WO2006040188A1

WO2006040188A1 - Product comprising a fibrous support and a benefit agent

Info

Publication number: WO2006040188A1
Application number: PCT/EP2005/011170
Authority: WO
Inventors: Evelyne Prat
Original assignee: Rhodia Chimie
Priority date: 2004-10-15
Filing date: 2005-10-14
Publication date: 2006-04-20

Abstract

The invention relates to a product comprising a fibrous support and a benefit agent. The product can provide benefits such as preventing bacteria proliferation. Thus the invention also relates to a process of treating a surface for example against bacteria proliferation, comprising the step of applying onto the surface a product according to the invention. This can provide cleaning, disinfection, suppression of odors, and/or prevention of malodors.

Description

TITLE Product comprising a fibrous support and a benefit agent

BACKGROUND OF THEN INVENTION The invention relates to a product comprising a fibrous support and a benefit agent. The product can provide benefits such as preventing bacteria proliferation. Thus the invention also relates to a process of treating a surface for example against bacteria proliferation, comprising the step of applying onto the surface a product according to the invention. This can provide cleaning, disinfection, suppression of odors, and/or prevention of malodors.

The relationship of a consumer to some products used for example to clean clothes, houses and more generally to clean, or to be applied onto skin, and its environment is changing. A product must bring more than the basic cleaning benefit: It has to provide a safe, healthy and pleasant environment which explains for example the success for formulations that "clean and disinfect and suppress malodors" at the same time. The bleach systems that are still used today both in laundry detergents and hard surface cleaning detergents meet that request. The drawbacks of these "bleach systems" are that they are sometimes very aggressive on delicate fabric or surfaces. On top of that, for the particular case of liquid laundry formulations, these bleach may lead to restrictions regarding freedom to formulate because of stability problems at alkaline pH or because of incompatibility with some ingredients of the formulation (enzymes).

An alternative to bleach formulations in hard surface cleaners to provide cleaning, disinfecting and/or malodor control has been found with the development of antimicrobial formulations containing quaternary ammonium compounds. However these quaternary ammonium compounds may lead to skin irritation and even allergy and acute dermatitis problems at the concentration level they are used in home care detergent. They may be detrimental to environment because of their toxicity versus algae and aquatic environment. Another limitation for the use of the quaternary ammonium compounds in the wipes is that they interact with some fibers and are difficult to release on the surfaces.

There is therefore a growing demand, for example in home and fabric care compositions, for products providing cleaning, disinfecting, suppressing and/or preventing malodors, while being safer and more respectful of the environment. In Hard Surface Cleaners, formulations containing ingredients derived from natural sources such as limonene, orange or citrus oil are known. Some relevant references about using essential oils for the disinfection of hard surfaces include the following:

- EP 1146111 : disinfection of hard surfaces and dishes with cinnamon oil, thymol, geraniol or eugenol, terpineol, verbenone.

- WO02085109: disinfection of hard surfaces in the house with thymol, geraniol, carvacrol, citral, terpinene, carvone, limonene.

In fabric care detergent there is also a need to provide odour and/or malodour control benefits to the clothes: - during the cleaning step to remove source of malodour, and/or

- while the consumer wears the clothes to neutralize the malodour resulting from perspiration.

For example WO9802044 describes the use of thymol, eugenol, verbenone, eucalyptol, terpineol, cinnamic acid in hard surfaces and laundry detergent formulations. However the natural ingredients mentioned above are not considered as completely safe, although they benefit from a great impact in consumers mind because they have a natural origin. There is today a growing concern regarding the safety and the ecotoxicity of some "natural extracts" such as limonene that are widely used in detergent formulations. Limonene (extracted from orange peel) for instance has been evidenced to be sensitizing with skin contact and to provide acute toxicity to fish and algae. Others essential oils are under scrutiny and the Directive European 2003/15/EC now limits the amount of some fragrances or oils in cosmetics and detergents in order to reduce the risk of skin irritation or sensitization that may occur by repeated exposure to these compounds.

