JP2022549738A - antibacterial particles - Google Patents

Abstract

A composition comprising a plurality of antimicrobial particles, each of the plurality of antimicrobial particles comprising (a) 25% to 99% water-soluble carrier, based on the total weight of the particle, and (b) a diphenyl ether antimicrobial agent and wherein each of said plurality of antimicrobial particles has a mass of about 1 mg to about 1 g. Preferably, each of said antimicrobial particles further comprises a perfume. More preferably, the composition is a particulate laundry detergent composition comprising said plurality of antimicrobial particles in combination with detergent particles.

Description

Through-the-wash laundry additives and fabric treatment compositions containing same.

Consumer products have evolved to address user needs for antimicrobial activity in addition to their original intended function. For example, antimicrobial laundry detergent products are desired by users because they wash fabrics as well as have an antimicrobial effect on fabrics. A wide variety of antimicrobial agents, such as, for example, diphenyl ether, are now known for use in consumer product formulations to provide antimicrobial benefits.

However, in the laundry detergent context, it is difficult to achieve the desired effectiveness of antimicrobial agents on fabrics. Specifically, during the wash cycle, most of the active ingredients, including the incorporated antimicrobial agents, are eventually washed away with the wash solution. As such, antimicrobial agents released from laundry detergents may only adhere to washed fabrics in small amounts. To compensate for this low loading rate of antimicrobial agents, manufacturers have to increase the concentration of antimicrobial agents in their laundry detergent products, which not only leads to increased costs, It also leads to environmental problems due to an increase in the amount of antibacterial agents that are washed away and released into the environment.

Additionally, certain antimicrobial agents, such as, for example, diphenyl ether, are known for use in liquid laundry detergent formulations to provide antimicrobial benefits. However, for solid granular laundry detergent products, such diphenyl ether antimicrobial agents, particularly 4-4'-dichloro-2-hydroxydiphenyl ether (commonly referred to as "Dichlosan" or tradename "Tinosan" from BASF) (commercially available under the trademark HP 100) has unfortunately been found to be less effective in antimicrobial when provided at the same concentration levels as liquid laundry detergent products. To compensate for such low antimicrobial efficacy, such antimicrobial agents must be provided at significantly higher concentration levels in granular laundry detergent products than in liquid laundry detergent products, which is costly. It is tough.

Therefore, there is a continuing need to improve the delivery efficiency and deposition rate of antimicrobial agents during the laundry process in order to maintain or improve overall antimicrobial efficacy while minimizing cost and environmental impact. .

The present invention provides a composition comprising a plurality of antimicrobial particles, each of the plurality of antimicrobial particles comprising (a) 25% to 99% water-soluble carrier, based on the total weight of the particle; ) a diphenyl ether antimicrobial agent, wherein each of said plurality of antimicrobial particles has a mass of about 1 mg to about 1 g.

Providing the same amount of antimicrobial agent, the antimicrobial particles of the present invention can be formulated to provide greater antimicrobial efficacy compared to addition to powder or liquid laundry detergent products. Without being bound by any theory, it is believed that such antimicrobial particles provide controlled/sustained release of antimicrobial agents into the wash liquor during the laundering process. Such controlled/sustained release results in lower wash liquor pH at later stages of the laundering process and lower specific antimicrobial agents (e.g., 4-4'-dichloro-2-hydroxydiphenyl ether in particular). It is particularly advantageous when exhibiting better fabric adhesion at pH.

Moreover, when provided alone as a fabric treatment product, such antimicrobial particles of the present invention provide greater dosing flexibility and more effective delivery of antimicrobial agents. Consumers can choose to overdose or underdose antimicrobial agents as desired, apart from surfactants or other cleaning actives in laundry detergent products. Consumers may also choose to add the antimicrobial particles of the present invention during certain stages of the laundry process, such as after washing or in the rinse cycle, to increase the deposition rate of such antimicrobial agents on fabrics. can be done.

Still further, such antimicrobial particles of the present invention can be readily incorporated into particulate laundry detergent compositions that also contain detergent particles. Particulate laundry detergent compositions typically have a much higher equilibrium pH than liquid laundry detergent compositions, and such a high pH environment is not beneficial for deposition of the specific antimicrobial agents discussed above. To solve this problem, it is possible to reformulate particulate laundry detergent compositions to lower the equilibrium pH, but the cost and complexity associated with such reformulations is significant. The antimicrobial particles of the present invention thus provide a simpler and more cost effective alternative solution. Without being bound by any theory, the water-soluble carrier in such antimicrobial particles functions to isolate the antimicrobial agent from the high pH environment of typical particulate laundry detergent products, thereby It is thought to improve the adhesion rate of such antibacterial agents.

Still further, improved cleaning action and better odor control action are surprisingly observed when such antimicrobial particles contain perfume ingredients. Without being bound by any theory, it is believed that the antimicrobial agents contained in such particles interact with perfume ingredients to modify the release profile and deposition of such perfume ingredients (especially perfume microcapsules) onto fabrics. It is considered to be improved.

These and other aspects of the invention will become more apparent upon reading the Detailed Description below.

Features and advantages of various embodiments of the invention will become apparent from the following description, including examples of specific embodiments intended to give a broad representation of the invention. Various modifications will become apparent to those skilled in the art from this description and practice of the invention. The scope of the invention is not intended to be limited to the particular forms disclosed, and the invention covers all modifications that fall within the spirit and scope of the invention as defined by the claims. Covers forms, equivalents, and alternatives.

The dimensions and values disclosed herein should not be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise indicated, each such dimension is intended to mean both the recited value and a functionally equivalent range enclosing that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."

As used herein, terms such as "a" and "an", as used in the claims, are understood to mean one or more of what is claimed or described. the terms "comprise", "comprises", "comprising", "contain", "contains", "containing", "Include," "includes," and "including" are all meant to be non-limiting.

The term "antimicrobial particles" refers to particles comprising one or more antimicrobial agents in a water-soluble carrier.

The term "aspect ratio" refers to the ratio of the longest dimension to the shortest dimension of a perfume particle. For example, if such perfume particles have a hemispherical or compressed hemispherical shape, the aspect ratio is the ratio of the base diameter to the height of the perfume particle.

The term "particulate laundry detergent composition" means a solid powdered or granular laundry detergent composition, preferably a flowable powdered or granular laundry detergent composition, such as an all-purpose detergent for fabrics or a heavy-duty detergent. Refers to detergents and laundry aids such as bleach activators, rinse aids, additives and pretreatment products.

The term "detergent granules" includes one or more surfactants, builders, bleach activators, enzymes, polymers, chelating agents, softeners, suds suppressors, suds boosters, brighteners, dye transfer inhibitors, and the like. refers to particles containing cleaning actives. Preferably such detergent granules comprise one or more surfactants, in particular anionic surfactants and/or nonionic surfactants.

The term "consisting essentially of" means that the composition contains less than about 10%, preferably less than about 5%, of ingredients other than the listed ingredients.

Further, the term "substantially free of" or "substantially free from" means that the specified material contains 0% to about 1% by weight, preferably 0% to about It is meant to be present in an amount of 0.5 wt%, more preferably 0 wt% to about 0.2 wt%. The term "essentially free" means that the specified material is present in an amount from 0% to about 0.1%, preferably from 0% to about 0.01% by weight, and more preferably analytically Means not present in detectable concentrations.

As used herein, all concentrations and ratios are by weight unless otherwise specified. All temperatures herein are in degrees Celsius (°C) unless otherwise indicated. All conditions herein are at 20° C. and atmospheric pressure unless otherwise specified. Unless otherwise specified, all polymer molecular weights are determined by weight average number molecular weight.

Antimicrobial Particles The compositions of the present invention comprise a plurality of antimicrobial particles, each of the plurality of antimicrobial particles comprising (a) from about 25% to about 99%, by total weight of the particles, of a water-soluble carrier; (b) a diphenyl ether antimicrobial agent, each of the plurality of antimicrobial particles having a mass of about 1 mg to about 1 g.

Preferably, each of said plurality of antimicrobial particles comprises from about 0.01% to about 3%, preferably from about 0.02% to about 2%, more preferably from about 0.02% to about 2%, based on the total weight of each said antimicrobial particle. 0.05% to about 1%, most preferably about 0.1% to about 0.5% of the diphenyl ether antimicrobial agent.

