarboxylates, for example polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.
Enzyme
Particularly contemplated enzymes include proteases, α -amylases, cellulases, lipases, peroxidases/oxidases, pectate lyases, laccases and mannanases, or mixtures thereof.
Suitable lipases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include those from: humicola (Humicola) (synonym thermophilic fungi (Thermomyces)), for example from h.lanuginosa (t.lanuginosus) as described in EP 258068 and EP 305216 or from h.insolens as described in WO 96/13580; pseudomonas lipases, for example from pseudomonas alcaligenes (p. alcaligenes) or pseudomonas pseudoalcaligenes (p. pseudoalcaligenes) (EP 218272), pseudomonas cepacia (p.cepacia) (EP 331376), pseudomonas stutzeri (GB 1,372,034), pseudomonas fluorescens (p. fluoroscens), pseudomonas strains SD 705(WO 95/06720 and WO 96/27002), p.wisconsinensis (WO 96/12012); bacillus lipases, for example from Bacillus subtilis (B.subtilis) (Dartois et al (1993), Biochemica et Biophysica Acta,1131,253-360), Bacillus stearothermophilus (B.stearothermophilus) (JP 64/744992) or Bacillus pumilus (B.pumilus) (WO 91/16422).
Further examples are lipase variants, such as those described in WO 92/05249, WO 94/01541, EP 407225, EP 260105, WO 95/35381, WO 96/00292, WO 95/30744, WO 94/25578, WO 95/14783, WO 95/22615, WO 97/04079 and WO 97/07202, WO 00/60063, WO09/107091 and WO 09/111258.
Preferred commercially available lipases include Lipolase
TMAnd Lipolase Ultra
TM、Lipex
TM(Novozymes A/S) and Lipoclearan
TM。
The process of the invention may be carried out in the presence of a phospholipase classified under EC 3.1.1.4 and/or EC 3.1.1.32. As used herein, the term phospholipase is an enzyme that is active on phospholipids.
Phospholipids, e.g. lecithin or phosphatidyl cholineA base consisting of glycerol esterified at the outer (sn-1) and middle (sn-2) positions with two fatty acids and phosphorylated at the third position; phosphoric acid, in turn, can be esterified to an amino alcohol. Phospholipases are enzymes involved in phospholipid hydrolysis. Can distinguish between various types of phospholipase activity, including phospholipase A
1And A
2Which hydrolyses one fatty acyl group (at the sn-1 and sn-2 positions, respectively) to form lysophospholipids; and lysophospholipase (or phospholipase B), which can hydrolyze the remaining fatty acyl groups in lysophospholipid. Phospholipase C and phospholipase D (phosphodiesterases) release diacyl glycerol or phosphatidic acid, respectively.
Suitable proteases include those of animal, vegetable or microbial origin. Microbial sources are preferred. Chemically modified or protein engineered mutants are included. The protease may be a serine protease or a metalloprotease, preferably an alkaline microbial protease or a trypsin-like protease. Preferred commercially available proteases include Alcalase
TM、Savinase
TM、Primase
TM、Duralase
TM、Dyrazym
TM、Esperase
TM、Everlase
TM、Polarzyme
TMAnd Kannase
TM(Novozymes A/S)、Maxatase
TM、Maxacal
TM、Maxapem
TM、Properase
TM、Purafect
TM、Purafect OxP
TM、FN2
TMAnd FN3
TM(Genencor International Inc.)。
The process of the invention may be carried out in the presence of a cutinase classified under EC 3.1.1.74. The cutinase to be used according to the invention may be of any origin. Preferably, the cutinase is of microbial origin, in particular of bacterial, fungal or yeast origin.
Suitable amylases (α and/or β) include those of bacterial or fungal origin, including chemically modified or protein engineered mutants, amylases include, for example, α -amylase obtained from a Bacillus, e.g., a particular strain of Bacillus licheniformis as described in more detail in GB 1,296,839, or a strain of Bacillus as disclosed in WO 95/026397 or WO 00/060060
TM、Termamyl
TM、Termamyl Ultra
TM、Natalase
TM、Stainzyme
TM、Fungamyl
TMAnd BAN
TM(Novozymes A/S)、Rapidase
TMAnd Purastar
TM(from Genencor International Inc.).
Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from: fungal cellulases produced by bacillus, pseudomonas, humicola, fusarium, thielavia, acremonium, e.g. from humicola insolens, thielavia terrestris, myceliophthora thermophila and fusarium oxysporum disclosed in US 4,435,307, US 5,648,263, US 5,691,178, US 5,776,757, WO 89/09259, WO 96/029397 and WO 98/012307. Commercially available cellulases include Celluzyme
TM、Carezyme
TM、Celluclean
TM、Endolase
TM、Renozyme
TM(Novozymes A/S)、Clazinase
TMAnd Puradax HA
TM(Genencor International Inc.) and KAC-500(B)
TM(KaoCorporation)。
Suitable peroxidases/oxidases include those of plant, bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful peroxidases include peroxidases from Coprinus, e.g., Coprinus cinereus, and variants thereof, such as those described in WO 93/24618, WO 95/10602, and WO 98/15257. Commercially available peroxidases include Guardzyme
TMAnd Novozym
TM51004(Novozymes A/S)。
Further suitable enzymes are disclosed in WO2009/087524, WO2009/090576, WO2009/148983 and WO 2008/007318.
Enzyme stabilizer
Any enzyme present in the detergent granule may be stabilised using conventional stabilisers, for example polyols such as propylene glycol or glycerol; a sugar or sugar alcohol; lactic acid; boric acid or a boric acid derivative, for example an aromatic borate ester, or a phenyl boronic acid derivative, for example 4-formylphenyl boronic acid, and the compositions may be formulated as described, for example, in WO 92/19709 and WO 92/19708.
When the alkyl group is long enough to form a branched or cyclic chain, the alkyl group includes branched, cyclic, and linear alkyl chains. The alkyl group is preferably linear or branched, more preferably linear.
The chelant may be present in the coated detergent particle.
Process for preparing detergent particles
In a second aspect of the invention, there is disclosed a process for the preparation of a detergent granule according to the first aspect, preferably comprising the steps of:
a) feeding a surfactant into an extruder and extruding it to form an extrudate having a diameter of at least 3mm, preferably at least 4 mm;
b) cutting the extrudate to form a core of detergent particles having a thickness less than its diameter, wherein the thickness is at least 0.2mm,
c) coating the core by applying 5-40 wt% of a coating material to form a layer of coating material, and preferably drying it;
d) applying a fragrance to form a layer on a surface of the layer of coating material.
Preferably, the coating material is an inorganic salt, more preferably selected from sodium carbonate and/or sodium sulphate. The perfume layer is preferably applied by spraying perfume in the form of a perfume oil or encapsulate onto the pre-coated detergent particles in a coating mixer. The coating mixer can be any of a number of mixers, including low speed mixers and drum mixers.
The extruder provides a further opportunity to mix other ingredients besides the surfactant, or even add further surfactant. However, it is generally preferred that all anionic surfactant or other surfactant provided in admixture with water (i.e. as a paste or as a solution) is added to the dryer to ensure that the water content can be subsequently reduced and that the material fed to and through the extruder is sufficiently dry. Thus, additional materials that can be incorporated into the extruder are mainly those used at very low levels in detergent compositions: for example fluorescers, shading dyes, enzymes, perfumes, silicone antifoams, polymer additives and preservatives. It has been found that the limit for mixing such additional material in the extruder is about 10 wt%, but it is desirable for the product quality to preferably keep it at most 5 wt%. Solid additives are generally preferred. Solid particulate structuring (wicking) materials or builders, for example zeolites, carbonates, silicates, are preferably not added to the extruded mixture. These materials are not required due to the self-structuring nature of the very dry LAS-based feed. If any is used, the total amount should be less than 5 wt%, preferably less than 4 wt%, and most preferably less than 3 wt%. At such levels, no significant structuring occurs and the inorganic particulate material is added for a different purpose, for example as a flow aid to improve the feeding of the particles into the extruder. The output of the extruder is shaped by the die plate used. The extruded material has a tendency to expand centrally relative to the periphery. We have found that if a cylindrical extrudate is regularly sliced as it exits the extruder, the resulting shape is a short cylinder with two convex ends. These particles are described herein as oblate spheroids or lentils. This shape is visually pleasing.