Limonene, geraniol, eugenol cinnamal and cinnamyl alcohol are amongst the essential oils that need to be incorporated at levels below 100 ppm for rinse off formulations and below 10 ppm for leave on formulations, in order to limit the risk of allergy and sensitization. These low amounts can limit the benefits thereof. The SCCNFP (Scientific Committee on cosmetic products and non food products intended for consumers) has published opinions proposing to extend these restrictions to a lot of others essential oils like costus root oil, peru balsam, pine needle oil, turpentine, cumin oil, hydroxycitronellal, verbena

There is a need for new products comprising compounds that address at least partially, at least some of the drawbacks and/or needs above, and which are Generally Recognised As Safe ("GRAS"). Hop extracts such as hop acids (alpha acids also referred to as Humulone and Beta acids also referred to as Lupulone) present in Hop have been long known and used for their bacteriostatic and bacteriocidal functions in the beer industry. Hop acids include the alpha and beta acids and their GRAS derivatives traditionnaly used for the preparation of beer like: humulone, cohumulone, adhumulone, iso humulone, iso cohumulone, iso adhumulones, dishydro iso alpha acids, tetrahydro isoalpha acids, hexahydro iso alpha acids, hexahydrolupulone, hexahydrocolupulone ( hexahydro beta acids)... A lot of literature is available on the use of these hop acids (used alone or in blends) to prevent the proliferation of gram÷ bacteria such as Lactobacilli which is a major contaminant in beer fermentation. It is assumed that hop compounds like iso alpha acids are weak acids that can cross cytoplasmic membranes and disrupt the pH gradient of the cell, which results in the starving of the cell. Examples of references about this topic include the following documents:

Simpson.W.J., Smith, A.R.W., J.appl.Bacteriol., 1992,72,327-334.

Simpson.W J., J. Inst.Brew., 1993,139,1041-1045.

Sakamoto.K., Van veen H.W, Saito. H, Kobayashi.H, Konings.W.N, Appl. And

Environmet.l Microbiol., 2002,68,11 , 5374-5378. Methods have been described to extract bacteriostatic agents from hop flower and use these extracts to neutralize resident gram + bacteria on skin, that when in contact with sweat will be responsible for the development of malodor. A method for producing a skin deodorant based on this bactericidal extract is described in document US 4,170,638. Beta acids from hop have been shown as demonstrating superior efficiency against development of gram + bacteria and claimed for use in food preservation. This is for example described in documents US 5,286,506 and US 6,475,537.

New methods have been described to optimize the stability of hop beta acids by converting them to hexahydro beta acids. This is for example described in document US 5,166,449.

Blends of hexahydrocolupulone and tetrahydroisohumulone have been described to inhibit listeria growth, in document US 5,455,038.

The efficacy of hop extracts as herbal medicine has been long established by tradition and is now supported by current research. Hop extract is reported to have been used topically to treat sores and skin injuries. It is used in skin creams and lotions as a skin emollient (Hops, Presentation to Herbal Medicine Seminar, Canterbury College of Natural medicine, New Zealand July, 2001 ). There is a revived interest for hop properties in modern medicine as evidenced by the recent scientific publications dealing with applications of its relaxant and bacteriostatic properties. Relevant references include the following: - Pharmacodynamic study of the lupulus' tranquilizing action. Boll Chim. Farm 1974.

- Antifungal ( Candida) activity of hops bitter resins and relative compounds , Report Research laboratories, Kirin Brewery, Muizobuchi and Sato , VoI 28, P39-44 (1985).

None of the references above describe products to be used by consumers and having a fibrous support.

BRIEF SUMMARY OF THE INVENTION

The invention provides a product comprising a fibrous support and a composition to be released from the support, wherein said composition comprises a hop extract.

The hop extract is a benefit agent. The product can be for example a wipe or pad, for example wet or substantially dry.