The diphenyl ether antimicrobial agents of the present invention can be either halogenated or non-halogenated, but are preferably halogenated. In a preferred embodiment, the diphenyl ether antimicrobial agent has formula (I):

（式中、
各Ｙは、塩素、臭素、又はフッ素から独立して選択され、好ましくは塩素又は臭素、より好ましくは塩素であり、
各Ｚは、ＳＯ_２Ｈ、ＮＯ_２、又はＣ_１～Ｃ_４アルキルから独立して選択され、
ｒは、０、１、２、又は３であり、好ましくは１又は２であり、
ｏは、０、１、２、又は３であり、好ましくは０、１又は２であり、
ｐは、０、１、又は２であり、好ましくは０であり、
ｍは、１又は２であり、好ましくは１であり、
ｎは、０又は１であり、好ましくは０である）のヒドロキシルジフェニルエーテルである。

(In the formula,
each Y is independently selected from chlorine, bromine or fluorine, preferably chlorine or bromine, more preferably chlorine;
each Z is independently selected from SO ₂ H, NO ₂ , or C ₁ -C ₄ alkyl;
r is 0, 1, 2 or 3, preferably 1 or 2,
o is 0, 1, 2 or 3, preferably 0, 1 or 2,
p is 0, 1 or 2, preferably 0,
m is 1 or 2, preferably 1,
n is 0 or 1, preferably 0).

In the definition of formula (I) above, 0 means nothing. For example, when p is 0, z is absent in formula (I). Each Y and each Z can be the same or different. In one embodiment, o is 1, r is 2 and Y is chlorine or bromine. In this embodiment, one chlorine atom is attached to the benzene ring while the bromine atom and the other chlorine atom are attached to the other benzene ring, or the bromine atom is attached to the benzene ring while the two chlorine atoms are attached to the other benzene ring. It is possible that it binds to the benzene ring.

More preferably, the diphenyl ether antimicrobial agent is selected from the group consisting of 4-4'-dichloro-2-hydroxydiphenyl ether, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, and combinations thereof. Most preferably, the diphenyl ether antimicrobial agent is more preferably 4-4'-dichloro-2-hydroxydiphenyl ether.

In addition to the diphenyl ether antimicrobial agents disclosed above, other antimicrobial agents may also be present, provided they are not present in concentrations that lead to destabilization of the formulation. Among other useful antimicrobial agents are chelating agents, which are particularly useful in reducing the resistance of Gram-negative microorganisms in hard water. An acid biocide may also be present.

In addition, each of the plurality of antibacterial particles of the present invention, in addition to the diphenyl ether antibacterial agent, is about 25% to about 99%, preferably about 30% to about 95%, based on the total weight of each antibacterial particle. , more preferably from about 40% to about 94%, most preferably from about 50% to about 93% of the water-soluble carrier.

A water-soluble carrier can be a material that is soluble in the wash solution in a short period of time, eg, less than about 10 minutes. Water-soluble carriers include water-soluble inorganic alkali metal salts, water-soluble alkaline earth metal salts, water-soluble organic alkali metal salts, water-soluble organic alkaline earth metal salts, water-soluble carbohydrates, water-soluble silicates, water-soluble urea, and any combination thereof.

Alkali metal salts may be selected, for example, from the group consisting of lithium salts, sodium salts, and potassium salts, and any combination thereof. Useful alkali metal salts are, for example, alkali metal fluorides, alkali metal chlorides, alkali metal bromides, alkali metal iodides, alkali metal sulfates, alkali metal bisulfates, alkali metal phosphates, alkali metal monohydrogen phosphates. acid salts, alkali metal dihydrogen phosphates, alkali metal carbonates, alkali metal monohydrogen carbonates, alkali metal acetates, alkali metal citrates, alkali metal lactates, alkali metal pyruvates, alkali metal silicates , alkali metal ascorbates, and combinations thereof.

Alkali metal salts include sodium fluoride, sodium chloride, sodium bromide, sodium iodide, sodium sulfate, sodium bisulfate, sodium phosphate, sodium monohydrogen phosphate, sodium dihydrogen phosphate, sodium carbonate, sodium hydrogen carbonate, Sodium acetate, sodium citrate, sodium lactate, sodium tartrate, sodium silicate, sodium ascorbate, potassium fluoride, potassium chloride, potassium bromide, potassium iodide, potassium sulfate, potassium bisulfate, potassium phosphate, monophosphate selected from the group consisting of potassium hydrogen phosphate, potassium dihydrogen phosphate, potassium carbonate, potassium monohydrogen carbonate, potassium acetate, potassium citrate, potassium lactate, potassium tartrate, potassium silicate, potassium, ascorbate, and combinations thereof may

Alkaline earth metal salts may be selected from the group consisting of salts of magnesium, salts of calcium, etc., and combinations thereof. Alkaline earth metal salts include alkali metal fluorides, alkali metal chlorides, alkali metal bromides, alkali metal iodides, alkali metal sulfates, alkali metal bisulfates, alkali metal phosphates, alkali metal monohydrogen phosphates , alkali metal dihydrogen phosphate, alkali metal carbonate, alkali metal monohydrogen carbonate, alkali metal acetate, alkali metal citrate, alkali metal lactate, alkali metal pyruvate, alkali metal silicate, alkali It may be selected from the group consisting of metal ascorbates, and combinations thereof. Alkaline earth metal salts are magnesium fluoride, magnesium chloride, magnesium bromide, magnesium iodide, magnesium sulfate, magnesium phosphate, magnesium monohydrogen phosphate, magnesium dihydrogen phosphate, magnesium carbonate, magnesium monohydrogen carbonate, acetic acid. Magnesium, magnesium citrate, magnesium lactate, magnesium tartrate, magnesium silicate, magnesium ascorbate, calcium fluoride, calcium chloride, calcium bromide, calcium iodide, calcium sulfate, calcium phosphate, calcium monohydrogen phosphate, dihydrogen phosphate It may be selected from the group consisting of calcium, calcium carbonate, calcium monohydrogen carbonate, calcium acetate, calcium citrate, calcium lactate, calcium tartrate, calcium silicate, calcium ascorbate, and combinations thereof.

Inorganic salts, such as inorganic alkali metal salts and inorganic alkaline earth metal salts, do not contain carbon. Organic salts, such as organic alkali metal salts and organic alkaline earth metal salts, contain carbon. The organic salt may be an alkali metal salt or an alkaline earth metal salt of sorbic acid (ie, asorbate). Sorbates may be selected from the group consisting of sodium sorbate, potassium sorbate, magnesium sorbate, calcium sorbate, and combinations thereof.

Water-soluble carriers include water-soluble inorganic alkali metal salts, water-soluble organic alkali metal salts, water-soluble inorganic alkaline earth metal salts, water-soluble organic alkaline earth metal salts, water-soluble carbohydrates, water-soluble silicates, and water-soluble urea. , and combinations thereof. Aqueous carriers include sodium chloride, potassium chloride, calcium chloride, magnesium chloride, sodium sulfate, potassium sulfate, magnesium sulfate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium acetate, potassium acetate, sodium citrate, Potassium citrate, sodium tartrate, potassium tartrate, sodium potassium tartrate, calcium lactate, water glass, sodium silicate, potassium silicate, dextrose, fructose, galactose, isoglucose, glucose, sucrose, raffinose, isomalt, xylitol, crystal sugar, colander It may be selected from the group consisting of metose, and combinations thereof. In one embodiment, the water soluble carrier may be sodium chloride. In one embodiment, the water-soluble carrier may be table salt.

Aqueous carriers include sodium bicarbonate, sodium sulfate, sodium carbonate, sodium formate, calcium formate, sodium chloride, sucrose, maltodextrin, corn syrup solids, corn starch, wheat starch, rice starch, potato starch, tapioca starch, clay, silica. acid salts, carboxymethylcellulose citrate, fatty acids, fatty alcohols, glyceryl diesters of hydrogenated tallow, glycerol, and combinations thereof.

Water-soluble carriers include water-soluble organic alkali metal salts, water-soluble inorganic alkaline earth metal salts, water-soluble organic alkaline earth metal salts, water-soluble carbohydrates, water-soluble silicates, water-soluble urea, starches, clays, water-insoluble It may be selected from the group consisting of silicates, carboxymethylcellulose citrate, fatty acids, fatty alcohols, glyceryl diesters of hydrogenated tallow, glycerol, polyethylene glycol, and combinations thereof.