Coating layer
The next step involves coating the extruded core by applying 5-40 wt% of the coating material to form a layer of coating material, and preferably drying it. The coating makes the particles easily colored. The coating makes the particles more suitable for use in detergent compositions which can be exposed to high humidity for a prolonged period of time.
The extruded particles can be considered as oblate spheroid ellipsoids having a major radius "a" and a minor radius "b". Thus, the ratio of surface area (S) to volume (V) can be calculated as:
where e is the eccentricity of the particle.
Detergent formulations with the disclosed detergent particles
According to another aspect of the invention, a detergent formulation is disclosed comprising from 50 to 100 wt% of detergent particles according to the invention. The detergent formulation is preferably present in a package.
Preferably, the package for commercial sale comprises from 0.01kg to 5kg, preferably from 0.02kg to 2kg, most preferably from 0.5kg to 2kg of detergent formulation.
Preferably, the detergent particle of the invention comprises all the ingredients required in a fully formulated detergent formulation, in which case the detergent formulation comprises 100 wt% of the detergent particle. In other preferred embodiments, the detergent particles of the present invention may be mixed with additional ingredients such as bleach, enzymes, perfume, uncoated detergent particles and various other ingredients to produce fully formulated detergent compositions. In such embodiments, at least 50 wt% of the detergent particles are present in the detergent formulation, more preferably at least 60 wt%, still more preferably at least 70 wt%, and even more preferably at least 80 wt% of the detergent particles.
Examples
Example 1: comparative detergent particles incorporating perfume in the core
Core manufacturing: the surfactant material is dried in a spray dryer to produce a spray dried powder having anionic surfactant and nonionic surfactant. The spray-dried powder was fed into a twin-screw co-rotating extruder equipped with a shaped orifice plate and cutting blades to extrude the core particles. During extrusion, a fragrance was added at a level of 0.527% to give a final fragrance level of 0.4 wt% throughout the formulation (including coatings and additional materials). The perfume comprises a mixture of free oil and perfume in encapsulated form.
In addition to the perfume, other ingredients (e.g., enzymes, dyes) are added to the extrudable mass during extrusion.
Coating application: the core particles obtained in the previous step are then coated with a coating material by spray deposition. Sodium carbonate is used as coating material. The core particles were charged into the fluidizing chamber of a stream 1 laboratory fluid bed dryer (Aeromatic-Fielder AG) and the core particles were sprayed with a sodium carbonate solution using a top spray configuration to form a layer of coating material coating the surfactant cores. The sodium carbonate solution was fed to the nozzle of stream 1 by means of a peristaltic pump (model Watson-marlow 101U/R). The composition of the coating material is given below.
The detergent granules obtained by the above process relate to the following composition:
core particle: 1000 g
Coating solution: 110 g of sodium carbonate are dissolved in 293 g of water.
The perfume concentration in the detergent granules prepared (comparative example 1) was measured using gas chromatography immediately after coating, and the measurements were repeated for 5 different detergent granules prepared in the same batch, and the results are shown in table 1. The measurement error of the perfume oil is ± 0.03%. The total loss during detergent particle preparation was calculated as follows: the actual theoretical amount of perfume in the coated particle is determined taking into account the achieved coating level, and then the remaining percentage is calculated by dividing the measured value by the theoretical value, and then the loss is calculated. Table 1 provides the data obtained.
TABLE 1
The data provided in table 1 show that when perfume is incorporated into the core (as in comparative example 1), which relates to extrusion and fluid bed coating processes after perfume addition, the average perfume loss in the detergent particle is 39%, and further it is observed that the perfume added in encapsulated form breaks up in the detergent particle.
