TW201506153A - Improved cleaning formulation and method - Google Patents

Abstract

The invention provides a formulation and method for the treatment of a substrate, the method comprising the treatment of the substrate with the formulation, the formulation comprising a multiplicity of solid cleaning particles and a multiplicity of dosing particles, wherein the dosing particles comprise at least one host material and at least one releasable material, wherein the host material comprises at least one partially or completely water soluble polymeric material and the at least one releasable material comprises at least one cleaning or post-cleaning agent or other treatment additive for the treatment of the substrate. The method and formulation are advantageously applied to the cleaning of textile fabrics.

Description

Improved cleaning formula and method

The present invention relates to the cleaning and treatment of substrates using a system comprising solid cleaning particles which may be polymeric, non-polymeric or mixtures thereof. In particular, the present invention discloses a method for formulating an additive into a lotion using blending particles to mix solid detergent particles, and a formulation for use in the method.

The aqueous cleaning method is the mainstream of household and industrial textile cleaning. This cleaning typically involves agitating the fabric in an aqueous solution of the detergent at elevated temperatures. It is customary to dosing operations, often with the addition of supplemental additives such as fabric conditioners, dye transfer inhibiting agents, anti-reattaching agents, perfumes or fortified hygiene products, together with detergents.

On the premise of achieving the desired degree of cleanliness, the efficiency of the textile cleaning process is typically characterized by the energy, water and detergent consumption associated with the process. Generally, the lower the requirement for these three parameters, the more efficient the cleaning method is considered. It is also important to reduce the downstream effects of water and detergent consumption as this minimizes the need for costly and environmentally hazardous discharge water disposal. Similarly, in providing any desired effect, any supplement The lower the amount of the filler additive used, the more efficient the operation.

This cleaning method, whether it relates to household washing machines or their industrial equivalents (commonly referred to as washer extractors), involves soaking the fabric followed by decontamination, aqueous soil suspension, and washing with water. A large amount of energy (or temperature), water and detergent usually result in better cleaning. However, the key issues are the water consumption that determines the energy demand (to heat the wash water), and the level of detergent dose (to achieve the desired detergent concentration). In addition, the water is highly defined by the mechanical action of the process on the fabric, which is another important performance parameter; it agitates the surface of the garment during cleaning and plays a key role in releasing the occluded soil. In aqueous laundry processes, this mechanical action is provided by the water level of any particular washing machine combined with the drum design. It is generally found that the higher the water level in the washtub, the better the mechanical action. This results in improved overall process efficiency (ie, reduced energy, water and detergent consumption) expectations, and the search for efficient mechanical effects.

WO-A-2007/128962 discloses a method and formulation for cleaning contaminated substrates which greatly reduces the use of water, energy and detergents, but still provides the mechanical action required for cleaning. The method comprises treating a moist substrate with a formulation comprising a plurality of polymeric particles, wherein the formulation is free of organic solvents. Preferably, the substrate is wetted to a substrate to water weight ratio of between 1:0.1 and 1:5 w/w, the formulation optionally comprising at least one cleaning material, which generally comprises detergent properties. Surfactant. In a preferred embodiment, the substrate comprises textile fibers, and the polymeric particles may, for example, comprise particles of polyamine, polyester, polyolefin, polyurethane, or copolymers thereof, but most Jiawei Nylon Particles form. WO-A-2012/056252 discloses a method for the most efficient use and removal of such polymeric particles in a cleaning process, and the PCT Application No. GB2012/050085, which is incorporated by reference, extends this method to the use of A polymerizable cleaning particle and a mixture of non-polymerizable and polymerizable cleaning particles.

Patent WO-A-2010/094959 proposes cleaning operation The desired equipment is separated from the cleaned substrate at the end of the polymerization or non-polymerizable cleaning particles. This provides a novel cleaning device design that requires the use of two different inner tubs that can be rotated independently and is suitable for industrial and household cleaning methods.

WO-A-2011/064581 provides a cleaning method A further apparatus for separating the efficiency of cleaning particles from the cleaned substrate at the end of the operation, comprising a hollowed tub and a removable outer wash barrel for preventing fluid and solid particulate matter from entering and exiting the wash basket Internally, the cleaning method entails attaching the outer skin to the wash basket during cleaning and then removing the skin prior to operating the separation cycle to remove the cleaning particles, which in turn removes the cleaned substrate from the wash basket.

In the further development of the device, WO-A-2011/098815 discloses a method and apparatus for continuously circulating cleaning particles in a cleaning process, thereby eliminating the need to provide a skin.

WO-A-2007/128962, WO-A-2012/056252, Improvements in textile cleaning as disclosed in PCT Application No. GB2012/050085, WO-A-2010/094959, WO-A-2011/064581, and WO-A-2011/098815, resulting in reduced water in cleaning operations, The amount of energy and detergent used. WO-A-2011/128680 patent also discloses The detergent is formulated into a method of the particle cleaning system wherein the detergent is broken down into its chemical constituents and added at different times during the cleaning operation. In particular, in order to provide the desired degree of stain removal, the cleansing portion of the formulation must be added before or during the main wash cycle, while the remaining expensive (and therefore more valuable) portions of the formulation are typically added during the wash. As a post treatment, the polymeric particles are then removed from the cleaning process. In general, the cleansing component comprises a surfactant, an enzyme, and an oxidizing agent or bleach, and the post-treating component includes, for example, an anti-reattachment agent, a perfume, and an optical brightener. Adding cleaning and post-treatment ingredients in this manner further reduces the amount of use and thus provides significant cost savings over conventional all-in-one detergent formulations.

Although the method of WO-A-2011/128680 is available at The cleaning and post-treatment ingredients in the detergent formulation are used during different periods of the cleaning operation, but it is still necessary to transport the ingredients to the fabric surface. It is typically achieved by diluting in a quantity of water and then spraying the dilution onto the wash. Although dilution in this case is much lower than conventional cleaning methods, it is essentially an ineffective means of formulating various detergent ingredients. In addition, this configuration requires an interruption period in the cleaning cycle to cause an increase in the total cycle time.

a singular tone as described in WO-A-2011/128676 The dispensing system can also be used for this purpose. In this system, each detergent ingredient is typically concentrated to contain a plurality of doses in the crucible which are gradually used over multiple wash cycles. Therefore, there is no need for the user to individually arrange the convenience of each cleaning. However, the crucible itself and the docking system used to insert the cleaning device may be complicated in structure and therefore costly.

Therefore, one aspect of the present invention provides a solution before it is solved. A method of diluting and transporting detergent ingredients. Thus it provides for the use of formulated particles in combination with solid detergent particles to release the additive over one or more wash cycles. The release of the additive can occur via the dissolution or decomposition of the formulated particles, or by diffusion from the formulated particles. The formulated particles may contain the detergent ingredients required for effective cleaning and post-treatment, and because they are intimately mixed with the solid cleaning particles, they can be carried directly to the surface of the fabric, thereby allowing the detergent ingredients to be delivered to the target in a fully targeted manner. Cleaning things. Therefore, separate dilution and spraying in water is not required to deliver the detergent ingredients, and a complicated sputum dispensing system is not required. As indicated above, although these particles can release the additive in one wash cycle, the release after multiple washings still provides convenience to the user.

The present invention also contemplates other beneficial effects by formulating particles. Additives. Examples include the addition of an antimicrobial agent to sterilize the fabric, or the addition of a large amount of optical brightener, anti-reattachment, fragrance, or dye transfer inhibiting agent. In each case, the benefit of formulating the particles is to deliver the solid cleansing particles in the simplest possible way, which is delivered directly and targeted to the surface of the fabric.

The invention is derived from the understanding of the inventors, The cleaning performance disclosed in WO-A-2007/128962, WO-A-2012/056252, and PCT Application No. GB2012/050085, especially at low temperatures, by blending particles from intimately mixed solid cleaning particles Reinforce by releasing detergent or post-cleaner or other processing additives.

Accordingly, a first aspect of the present invention provides a formulation comprising a plurality of solid cleaning particles and a plurality of compounding particles, wherein the compounding particles Included in at least one parent material and at least one releasable material, wherein the parent material comprises at least one partially or fully water-soluble polymeric material, and the at least one releasable material comprises at least one cleaning agent or post-cleaning agent or Other processing additives.

In a particular embodiment, the formulation is used to clean a contaminated substrate, and the at least one releasable material comprises at least one cleaning agent.