Water-soluble carriers may be selected from the group consisting of disaccharides, polysaccharides, silicates, zeolites, carbonates, sulfates, citrates, and combinations thereof.

A water-soluble carrier can be a water-soluble polymer. Water-soluble polymers include polyvinyl alcohol (PVA), modified PVA; polyvinylpyrrolidone; PVA copolymers such as PVA/polyvinylpyrrolidone and PVA/polyvinylamine; partially hydrolyzed polyvinyl acetate; polyalkylene oxides such as polyethylene oxide; cellulose; alkylcellulose-based materials such as methylcellulose, ethylcellulose and propylcellulose; cellulose ethers; cellulose esters; cellulose amides; polysaccharides including starches, modified starches; gelatin; alginates; xyloglucans; pectin, xanthan, and natural gums such as carrageenan, locust bean, arabic, tragacanth; and combinations thereof. In one embodiment, the polymers are polyacrylates, especially sulfonated polyacrylates and water-soluble acrylate copolymers; Contains hydroxypropyl methylcellulose, maltodextrin, polymethacrylate. In yet another embodiment, the water-soluble polymer may be selected from PVA; PVA copolymers; hydroxypropylmethylcellulose (HPMC); and mixtures thereof.

Water-soluble carriers include polyvinyl alcohol, modified polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl alcohol/polyvinylpyrrolidone, polyvinyl alcohol/polyvinylamine, partially hydrolyzed polyvinyl acetate, polyalkylene oxide, polyethylene glycol, acrylamide, acrylic acid, cellulose, alkyl cellulose. based materials, methyl cellulose, ethyl cellulose, propyl cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids and salts, polyamino acids or peptides, polyamides, polyacrylamides, maleic/acrylic acid copolymers, polysaccharides, Starch, modified starch, gelatin, alginate, xyloglucan, hemicellulosic polysaccharides, xylan, glucuronoxylan, arabinoxylan, mannan, glucomannan, galactoglucomannan, natural gums, pectin, xanthan, carrageenan, locus bean, arabic, tragacanth, Polyacrylates, sulfonated polyacrylates, water-soluble acrylate copolymers, alkylhydroxycellulose-based materials, methylcellulose, sodium carboxymethylcellulose, modified carboxy-methylcellulose, dextrin, ethylcellulose, propylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, maltodextrins, polymethacrylates, It may be selected from the group consisting of polyvinyl alcohol polymer, hydroxypropyl methylcellulose, and mixtures thereof.

The water-soluble carrier may comprise a material selected from the group consisting of; formula H--(C ₂ H ₄ O) _x --(CH(CH ₃ )CH ₂ O) _y --(C ₂ H ₄ O) _z Polyalkylene polymers of —OH, where x is from about 50 to about 300, y is from about 20 to about 100, and z is from about 10 to about 200; formula (C ₂ H ₄ O) polyethylene glycol fatty acid ester of _q -C(O)O-( _CH2 ) _r - _CH3 , where q is from about 20 to about 200 and r is from about 10 to about 30; Polyethylene glycol fats of the formula HO--(C ₂ H ₄ O) _s --CH ₂ ) _t )--CH ₃ , where s is from about 30 to about 250 and t is from about 10 to about 30. alcohol ethers; and mixtures thereof. Formula H—(C ₂ H ₄ O) _x —(CH(CH ₃ )CH ₂ O) _y —(C ₂ H ₄ O) _z —OH, where x is from about 50 to about 300 and y is from about 20 to about 100 and z is from about 10 to about 200) can be block copolymers or random copolymers.

Water-soluble carriers may include: polyethylene glycol; formula H--(C ₂ H ₄ O) _x --(CH(CH ₃ )CH ₂ O) _y --(C ₂ H ₄ O) _z --OH, where , x is from about 50 to about 300, y is from about 20 to about 100, and z is from about ₁₀ to about ₂₀₀ ) _; O)O— ₍ CH ₂ ) _r —CH ₃ , where q is from about 20 to about 200 and r is from about 10 to about 30; ₄ O) _s —(CH ₂ ) _t )—CH ₃ where s is from about 30 to about 250 and t is from about 10 to about 30. A polyethylene glycol fatty alcohol ether.

Water-soluble carriers have the formula H—(C ₂ H ₄ O) _x —(CH(CH ₃ )CH ₂ O) _y —(C ₂ H ₄ O) _z —OH, where x is from about 50 to about 300, y is from about 20 to about 100, and z is from about 10 to about 200) from about 20% to about 80% by weight.

Water-soluble carriers have the formula (C ₂ H ₄ O) _q —C(O)O—(CH ₂ ) _r —CH ₃ , where q is from about 20 to about 200 and r is from about 10 to about 1% to about 20% by weight of polyethylene glycol fatty acid ester particles.

Water-soluble carriers have the formula HO--(C ₂ H ₄ O) _s --CH ₂ ) _t )--CH ₃ , where s is from about 30 to about 250 and t is from about 10 to about 30. from about 1% to about 10% by weight of polyethylene glycol fatty alcohol ether particles of ).

Preferably, the water-soluble carrier comprises polyethylene glycol, sodium acetate, sodium bicarbonate, sodium chloride, sodium silicate, polypropylene glycol polyoxoalkylene, polyethylene glycol fatty acid esters, polyethylene glycol ethers, sodium sulfate, starch, and mixtures thereof. may be selected from the group of More preferably, the water-soluble carrier may be polyethylene glycol (PEG). PEG is convenient for use in making particles because it can be sufficiently water soluble to dissolve during the wash cycle when the particles have a mass in the range disclosed herein. can be material. Furthermore, PEG can be easily processed as a melt. The onset of melting temperature of PEG can vary as a function of the molecular weight of PEG. PEG is relatively low cost, can be formed into many different shapes and sizes, minimizes diffusion of unencapsulated perfume, and is well soluble in water. PEG is available in various weight average molecular weights. In particularly preferred embodiments of the invention, the water-soluble carrier has a Polyethylene glycol (PEG) characterized by a weight average molecular weight (Mw) of Daltons. A particularly suitable PEG is commercially available from BASF under the trade name PLURIOL E 8000 (8000 in the trade name but a weight average molecular weight of 9000), although other PLURIOL products are also suitable.

Preferably, but not necessarily, each of the plurality of antimicrobial particles is about 0.1% to about 30%, preferably about 0.5% to about 20%, based on the total weight of each antimicrobial particle. and, more preferably, one or more perfume ingredients in an amount ranging from about 1% to about 15%. Incorporation of a perfume ingredient into the antimicrobial particles of the present invention surprisingly and unexpectedly results in a perfume ingredient not incorporated in any particle, or particles comprising a water-soluble carrier but essentially no antimicrobial agent. Improved cleansing action and better odor control action compared to incorporated perfume ingredients have been found. Without being bound by any theory, the presence of the antimicrobial agent interacts with perfume ingredients to improve the release profile and deposition of such perfume ingredients (particularly perfume microcapsules) on fabrics. considered to be obtained.

The one or more perfumes are preferably free perfumes, pro-perfumes, encapsulated perfumes (i.e. perfumes carried by carrier materials such as starches, cyclodextrins, silicas, zeolites, or clays), perfume microcapsules, and is selected from the group consisting of combinations of Preferably, the antimicrobial particles of the present invention comprise perfume microcapsules (PMC), especially friable PMC. For the purposes of the present invention, the term "perfume microcapsules" or PMCs encompasses both perfume microcapsules and perfume nanoparticles. In one embodiment, the PMC comprises a melamine/formaldehyde shell commercially available from Appleton, Quest International, International Flavors & Fragrances or other suitable sources. In a preferred embodiment, the PMC shell is coated with a polymer to enhance the PMC's ability to adhere to fabrics. The antimicrobial particles of the present invention contain from about 0.1% to about 20%, preferably from about 1% to about 15%, more preferably from about 5% to about 10%, based on the total weight of each of the antimicrobial particles. It may contain perfume microcapsules. In particularly preferred embodiments, each of the antimicrobial particles comprises a combination of free perfume and perfume microcapsules. More preferably, the weight ratio of free perfume to perfume microcapsules in each said antimicrobial particle is from about 1:5 to about 20:1, preferably from about 1:2 to about 10:1, more preferably about 1:1. to about 5:1, most preferably from about 1.5:1 to about 3:1.