Example 2: detergent particles having a perfume-containing coating prepared according to the present invention.
Core manufacturing: core particles were prepared using a method similar to that disclosed in example 1. The only difference in this process was that in the detergent granules prepared in example 2, no perfume was added to the extruder during extrusion. Thus, the core of example 2 is free of perfume.
Coating application: the core particles obtained in the preceding step are then coated with a sodium carbonate solution by spray deposition, analogously to what is illustrated in example 1. The intra-granular porosity of the detergent particles after application of the coating layer was measured using a Quantachrom Helium Pycnometer, model ultrapycnometer R1000, and found to be 0.06 volume fraction.
Applying a spice layer: the detergent granules pre-coated with the sodium carbonate layer were then transferred to a drum mixer. To a batch of 300Kg of detergent particles in a drum mixer, 2.73Kg of free oil was sprayed onto the detergent particles through a single phase nozzle 4012 (from Spray systems) at a maximum pressure of 0.5bar for a period of about 90 seconds, after which 1.06Kg of perfume in encapsulated form was sprayed through an internal atomising two phase nozzle SU43 (from Spray systems) at an atomisation pressure of 0.8bar for a period of about 70 seconds. Thereafter mixing was continued for another 90 seconds and then the detergent granules having a coating layer comprising a sodium carbonate layer and a perfume layer were discharged.
The perfume content of the detergent granules produced by example 2 was measured analytically by gas chromatography. The perfume content and the percentage loss in samples of 5 different detergent granules prepared in the same batch were determined and the results are listed in table 2.
TABLE 2
As seen in table 2, the detergent particles with the composition according to the invention (example 2) had a coating containing free oil and perfume in encapsulated form, showing no significant perfume loss, and SEM analysis showed that the perfume in encapsulated form was mainly intact.
Example 3: determination of the flow rate of the detergent particles of the invention:
the flow rate (or CDFR) of the detergent granules of example 2 was determined by the following method. A sample of the detergent particles was placed in a glass tube having a diameter of 59.5 mm, the time taken for a fixed volume (718.78mL) to flow out of a hole having a diameter of 40 mm was measured, and then the flow rate in mL/s was calculated, and is provided in table 3.
TABLE 3
The data above shows the flow rate of the detergent granules of example 2 immediately after perfume application (day 0) and the change in flow rate after 12 weeks of storage, reflecting little change in flow during this period, indicating that the granules are free-flowing after storage.
Claims (15)
1. A detergent particle having a core and a coating surrounding the core, the detergent particle having orthogonal dimensions x, y and z, wherein x is from 0.2 to 2mm, y is from 2 to 8mm and z is from 2 to 8mm, and the particle comprises:
20-39 wt% of a surfactant;
ii.5-40 wt% of a coating material; and the combination of (a) and (b),
a perfume;
wherein the core comprises a total surfactant content of from 95 parts to 100 parts, and the coating comprises from 95 parts to 100 parts of the coating material and the perfume.
2. The detergent particle according to claim 1, wherein the coating material is an inorganic material, preferably an inorganic salt selected from sodium carbonate, sodium sulphate or mixtures thereof.
3. The detergent particle according to claim 1 or 2, wherein the coating material forms a layer covering the core and the perfume forms a layer covering at least a part of the outer surface of the layer of coating material.
4. The detergent particle according to any preceding claim, wherein the perfume layer comprises a perfume in the form of a free oil, an encapsulate, or a mixture thereof.
5. A detergent particle according to claim 4, wherein the perfume layer is multi-layered, comprising a layer of perfume in the form of an encapsulate covered with a layer of free oil.
6. A detergent particle according to claim 5, wherein the free oil layer of the multiple perfume layers is proximal and covers the outer surface of the coating material layer.
7. The detergent particle according to any preceding claim, wherein the surfactant is selected from anionic surfactants, nonionic surfactants or mixtures thereof.
8. A detergent particle according to claim 7, wherein the total surfactant content of the detergent particle comprises from 15 to 85 parts anionic surfactant and from 5 to 75 parts nonionic surfactant.