In particular, the at least one releasable material comprises at least one detergent, most particularly at least one detergent, which typically comprises at least one surfactant. The at least one releasable material optionally comprises, alone or separately, at least one post-cleaner.

Accordingly, the cleaning and post-cleaning agents are, in particular, cleaning chemicals or post-cleaning chemicals which are generally constituents of detergent formulations for conventional cleaning methods. Thus, the cleaning agent is typically a surfactant, an enzyme, an oxidizing agent or a bleaching agent, and suitable post-cleaning agents include, but are not limited to, optical brighteners, anti-reattach agents, dye transfer inhibiting agents, and fragrances.

The parent material comprises an inactive polymeric or non-polymeric material for transporting the releasable material in a controlled manner to the surface of the cleaning article, but not participating in the active portion of the cleaning process. A variety of materials can be used for this purpose, as the formulation particles can be of many different types.

Thus, in a particular embodiment of the invention, the polymeric material is a hydrogel comprising a polymeric material and water in a gelled state. The water content of the hydrogel can generally range from 30 to 98% w/w, but is generally between 40 and 85% w/w. The polymeric material in the hydrogel typically comprises, for example, poly(vinyl alcohol) (PVOH), poly(vinyl acetate) (PVA), poly(ethyl vinyl alcohol) (EVOH), poly(ethylene glycol) (PEG), Poly(acrylate) (PAC), Gelatin, hyaluronic acid, carboxymethyl cellulose (CMC), starch, algin, or other poly(saccharides), or blends or copolymers of these materials, or salts thereof. In this particular embodiment, the releasable material can be physically dispersed within the hydrogel or can be dissolved in the water component of the hydrogel to form a formulated particle. Varying the molecular weight and degree of hydrolysis of the hydrogel controls the rate at which the releasable material is released from the formulation during use. Thus, in a specific embodiment in which the PVOH is in the form of a hydrogel, poly(vinyl alcohol) having a degree of hydrolysis of 98% or more is generally used for the purpose of the present invention.

In an alternative embodiment of the invention, the particle package is formulated Containing solid pellets by compacting a matrix material comprising a polymerizable powder and/or a non-polymerizable powder under pressure and temperature combination, with at least one releasable material, and optionally additional materials (eg, a decomposing agent, Formed by a lubricant and a binder. The hardness and therefore the rate of dissolution and release of the at least one releasable material upon use can be varied by adjusting the granulation pressure and temperature. It will be appreciated that granulating the powder can readily prepare a mixture of one or more polymers. Examples of suitable polymer-forming powders suitable for granulation include chitosan, lactose, cellulose, starch, microcrystalline cellulose (MCC), croscarmellose sodium, hydroxy Propylcellulose (HPC), hydroxypropylmethylcellulose (HPMC), hydroxyethylcellulose (HEC), poly(vinyl alcohol) (PVOH), poly(vinyl acetate) (PVA), poly(ethylene Pyrrolidone) (PVP), crosslinked PVP, poly(ethylene glycol) (PEG), and gelatin, or a salt thereof. Poly(vinyl alcohol) having a degree of hydrolysis of 94% is generally suitable for the purposes of the present invention.

In a further alternative embodiment of the invention, the formulation particles may comprise a degradable parent material comprising a polymer such as poly(lactose) (PLA), poly(glycolic acid) (PGA), poly(vinyl alcohol) ( PVOH) (Mowiflex ^® - melt extruded form of the polymer), poly(vinyl acetate) (PVA), poly(vinyl pyrrolidone) (PVP), polyamide, polyester, and blends of these materials And a copolymer, or a salt thereof. In this particular embodiment, the releasable material is mixed with the polymer by melt lamination, such as in a twin screw extruder.

The formulated particles typically retain more than one substrate processing operation and as a result can be reused in further operations.

The solid cleaning particles can comprise polymeric and/or non-polymeric cleaning particles.

The solid polymerizable cleaning particles may comprise a foamed or unfoamed polymeric material. Furthermore, the polymeric particles may comprise linear or crosslinked polymers.

The solid polymerizable cleaning particles preferably comprise a polyalkylene (such as polyethylene and polypropylene), a polyamide, a polyester, or a polyurethane. In general, however, the polymeric particles comprise polyamidamine or polyester particles, especially particles of nylon, polyethylene terephthalate or tert-butyl terephthalate, which are often in the form of beads. The polyamines and polyesters have been found to be particularly effective for aqueous stain/contamination removal, while polyalkylenes are particularly useful for oily stain removal. The polymerizable solid cleaning particles are generally substantially cylindrical or spherical in shape and have an average density in the range of 0.5 to 2.5 g/cm 3 and an average volume in the range of 5 to 275 mm 3 .

Copolymers of the above polymeric materials may optionally be included in the polymeric cleaning particles. In particular, the properties of the polymeric material can be tailored to the specified requirements by including a monomeric unit that imparts specific properties to the copolymer. Therefore, the copolymer can be designed to contain, inter alia, ionic charging. Or a monomer containing a polar moiety or an unsaturated organic group to attract a specific contaminant.

Suitable solid non-polymerizable cleaning particles can comprise particles of glass, cerium oxide, stone, wood, or any metal or ceramic material. Suitable metals include, but are not limited to, zinc, titanium, chromium, manganese, iron, cobalt, nickel, copper, tungsten, aluminum, tin, and lead, and alloys thereof. Suitable ceramics include, but are not limited to, alumina, zirconia, tungsten carbide, tantalum carbide, and tantalum nitride. The solid non-polymerizable cleaning particles are generally substantially cylindrical or spherical in shape, and have an average density in the range of 3.5 to 12.0 g/cm 3 and an average volume of 5 to 275 mm 3 .

Mixtures of polymeric and non-polymeric solid cleaning particles can be used in certain embodiments of the invention.

A second aspect of the invention provides a method of treating a substrate comprising treating a substrate in a formulation of the first aspect of the invention.

The process of the invention is carried out in an aqueous environment in the presence of a limited amount of water. In other words, the amount of water present during the practice of the method of the present invention is much less than in the prior art method, thus providing one of the primary benefits attached to the method.

In particular, the treatment method comprises a method of cleaning a contaminated substrate, whereby generally the at least one releasable material comprises at least one cleaning agent, most particularly at least one detergent, which typically comprises at least one surfactant. The at least one releasable material optionally comprises, alone or separately, at least one post-cleaner and/or at least one other treatment additive.

According to the method of the present invention, the releasable material is contained The formulated particles of these agents are delivered to the surface of the substrate with controlled local release. In this manner, the cleaning agent and post-cleaner, and any other processing additives are delivered in a viable, fully targeted manner, thereby reducing the amount of releasable material required to achieve the desired cleaning, post-cleaning or treatment effect. In addition, it is not necessary to use complicated crucibles or other dosage devices, and it is not necessary to use additional water to transport the reagents to the fabric surface. Release of the releasable material from the formulated particles can be controlled by selecting a suitable precursor material to be completely released in one wash cycle or over several wash cycles. In the latter case, the formulated particles can still be stored in a suitable cleaning apparatus for carrying out the method of the present invention, thereby eliminating the need for separate dispensing in each cleaning cycle and providing greater convenience to the user.

The invention in which the particles are formulated to comprise a degradable parent material In a particular embodiment, under typical conditions of a cleaning operation, the operation of the method of the present invention causes the formulated particles to be corroded by chemical degradation, for example, under alkaline conditions and/or by physical dissolution and/or mechanical wear.

Polymeric or non-polymeric solid cleaning particles or mixtures thereof Typically, the substrate (cleansing) dry weight is added to the substrate with a degree of addition of 0.1:1 to 30:1 particles.

The substrate treated by the method of the present invention may comprise a wide range of substrates Any of the substrates, including, for example, plastic materials, leather, paper, cardboard, metal, glass, or wood. In practice, however, the substrate is preferably comprised of textile fibers which may be natural fibers such as cotton, or synthetic textile fibers such as nylon 6,6 or polyester, or blends of natural and synthetic fibers.

Formulating particle systems to clean the total mass of the particle formulation A ratio of 0.1-50.0% w/w is added. The shape of the blended particles is real It is cylindrical or spherical in shape and has an average density in the range of 0.5 to 2.5 g/cm 3 and an average volume of 5 to 275 mm 3 .