Preferably, but not necessarily, each of the plurality of antimicrobial particles further comprises a quaternary ammonium compound to provide additional fabric softening action. Specifically, the quaternary ammonium compounds, when released from the antimicrobial particles of the present invention during washing, adhere to the fabric fibers from the wash liquor, providing a softness sensation to the consumer. For example, each of the plurality of antimicrobial particles is about 5% to about 45%, preferably about 10% to about 40%, more preferably about 15% to about 35%, based on the total weight of each antimicrobial particle. The quaternary ammonium compounds are formed from parent fatty acid compounds having an iodine number of from about 18 to about 60, preferably from about 20 to about 60. Preferably, the quaternary ammonium compound is an ester quaternary ammonium compound, more preferably di-(tallowyloxyethyl)-N,N-methylhydroethylammonium methylsulfate.

In addition to the quaternary ammonium compounds described above, the antimicrobial particles of the present invention may further include a cationic polymer that promotes adhesion of the quaternary ammonium compound to fabrics and softens the fabrics. functions to improve the performance of Each of the plurality of antimicrobial particles may contain from about 0.5% to about 10%, preferably from about 1% to about 5%, of such cationic polymer, based on the total weight of each antimicrobial particle. The cationic polymer is preferably a cationic polysaccharide, more preferably a polymeric quaternary ammonium salt of hydroxyethylcellulose reacted with an epoxide substituted with trimethylammonium groups. More preferably, the weight ratio of quaternary ammonium compound to cationic polymer in each such particle is from about 3:1 to about 30:1, optionally from about 5:1 to about 15:1, optionally about 5:1. It can range from 1 to about 10:1, optionally about 8:1. Without wishing to be bound by theory, the mass fraction of quaternary ammonium compound and the mass fraction of cationic polymer may provide assistance from the cationic polymer to transfer the quaternary ammonium to the treated fabric. A sufficient level of deposition of the compound is deposited.

To provide a consumer-preferred aesthetic appearance or a visual cue emphasizing a particular ingredient or benefit, each of the plurality of antimicrobial particles, based on the total weight of each of the antimicrobial particles, contains about 0.0001 % to about 1%, preferably about 0.001% to about 0.5%, more preferably about 0.005% to about 0.1% of one or more colorants. Colorants may be selected from the group consisting of dyes, pigments, and combinations thereof. Preferably, the colorant imparts a color to the antimicrobial particles selected from the group consisting of blue, green, yellow, orange, pink, red, purple, gray, and the like.

The antimicrobial particles of the present invention may further comprise water-soluble or water-dispersible fillers such as sodium chloride, sodium sulfate, sodium carbonate, sodium bicarbonate, sugars, starches, modified cellulose, silica, zeolites, clays, and the like. Preferably, each of the particles may contain from about 0.1% to about 7% clay based on the total weight of each such particle. More preferably the clay is bentonite.

It is particularly preferred that the antimicrobial particles of the present invention are substantially free or essentially free of surfactants. This is because the presence of such surfactants can accelerate the dissolution or dispersion of the antimicrobial agent in water and reduce adhesion to fabrics, which is undesirable in the context of the present invention. . More preferably, the antimicrobial particles of the present invention are substantially free or essentially free of any cleaning actives.

The antimicrobial particles of the present invention preferably contain less than about 10%, optionally less than about 8%, optionally less than about 5%, optionally less than about 3% water by total weight of each of the antimicrobial particles. include. It is believed that reducing or having water content in these ranges results in more stable particles. It is believed that the smaller the mass fraction of water, the more stable the particles.

Each antimicrobial particle of the present invention has a mass of about 1 mg to about 1 g, preferably about 5 mg to about 500 mg, more preferably about 10 mg to about 250 mg, most preferably about 15 mg to about 125 mg.

The particles can be formed into tablets, pills, spheres, and the like. They are selected from the group consisting of spheres, hemispheres, compressed hemispheres, cylinders, discs, circles, lentils, ovals, cubes, rectangles, stars, flowers, and any combination thereof. It can have any shape. A lentil shape refers to the shape of a lentil. A compressed hemispherical shape refers to a shape corresponding to a hemispherical shape that is at least partially flat such that the curvature of the curved surface is, on average, less than the curvature of a hemispherical shape having the same radius. Compressed hemispherical particles have an aspect ratio of from about 2.0 to about 5, alternatively from about 2.1 to about 4.5, alternatively from about 2.2 to about 4 (i. base diameter ratio). Elliptical particles refer to particles having a largest dimension and a secondary dimension orthogonal to the largest dimension, wherein the ratio of the largest dimension to the secondary dimension is greater than about 1.2, preferably greater than about 1.5, More preferably greater than about two. Preferably, the antimicrobial particles of the present invention have a hemispherical or compressed hemispherical shape.

Preferably, the antimicrobial particles have a longest dimension of about 3 mm to about 10 mm, preferably about 4 mm to about 9 mm, more preferably about 5 mm to about 8 mm, and/or about 1 to about 5, preferably about 1.5 to It features an aspect ratio of about 4, more preferably about 2 to about 4.

In a preferred but not essential embodiment of the invention, the antimicrobial particles of the invention have a density lower than that of water, allowing them to float on water and to be more noticeable to the consumer during cleaning. For example, such antimicrobial particles may be from about 0.5 g/cm3 to about 0.98 g/cm3, preferably from about 0.7 g/cm3 to about 0.95 g/cm3, more preferably from about 0.8 g/cm3 to about It may have a density in the range of 0.9 g/cm3.

A plurality of antimicrobial particles of the present invention can have different shapes, sizes, masses and/or densities.

Use of Antimicrobial Particles in Standalone Particulate Products Particulate products, especially fine particles that are not dusts, are preferred by many consumers. The particulate product can be easily loaded by the consumer directly from the package into the washing machine or into the loading compartment of the washing machine. Alternatively, the consumer can dose the particulate product from the package into a dosing cup, optionally provided with one or more dosing indicia, and then doze the particles into the dosing compartment of the washing machine or directly into the drum. . For products where a dosing cup is used, particulate products tend to be less soiled than liquid products.

A plurality of the antimicrobial particles described above can be provided as a stand-alone particulate product for through-the-wash fabric treatment that is convenient for the consumer to load into the washing machine. A stand-alone particulate product may consist essentially of the antimicrobial particles of the present invention, or other particles similar to the antimicrobial particles, such as containing little or no surfactant, or similar in size to the antimicrobial particles. of perfume particles, softener particles, bleach particles, and the like. A stand-alone particulate product may be provided in a package separate from the package of the detergent composition. Having the antimicrobial particles in a package separate from the detergent composition package can be beneficial in that the consumer can choose the amount of antimicrobial agent to be dosed, regardless of the amount of detergent composition used. . This gives the consumer the opportunity to customize the amount of antimicrobial agent used according to their needs and thereby the resulting antimicrobial action, which is a very valuable benefit to the consumer.

Particulate Laundry Detergent Products Comprising Antimicrobial Particles In a preferred but not essential embodiment of the present invention, the antimicrobial particles of the present invention are present in a particulate laundry detergent composition that also comprises detergent particles. Preferably, the plurality of antimicrobial particles are present in the particulate laundry detergent composition as a minor portion, e.g. is present in an amount ranging from about 0.1% to about 20%, more preferably from about 0.5% to about 15%, and most preferably from about 1% to about 10%.