9. A detergent particle according to any preceding claim, wherein the particle comprises from 0.001 to 3 wt% perfume.
10. The detergent particle of any preceding claim, wherein the detergent particle is a prolate spheroid ellipsoid.
11. A detergent particle according to any preceding claim in which the amount of coating on each particle is from 5 to 45 wt%, preferably from 5 to 15 wt%, by weight of the particle.
12. A detergent granule according to any preceding claim wherein the granule comprises from 0 to 15 wt% water, preferably from 1 to 5 wt% water.
13. A detergent particle according to any preceding claim, wherein the core of the detergent particle is an extrudate.
14. A detergent formulation comprising a detergent particle according to any one of the preceding claims 1 to 12, wherein the detergent particle comprises from 50 to 100 wt% of the detergent formulation in a package.
15. A detergent formulation according to claim 13, wherein at least 90 to 100% of the detergent particles are within a 20% variation in the x, y and z dimensions from largest to smallest coated detergent particles.
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|---|---|---|---|
| EP17176871 | 2017-06-20 | ||
| EP17176871.6 | 2017-06-20 | ||
| PCT/EP2018/065056 WO2018234056A1 (en) | 2017-06-20 | 2018-06-07 | Particulate detergent composition comprising perfume |
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| CN110785481A true CN110785481A (en) | 2020-02-11 |
| CN110785481B CN110785481B (en) | 2021-04-13 |
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| CN201880041299.1A Active CN110785481B (en) | 2017-06-20 | 2018-06-07 | Granular detergent composition comprising perfume |
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|---|---|
| EP (1) | EP3642319B1 (en) |
| CN (1) | CN110785481B (en) |
| WO (1) | WO2018234056A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115074190A (en) * | 2021-03-12 | 2022-09-20 | 守护家健康生活有限公司 | Composite multilayer structure capable of being biodegraded and cleaned and manufacturing method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HUE062018T2 (en) * | 2020-07-06 | 2023-09-28 | Procter & Gamble | A process for making a particulate laundry detergent composition |
| TWI812925B (en) * | 2021-02-22 | 2023-08-21 | 守護家健康生活有限公司 | Composite multilayer structure for biodegradable cleaning and method of making same |
Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2140820A (en) * | 1983-06-01 | 1984-12-05 | Colgate Palmolive Co | Perfume-containing carrier having surface-modified particles for detergent composition |
| US5167852A (en) * | 1989-11-13 | 1992-12-01 | Lever Brothers Company, Division Of Conopco Inc. | Process for preparing particulate detergent additive bodies and use thereof in detergent compositions |
| EP0550086A1 (en) * | 1991-12-31 | 1993-07-07 | Unilever N.V. | Process for making a granular detergent composition |
| CA2013088C (en) * | 1989-03-30 | 1995-03-21 | Fabrizio Bortolotti | Detergent compositions and process for preparing them |
| CN1161713A (en) * | 1994-08-26 | 1997-10-08 | 普罗格特-甘布尔公司 | Agglomeration for producing detergent composition by using spray drying towers |
| CN1163633A (en) * | 1994-09-20 | 1997-10-29 | 普罗格特-甘布尔公司 | Process for making high density detergent composition in single mixer/densifier with selected recycle streams |