A further embodiment of the invention contemplates a A method of treating a substrate with a cleaning agent after the surface of the substrate, the method comprising treating the substrate with a plurality of solid cleaning particles and a plurality of formulated particles, wherein the formulated particles comprise a detergent-free additive. This particular embodiment is again carried out in the presence of washing water and involves the use of formulated particles containing a post-cleaning agent. Examples of this particular embodiment may, for example, involve formulation with an optical brightener, an anti-reattachment agent, a fragrance, or a dye transfer inhibiting agent.

A third aspect of the invention provides cleaning of a cleaning device a method comprising treating an internal system of the apparatus with a formulation comprising a plurality of solid cleaning particles and a plurality of formulated particles, wherein the formulated particles comprise at least one parent material and at least one releasable material, wherein the parent material comprises at least one Partially or completely water soluble polymeric material, and the at least one releasable material comprises an antimicrobial agent. In carrying out the method, the formulation is circulated during idle periods between wash cycles to release the antimicrobial agent into the internal water storage area or conduit of the cleaning device, thereby increasing the hygiene of the device itself.

In an exemplary embodiment of the invention, the compounding particles Remains more than a single wash, so it can be reused. In this particular embodiment, the formulated particles are collected at the end of the process and can then be reused in further substrate processing. After one or more reuses, the particles are depleted and any residue must be removed and discarded.

Therefore, the fourth aspect of the present invention provides a substrate at the substrate The side where the particles or their residues are removed from the cleaning device during or after the treatment The method comprises dissolving the formulated particles. Thus, in general, the temperature or pH of the system can be adjusted while the formulation particles are immediately and completely dissolved by a heat or pH trigger to facilitate complete removal from the system without damaging the solid cleaning particles.

The cleaning system provided by the present invention is designed to improve cleaning Mechanical interaction between all particles of the formulation and the fabric, and facilitates easy removal of the solid cleaning particles from the fabric after completion of cleaning or other post-cleaning procedures, thereby facilitating their reuse in subsequent procedures of the method . However, the invention is not limited to the steps of cleaning, post-cleaning, and other processing of fabrics, and can be applied to any solid particle cleaning method such as dishwashing or carpet cleaning.

A first aspect of the invention contemplates a formulation comprising a plurality of solid cleaning particles and a plurality of formulated particles, wherein the formulated particles comprise at least one parent material and at least one releasable material, as defined above.

Suitable examples of formulating particles in this formulation include, but are not limited to, poly(vinyl alcohol) (PVOH) hydrogels wherein PVOH has a degree of hydrolysis of 98% or greater and an average molecular weight of from 89,000 to 186,000 Daltons. Most suitably, these PVOH hydrogels are blended with carboxymethylcellulose (CMC), wherein PVOH has a degree of hydrolysis of more than 99%, and an average molecular weight of 146,000 to 186,000 Daltons, and CMC has an average molecular weight of 250,000 Daltons. .

In general, detergents formulated with formulated particles contain bounds Surfactants, enzymes, oxidizing agents and bleaching agents, and then cleaning agents include, for example, optical brighteners, anti-reattaching agents, dye transfer inhibiting agents, and fragrances.

The cleaning agent may also include, for example, a detergent, a clamping device, as the case may be. Agents, dye transfer inhibiting agents, dispersing agents, enzyme stabilizers, catalytic materials, bleach activators, polymeric dispersants, clay soil removers, and suds suppressors.

Examples of suitable surfactants can be selected from nonionic and / or anionic and / or cationic surfactants, and / or amphoteric and / or zwitterionic and / or semi-polar nonionic surfactants. The surfactant generally comprises from about 0.1%, about 1% or even from about 5% w/w to about 99.9% by mass of the formulated particles, to about 80%, about 35%, or even about 30% w/ of the mass of the formulated particles. w, or any range of amounts defined by it, exists.

Examples of suitable enzymes include, but are not limited to, hemicellulose Enzymes, peroxidases, proteolytic enzymes, other cellulases, other polyxylases, lipolytic enzymes, phospholipases, esterases, cutinases, pectinases, keratases, Reductase, oxidase, phenol oxidase, lipoxygenase, ligninase, polytriglucosidase, tannase, pentosanase, malanases, beta-polyglucose, arabinosidase (arabinosidases) ), a glucouronic acid enzyme, a chondroitinase, a laccase, a polymannanase, an amylase, or a mixture thereof. A typical combination may comprise a mixture of an enzyme (such as a proteolytic enzyme, a lipolytic enzyme, a cutinase, and/or a cellulase) in combination with an amylase.

Enzyme stabilizers are also included in the cleaning agent as appropriate. on In this regard, the enzyme used in detergents can be stabilized by various techniques, such as combining a water-soluble source of calcium and/or magnesium ions in the composition.

Examples of suitable bleaching compounds include, but are not limited to, peroxygen a compound comprising hydrogen peroxide, an inorganic peroxy salt such as perborate, percarbonate, perphosphate, perrhenate, and monopersulfate (eg, sodium perborate tetrahydrate and sodium percarbonate) And organic peroxyacids such as peracetic acid, monoperoxyphthalic acid, diperoxydodecanedioic acid, N,N'-p-xylylenediyl-bis(6-aminoperoxy) Hexanoic acid), N,N'-phthalicylamino peroxyhexanoic acid, and guanidino peroxyacid. Bleach activators include, but are not limited to, carboxylates such as tetraethyleneethylenediamine and sodium decyloxybenzenesulfonate.

Suitable detergents include, but are not limited to, alkali gold of polyphosphoric acid Genus, ammonium and alkanolammonium salts, alkali metal silicates, alkaline earth and alkali metal carbonates, aluminosilicates, polycarboxylate compounds, ether hydroxy polycarboxylates, maleic anhydride and ethylene or vinyl a copolymer of methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulphonic acid, and carboxymethyl-oxysuccinic acid, various alkali metal, ammonium and substituted ammonium salts of polyacetic acid Such as ethylenediaminetetraacetic acid and nitrostriacetic acid, and polycarboxylic acids such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid Carboxymethyloxysuccinic acid, and soluble salts thereof.

One or more copper, iron and/or manganese chelating agents, and/or one or more dye transfer inhibiting agents may also be included. Suitable dye transfer inhibiting agents include chitosan, polyvinylpyrrolidone polymers (crosslinked or uncrosslinked), polyamine N-oxide polymers, N-vinylpyrrolidone and N-vinyl Imidazole copolymer, polyvinyl Oxazolinone, polyvinylimidazole, sodium bentonite, calcium bentonite, montmorillonite, kaolin, or mixtures or salts thereof.

The detergent may also contain a dispersing agent as appropriate. Suitable water soluble The organic dispersant is a homo- or copolymeric polycarboxylic acid or a salt thereof, wherein the polycarboxylic acid may comprise at least two carboxyl radicals separated from each other by not more than two carbon atoms.

Examples of post-cleaning anti-adhesion agents include, but are not limited to CMC, polyacrylate and polyethylene glycol (PEG), or a salt thereof.

Suitable post-cleaning fragrances include, but are not limited to, multi-component organic chemical formulations which may contain alcohols, ketones, aldehydes, esters, ethers, nitrile olefins, and mixtures thereof. Commercially available compounds that provide sufficient practicability to provide residual aroma include Galaxolide (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopentane (g) )-2-benzopyran), Lyral (3- and 4-(4-hydroxy-4-methyl-pentyl)cyclohexene-1-carboxaldehyde), and Ambroxan ((3aR,5aS,9aS, 9bR)-3a,6,6,9a-tetramethyl-2,4,5,5a,7,8,9,9b-octahydro-1H-benzo[e][1]benzopyran). An example of a commercially available fully formulated fragrance is Amour Japonais supplied by Symrise ^® AG.

Suitable post-cleaning optical brighteners include, but are not limited to, several organic chemical classes, the most popular of which are stilbene derivatives, while other suitable classes include benzoic acid. Azole, benzimidazole, 1,3-diphenyl-2-dihydropyrazole, coumarin, 1,3,5-three -2-yl, and naphthyl imine. Examples of such compounds include, but are not limited to, 4,4'-bis[[6-anilino-4-(methylamino)-1,3,5-three -2-yl]amino]stilbene-2,2'-disulfonic acid, 4,4'-bis[[6-anilino-4-[(2-hydroxyethyl)methylamino]-1 , 3,5-three -2-yl]amino]stilbene-2,2'-disulfonic acid, disodium salt, 4,4'-bis[[2-anilino-4-[bis(2-hydroxyethyl)amine Base]-1,3,5-three -6-yl]amino]stilbene-2,2'-disulfonic acid disodium salt, 4,4'-bis[(4,6-diphenylamino-1,3,5-three 2-yl) amino] stilbene-2,2 '- disulfonic acid disodium salt, 7-diethylamino-4-methylcoumarin, 4,4-bis [(2-anilino Base -4- Lolinyl-1,3,5-three -6-yl)amino]-2,2'-stilbene-disulfonic acid, disodium salt, and 2,5-bis(benzo Zin-2-yl)thiophene.