The particulate laundry detergent composition comprises from about 10% to about 99.9%, preferably from about 20% to about 95%, more preferably from about 30% to about It may contain detergent particles in an amount ranging from 90%, most preferably from about 40% to about 80%. The detergent particles of the present invention contain one or more surfactants, builders, bleach activators, enzymes, polymers, chelating agents, softeners, suds suppressors, suds boosters, brighteners, dye transfer inhibitors, and the like. It may contain cleaning actives. The detergent particles can be spray dried particles and/or agglomerated particles and/or extruded particles. Such detergent particles include surfactant particles (including surfactant agglomerates, surfactant extrudates, surfactant needles, surfactant noodles, surfactant flakes); polymer particles (e.g. cellulosic polymers); particles, polyester particles, polyamine particles, terephthalate polymer particles, polyethylene glycol polymer particles, etc.); builder particles (e.g. sodium carbonate and sodium silicate co-builder particles, phosphate particles, zeolite particles, silicate particles, carbonate filler particles (e.g. sulfate particles); dye transfer inhibitor particles; dye fixative particles; bleaching agent particles (e.g. percarbonate particles, especially carbonates, sulfates, silicates, Bleaching catalyst particles such as coated percarbonate particles, such as percarbonate coated with borosilicate or any combination thereof, perborate particles, transition metal bleach catalyst particles or oxaziridinium bleach catalyst particles , preformed peracid particles, especially coated preformed peracid particles, and co-bleach particles of a bleach activator and a source of hydrogen peroxide and optionally a bleach catalyst); benzenesulfonate bleach activator particles and tetraacetylethylenediamine bleach activator particles); chelator particles (e.g. chelator aggregates); tinting dye particles; brightener particles; enzyme particles (e.g. protease globules, lipase globules, cellulase globules, amylase globules, mannanase globules, pectate lyase globules, xyloglucanase globules, bleaching enzyme globules, cutinase globules, and co-globules of any of these enzymes); clay particles; (such as montmorillonite particles, or particles of clay and silicone); flocculant particles (such as polyethylene oxide particles); wax particles (such as wax agglomerates).

Preferably, such detergent particles comprise from about 10% to about 90%, preferably from about 15% to about 80%, more preferably from about 20% to about 70%, based on the total total weight of the detergent particles. Surfactant particles comprising a surfactant. More preferably, the surfactant is selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants and combinations thereof. be done. Most preferably, the detergent granules of the present invention contain anionic surfactants and/or nonionic surfactants.

The detergent particles of the present invention can be characterized by a median weight particle size (Dw50) of from about 250 μm to about 1000 μm, preferably from about 300 μm to about 950 μm, more preferably from about 400 μm to about 850 μm. Preferably, such detergent particles have a white or light colored appearance, while the antimicrobial particles are blue, green, yellow, orange, pink, blue, green, yellow, orange, pink, etc. to provide visual contrast with the detergent particles. It has a red, purple or gray color.

In addition to the aforementioned antimicrobial particles and detergent particles, the particulate laundry detergent compositions of the present invention may contain one or more detergent ingredients. Suitable detergent ingredients include anionic detersive surfactants, nonionic detersive surfactants, cationic detersive surfactants, zwitterionic detersive surfactants, amphoteric detersive surfactants, and any combination thereof. polyester soil release polymers such as carboxylate polymers, polyethylene glycol polymers, terephthalate polymers; amine polymers; cellulosic polymers; Dye-fixing polymers such as oligomers, polymers comprising hexamethylenediamine derivative polymers, optionally in a 1:4:1 ratio, and any combination thereof; zeolites, phosphates, citrates, and any combination thereof. buffers and alkalinity sources, including carbonates and/or silicates; fillers, including sulfates and bio-filler materials; bleach activators, sources of available oxygen, preformed peracids, bleach catalysts , reducing bleaches, and any combination thereof; chelating agents; photobleaching agents; hueing agents; brightening agents; enzymes, including cutinase, and any combination thereof; fabric softeners, including clays, silicones, quaternary ammonium fabric softeners, and any combination thereof; flocculating agents such as polyethylene oxide; perfumes encapsulated in starch Perfumes including accords, perfume microcapsules, perfume-filled zeolites, Schiff base reaction products of ketone perfume raw materials with polyamines, blooming perfumes, and any combination thereof; soap rings, lamellar aesthetic particles, gelatin beads, carbonates and/or or aesthetic agents comprising sulfate speckles, clays, and any combination thereof; and any combination thereof.

In preferred embodiments of the present invention, the particulate laundry detergent composition contains from about 1% to about 40%, typically from about 2% to 25%, by weight of the total weight of such composition. or even one or more builders (not including carbonates as described above) in amounts ranging from about 5% to about 20%, or from 8% to 15% by weight. Builders, as used herein, improve the cleaning efficiency of surfactants by, for example, removing or reducing "free" calcium/magnesium ions in the cleaning solution and "softening" or reducing the hardness of the cleaning solution. Refers to any ingredient or component that can be enhanced or improved.

It is particularly desirable for such particulate laundry detergent compositions to have relatively low levels of phosphate, zeolite, and silicate builders. Preferably, it contains a total of up to 15% by weight of phosphate builder, zeolite builder and silicate builder. More preferably, such particulate laundry detergent compositions contain, based on the total weight of the composition, from 0% to about 5% phosphate builder, from 0% to about 5% zeolite builder, and from 0% to about 10% by weight of silicate builders, the total amount of these builders being no more than 10% by weight. Even more preferably, the particulate laundry detergent composition comprises, based on the total weight of the composition, from 0% to about 2% phosphate builder, from 0% to about 2% zeolite builder, and from 0% % to about 2% by weight of silicate builders, the total amount of these builders being no more than 5% by weight. Most preferably, the particulate laundry detergent composition comprises from 0% to about 1% phosphate builder, 0% to about 1% zeolite builder, and 0% by weight, based on the total weight of the composition. % to about 1% by weight of silicate builders, the total amount of these builders being no more than 2% by weight. The composition may further comprise any other co-builder, chelating agent, or generally any material that removes calcium ions from solution, such as by sequestration, complexation, precipitation, or ion exchange. In particular, the composition may comprise a material having a calcium binding capacity of at least 50 mg/g and a calcium binding constant log K Ca ²⁺ of at least 3.50 at a temperature of 25° C. and an ionic strength of 0.1 M.

The particulate laundry detergent compositions of the present invention may contain one or more solid carriers selected from the group consisting of sodium chloride, potassium chloride, sodium sulfate, and potassium sulfate. In preferred but not required embodiments, such particulate laundry detergent compositions comprise from about 20% to about 65% by weight sodium chloride and/or from about 20% to about 65% by weight sodium sulfate. When the particulate laundry detergent composition is in concentrated form, the total amount of sodium chloride and/or sodium sulfate in such composition can be, for example, from about 0% to about 60% total weight.

Methods of Using the Antimicrobial Particles The antimicrobial particles of the present invention are particularly useful in machine wash or hand wash fabric treatments to provide antimicrobial action and, optionally, improved fabric cleanliness and odor control action. be. These allow the consumer to obtain antimicrobial activity throughout the wash, especially the wash subcycle. By providing antimicrobial action during the wash subcycle, the consumer need only place the detergent composition and antimicrobial particles in a single location, such as the wash tub, before or immediately after starting the washing machine.

A method for treating clothing may include providing the clothing to a washing machine. Clothing items come into contact with a composition comprising a plurality of antimicrobial particles disclosed herein during the wash subcycle of a washing machine. The particles can dissolve in water provided as part of the wash subcycle to form a liquor. Dissolution of particles can occur during the wash subcycle.

A washing machine has at least two basic sub-cycles within its operating cycle: a wash sub-cycle and a rinse sub-cycle. The wash sub-cycle of the washing machine is the cycle of the washing machine that begins when the wash tub is first filled or partially filled with water. The main purpose of the wash subcycle is to remove or lift soil from the garment and suspend this soil in the wash liquor. Typically, the wash liquid is drained at the end of the wash subcycle. The rinse sub-cycle of the washing machine occurs after the wash sub-cycle and has the primary purpose of rinsing the soil, optionally with any benefit agents provided to the wash sub-cycle from the garments.

The method may optionally include the step of contacting the garment during the wash subcycle with a detergent composition comprising an anionic surfactant. Most consumers provide the detergent composition to the wash tub during the wash subcycle. Detergent compositions may include anionic surfactants and optionally other benefit agents including, but not limited to, fragrances, bleaches, brighteners, tinting dyes, enzymes, and the like. During the wash sub-cycle, benefit agents provided with the detergent composition are contacted with or applied to the garments placed in the wash bath. Typically, the benefit agent of the detergent composition is dispersed in the water and benefit agent wash liquor.

During the wash sub-cycle, the wash bath may be filled with water or at least partially filled with water. The antimicrobial particles can be dissolved in water to form a cleaning solution containing the constituents of the particles. Optionally, if a detergent composition is used, or if antimicrobial particles are incorporated into a particulate laundry detergent composition, the wash liquor may contain components of the detergent composition and dissolved particles. The particles can be placed in the wash tub of the washing machine before the clothes are placed in the wash tub of the washing machine. The particles can be placed in the wash tub of the washing machine after the articles of clothing have been placed in the wash tub of the washing machine. The particles can be placed in the wash tank before filling or partially filling the wash tank with water, or after filling the wash tank with water is complete.