According to another aspect, the invention provides a process of treating a surface for preventing bacteria proliferation, cleaning, disinfecting, suppressing odors, and/or preventing malodor, comprising the step of applying onto the surface the product above. According to another aspect, the invention provides the use of a hop extract in a product comprising a fibrous support and a composition to be released from the support, wherein said composition comprises a hop extract.

The product, the process, can provide the treatment for preventing bacteria proliferation, cleaning, disinfecting, suppressing odors, and/or preventing of malodors, while addressing at least some concerns about safety (the composition being GRAS), and/or being non sensitizing for users.

For clothes the product can provide disinfecting as well as odor and/or malodor control benefits, while trying to prevent any risk of sensitization by skin contact/ inhalation, during the cleaning step to remove source of malodor and/or while the consumer wears the clothes to neutralize the gram + bacteria that can be present on skin and are responsible for the malodor generation. This is true for the detergent used to clean clothes in the home as well as for the detergents used to clean linen and clothes, carpets and upholstery in collectivities such as schools, restaurants, hotels, hospitals, elderly homes where the risk of contamination by gram + bacteria is even greater. This operation of disinfecting clothes and/or preventing malodor generation due to resident bacteria on skin (like staphylococcus aureus and staphylococcus epidermis) can be done without being detrimental to the skin and without risking to generate irritation and sensitization through skin contact and inhalation.

For home surfaces like kitchen, fridge, bathroom, floors, toilet bowl, upholstery, carpets, the product can provide bacteriostatic, bactericidal and/or malodor treatment to surfaces in the home, like those that are susceptible to be contaminated by gram + bacteria, while diminishing the risks of sensitization of the consumer by skin contact and/or inhalation. In public places such as restaurants, restaurants kitchen and crockery, restaurant and hotel bathrooms, public lavatories, surfaces in hospitals, the product can provide bacteriostatic, bactericidal and/or malodor treatment, while preventing any risk of sensitization by skin contact and/or inhalation.

For surfaces in contact with food or animals ( dead or alive) in the industrial environment like vessel tanks for food and beverage preparation, animal farms , animal transportation, garbage trucks, the product can provide bacteriostatic , bactericidal and/or malodor treatment to surfaces while trying to prevent any risk of sensitization by skin contact and/or inhalation.

For personal-care products, for example for antiperspirant products, or perfumes, or refreshing product, the product can prevent malodor, for example by preventing bacteria proliferation.

It is believed that the hop extract of the composition can be especially efficient against proliferation of the following:

• Listeria monocytocytogenes (+)

• Staphylococcus aureus (+)

• Salmonella enteritidis (-)

• Streptococci (+) • Lactobacilli (+) (first use as bacteriostatic agent in beer....)

• Corynebacteria (+)

• Diplococci (+)

• Mycobacteria (+)

• Streptococci (+) ® Streptomyces (+) • Clostridia bacteria (+)

• Bacillus bacteria (+), and/or

• Micrococci (+).

DETAILED DESCRIPTION OF THE INVENTION

Definitions

In the present specification "hop extract" refers to compounds or compositions of matter obtained from hop, as well as compounds or compositions of matters chemically derived thereof. In the present specification "composition comprising a hop extract" refers to the matter being different from the fibrous support. The products according to the invention are usually prepared by adding matter (ingredients alone or mixtures, in dry form or in liquid form) to a fibrous support, and optionally further processing steps, such as drying for example. The composition refers to that matter added to fibrous support and remaining in the product after the optional processing steps.

In the present specification "hard surface" refers to any surface found in homes or institutional buildings, or in industrial buildings, or in furniture, provided that the surface is not a fabric such as clothes, furniture fabrics, curtains, sheets. Hard surfaces especially include dishware, silverware, and any other surfaces that need to be cleaned regularly. Of course hard surfaces do not include skin or hair.

Hop extract

The composition of the invention comprises a hop extract.