| CN1250474A (en) * | 1997-03-13 | 2000-04-12 | 亨克尔两合股份公司 | House hold detergent or cleaning action shaped bodies |
| CN1276829A (en) * | 1997-10-23 | 2000-12-13 | 亨克尔两合股份公司 | Method for producing scent intensifying washing and cleaning detergents |
| WO2003082569A1 (en) * | 2002-03-27 | 2003-10-09 | Colgate-Palmolive Company | Cleaning wipe for dishwashing application |
| CN1156564C (en) * | 1996-02-26 | 2004-07-07 | 尤尼利弗公司 | Production of anionic detergent particles |
| CN1894393A (en) * | 2003-12-19 | 2007-01-10 | 荷兰联合利华有限公司 | Detergent granules and process for their manufacture |
| EP1767614A1 (en) * | 2005-09-23 | 2007-03-28 | Takasago International Corporation | Process for the manufacture of a spray dried powder |
| CN103154225A (en) * | 2010-10-14 | 2013-06-12 | 荷兰联合利华有限公司 | Laundry detergent particles |
| CN103154224A (en) * | 2010-10-14 | 2013-06-12 | 荷兰联合利华有限公司 | Particulate detergent compositions comprising fluorescer |
| CN103154229A (en) * | 2010-10-14 | 2013-06-12 | 荷兰联合利华有限公司 | Packaged particulate detergent composition |
| CN103201373A (en) * | 2010-10-14 | 2013-07-10 | 荷兰联合利华有限公司 | Laundry detergent particles |
Family Cites Families (46)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1296839A (en) | 1969-05-29 | 1972-11-22 | ||
| GB1372034A (en) | 1970-12-31 | 1974-10-30 | Unilever Ltd | Detergent compositions |
| DK187280A (en) | 1980-04-30 | 1981-10-31 | Novo Industri As | RUIT REDUCING AGENT FOR A COMPLETE LAUNDRY |
| DE3278670D1 (en) | 1981-07-13 | 1988-07-21 | Procter & Gamble | Foaming surfactant compositions |
| JPH0697997B2 (en) | 1985-08-09 | 1994-12-07 | ギスト ブロカデス ナ−ムロ−ゼ フエンノ−トチヤツプ | New enzymatic detergent additive |
| ATE110768T1 (en) | 1986-08-29 | 1994-09-15 | Novo Nordisk As | ENZYMATIC DETERGENT ADDITIVE. |
| NZ221627A (en) | 1986-09-09 | 1993-04-28 | Genencor Inc | Preparation of enzymes, modifications, catalytic triads to alter ratios or transesterification/hydrolysis ratios |
| ES2076939T3 (en) | 1987-08-28 | 1995-11-16 | Novo Nordisk As | RECOMBINANT LUMPY OF HUMICOLA AND PROCEDURE FOR THE PRODUCTION OF RECOMBINANT LIPAS OF HUMICOLA. |
| JPS6474992A (en) | 1987-09-16 | 1989-03-20 | Fuji Oil Co Ltd | Dna sequence, plasmid and production of lipase |
| GB8803036D0 (en) | 1988-02-10 | 1988-03-09 | Unilever Plc | Liquid detergents |
| JP3079276B2 (en) | 1988-02-28 | 2000-08-21 | 天野製薬株式会社 | Recombinant DNA, Pseudomonas sp. Containing the same, and method for producing lipase using the same |
| US5648263A (en) | 1988-03-24 | 1997-07-15 | Novo Nordisk A/S | Methods for reducing the harshness of a cotton-containing fabric |
| JP2728531B2 (en) | 1988-03-24 | 1998-03-18 | ノボ ノルディスク アクティーゼルスカブ | Cellulase preparation |
| GB8915658D0 (en) | 1989-07-07 | 1989-08-23 | Unilever Plc | Enzymes,their production and use |
| JP3112937B2 (en) | 1990-04-14 | 2000-11-27 | カリ―ヒエミー アクチエンゲゼルシヤフト | Alkaline Bacillus lipase, DNA sequence encoding the same and Bacillus producing this lipase |
| ATE169671T1 (en) | 1990-09-13 | 1998-08-15 | Novo Nordisk As | LIPASE VARIANTS |
| SK120893A3 (en) | 1991-04-30 | 1994-08-10 | Procter & Gamble | Liquid detergent mixtures with boric-polyol complex for inhibition of proteolytic enzyme |
| EP0511456A1 (en) | 1991-04-30 | 1992-11-04 | The Procter & Gamble Company | Liquid detergents with aromatic borate ester to inhibit proteolytic enzyme |