Other additives may be formulated of the process according to the invention comprises an antimicrobial agent, suitable examples include, but are not limited to, a silver ion-containing zeolite, alkyl dimethyl benzyl ammonium chloride (benzalkonium chloride), Triclosan ^®, and silver nitrate.

In a particular embodiment of the invention, the particle package is formulated A parent-containing material comprising a hydrogel of a blend of PVOH and CMC, and a releasable material comprising a silver-containing zeolite, w/w% of PVOH, CMC and silver-containing zeolite being 56, 35 and 9%, respectively.

In a further embodiment, the blending particles comprise The parent material of the PVOH hydrogel, and the releasable material contains alkyl dimethyl benzyl ammonium chloride. The proportion of the material in the particles is PVOH: alkyl dimethyl benzyl ammonium chloride (w: w) = 9.6 :1.

Solid-state cleaning and formulation of particles with good flow Shape and size in close contact with contaminated substrates (generally containing textiles). Thus, in the context of the present invention, the particles are generally cylindrical or spherical particles. Combinations of particle size, shape and density have been found to optimize the mechanical interaction of the particles with the fabric, which is vigorous enough to provide effective cleaning while being uniform and gentle to reduce fabric damage as compared to conventional aqueous procedures. In this regard, the uniformity of the mechanical action produced by the selected particles across the entire surface of the fabric is particularly critical. This uniform The mechanical action is also critical to the topical and controlled application of detergents, post-cleaners, and other processing additives from the blending of particles across the surface of the substrate.

The particle parameters are also controlled to easily separate particles from the wash at the end of the cleaning process. Thus, the particle size and shape can be controlled to minimize substrate entanglement, and the combination of suitable particle density and high free volume (liquid gap) in the rolling process of the washing machine facilitates particle removal. It is particularly relevant in the context of fabric processing.

In the second aspect of the invention, the ratio of solid cleaning particles to substrate is typically in the range of from 30:1 to 0.1:1 w/w (dry weight of substrate (cleaning)), preferably 10:1. A particularly advantageous result is obtained in the range of 1:1 w/w, in a ratio of between 5:1 and 1:1 w/w, in particular about 2:1 w/w. Thus, for example, cleaning 5 grams of fabric uses 10 grams of solid cleaning particles, so that up to 5 grams of formulated particles can be used in addition to the formulated cleaning and after cleaning agents and other processing additives.

In order to provide additional lubrication to the system, the transport properties within the system are improved and water is added to the system. Contaminated substrates may be wetted with main pipes or tap water before being placed in the cleaning equipment. In any case, water is added to the process to obtain a certain water to substrate ratio, which is typically between 2.5:1 and 0.1:1 w/w; this ratio is more often from 2.0:1 to 0.8:1. Between the ratios of 1.5:1, 1.2:1 and 1.1:1, particularly advantageous results are obtained.

As indicated previously, the method of the invention is particularly useful for cleaning textile fibers and fabrics. The conditions used in this cleaning system are very consistent with those applied to conventional wet cleaning textile fibers, and the results are usually made from fabrics. Quality and pollution level are determined. Thus, typical steps and conditions are those known to those skilled in the art, and the fabric is typically treated in accordance with the method of the present invention at a temperature of, for example, between 5 and 95 ° C for a period of from 10 minutes to 1 hour, followed by rinsing in water and dry. In order to increase the convenience of the user, the release of the additive from the formulated particles is controlled to be completed in one wash or after a series of washings.

By mixing particles with detergents and post-cleaners, and others The main component of the treatment additive to the surface of the fabric to ensure excellent cleaning and post-cleaning performance. No problems with solid-state cleaning or formulation of particle-adhering fibers were observed at the end of the cleaning operation, and all of the particles could then be removed from the substrate of the cleaning article. The method of the present invention can be carried out particularly advantageously using a cleaning apparatus as disclosed in WO-A-2010/094959, WO-A-2011/064581, and WO-A-2011/098815.

In addition, as shown previously, it has been proven to reuse solid cleaning particles. As feasible. In addition, the formulated particles typically remain in more than one wash and can be similarly reused.

Detergent, post-cleaner, or other treatment additive Release from the formulated particles onto the contaminated substrate, mechanical corrosion experienced by the particles in the washing step, chemical corrosion of the particles (eg hydrolysis), enzymatic degradation of the particles, physical dissolution of the particles, decomposition of the particles, or releasable materials Occurs from particle diffusion, or some or all combinations of these effects.

A further embodiment of the invention contemplates a substrate The surface is treated by an additive, which comprises solidifying the contaminated substrate The cleaning particles are treated with washing water and additionally mixed with the appropriate processing additives. Suitable examples may include releasing the antimicrobial agent onto the surface of the fabric for sterilization purposes.

The invention also contemplates an idle period between cleaning cycles In the meantime, the method of formulating the particles to release the antimicrobial agent into the internal water storage area or conduit of the cleaning device, thereby improving the hygiene of the device itself.

In addition, the present invention also uses, for example, heat or pH triggers. It is rapidly dissolved to completely remove the particles of the formulated particles or the particles, but does not harm the solid cleaning particles.

The method of the second aspect of the present invention generally relates to cleaning a contaminated substrate, and the steps thereof comprise: (a) cleaning the contaminated substrate with a plurality of solid cleaning particles and a plurality of formulated particles; (b) performing the first time Extracting excess water; (c) performing the first separation of the solid cleaning particles and formulating particles; (d) rinsing; (e) performing a second extraction of excess water; (f) taking step (d) as appropriate (e) repeating at least once; and (g) performing a second separation of the solid cleaning particles and the formulated particles.

The second aspect of the invention can be used in small or large batchwise processes and is suitable for use in household and industrial cleaning processes.

The method of the present invention can be applied to cleaning any substrate in a wide range of substrates including, for example, plastic materials, leather, paper, cardboard, metal, glass, or wood. However, in practice, this method is mainly suitable for clearing Cleansing substrates comprising textile fibers and fabrics, and has proven to be particularly successful in the effective cleaning of textiles, which may, for example, comprise natural fibers such as cotton, or synthetic and synthetic textile fibers such as nylon 6,6, polyester, acetate Or a blend of its fibers.

However, when applied to textiles, it is used in this cleaning system. The conditions do allow for the use of cleaning temperatures that are much lower than wet cleaning textiles typically used in conventional textiles, with the result providing significant environmental and economic benefits.

The invention will now be further described with reference to the following examples, But it does not limit its scope.

[Examples] Example 1 Sterilization of stained cloth at room temperature and neutral pH (including silver zeolite)

Approximately 18.5 g of PVOH (> 99% hydrolyzed, molecular weight 146,000 to 186,000 Daltons, Sigma Aldrich model 363,065), and 3.0 g of a silver-containing zeolite ^{(Microsilver BG Tec Plus TM, Biogate} AG, Nurnberg, Germany) were added 230 g of water (See Table 1). The PVOH was dissolved in water by heating and stirring to form a 7.4% w/w solution in which the silver-containing zeolite was dispersed as fine particles. The solution was then cooled to about 40 ° C, after which 11.5 grams of CMC (Sigma Aldrich Model 419, 311) having a molecular weight of about 250,000 Daltons was added and mixed by hand stirring. The article is emulsified to form a white pulp during mixing of the CMC. The slurry was then coated on a non-stick surface at a thickness of about 10 mm, followed by drying at 65 ° C for 72 hours in a ventilated oven (Sample 1).

A control sample (Control 1) was prepared in a manner similar to that described above, However, the silver-containing zeolite is omitted. The exact amounts used to prepare Sample 1 and Control 1 are shown in Table 1. The corresponding composition percentage (w/w) is shown in Table 2.

The composition (w/w) of the dried sample 1 and the control 1 is shown in Table 3.