When the detergent composition is used by a consumer in practicing the method of treating clothing, the detergent composition and granules may be provided in separate packages. For example, the detergent composition can be a liquid detergent composition provided from a bottle, sachet, water-soluble pouch, throw-in cup, throw-in bowl, or cartridge associated with a washing machine. Particles can be provided from individual packages such as, by way of non-limiting example, cartons, bottles, water-soluble pouches, drop-in cups, sachets, and the like. When the detergent composition is in a solid form such as a powder, a water-soluble fibrous substrate, a water-soluble sheet, a water-soluble film, a water-soluble film, a water-insoluble fibrous web carrying the solid detergent composition, the particles are solid detergent. can be provided with the composition. For example, particles can be provided from a container containing a mixture of solid detergent composition and particles. Optionally, the particles can be provided from pouches formed with the detergent composition, which are water-soluble fibrous substrates, water-soluble sheets, water-soluble films, water-soluble films, water-insoluble fibrous webs carrying the solid detergent composition. .

The wash liquor used to dissolve the antimicrobial particles and treat the fabrics has a pH value selected to be most suitable for the fabrics to be washed, e.g. It can have a range of pH. The water temperature preferably ranges from about 5°C to about 100°C. The water to fabric ratio is typically from about 1:1 to about 30:1. The cleaning fluid may comprise 40 liters or less of water, or 30 liters or less, or 20 liters or less, or 10 liters or less, or 8 liters or less, or even 6 liters or less. The cleaning fluid may contain more than 0 to 15 liters, or 2 to 12 liters, or even 8 liters or less of water. For dilute wash conditions, the wash solution may comprise 150 liters or less of water, 100 liters or less of water, 60 liters or less of water, or 50 liters or less of water, particularly for hand wash conditions, depending on the number of rinses. .

Typically, 0.01 Kg to 2 Kg of fabric per liter of wash liquor is introduced into the wash liquor. Typically from 0.01 Kg, or from 0.05 Kg, or from 0.07 Kg, or from 0.10 Kg, or from 0.15 Kg, or from 0.20 Kg, or from 0.25 Kg per liter of cleaning liquid , up to 1.8 Kg, or up to 1.6 Kg, or up to 1.5 Kg, or up to 1.3 Kg, or up to 1.1 Kg, or up to 0.9 Kg, or up to 0.7 Kg, or up to 0.5 Kg Pour into cleaning solution.

Production of Antimicrobial Particles For carriers that can be conveniently processed as a melt, a rotoforming process can be used. A mixture of molten carrier and other materials that make up the particles is prepared, for example, in a batch process or a continuous mixing process. The molten mixture can be pumped through a rotoformer, for example a Sandvik ROTOFORM 3000 with a belt of width 750 mm and length 10 m. The rotoforming device can have a rotating cylinder. The cylinder may have 2 mm diameter holes set at 10 mm spacing in the cross machine direction and 9.35 mm spacing in the machine direction. The cylinder may be set approximately 3 mm above the belt. The belt speed and cylinder rotation speed can be set at about 10 m/min. The molten mixture can pass through openings in the rotating cylinder and be deposited on a moving conveyor provided below the rotating cylinder.

The molten mixture can be cooled on a moving conveyor to form a plurality of solid particles. Cooling may be provided by ambient cooling. Optionally, cooling may be provided by spraying normal or cold water on the underside of the conveyor.

Once the particles are sufficiently cohesive, they may be transferred from the conveyor to processing equipment downstream of the conveyor for further processing and/or packaging.

Optionally, the particles can be provided containing a gas. Such gas occlusion, such as air occlusion, can help the particles dissolve more quickly during cleaning. Gas storage can be effected, as a non-limiting example, by injecting gas into the molten precursor material and pulverizing the mixture.

Particles can also be made using other approaches. For example, granulation or press agglomeration may be suitable. In granulation, a precursor material containing the constituent materials of the particles is consolidated and homogenized by a rotary mixing tool and granulated to form particles. Particles of a wide variety of sizes can be produced for the substantially water-free precursor material.

In compression agglomeration, a precursor material containing the constituent materials of the particles is compacted under pressure and under the influence of shear to plasticize and homogenize before being subjected to compression agglomeration by a forming/shaping process. - release from the aircraft. Press agglomeration techniques include extrusion, molding by roller compaction, pelletizing, and tabletting.

The precursor material containing the constituent materials of the particles can be delivered to a planetary roll extruder or a twin screw extruder with co-rotating or counter-rotating screws. The barrel and extrusion granulation head can be heated to the desired extrusion temperature. Consolidating and plasticizing the precursor material containing the constituent materials of the particles under pressure and extruding in the form of threads through a multi-hole extrusion die in the extruder head and sizing using cutting blades. can be done. The hole diameter of the extrusion header may be selected to provide appropriately sized particles. The extruded particles can be shaped using a spheronizer to provide particles having a spherical shape.

Optionally, the extrusion and compression steps may be performed in a low pressure extruder such as, for example, a flat die pelletizing press available from Amandus Kahl, Reinbek, Germany. Optionally, the extrusion and compression steps may be performed in a low pressure extruder such as BEXTRUDER available from Hosokawa Alpine Aktiengesellschaft, Augsburg, Germany.

Particles can be made using molding by roller compaction. In molding by roller compaction, a precursor material containing the constituent material of the particles is introduced between two rollers and rolled under pressure between the two rollers to form a sheet of compact. The rollers provide a high linear pressure on the precursor material. The rollers can be heated or cooled as desired, depending on the processing characteristics of the precursor material. The sheet of consolidate is divided into small pieces by cutting. The pieces can be further shaped, for example, by using a spheronizer.

TEST METHODS To fully appreciate the invention described and claimed herein, the following techniques were used to determine the properties of the perfume granules, detergent granules, and particulate laundry detergent compositions of the present invention. should be used.

Test 1: Antimicrobial Test The antimicrobial efficacy of a sample granular laundry detergent composition is determined as follows.
Each defined sample of granular laundry detergent composition to be tested (eg, 15.29 g) is dissolved in 1 L of water at a water hardness level of 342 mg/L. Such water is formed by dissolving 0.034 g CaCl ₂ and 0.139 g MgCl ₂ .6H ₂ O in 1 L of deionized (DI) water. After the solution was mixed with a magnetic stirrer for about 4 minutes, it was subjected to the "Degerming Test Method for Laundry Detergent" published by the Japanese Detergent and Soap Fair Trade Council. Dispense 265 ml of such solution into the exposure chamber of the wash tumbler as described in .

Separately, a stainless steel spindle bends a single continuous piece of stainless steel wire about 1/16 inch in diameter to create three horizontal extensions, each about 2 inches long, which are lengthened by about 1/16 inch. It is made up of two 2 inch verticals joined together. The spindle is used as a carrier for wrapping the cloth ballast.

About 300 g of cotton cloth is then boiled and rinsed with 3 L of distilled or DI water containing about 1.5 g sodium carbonate and about 1.5 g non-ionic wetting agent for 1 hour. The fabric is then rinsed with boiling water and then cold water until all visual traces of foam formed by the wetting agent are gone. The fabric is then drained and allowed to air dry at ambient temperature for at least 24 hours. The washed and dried fabric is then cut into strips each about 2 inches wide and weighing about 15±0.1 g. A piece of such a cotton cloth strip is then taken and one end is fixed to the outer horizontal extension of the stainless steel spindle. This cotton fabric strip is wrapped around the three horizontal extensions of the spindle with sufficient tension, about 12-13 turns, until the entire fabric strip is wrapped around the spindle. Staples or pins can be used to secure the loose ends of the fabric strips. The fabric-wrapped spindles can then be sterilized in the individual exposure chambers of the washing tumblers described above, or separately from the exposure chambers. Both the fabric wrapped around the spindle and the exposure chamber must be dry before the spindle is placed in the exposure chamber.