The composition of whole hop varies according to the varieties. An example of a typical composition has been given by Stevens, R. (1987), Hops, an Introduction to Brewing

Science and Technology, Series II, Vol. I, p23.

An example of a whole hop composition is the following:

Alpha acids: 8% Beta acids: 4%

Other resins: 3%

Essential oils: 1 %

Tannins: 4%

Proteins: 15% Water: 9,5%

Monosaccharides: 2% Lipids and waxes: 3% Aminoacids: 0,1% Pectin: 2% Ash: 8% Cellulose, lignin: 40,4%

Whole hop is usually processed through liquid CO₂ or supercritical CO₂ to obtain the useful fractions of active components like alpha acids, beta acids and essential oils. The alpha and beta acids can be further processed and isomerised. Typical commercial hop extracts of interest for the invention are available on the market for brewery applications at Hopsteiner ( Germany), John I. Haas ( USA), Botanix (UK) .

They comprise blends or pure extracts of active matter such as Hop beta acids, Hop alpha acids and their isomerised or reduced derivatives. Some examples of Hop extracts composition are given hereafter for illustration: 1) solutions of iso alpha acids, available for instance as alkaline solution of potassium salt of isoalpha acids (commercial product: Iso- extract -30% from Hopsteiner).

2) solutions of reduced (rho) iso alpha acids, available for instance as alkaline solutions of potassium salts (commercial product: Rho-lso-Extract-10% from Hopsteiner).

3) Solutions of tetrahydro iso alpha acids, available as alkaline solutions of potassium salts (commercial product: Tetra Iso extract-10% from Hopsteiner).

4) Solutions of tetrahydro iso alpha acids and hexahydro alpha acids, available as alkaline solutions of the potassium salts (commercial product: Hexahop Gold from John I Haas).

5) Solutions of beta acids available for instance as alkaline solutions of the potassium salts ( commercial product: Beta acid solution 10% from John I Haas).

6) Amber resins consisting of purified reduced (Rho) iso alpha acids ( commercial product: Rho Concentrate from Hopsteiner).

7) Amber resins consisting of Beta acids ( 40-50%) and oils ( commercial product: Light stable Beta aroma extract from Hopsteiner).

The bitter acids component of the hops used in beer making and particularly the beta- acids have now been found to be useful as bactericides in food products. The most prevalent groups of bitter acids found as components of hops are the alpha-acids and the beta-acids, also referred to as humulones and lupulones, respectively. Both contribute bitterness to beer, but the alpha-acids are much more intense in this regard than the beta-acids. Producers of hop extracts isolate the alpha and beta acids commercially by various chromatographic techniques and have recently developed a technique to separate the two acid fractions using liquid carbon dioxide under supercritical conditions. A by-product of the operation is a product which contains approximately 61 weight percent beta-acids, the remainder consisting essentially of hops resins. This by-product can be standardized with malto-dextrin or other food grade carrier, spray-dried, and used as an antibacterial food ingredient. A preferred beta hop acids component is commercially available as a natural flavor extract containing 1 weight percent beta hop acids.

The alpha-acids contained in hops are commonly known as humulone, cohumulone and adhumulone, while the beta-acids contained in hops are commonly known as lupulone, colupulone and adlupulone. Derivatives of the hop acids or hop resins which have demonstrated antibacterial properties such as hexahydrocolupulone and tetrahydroisohumulone, as disclosed in U.S. Pat. No. 5,455,038, are specifically contemplated for use in association with the present invention. Also considered as specifically contemplated for use in association with the present invention is the use of the acid salt forms of the hops acids or hops resins.

The hop extract advantageously comprises an active matter having:

- alpha hop acid (Humulone), isomers thereof, reduced derivatives thereof, - beta hop acid (Lupulone), isomers thereof, reduced derivatives thereof, or

- mixtures thereof.

The hop extract comprises preferably at least 5% by weight the active matter.