| DK72992D0 (en) | 1992-06-01 | 1992-06-01 | Novo Nordisk As | ENZYME |
| DK88892D0 (en) | 1992-07-06 | 1992-07-06 | Novo Nordisk As | CONNECTION |
| JP3618748B2 (en) | 1993-04-27 | 2005-02-09 | ジェネンコー インターナショナル インコーポレイテッド | New lipase variants for use in detergents |
| JP2859520B2 (en) | 1993-08-30 | 1999-02-17 | ノボ ノルディスク アクティーゼルスカブ | Lipase, microorganism producing the same, method for producing lipase, and detergent composition containing lipase |
| CA2173946A1 (en) | 1993-10-13 | 1995-04-20 | Anders Hjelholt Pedersen | H2o2-stable peroxidase variants |
| JPH07143883A (en) | 1993-11-24 | 1995-06-06 | Showa Denko Kk | Lipase gene and mutant lipase |
| WO1995022615A1 (en) | 1994-02-22 | 1995-08-24 | Novo Nordisk A/S | A method of preparing a variant of a lipolytic enzyme |
| AU2067795A (en) | 1994-03-29 | 1995-10-17 | Novo Nordisk A/S | Alkaline bacillus amylase |
| DE69528524T2 (en) | 1994-05-04 | 2003-06-26 | Genencor Int | LIPASES WITH IMPROVED TENSIOSTABILITY |
| WO1995035381A1 (en) | 1994-06-20 | 1995-12-28 | Unilever N.V. | Modified pseudomonas lipases and their use |
| AU2884695A (en) | 1994-06-23 | 1996-01-19 | Unilever Plc | Modified pseudomonas lipases and their use |
| BE1008998A3 (en) | 1994-10-14 | 1996-10-01 | Solvay | Lipase, microorganism producing the preparation process for the lipase and uses thereof. |
| WO1996013580A1 (en) | 1994-10-26 | 1996-05-09 | Novo Nordisk A/S | An enzyme with lipolytic activity |
| JPH08228778A (en) | 1995-02-27 | 1996-09-10 | Showa Denko Kk | New lipase gene and production of lipase using the same |
| CN101955921A (en) | 1995-03-17 | 2011-01-26 | 诺沃奇梅兹有限公司 | Novel endoglucanases |
| CN1193346A (en) | 1995-07-14 | 1998-09-16 | 诺沃挪第克公司 | Modified enzyme with lipolytic activity |
| AU6655196A (en) | 1995-08-11 | 1997-03-12 | Novo Nordisk A/S | Novel lipolytic enzymes |
| DE69735767T2 (en) | 1996-09-17 | 2007-04-05 | Novozymes A/S | cellulase |
| DE69718351T2 (en) | 1996-10-08 | 2003-11-20 | Novozymes As | DIAMINOBIC ACID DERIVATIVES AS DYE PRECURSORS |
| US6939702B1 (en) | 1999-03-31 | 2005-09-06 | Novozymes A/S | Lipase variant |
| MXPA01009706A (en) | 1999-03-31 | 2002-05-14 | Novozymes As | Polypeptides having alkaline alpha-amylase activity and nucleic acids encoding same. |
| WO2005059083A1 (en) | 2003-12-19 | 2005-06-30 | Unilever N.V. | Detergent granules and process for their manufacture |
| DE602006020852D1 (en) | 2006-07-07 | 2011-05-05 | Procter & Gamble | detergent compositions |
| BRPI0822220A2 (en) | 2008-01-04 | 2015-06-23 | Procter & Gamble | Enzyme Containing Compositions and Tinting Agent for Tissues |
| EP2085070A1 (en) | 2008-01-11 | 2009-08-05 | Procter & Gamble International Operations SA. | Cleaning and/or treatment compositions |
| MX2010009456A (en) | 2008-02-29 | 2010-09-24 | Procter & Gamble | Detergent composition comprising lipase. |
| MX2010009457A (en) | 2008-02-29 | 2010-09-24 | Procter & Gamble | Detergent composition comprising lipase. |
| BRPI0913570A2 (en) | 2008-06-06 | 2015-12-15 | Procter & Gamble | detergent composition comprising a variant of a family xyloglucanase |
-
2018
- 2018-06-07 WO PCT/EP2018/065056 patent/WO2018234056A1/en active Search and Examination
- 2018-06-07 CN CN201880041299.1A patent/CN110785481B/en active Active