1.8 g of dry sample 1 and control 1 were weighed to an accuracy of ±0.0005 g. These dry weights are shown as w ₁ . The two materials were then soaked in water overnight to form an expanded hydrogel. Any excess water is aspirated from its surface and the sample is weighed again. The weight of the expanded hydrogel is shown as w ₂ . The expansion ratio of the hydrogel is then calculated by: expansion ratio (before rolling) = w ₂ /w ₁ and then the expanded sample 1 and the control 1 hydrogel are cut into pieces having a size of about 2 to 4 mm, and each water is The gel-type tablets were separately placed in a sealed plastic case (having a size of about 17 x 12 x 5.5 cm) having 6 g of water each having a piece size of about 10 x 10 cm, and inoculated with 1 ml of Pseudomonas aeruginosa ( Pseudomonas Aeruginosa ) suspension cloth. The degree of inoculation was 2.5 × 10 ⁸ colony forming units (cfu) / cloth. The vaccination system was carried out by Microbiological Consultant Services (MCS) located in Hope Valley, Stoney Middleton, England. The inoculated cloth is shipped in a sterile plastic bag.

A second control cloth sample (Control 2) was prepared. This cloth was also inoculated with 1 ml of P. aeruginosa suspension at a rate of 2.5 x 10 ⁸ cfu/cloth and also placed in a sealed box with 6 g of water, as described above. However, this box does not contain any hydrogel. All boxes (Sample 1, Control 1 and Control 2) were then rolled in a tumble dryer at 50 rpm for 60 minutes at room temperature.

Retract the cloth and hydrogel after rolling. The cloth was shipped to the MCS as a sterile plastic bag where the microbial activity was analyzed. The cloth was suspended in 9 ml of diluent and stirred vigorously to release any residual bacteria. After 3 days of culture at (31 ± 1) °C on Tryptone Soya Agar, the resulting suspension was analyzed using standard plate counting.

The hydrogel dry (to remove excess surface water), and reweighed to produce a wet hydrogel weight w _3, and the expansion ratio of the measured rolling hydrogel. The hydrogel sheets were then completely dried at 65 ° C and then weighed again to produce a dry weight w ₄ after rolling. The swelling ratio of the hydrogel after rolling was measured by the following: expansion ratio after rolling = w ₃ / w ₄ Percentage of dry weight loss of hydrogel during rolling was calculated as follows: % dry weight loss = (w ₁ - w ₄ ) × 100/w ₁

The number of colony forming units per cloth after the cultivation was shown in Table 4.

The dry and expanded weights of the hydrogel before and after rolling are shown in Table 5.

The expansion ratio of the hydrogel before and after rolling is shown in Table 6.

The percentage of dry weight loss caused by rolling of Sample 1 and Control 1 is shown in Table 7.

As is apparent from Table 4, the cloth treated with the hydrogel containing the silver-containing zeolite antimicrobial agent (sample 1) showed higher resistance than the silver-free zeolite. The microgel-treated hydrogel-treated cloth (Control 1), or the water-only cloth (Control 2) had fewer (more than 1000-fold) bacteria. The weight loss of the sample 1 hydrogel and the control 1 hydrogel during the rolling treatment were 17.6% and 19.2%, respectively (see Table 7).

Dry weight loss means some condensation during the rolling action The material of the glue dissolves and is transferred to the water and cloth contained in the box. In the case of the sample 1 hydrogel, some of the silver-containing zeolite was also transferred to water and cloth, thus effectively sterilizing the cloth. In contrast, the Control 1 hydrogel showing a dry weight loss similar to the sample 1 hydrogel did not have this bactericidal effect.

Example 2 Sterilization of soiled cloth at room temperature and neutral pH (alkyldimethylbenzyl chloride)

A second series of PVOH having different degrees of hydrolysis and molecular weight was used as a carrier for the water-soluble antimicrobial agent alkyldimethylbenzylammonium chloride. PVOH was obtained from Sigma Aldrich and is listed in Table 8 for the main characteristics of its degree of hydrolysis and molecular weight.

Samples were prepared by mixing 7.5 grams of various PVOH, 107 grams of water, and 1.5 grams of a 50% aqueous solution of alkyl dimethyl benzylammonium chloride (Sigma Aldrich Model 63, 249); these mixtures were heated and manually stirred until PVOH dissolved. A series of control samples without alkyl chloride benzyl ammonium chloride were also prepared in a similar manner. The solution was cast in a non-stick container and dried at 65 ° C for 3 days. The amount used (to ±0.005 g) is shown in Table 9.

The percentage of alkyl dimethyl benzyl ammonium chloride in the dried sample containing the reagent is shown in Table 10.

The dried gel was expanded in water at 65 ° C for 45 minutes and excess water was aspirated from its surface. The gel was then cut into pieces having a size of about 2 to 4 mm, and each hydrogel-type piece was separately placed in a sealed plastic case (having a size of about 17 x 12 x 5.5 cm) having 6 ml of water. Each has a piece of cloth having a size of about 10 x 10 cm and inoculated with 1 ml of a suspension of Pseudomonas aeruginosa. The degree of inoculation was 2.4 × 10 ⁸ cfu / cloth. Vaccination was again carried out by MCS. The inoculated cloth is shipped in a sterile plastic bag. The box was then rolled in a tumble dryer at room temperature for 60 minutes at 50 rpm.

In addition to the cloth rolled with the hydrogel sheet, another piece of the cloth inoculated with 1 ml of the P. aeruginosa suspension as described above was rolled in a sealed box with 6 ml of water at 50 rpm for 60 minutes at room temperature, but without any Hydrogel (Control 2).

After rolling, the cloth was removed, placed in a sterile plastic bag and sent to the MCS for microbiological analysis. Suspend these cloths in a dilution of 9 ml In the agent, and vigorously agitate to release any residual bacteria. After 3 days of culture at (31 ± 1) °C on Tryptone Soya Agar, the resulting suspension was analyzed using standard plate counting. The results are shown in Table 11.

Initial Pseudomonas aeruginosa inoculation = 2.4 × 10 ⁸ cfu / cloth

Table 11 shows that the cloth treated with the hydrogel having alkyldimethylbenzylammonium chloride showed a hydrogel-treated cloth or a water-only cloth after the culture. 2) Less (more than 10 ⁶ times) bacteria. This leads to the conclusion that the bactericidal effect is caused by the alkyl dimethyl benzyl ammonium ammonium chloride released from the hydrogel and which occurs at room temperature and neutral pH.

Example 3 Dye Transfer Inhibition of Polyvinyl Alcohol (PVOH) from Composite Crosslinked Polyvinylpyrrolidone

This example demonstrates the dye transfer inhibiting effect imparted by the molten composite particles containing the active agent (crosslinked PVP) and polyvinyl alcohol as a parent material. It also demonstrates that the DTI effect lasts several washes (at least 5 times).

Material Preparation

Cross-linked PVP (Polyplasdone XL-10, supplied by AshlandsSpeciality Ingredients of Wayne NJ 07470, USA) and Kuraray Europe GmbH (Frankfurt D-65926, Germany) were used with a 27 mm diameter Leistritz ZSE 27 HP 44D twin screw extruder. ) PVOH compound supplied. The PVOH rating is Mowiflex LP TC 661. The loading degree of PVP is 25% (weight ratio). PVOH has a degree of hydrolysis of about 94%. PVOH and PVP were fed at 15 and 5 kg/hr from separate feeders, resulting in a total output of 20 kg/hr and a PVP content of 25%.

The temperature distribution of the extruder barrel is shown in Table 12:

Therefore, the extrusion temperature is higher than the melting point of PVOH but lower than the degradation temperature of the crosslinked PVP. The vacuum line is connected to the extrusion barrel to degas the material and prevent foaming. The squeeze belt is then cooled in water and air. The cut pellet size is approximately 3 mm.

Dye Transfer Inhibition (DTI)

The DTI test was carried out in a household BekoWM 5120W washing machine (capacity 5 kg) with cleaning granules of Technyl XA 1493 (Nylon 6, 6 supplied by Solvay, Lyon, France).

The red dye source is two new unwashed red T-shirts (Fruit of the Loom, XXL). The ballast is composed of used polyester clean room overalls. The weight of the cleaning product is defined as the weight of the T-shirt plus Upper ballast weight. The weight ratio of Technyl XA 1493 cleaning granules to the cleaning product is 2:1.