Some preferred and/or advantageous and/or particular embodiments of the invention are presented below.

Fibrous Support & Product forms

The fibrous support can be a woven or non woven fiber web. Fibers of interest include cellulose fibers or celloluse derivatives fibers, PET (polyethylene terephtalate) fibers, polyamide fibers, polypropylene fibers, cotton fibers, and mixtures thereof.

The support can be for example a non woven fabric based on polypropylene fibers, cellulose fiber or cellulose derivatives fibers, PET fibers, or mixtures thereof. Fibrous supports that can be used are typical of products such as wipes, diapers, pads, or cotton puffs, and are known by the one skilled in the art, for every specific use. In one embodiment the product is a substantially dry wipe or pad, the composition being substantially dry.

In another embodiment the product is a wet wipe or pad, the composition comprising an aqueous, alcoholic or hydroxyalcoholic medium.

Examples of products according to the invention include a personal-care wipe or pad, a home-care wipe or pad, a personal-care wipe or pad or a baby-care wipe or pad. Examples of products according to the invention especially include:

- a baby-care dry wipe or pad, wherein the hop extract is released onto baby skin when the dry wipe or pad applied onto wet skin,

- a diaper, wherein the hop extract is released onto skin when a liquid such as urine is contacted to the diaper.

Advantageous compositions comprising the hop extract The composition comprising the hop extract can be in different forms. The form usually depends upon the use of the product. Thus the composition can be in a liquid form (for example in wet products such as wet wipes or pads) or in a solid form (for example in dry products such as dry wipes or pads or diapers).

Liquid composition can be dispensed onto the fibrous support for example by spraying, by pouring.

The amount of hop extract in the composition is preferably of lower than 5% by weight, and preferably of higher than 100 ppm by weight.

In one embodiment the composition comprises from 0.5% to 5% by weight of the hop extract. In another embodiment the composition comprises from 100 ppm to 0.5% by weight of the hop extract.

Preferably, the amount of active matter in the composition is of lower than 5% by weight, and preferably of higher than 100 ppm by weight.

Where the composition is a liquid composition, said composition can comprise a liquid medium, preferably an aqueous medium, an alcoholic medium, or a hydroxy-alcoholic medium. The medium can be a part of the composition, a part of a concentrate composition, or a part of a diluted composition, for example the diluting medium. Further ingredients

The composition will usually comprise further ingredients of home-care or fabric-care or institutional-cleaning or industrial-cleaning or diapers, or baby-care, or other personal- care (such as antiperspirant, after shaving, removal of make-up) products. The further ingredients usually depend upon the use, destination and/or form of the product. These further ingredients are known by the one skilled in the art of preparing products comprising several ingredients (or "formulations") to serve a use or a market.

Thus, the composition can comprise at least one surfactant. Compositions that comprise a surfactant are for example useful in compositions that are to provide cleaning or degreasing, such as dish-washing compositions (hand dishwashing or automatic dishwashing), laundry compositions, hard-surface cleaning compositions, industrial cleaning or degreasing compositions.

Useful surfactants include anionic, non ionic, cationic, amphoteric (including zwitterionic) surfactants and mixtures thereof. Anionic Surfactants

Anionic surfactants useful in the present invention are preferably selected from the group consisting of, linear alkylbenzene sulfonates, alpha olefin sulfonates, paraffin sulfonates, methyl ester sulfonates, alkyl sulfates, alkyl alkoxy sulfates, alkyl sulfonates, alkyl alkoxy carboxylate, alkyl alkoxylated sulfates, sarcosinates, taurinates, and mixtures thereof.