- 2018-06-07 EP EP18729125.7A patent/EP3642319B1/en active Active
Patent Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4536315A (en) * | 1983-06-01 | 1985-08-20 | Colgate Palmolive Co. | Perfume-containing carrier having surface-modified particles for laundry composition |
| GB2140820A (en) * | 1983-06-01 | 1984-12-05 | Colgate Palmolive Co | Perfume-containing carrier having surface-modified particles for detergent composition |
| CA2013088C (en) * | 1989-03-30 | 1995-03-21 | Fabrizio Bortolotti | Detergent compositions and process for preparing them |
| EP0390251B1 (en) * | 1989-03-30 | 1995-05-24 | Unilever N.V. | Detergent compositions and process for preparing them |
| US5167852A (en) * | 1989-11-13 | 1992-12-01 | Lever Brothers Company, Division Of Conopco Inc. | Process for preparing particulate detergent additive bodies and use thereof in detergent compositions |
| EP0550086A1 (en) * | 1991-12-31 | 1993-07-07 | Unilever N.V. | Process for making a granular detergent composition |
| CN1161713A (en) * | 1994-08-26 | 1997-10-08 | 普罗格特-甘布尔公司 | Agglomeration for producing detergent composition by using spray drying towers |
| CN1163633A (en) * | 1994-09-20 | 1997-10-29 | 普罗格特-甘布尔公司 | Process for making high density detergent composition in single mixer/densifier with selected recycle streams |
| CN1156564C (en) * | 1996-02-26 | 2004-07-07 | 尤尼利弗公司 | Production of anionic detergent particles |
| CN1250474A (en) * | 1997-03-13 | 2000-04-12 | 亨克尔两合股份公司 | House hold detergent or cleaning action shaped bodies |
| CN1276829A (en) * | 1997-10-23 | 2000-12-13 | 亨克尔两合股份公司 | Method for producing scent intensifying washing and cleaning detergents |
| WO2003082569A1 (en) * | 2002-03-27 | 2003-10-09 | Colgate-Palmolive Company | Cleaning wipe for dishwashing application |
| CN1894393A (en) * | 2003-12-19 | 2007-01-10 | 荷兰联合利华有限公司 | Detergent granules and process for their manufacture |
| CN100384975C (en) * | 2003-12-19 | 2008-04-30 | 荷兰联合利华有限公司 | Detergent granules and process for their manufacture |
| EP1767614A1 (en) * | 2005-09-23 | 2007-03-28 | Takasago International Corporation | Process for the manufacture of a spray dried powder |
| CN103154225A (en) * | 2010-10-14 | 2013-06-12 | 荷兰联合利华有限公司 | Laundry detergent particles |
| CN103154224A (en) * | 2010-10-14 | 2013-06-12 | 荷兰联合利华有限公司 | Particulate detergent compositions comprising fluorescer |
| CN103154229A (en) * | 2010-10-14 | 2013-06-12 | 荷兰联合利华有限公司 | Packaged particulate detergent composition |
| CN103201373A (en) * | 2010-10-14 | 2013-07-10 | 荷兰联合利华有限公司 | Laundry detergent particles |
| EP2627757B1 (en) * | 2010-10-14 | 2016-11-02 | Unilever PLC | Laundry detergent particles |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115074190A (en) * | 2021-03-12 | 2022-09-20 | 守护家健康生活有限公司 | Composite multilayer structure capable of being biodegraded and cleaned and manufacturing method thereof |
| CN115074190B (en) * | 2021-03-12 | 2023-12-12 | 守护家健康生活有限公司 | Composite multi-layer structure capable of biological decomposition and cleaning and its manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3642319A1 (en) | 2020-04-29 |
| CN110785481B (en) | 2021-04-13 |
| WO2018234056A1 (en) | 2018-12-27 |
| EP3642319B1 (en) | 2020-12-30 |
| BR112019026538A2 (en) | 2020-06-23 |
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