The fabric-wrapped spindle is then placed in the exposure chamber of a wash tumbler containing 265 ml of the wash solution previously described. The exposure chamber is then agitated at a speed of about 60 rpm for about 20 minutes. After 20 minutes of agitation, spin dry the fabric-wrapped spindle for about 2 minutes and discard the wash solution. Subsequently, 265 ml of fresh hard water as described above is dispensed into the same exposure chamber to rinse the fabric-wrapped spindle. After agitating the exposure chamber for an additional 3 minutes at the same agitation speed, the spindle with the fabric wrapped around it is spun dry again for approximately 2 minutes, after which the rinse solution is discarded. The fabric-wrapped spindle is rinsed again using the same procedure as before and spun dry.

The cotton cloth strip is then removed from the spindle and allowed to air dry overnight at ambient temperature. The dried cotton cloth strips are then cut into 2 cm x 2 cm squares and ten such cotton cloths are stacked to form one test specimen. Its weight is about 0.40±0.05 g.

Such specimens are then subjected to the "Bacteriostatic Activity Evaluation" described in Section 8.1 of the Japanese Industrial Standards (JIS) L1902-2015 standard, while 8.1.4 .Calculate the number of bacteria according to section 5.2 (instead of calculating the amount of ATP described in section 8.1.4.5.3).

Test 2: Dissolution Rate Test The "Dissolution Rate Test" is used to measure the dissolution rate of particles.

The test is performed by adding 400 ml of deionized water to a 400 ml clear glass beaker at room temperature (25° C.) and then dispersing approximately 1 g of the test particles in the deionized water. Using a stopwatch, count the total time required before the particles are completely dissolved.

Test 3: Particle Aspect Ratio For non-spherical particles, vernier calipers can be used to measure the longest and shortest dimensions of the particle. To reduce data variability, typically 10 particles can be measured and the average result used. Particle aspect ratios herein are calculated using the following formula: aspect ratio = longest dimension/shortest dimension.

Test 4: Perfume Bloom and Fabric Cleanliness Test The Dissolving Head-Space Count test is used to demonstrate the improved bloom and fabric cleaning action of perfume. This is in many ways similar to the conditions that can occur when a consumer uses particles to treat laundry.

In the dissolution headspace count test method, the particles to be tested are placed in distilled water and the amount of perfume raw material (PRM) migrated into the air in the headspace above the water surface is measured as counts at various times. Lysed headspace counts are measured using a 7100 Ultra Fast GC Analyzer MicroSense5 ZNOSE with accompanying software MicroSense version 5.37 (available from Electronic Sensor Technology, Newbury Park, Calif., USA). This instrument system is a compact high-speed gas chromatograph that includes a gas chromatographic sensor, pneumatic controls, and supporting electronics. The gas chromatographic sensor is based on a 6-port valve and oven, a preconcentration trap, a short gas chromatographic column, and a surface acoustic wave detector. A system controller based on a laptop computer operates the system, analyzes data, and provides the user interface. Details on how to use the ZNOSE can be found in the 7100 Ultra Fast GC Analyzer Operation Manual MicroSense 5. To perform the dissolution headspace count test, set ZNOSE to: 5 ps2a1b_35 (DBS column); 1 second pump sample time; 0.5 second data collection; Heat up at a rate of 5°C/5cc; surface acoustic wave detector set at 35°C. A total of 20 g of 25° C. deionized (DI) water is added to a clean 40 ml sample bottle (such as VWR scientific cat. #EP 140-40C). A total of 0.040 g of test particles or a 0.040 g portion of test particles is added to 20 g of water in a sample bottle to provide a sample of test particle material at a concentration of 2.0 mg/mL in DI water. After adding the test particle material, a 3 mm thick PTFE silicone septum is secured to the sample vial and the ZNOSE inlet needle, along with another needle attached to the carbon filter, is immediately inserted into the headspace of the sample vial. ZNOSE measurements are made every 90 seconds and are continued for at least 45 minutes at ambient room temperature between 22°C and 27°C without any agitation of the sample or vial. Headspace counts for each PRM are recorded for each 90 second measurement time point. The lysed headspace count reported at a given time point is the sum of the counts of all PRMs detected in the headspace at that time point.

The dissolved headspace count is a function of the concentration in the headspace of the particular perfume raw material under consideration. The higher the headspace count, the higher the concentration of perfume in the headspace.

The examples described herein are meant to illustrate the invention, but are not used to limit or otherwise define the scope of the invention.

Example 1 Antimicrobial Particles The following are exemplary antimicrobial particles AE according to the present invention.

^１ＢＡＳＦからＴｉｎｏｓａｎ（登録商標）ＨＰ１００として提供される。１，２－プロピレングリコールの溶液中に４－４’－ジクロロ－２－ヒドロキシジフェニルエーテルを３０％含有している。本明細書で提供される濃度は、純粋な活性レベルであり、原料レベルではない。
^２Ｃ１８不飽和ＤＥＥＨＭＡＭＳ（ジエチルエステルヒドロキシエチルメチルアンモニウムメチルサルフェート）ＥＶＯＮＩＫ製。ヨウ素価は約４２である。
^３ダウケミカルから入手可能なポリマーＰＫ。重量平均分子量４００ｋＤａ、電荷密度０．１８、及び無水グルコース（anydroglucose）繰り返し単位当たりの窒素の平均重量パーセント０．２８％のカチオン性ヒドロキシエチルセルロースである。

¹ Supplied as Tinosan® HP100 from BASF. It contains 30% of 4-4'-dichloro-2-hydroxydiphenyl ether in a solution of 1,2-propylene glycol. The concentrations provided herein are pure active levels, not raw material levels.
² C18 unsaturated DEEHMAMS (diethyl ester hydroxyethylmethylammonium methylsulfate) from EVONIK. The iodine number is about 42.
³ Polymer PK available from Dow Chemical. It is a cationic hydroxyethyl cellulose with a weight average molecular weight of 400 kDa, a charge density of 0.18, and an average weight percent of nitrogen per anhydroglucose repeat unit of 0.28%.

Example 2: Antimicrobial Particles in Particulate Laundry Detergent Products The inventive antimicrobial particles of Example 1 are incorporated into particulate laundry detergent products of Formulations IV below.

^１実施例１の本発明の抗菌ビーズＡ～Ｅのいずれか１つ又はこれらの混合物。

¹ Any one of the inventive antimicrobial beads AE of Example 1 or mixtures thereof.

Example 3: Comparative study demonstrating higher deposition rates of antimicrobial agents when incorporated into antimicrobial beads A sample of the present invention (Sample A) is provided comprising antimicrobial particles of the present invention. A comparative sample (Sample B) containing particles (no antimicrobial agent) and another antimicrobial agent (not incorporated into the particles) is also provided.

Specifically, Sample A contained 13.5 grams of antimicrobial particles formed by 13.42 grams of PEG9000 and 0.08 grams of Tinosan® HP100. The antimicrobial particles of sample A are made by the following procedure:
- Pre-melt the PEG 9000 material in an oven at 75°C overnight;
- Weigh molten PEG 9000 material in a 250 mL beaker;
• Weigh 4-4'-dichloro-2-hydroxydiphenyl ether antimicrobial agent in the same beaker;
- Place the beaker in a water bath at 85°C;
- Mix the contents in the beaker with a blender (4-blade agitator) for 10 minutes at a speed of 250 RPM;
- Transfer the mixture into a bead mold;
- The mold is left at room temperature so that the mixture in the mold cools and solidifies;
• Collect the solidified antimicrobial beads from the mold.

Sample B separately contained 13.42 grams of PEG9000 particles and 0.08 grams of Tinosan® HP100. The PEG9000 particles of Sample B are formed by the following procedure:
- Pre-melt the pre-melted material PEG 9000 in an oven at 75°C overnight;
- Preheat the mold and scraper in an oven at 75°C;
- Transfer the molten PEG 9000 material to the preheated mold;
- Leave the mold at room temperature so that the molten PEG 9000 material in the mold cools and solidifies;
• Recover the solidified PEG 9000 beads from the mold.

Samples A and B are then used to treat fabrics, respectively, according to the following laundering conditions.
Washing machine: Haier Dual Agitation TLA 1466
Wash cycle: 2 minutes dissolution / 10 minutes soak / 15 minutes wash / 4 minutes rinse*2 / spin dry Load size: 1.7 kg total including 4 sheets of CW98 (cotton) (new cotton: new polyester 8:2)
Hardness: 9 gpg Ca:Mg=4:1
HMI:Fe:Cu:Mn 6:1:4
Water temperature: 25°C

Four pieces of CW98 cotton (10×10 cm) from each wash were hung to dry and analyzed for deposition of 4-4′-dichloro-2-hydroxydiphenyl ether.