One type of anionic surfactant which can be utilized encompasses alkyl ester sulfonates. These are desirable because they can be made with renewable, nonpetroleum resources. Preparation of the alkyl ester sulfonates surfactants components can be effected according to known methods disclosed in the technical literature. For instance, linear esters of C₈-C₂O carboxylic acids can be sulfonated with gaseous SO₃ according to "The Journal of the American Oil Chemists Society," 52 (1975), pp. 323-329. Suitable starting materials would include natural fatty substances as derived from tallow, palm, and coconut oils, etc. The preferred alkyl ester sulfonate surfactant, especially for laundry applications, comprises alkyl ester sulfonate surfactants of the structural formula: 0

R³-CH-C-OR⁴

I SO₃M wherein R³ is a C₈-C₂₀ hydrocarbyl, preferably an alkyl, or combination thereof, R⁴ is a Ci -C₆ hydrocarbyl, preferably an alkyl, or combination thereof, and M is a soluble salt- forming cation. Suitable salts include metal salts such as sodium, potassium, and lithium salts, and substituted or unsubstituted ammonium salts, such as methyl-, dimethyl, - trimethyl, and quaternary ammonium cations, e.g. tetramethyl-ammonium and dimethyl piperdinium, and cations derived from alkanolamines, e.g. monoethanol-amine, diethanolamine, and triethanolamine. Preferably, R³ is Ci₀-C₁₆ alkyl, and R⁴ is methyl, ethyl or isopropyl. Especially preferred are the methyl ester sulfonates wherein R³ is C₁₄-Ci₆ alkyl.

Alkyl sulfate surfactants are another type of anionic surfactant of importance for use herein. In addition to providing excellent overall cleaning ability when used in combination with polyhydroxy fatty acid amides (see below), including good grease/oil cleaning over a wide range of temperatures, wash concentrations, and wash times, dissolution of alkyl sulfates can be obtained, as well as improved formulability in liquid detergent formulations are water soluble salts or acids of the formula ROSO₃M wherein R preferably is a C₁₀-C₂₄ hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C₁₀- C₂₀ alkyl component, more preferably a Ci₂-C₁₈ alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali or alkaline (Group IA or Group HA) metal cation (e.g., sodium, potassium, lithium, magnesium, calcium), substituted or unsubstituted ammonium cations such as methyl-, dimethyl and trimethyl ammonium and quaternary ammonium cations, e.g., tetramethylammonium and dimethyl piperdinium, and cations derived from alkanolamines such as ethanolamine, diethanolamine, triethanolamine, and mixtures thereof, and the like. Typically, alkyl chains of C₁₂-C₁₆ are preferred for lower wash temperatures (e.g., below about 5O⁰C) and C₁₆-Ci₈ alkyl chains are preferred for higher wash temperatures (e.g., above about 50^°C). Examples of these surfactants include surfactants sold by Rhodia under the Rhodapan Trade Name.

Alkyl alkoxylated sulfate surfactants are another category of useful anionic surfactant. These surfactants are water soluble salts or acids typically of the formula RO(A)₁₇₁SO₃M wherein R is an unsubstituted Ci₀-C₂₄ alkyl or hydroxyalkyl group having a Ci₀-C₂₄ alkyl component, preferably a Ci₂-C₂₀ alkyl or hydroxyalkyl, more preferably C₁₂- C₁₈ alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such as tetramethyl- ammonium, dimethyl piperidinium and cations derived from alkanolamines, e.g. monoethanolamine, diethanolamine, and triethanolamine, and mixtures thereof. Exemplary surfactants are C₁₂-C₁₈ alkyl polyethoxylate (1.0) sulfate, C₁₂-Ci₈ alkyl polyethoxylate (2.25) sulfate, C₁₂-Ci₈ alkyl polyethoxylate (3.0) sulfate, and Ci₂-C₁₈ alkyl polyethoxylate (4.0) sulfate wherein M is conveniently selected from sodium and potassium. Surfactants for use herein can be made from natural or synthetic alcohol feedstocks. Chain lengths represent average hydrocarbon distributions, including branching. Examples of these surfactants include surfactants sold by Rhodia under the Rhodapex Trade Name. Other Anionic Surfactants - Other anionic surfactants useful for detersive purposes can also be included in the compositions hereof. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C₈-C₂₀ linear alkylbenzenesulphonat.es, for example sold by Rhodia under the Rhodacal trande name, C₈-C₂₂ primary or secondary alkanesulphonates, C₈-C₂₄ olefinsulphonates, sulphonated polycarboxylic acids prepared by sulphonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No. 1 ,082,179, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isothionates such as the acyl isothionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate, for example sold by Rhodia under the Geropon trade name (especially saturated and unsaturated C₁₂-C₁₈ monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C₆-C₁₄ diesters), N-acyl_sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described below), branched primary alkyl sulfates, alkyl polyethoxy carboxylates such as those of the formula RO(CH₂CH₂O)_kCH₂COO^"M+ wherein R is a C₈-C₂₂ alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation, and fatty acids esterified with isethionic acid and neutralized with sodium hydroxide. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and Il by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23. Nonionic Surfactants