One and a half pieces of sebum cloth (one piece measured as 23 x 61 cm) (product code SBL 2004, WFK Testgewebe GmbH, D-41379, Germany) and four pieces of cotton cloth (17 x 28 cm) were also added to the washing. The series of materials that make up this cleaning are shown in Table 13:

It should be noted that this wash contains 500 grams of PVOH/25% PVP; therefore, the weight of PVP present at the beginning of the procedure is 125 grams.

The items of each cleaning article are placed in a net mesh bag; the particles are thoroughly mixed with the fabric material. The fabric material is layered into the laundry bag to evenly disperse the articles throughout the laundry bag, and the laundry bag is tightened and sealed.

The laundry bag was washed in a Beko household washing machine using a 40 ° C cotton cycle with 11.2 grams of Xeros Pack I detergent and the speed was set to 1200 rpm. Therefore, the ratio of the Xeros Pack I detergent to the laundry (weight ratio) is about 8 grams per kilogram of cleaning.

The white cotton cloth was taken back at the end of the cleaning cycle, suspended at room temperature and dried, and then analyzed for color characteristics using a Konica Minolta CM-3600A spectrophotometer to obtain L*, a* and b* values. Spectrophotometer The aperture size is 25.4 mm, which uses a 100% UV component and does not accept specular component. The measured values of the 16 areas of the cloth (4 areas per piece of cloth) are averaged.

Further Cleaning

The particles (Technyl and PVOH/PVP particles) were withdrawn after the first wash. Prepare another batch of new T-shirts, sebum and white cloth, and clean polyester ballast cleaning. The PVOH/PVP particles were added to the new load and another wash was performed as described in (1.2) above. This step was repeated a total of 5 washes. The CEI, L*, a*, and b* values of the white cloth were recorded after each cleaning.

"result"

Table 14 shows the recorded a* values; the control was performed without the formulated particles. Table 14 also shows the Da* values, where Da* is defined as the a* change from the original unwashed cloth a*. It also shows the percentage of Da* reduction for each wash, where: Da* reduction percentage = 100 × {1 - (Da * / Da * _control )}

It is a measure of the dye transfer inhibition effect. If the a* value of the cleaned cloth returns to the original value, then this parameter is 100%; if the a* value is unchanged compared to the control (ie, the formulated particles have no DTI), then this parameter is zero.

Thus, as can be seen from Table 14, 500 grams of PVOH/25% PVP particles inhibited the transfer of the red dye to the white cloth and the effect continued for at least 5 washes. The average "Da* reduction percentage" for the five washes was 53%. It also Indicates the average "Da* reduction percentage" per gram of DTI in the calculated material; it is calculated by dividing the average "Da* reduction percentage" by the amount of original DTI material in the formulated particles. For example, 500 grams of PVOH particles having 25% PVP material are used in this embodiment, thus using 125 grams of DTI material.

Thus the "average Da* reduction percentage" per gram of DTI = 53/125 = 0.43% / gram.

Example 4 Dye transfer inhibition obtained by combining polyvinyl alcohol (PVOH) with chitosan

This example demonstrates the dye transfer inhibiting effect imparted by the molten composite particles containing the active agent (chitosan) and the polyvinyl alcohol as the parent material. It also demonstrates that the DTI effect lasts for a few uses (at least 5 times).

Material Preparation

Using a Leistritz ZSE 27 HP 44D twin screw extruder with a screw diameter of 27 mm (as described in Example 3), chitosan (ChitoClear 40500, Primex EHF, 580 Siglufjordur, Iceland) and PVOH supplied by Kuraray (MowiflexLP TC 661) composite. The degree of loading of chitosan was 25% by weight, and PVOH had a degree of hydrolysis of about 94%. PVOH and chitosan were fed at 15 and 5 kg/hr, respectively, from individual feeders, resulting in a total output of 20 kg/hr and a chitosan content of 25%.

The temperature distribution of the drum was the same as described in Example 3. Therefore, the extrusion temperature is higher than the melting point of PVOH but lower than the degradation temperature or melting temperature of chitosan. Connect the vacuum line to the extrusion barrel to take off the material Breathe and prevent foaming. The squeeze belt is then cooled in water and air. The cut pellets are approximately 3 mm in size.

Dye Transfer Inhibition

The experimental protocol for DTI assessment was as described in Example 3 above, except that 500 grams of PVOH/25% chitosan formulation particles were mixed to clean the particles. Therefore, the total amount of chitosan present is 125 grams. A "control" wash (no mix of particles) was also performed.

"result"

Table 15 shows the recorded a* values. The Beko washing machine used in this experiment was different from Example 3, so the straight method directly compared a*; however, the "Da* reduction percentage" value between different machines can be compared. The control is the cleaning of the unadjusted particles.

Therefore, as can be seen from Table 15, 500 g of PVOH/25% The butan granules inhibit the transfer of the red dye to the white cloth and the effect continues for at least 5 washes. The average "Da* reduction percentage" for the 5 washes was 71%. The amount of chitosan in 500 g of particles having 25% chitosan was 125 g.

Therefore, the "average Da* reduction percentage" per gram of DTI is derived from: Average Da* reduction per gram = 71/125% / gram = 0.57% / gram.

Therefore, PVOH/25% chitosan per gram of DTI material The "average Da* reduction percentage" value is greater than PVOH/25% PVP (Example 3), indicating that chitosan is a more potent DTI agent.

Example 5 Dye transfer inhibition by combining polyvinyl alcohol (PVOH) with sodium bentonite

This example demonstrates the dye transfer inhibiting effect imparted by the molten composite particles containing the active agent (sodium bentonite) and polyvinyl alcohol as a parent material. It also demonstrates that the DTI effect lasts 4 washes.

Material Preparation

Sodium bentonite (Sigma Aldrich Chemicals, Gillingham, UK, product number 285234) and PVOH supplied by Kuraray were used in the Smithers Rapra facility in Shawbury, England, using an APV MP2030 30 mm screw (28 L/D) twin screw extruder. MowiflexLP TC 661 composite. PVOH and sodium bentonite were fed from 5.4 and 0.96 kg/hr, respectively, from individual feeders, resulting in a total output of 6.36 kg/hr. Therefore, the degree of loading of the sodium bentonite was 15.1% by weight. It is the highest available and less than the loading of PVP (Example 3) and chitosan (Example 4), where a 25% loading is obtained.

The temperature distribution of the drum is shown in Table 16:

The cut pellets are approximately 3 mm in size.

Dye Transfer Inhibition

The experimental agreement is as described in the above embodiment 3, except here In the case, 500 g of PVOH/15% sodium bentonite was used to formulate the granules; the total weight of the sodium bentonite present was 75 g. A "control" wash (no mix of particles) was also performed.

"result"

The recorded a* values are shown in Table 17, which also shows the values of the Da* and Da* reduction percentages, as defined above. Calculate the average of 4 washes (measured a* reduction).

Thus, Table 17 shows that 500 grams of PVOH/15% sodium bentonite particles inhibited the transfer of the red dye to the white cloth and the DTI effect continued for 4 washes. However, the DTI effect was not noticeable at the 5th wash. This is in contrast to Example 3 (PVP) and Example 4 (chitosan) where the DTI is maintained at least 5 washes.

The "Da* reduction percentage" average of the 4 washes was 30%. The amount of sodium bentonite in 500 g of particles having 15% sodium bentonite was 75 g.

Therefore, the "average Da* reduction percentage" per gram of DTI material is obtained from: Average Da* reduction percentage per gram = 30/75% / gram = 0.40% / gram.

It is apparent that the DTI of PVOH/15% sodium bentonite particles extends only to 4 washes, while the DTI of PVOH/25% PVP (Example 3) and PVOH/25% chitosan (Example 4) are maintained for 5 washes. .

"Da* reduction percentage" value is also better than PVOH/25% PVP (Example 3) and PVOH/25% chitosan (Example 4) were low; however, PVOH/sodium bentonite DTI material loading was also lower. A comparison of the effects of different DTI materials can be accomplished by a "Da* percent reduction" value per gram of DTI in the material. These figures are shown in Table 18.

Thus, as can be seen from Table 18, chitosan is the most effective DTI material, followed by PVP, followed by sodium bentonite.