Specifically, 4-4'-dichloro-2-hydroxydiphenyl ether is extracted from fabric by using methanol with ASE (Accelerate Solvent Extraction). Approximately 3 g of fabric is accurately weighed and filled into a steel ASE tube followed by an extraction protocol using methanol as the extraction solvent at 100° C., 2000 psi for 5 minutes. The extracted contents are collected, transferred to a 25 ml flask, made up to volume with methanol and then diluted 25-fold with an additional 50:50 methanol:water to prepare the injection sample.

Injected samples are then subjected to gradient reversed phase high performance liquid chromatographic (HPLC) separation on a C18 column and quantified by a tandem mass spectrometer (MS/MS) operating under multiple reaction monitoring (MRM) conditions in negative mode. The LC-MS/MS test involved injecting 5 ul of injection sample, which was run on a Waters Acquity UPLC C18 column for 3 minutes in 70% mobile phase A (1% formic acid in water)/30% mobile phase B (0 in methanol). .1% formic acid) to 5% mobile phase A/95% mobile phase B, with the final gradient maintained for an additional 3 minutes. Antimicrobial agent 4-4'-dichloro-2-hydroxydiphenyl ether is detected in negative MRM mode. Ion pairs with m/z 253>142 are used as quantitative transitions and m/z with 253>125 are used as identifications.

For standard curve generation, spiked matrix standards ranging from 0.5 g/ml to 500 ng/ml are injected. The concentration of 4-4′-dichloro-2-hydroxydiphenyl ether in the injected sample is determined by back calculation using a weighted (1/x ² ) quadratic regression of the calibration curve.

The results of deposition of 4-4'-dichloro-2-hydroxydiphenyl ether on fabrics treated with Sample A and Sample B are as follows.

The above results show that the adhesion rate of 4-4′-dichloro-2-hydroxydiphenyl ether is significantly higher when it is incorporated into particles and when it is added separately. is shown.

The dimensions and values disclosed herein should not be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise indicated, each such dimension is intended to mean both the recited value and a functionally equivalent range enclosing that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm."

All documents cited herein, including any cross-referenced or related patents or patent applications and any patent applications or patents to which this application claims priority or benefit, exclude or limit Unless otherwise stated, all of which are incorporated herein by reference. Citation of any document is not considered prior art to any invention disclosed or claimed herein, or taken alone or in combination with any other reference(s) Any such invention is not considered to teach, suggest or disclose at times. Further, if any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition given to that term in this document shall control. shall be

While specific embodiments of the invention have been illustrated and described, it will be apparent to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims (11)

A composition comprising a plurality of antimicrobial particles, each of said plurality of antimicrobial particles comprising:
a) from 25% to 99% of a water-soluble carrier relative to the total weight of the particles;
b) a diphenyl ether antimicrobial agent,
The composition, wherein each of said plurality of antimicrobial particles has a mass of 1 mg to 1 g. Each of the plurality of antimicrobial particles is 0.01% to 3%, preferably 0.02% to 2%, more preferably 0.05% to 1%, most preferably 0.05% to 1%, based on the total weight of each antimicrobial particle Preferably 0.1% to 0.5% of said diphenyl ether antimicrobial agent, said diphenyl ether antimicrobial agent is preferably 4-4'-dichloro-2-hydroxydiphenyl ether, 2,4,4'-trichloro-2 A composition according to claim 1, selected from the group consisting of '-hydroxydiphenyl ethers, and combinations thereof, wherein said diphenyl ether antimicrobial agent is more preferably 4-4'-dichloro-2-hydroxydiphenyl ether. Each of the plurality of antimicrobial particles contains 30% to 95%, more preferably 40% to 94%, and most preferably 50% to 93% of the water-soluble carrier relative to the total weight of each antimicrobial particle. , the water-soluble carrier is preferably a water-soluble polymer, and the water-soluble carrier is preferably polyethylene glycol, sodium acetate, sodium bicarbonate, sodium chloride, sodium silicate, polypropylene glycol polyoxoalkylene, polyethylene glycol selected from the group consisting of fatty acid esters, polyethylene glycol ethers, sodium sulfate, starch, and combinations thereof, wherein said water-soluble carrier is most preferably between 1,000 and 20,000 daltons, preferably between 1,500 and 15,000 daltons; 3. A composition according to claim 1 or 2, which is a polyethylene glycol characterized by a weight average molecular weight (Mw) of 2,000 to 13,000 Daltons. Each of the plurality of antimicrobial particles further comprises 0.1% to 30%, preferably 0.5% to 20%, more preferably 1% to 15% of perfume, based on the total weight of each antimicrobial particle. wherein said perfume is preferably selected from the group consisting of free perfume, pro-perfume, encapsulated perfume, perfume microcapsules, and combinations thereof; said perfume is more preferably a mixture of free perfume and perfume microcapsules Most preferably, the weight ratio of free perfume to perfume microcapsules in each said antimicrobial particle is from 1:5 to 20:1, preferably from 1:2 to 10:1, more preferably from 1:1 to A composition according to any one of claims 1 to 3, which is 5:1, most preferably 1.5:1 to 3:1. each of said plurality of antimicrobial particles further comprises 5% to 45%, preferably 10% to 40%, more preferably 15% to 35% of a quaternary ammonium compound, based on the total weight of said each antimicrobial particle; wherein said quaternary ammonium compound is formed from a parent fatty acid compound having an iodine value of 18 to 60, preferably 20 to 60, said quaternary ammonium compound is preferably an ester quaternary ammonium compound , said quaternary ammonium compound is more preferably di-(tallowyloxyethyl)-N,N-methylhydroethylammonium methylsulfate. . Each of the plurality of antimicrobial particles further comprises 0.5% to 10%, preferably 1% to 5%, of a cationic polymer relative to the total weight of each antimicrobial particle, and the cationic polymer is preferably is a cationic polysaccharide and said cationic polymer is more preferably a polymeric quaternary ammonium salt of hydroxyethylcellulose reacted with an epoxide substituted with trimethylammonium groups. Each of the plurality of antimicrobial particles has an amount of 0.0001% to 1%, preferably 0.001% to 0.5%, more preferably 0.005% to 0.5%, based on the total weight of each antimicrobial particle. A composition according to any one of the preceding claims, further comprising 1% of a colorant, preferably said colorant is selected from the group consisting of dyes, pigments and combinations thereof. each of the plurality of antimicrobial particles,
i) a shape, preferably selected from the group consisting of spherical, hemispherical, compressed hemispherical, cylindrical, discoid, circular, lentil-shaped, oval, cubic, rectangular, star-shaped, flower-shaped and combinations thereof; each of said perfume particles has a hemispherical or compressed hemispherical shape; and/or
ii) a longest dimension between 3 mm and 10 mm, preferably between 4 mm and 9 mm, more preferably between 5 mm and 8 mm, and/or
iii) an aspect ratio of 1 to 5, preferably 1.5 to 4, more preferably 2 to 4, and/or
iv) in the range of 0.5 g/cm ³ to 0.98 g/cm ³ , preferably 0.7 g/cm ³ to 0.95 g/cm ³ , more preferably 0.8 g/cm ³ to 0.9 g/cm ³ density of
The composition according to any one of claims 1 to 7, characterized in that Said composition is a particulate laundry detergent composition and said plurality of antimicrobial particles preferably comprises from 0.05% to 30%, preferably 0.05% to 30%, based on the total weight of said particulate laundry detergent composition. Present in the particulate laundry detergent composition in an amount ranging from 1% to 20%, more preferably from 0.5% to 15%, most preferably from 1% to 10%. A composition according to claim 1. Said particulate laundry detergent composition further comprises 10% to 99.9%, preferably 20% to 95%, more preferably 30% to 90%, most preferably 40% to 80% detergent particles, said each of the detergent particles preferably contains from 10% to 90% by weight of an anionic surfactant, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, a zwitterionic surfactant, and combinations thereof. A method for processing an article of clothing, comprising:
a) providing the garments to the washing machine;
b) contacting the garment with the composition of any one of claims 1-10 during the wash subcycle of the washing machine.