Example 6 Dye transfer inhibition obtained by combining foaming polyvinyl alcohol (PVOH) with chitosan

This example demonstrates the dye transfer inhibiting effect imparted by the molten composite particles containing the active agent (chitosan) and the polyvinyl alcohol as the parent material. It is a "quick release particle" that releases most of the DTI material very quickly, in this case only 3 times.

Material Preparation

In the facility of Smithers Rapra, Shawbury, UK, a PPV (Sigma Aldrich Chemicals, part number 448869) and PVOH supplied by Kuraray (Mowiflex LP TC 661) were used with APV MP2030 30 mm twin screw extruder (28 L/D). )complex. PVOH and chitosan were fed from 6.4 and 1.6 kg/hr, respectively, from individual feeders, resulting in a total output of 8 kg/hr. Therefore, the degree of loading of chitosan is 20% by weight.

The temperature distribution of the drum is shown in Table 19:

Therefore, the extrusion temperature is higher than the melting point of PVOH but lower than the melting point of chitosan. The cut pellets are approximately 3 mm in size. There is a significant jet in the extrusion barrel which causes the particles to foam.

Dye Transfer Inhibition

The experimental protocol was as described in Example 3 above except that in this case 200 grams of PVOH/20% chitosan was used to formulate the particles (equal to 40 grams of chitosan). A "control" wash (no mix of particles) was also performed.

"result"

The recorded a* values are shown in Table 20, which also shows the values of the Da* and Da* reduction percentages, as defined above.

Table 20 shows that PVOH/20% chitosan particles inhibit the transfer of red dye to white cloth and the DTI effect exceeds single use. However, because of the foaming nature of the particles, the particles are consumed in a smaller number of washes than in Example 4 in which the particles are not foamed. The life of the particles is estimated to be 3-4 washes.

Example 7 Comparison of DTI of chitosan released from formulated granules and chitosan powder

This experiment compares the chitosan blends that release chitosan Granules, relative to the DTI effect of washing the same amount of chitosan powder. It demonstrates that the formulated granules are as effective as the powder and have the advantage of increasing the convenience of the end user.

Example 4 demonstrates that the chitosan in the formulated granules reduces dye transfer in at least 5 washes. In this example, the amount of chitosan released per wash was estimated, and then washed with an equivalent amount of chitosan, but added as loose powder. Thus the dTI of the chitosan in the form of a) formulated particles and b) powder is compared.

Approximately 50 PVOH/chitosan composite particles were removed after the 5th wash of Example 4. It was dried in a fan oven at approximately 65 ° C for 90 minutes. Unused PVOH/25% chitosan particles were then dried in the same manner. The weight of approximately 50 dry granules was measured; the percent weight loss was determined therefrom, and the amount of chitosan released by the 5 washes was estimated. The weight of the particles is shown in Table 21.

The results of Table 21 can be calculated to give a percent weight loss of PVOH/chitosan particles after 5 washes of 83.0%, or 16.6% per wash.

In Example 4, 500 grams of PVOH/25% chitosan particles were initially added; it contained 125 grams of chitosan. Assuming that PVOH or chitosan has no preferential removal, it can be estimated that 103.7 grams (= 83.0% x 125 grams) of chitosan has been released after 5 washes. false It is estimated that the amount of chitosan released per wash is the same in each of the five washes, and it is estimated that 20.7 g of chitosan is released per wash.

Thus, using the protocol described in Example 3, experiments were carried out with 20.7 grams of chitosan powder (ChitoClear 40500).

"result"

The a* value of 20.7 g of chitosan powder was 1.84±0.28. In Example 4, when chitosan was released from the formulated granules, the a* average of 5 washes was 2.26. The difference between the values is less than 1 unit, indicating that the naked eye cannot detect, that is, for the naked eye, the multi-formed particles releasing chitosan have the same DTI performance as the equivalent chitosan loose powder. However, multi-formulation particles have the advantage of being extremely convenient for the end user.

Example 8 DTI of spheroidized pellets containing chitosan

This example demonstrates the dye transfer inhibiting effect imparted by the granulated particles containing the active agent (chitosan) and microcrystalline cellulose (MCC) as a parent material and polyvinyl alcohol. It also proves that the DTI effect continues to be used multiple times.

Material Preparation

The materials listed in Table 22 were granulated in a household food mixer.

Use the materials listed in Table 22 via Caleva Bench top Variable density extruder extrusion, which uses a custom template of 4 mm. The extrudate was then spheroidized using a Caleva Bench Top MBS 250 spheronizer (Spheroniser) to form substantially spherical pellets of approximately 4 mm in diameter. It was dried overnight in an oven at about 60 °C. The role of PVOH is to bind chitosan to MCC.

Dye Transfer Inhibition

The experimental protocol was as described in Example 3 above except that in this case 100 grams of chitosan/MCC/PVOH spheroidized particles (equal to 40 grams of chitosan) were used. A "control" wash (no mix of particles) was also performed.

"result"

The results are shown in Table 23.

Therefore, as can be seen from Table 23, the spheroidized particles are effectively reduced. The dye is transferred and the effect continues for at least 5 washes. It should be noted that the chitosan content in the granules was 49 g.

In the full description of the specification and the scope of the patent application, the text The word "comprise" and "comprises" and its variants mean "including but not limited to" and it is not intended to (and not) exclude other parts, additives, ingredients, integers, or steps. In the description and claims of the specification, the singular encompasses the plural, unless the In particular, it should be understood that in the use of indefinite articles, this specification means plural and singular, unless Additional requirements.

It will be appreciated that features, integers, features, compounds, chemical moieties, or groups recited in connection with the specific aspects, embodiments, or embodiments of the invention may be applied to any other aspect or specifics described herein. Embodiments or examples, unless incompatible with each other. All of the features disclosed in the specification, including any accompanying claims, abstract and drawings, and/or all steps of any method or procedure so disclosed may be combined in any combination, except at least some of these features and / or a combination of step exclusions. The invention is not limited to the details of any of the above specific embodiments. The present invention extends to any novel portion or any novel combination of the features disclosed in the specification, including any accompanying claims, abstract, and drawings, or any novel portion or novelty of the steps of any method or procedure so disclosed. combination.

The reader should note that all documents and documents presented at the same time or prior to this specification in connection with the present application are hereby incorporated by reference in their entirety in their entirety in the entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire disclosure

Claims (63)

A formulation comprising a plurality of solid cleaning particles and a plurality of dosing particles, wherein the formulation particles comprise at least one parent material and at least one releasable material, wherein the parent material comprises at least one partially or fully water soluble polymeric material, And the at least one releasable material comprises at least one post cleaning agent and/or post-cleaner and/or other processing additive for treating the substrate. The formulation of claim 1, which is for cleaning a contaminated substrate, wherein the at least one releasable material comprises at least one detergent. The formulation of claim 1 or 2, wherein the at least one releasable material comprises at least one post-cleaner. The formulation of claim 3, wherein the post-cleaning agent comprises at least one optical brightening agent, anti-reattachment agent, fragrance, or dye transfer inhibiting agent. The formulation of any one of claims 1 to 4, wherein the at least one other treatment additive comprises at least one antimicrobial agent. The application of the formulation patentable scope of item 5, wherein the antimicrobial agent is selected from a silver ion-containing zeolite, alkyl dimethyl benzyl ammonium chloride (benzalkonium chloride), Triclosan ^®, and silver nitrate. The formulation of claim 4, wherein the at least one anti-reattachment agent is selected from the group consisting of CMC, polyacrylate or polyethylene glycol (PEG), or a salt thereof. The formulation of claim 4, wherein the at least one dye transfer inhibitor is selected from the group consisting of chitosan, polyvinylpyrrolidone polymer (crosslinked or uncrosslinked), polyamine N-oxide Polymer, copolymer of N-vinylpyrrolidone and N-vinylimidazole, polyvinyl Oxazolinone, polyvinylimidazole, sodium bentonite, calcium bentonite, montmorillonite, kaolin, or mixtures or salts thereof. The formulation of any one of claims 1 to 8 wherein the detergent comprises at least one detergent. The formulation of claim 9, wherein the detergent comprises at least one surfactant selected from the group consisting of nonionic and/or anionic and/or cationic surfactants, and/or amphoteric and/or Zwitterionic and/or semi-polar nonionic surfactants. A formulation as claimed in any one of the preceding claims, wherein the detergent comprises at least one enzyme, oxidizing agent or bleach. The formulation of claim 10, wherein the surfactant is present at a level of from 5% to 30% by weight of the formulated particles. The formulation according to any one of the preceding claims, wherein the at least one cleaning agent additionally comprises a detergent, a chelating agent, a dye transfer inhibitor, a dispersing agent, an enzyme stabilizer, a catalytic material, a bleach activator, and a polymerizable property. Dispersants, clay soil removers, and/or foam inhibitors. The formulation of any one of claims 1 to 3, wherein the formulation particles comprise a detergent-free additive. A formulation as claimed in claim 14 which contains an antimicrobial agent which is released onto the surface of the fabric for sterilization purposes. A formulation as claimed in any one of the preceding claims, wherein the parent material comprises an inactive polymeric material comprising a hydrogel. The formulation of claim 16 wherein the water content of the hydrogel is between 30 and 98% w/w. The formulation of claim 16 or 17, wherein the polymeric material in the hydrogel is selected from the group consisting of polyvinyl alcohol, poly(vinyl acetate), poly(ethyl vinyl alcohol), poly(ethylene glycol). , poly(acrylate), gelatin, hyaluronic acid, carboxymethylcellulose, starch, seaweed gum, or other poly(saccharides), and blends or copolymers of these materials, or salts thereof. The formulation of any one of claims 1 to 15, wherein the formulated particles comprise solid pellets comprising a polymerizable powder and/or a non-polymerizable powder by compression under a combination of pressure and temperature. The parent material is formed with at least one releasable material. The formulation of claim 19, wherein the formulation particles additionally comprise at least one material selected from the group consisting of a decomposing agent, a lubricant, and a binder. The formulation of claim 19 or 20, wherein the polymer forming powder suitable for granulation may be selected from the group consisting of chitosan, lactose, cellulose, starch, microcrystalline cellulose, and crosslinked carboxymethyl Croscarmellose sodium, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxyethylcellulose, poly(vinyl alcohol), poly(vinyl acetate), crosslinked or uncrosslinked Poly(vinylpyrrolidone), poly(ethylene glycol), and gelatin, or a salt thereof. The formulation of any one of claims 1 to 15, wherein the formulated particles comprise at least one degradable parent material. The formulation of claim 22, wherein the degradable parent material is selected from the group consisting of poly(lactose), poly(glycolic acid), polyvinyl alcohol, poly(vinyl acetate), poly(vinylpyrrolidone). Polyamide, polyester, and blends and copolymers of these materials, or salts thereof. The formulation of claim 22 or 23, wherein the releasable material is mixed with the parent material by melt compounding in a twin screw extruder. The formulation of any of the preceding claims, wherein the solid cleaning particles can be polymeric and/or non-polymeric cleaning particles. The formulation of claim 25, wherein the polymeric cleaning particles comprise a foamed or unfoamed polymeric material. The formulation of claim 25 or 26, wherein the polymeric particles comprise a linear or crosslinked polymer. The formulation of claim 25, 26 or 27, wherein the polymeric cleaning particles comprise a polyalkylene, a polyamine, a polyester, or a polyurethane. The formulation of claim 28, wherein the polymerizable particles comprise particles of nylon, polyethylene terephthalate or polybutylene terephthalate. The formulation according to any one of the preceding claims, wherein the polymerizable solid cleaning particles have an average density in the range of 0.5 to 2.5 g/cm 3 and an average volume in the range of 5 to 275 mm 3 . The formulation of any of the preceding claims, wherein the polymeric cleaning particles comprise a copolymer comprising an ionic charge, or a monomer comprising a polar moiety or an unsaturated organic group. The formulation of claim 25, wherein the non-polymerizable cleaning particles comprise particles of glass, cerium oxide, stone, wood, metal, or ceramic material. The formulation of claim 32, wherein the metal is selected from the group consisting of zinc, titanium, chromium, manganese, iron, cobalt, nickel, copper, tungsten, aluminum, tin, and lead, and alloys thereof. The formulation of claim 32, wherein the ceramic is selected from the group consisting of alumina, zirconia, tungsten carbide, tantalum carbide, and tantalum nitride. A formulation according to any one of the preceding claims, wherein the non-polymerizable cleaning particles have an average density in the range of from 3.5 to 12.0 g/cm 3 and an average volume in the range of from 5 to 275 mm 3 . The formulation of any of the preceding claims, wherein the solid cleaning particles are substantially cylindrical or spherical in shape. A formulation as claimed in any one of the preceding claims, wherein the formulated particles are added in a proportion of from 0.1 to 50.0% w/w of the total mass of the formulation. The formulation of any of the preceding claims, wherein the formulated particles are substantially cylindrical or spherical in shape. A formulation as claimed in any one of the preceding claims, wherein the formulated particles have an average density in the range of from 0.5 to 2.5 grams per cubic centimeter and an average volume in the range of from 5 to 275 cubic millimeters. A formulation as claimed in any one of the preceding claims, wherein the formulated particles can be reused in further substrate processing. A method of treating a substrate, wherein the method comprises treating the substrate with a formulation as described in any one of claims 1 to 40. The method of claim 41, wherein the method is carried out in an aqueous environment in the presence of a limited amount of water. The method of claim 41, wherein the method comprises a method of cleaning a contaminated substrate, wherein the at least one releasable material comprises at least one cleaning agent. The method of claim 41, wherein the at least one releasable material comprises at least one post-cleaner. The method of claim 41, 42 or 44, wherein the formulated particles comprise a detergent-free additive. The method of claim 45, which comprises releasing the antimicrobial agent onto the surface of the fabric for sterilization purposes. The method of claim 45, comprising treating the fabric with at least one anti-reattachment agent. The method of claim 47, wherein the at least one anti-reattachment agent is selected from the group consisting of CMC, polyacrylate, polyethylene glycol (PEG), poly(vinylpyrrolidone) (may be crosslinked or Uncrosslinked), sodium bentonite, and chitosan, or a salt thereof. The method of any one of claims 41 to 48, wherein the solid cleaning particles are added to the substrate by a degree of addition of the particles of from 30:1 to 0.1:1 depending on the dry weight of the substrate. The method of claim 49, wherein the ratio of the solid cleaning particles to the substrate ranges from 10:1 to 0.1:1 w/w, based on the dry weight of the substrate. The method of claim 49, wherein the ratio is between 5:1 and 1:1 depending on the dry weight of the substrate. The method of any one of claims 41 to 51, wherein the substrate comprises a plastic material, leather, paper, cardboard, metal, glass, or wood. The method of any one of claims 41 to 51, wherein the substrate comprises textile fibers. The method of claim 53, wherein the textile fiber comprises natural or synthetic fibers, or a blend thereof. The method of any one of claims 41 to 54, wherein water is added to the system to provide a water to substrate ratio of between 2.5:1 and 0.1:1 w/w. The method of claim 55, wherein the ratio is between 2.0:1 and 0.8:1. The method of any one of claims 41 to 44 or 49 to 56, which is for cleaning textile fibers, wherein the treatment is carried out at a temperature between 5 and 95 ° C for 10 minutes to 1 The time between hours. The method of any one of claims 41 to 57, wherein the solid cleaning particles are reused in a further step in accordance with the method. The method of any one of claims 41 to 58 wherein the formulated particles are reused in a further step in accordance with the method. The method of any one of claims 41 to 44, or the method of claim 49, wherein the method comprises the steps of: cleaning the contaminated substrate, wherein the steps of the method comprise: (a) cleaning the contaminated substrate with a plurality of solid cleaning particles and a plurality of formulated particles; (b) performing the first extraction of excess water; (c) performing the first separation of the solid cleaning particles and the formulated particles; (d) Rinsing; (e) performing a second extraction of excess water; (f) repeating steps (d) and (e) at least once as appropriate; and (g) performing a second separation of the solid cleaning particles and compounding particles . A cleaning method for a cleaning apparatus, the method comprising treating an internal system of the apparatus with a formulation comprising a plurality of solid cleaning particles and a plurality of formulated particles, wherein the formulated particles comprise at least one parent material and at least one releasable material, wherein The parent material comprises at least one partially or fully water soluble polymeric material, and the at least one releasable material comprises an antimicrobial agent. A method of removing formulated particles or residues thereof from a cleaning apparatus during or after processing of the substrate, the method comprising dissolving the formulated particles. The method of claim 62, wherein the temperature or pH of the system is adjusted to dissolve the insoluble material of the formulated particles.