Suitable nonionic detergent surfactants are generally disclosed in U.S. Patent 3,929,678, Laughlin et al., issued December 30, 1975, at column 13, line 14 through column 16, line 6, incorporated herein by reference. Exemplary, non-limiting classes of useful nonionic surfactants include: alkyl dialkyl amine oxide, for example sold by Rhodia under the Rhodamox trade name, alkyl ethoxylate, for example sold by Rhodia under the Rhodasurf trade name, alkanoyl glucose amide, alkyl betaines, for example sold by Rhodia under the Mirataine trade name, and mixtures thereof. Other nonionic surfactants for use herein include:

The polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols. In general, the polyethylene oxide condensates are preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 12 carbon atoms in either a straight chain or branched chain configuration with the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in a amount equal to from about 5 to about 25 moles of ethylene oxide per mole of alkyle phenol. Commercially available nonionic surfactants of this type include surfactants sold by Rhodia under the lgepal trade name . These are commonly referred to as phenol alkoxylates, (e.g., alkyl phenol ethoxylates).

The condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 10 to about 20 carbon atoms with from about 2 to about 18 moles of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type include TergitolB 15-S-9 (the condensation product of Cn-C₁₅ linear secondary alcohol with 9 moles ethylene oxide), Tergitol 24-L-6 NMW (the condensation product Of C₁₂-C₁₄ primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; Neodol® 45-9 (the condensation product of C₁₄-C₁₅ linear alcohol with 9 moles of ethylene oxide), Neodol® 23-6.5 (the condensation product of C₁₂-C₁₃ linear alcohol with 6.5 moles of ethylene oxide), Neodol® 45-7 (the condensation product of C₁₄-C₁₅ linear alcohol with 7 moles of ethylene oxide), Neodol® 45-4 (the condensation product of C₁₄-C₁₅ linear alcohol with 4 moles of ethylene oxide), marketed by Shell Chemical Company, Rhodasurf IT, DB, and B marketed by Rhodia, Plurafac LF 403, marketed by BASF, and Kyro® EOB (the condensation product of C₁₃-C₁₅ alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company. Other commercially available nonionic surfactants include Dobanol 91-8® marketed by Shell Chemical Co. and Genapol UD-080® marketed by Hoechst. This category of nonionic surfactant is referred to generally as "alkyl ethoxylates."

The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of these compounds preferably has a molecular weight of from about 1500 to about 1800 and exhibits water insolubility. The addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide. Examples of compounds of this type include certain of the commercially-available Pluronic® surfactants, marketed by BASF, and Antarox, marketed by Rhodia.

The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000. This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11 ,000.

Examples of this type of nonionic surfactant include certain of the commercially available TetronicB compounds, marketed by BASF.

Semi-polar nonionic surfactants are a special category of nonionic surfactants which include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.

Semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula: O

R³(OR⁴)χN(R⁵)₂

wherein R³ is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms; R⁴ is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3; and each R⁵ is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups. The R⁵ groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure. These amine oxide surfactants in particular include Ci₀-Ci₈ alkyl dimethyl amine oxides and C₈-Ci₂ alkoxy ethyl dihydroxy ethyl amine oxides.

Alkylpolysaccharides disclosed in U.S. Patent 4,565,647, Llenado, issued January 21 , 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties. (Optionally the hydrophobic group is attached at the 2-, 3-, A-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside.) The intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, A-, and/or 6- positions on the preceding saccharide units.

Optionally, and less desirably, there can be a polyalkylene-oxide chain joining the hydrophobic moiety and the polysaccharide moiety. The preferred alkyleneoxide is ethylene oxide. Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched containing from about 8 to about 18, preferably from about 10 to about 16, carbon atoms. Preferably, the alkyl group is a straight chain saturated alkyl group. The alkyl group can contain up to about 3 hydroxy groups and/or the polyalkyleneoxide chain can contain up to about 10, preferably less than 5, alkyleneoxide moieties. Suitable alkyl polysaccharides are octyl, nonyl, decyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides, glucoses, fructosides, fructoses and/or galactoses. Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta-, and hexa-glucosides.

The preferred alkylpolyglycosides have the formula: R²0(C_nH_2nO)_t(glycosyl)_x wherein R² is selected from the group consisting of alkyl, alkyl-phenyl, hydroxyaikyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the l-position). The additional glycosyl units can then be attached between their 1 position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominantly the 2-position.

Non ionic surfactant include fatty acid amide surfactants having the formula: O

R⁶-C-N(R⁷)₂ wherein R⁶ is an alkyl group containing from about 7 to about 21 (preferably from about

9 to about 17) carbon atoms and each R⁷ is selected from the group consisting of hydrogen, C₁-C₄ alkyl, C₁-C₄ hydroxyaikyl, and -(C²H₄O)_xH where x varies from about 1 to about 3. Preferred amides are C₈-C₂O ammonia amides, monoethanolamides, diethanolamides, and isopropanolamides. Cationic Surfactants

Cationic detersive surfactants can also be included in detergent compositions of the present invention. Cationic surfactants include the ammonium surfactants such as alkyldimethylammonium halogenides, and those surfactants having the formula: [R²(0R³)_y] [R⁴(OR³)_y]₂R⁵N⁺X^" wherein R² is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R³ is selected from the group consisting Of-CH₂CH₂-, -CH₂CH(CH₃)-, -CH₂CH(CH₂OH)-, -CH₂CH₂CH₂-, and mixtures thereof; each R⁴ is selected from the group consisting of C₁-C₄ alkyl, C₁-C₄ hydroxyaikyl, benzyl, ring structures formed by joining the two R⁴ groups, -CH₂CHOHCHOHCOR⁶CHOH-CH₂OH wherein R⁶ is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0; R⁵ is the same as R⁴ or is an alkyl chain wherein the total number of carbon atoms of R² plus R⁵ is not more than about 18; each y is from 0 to about 10 and the sum of the y values is from 0 to about 15; and X is any compatible anion.

Other cationic surfactants useful herein are also described in U.S. Patens

4,228,044, Cambre, issued October 14, 1980, incorporated herein by reference. Other Surfactants

Ampholytic surfactants can be incorporated into the detergent compositions hereof. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched. One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 to Laughlin et al., issued

December 30, 1975 at column 19, lines 18-35 for examples of ampholytic surfactants.

Preferred amphoteric include C₁₂-C₁₈ alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C₆-C₁₂ alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C₁₂-C₁₈ betaines and sulfobetaines ("sultaines"),

C₁₀-C-_I8 amine oxides, and mixtures thereof.

Zwitterionic surfactants can also be incorporated into the detergent compositions hereof. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds.

See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column

19, line 38 through column 22, line 48 for examples of zwitterionic surfactants.

Ampholytic and zwitterionic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.

Other optional ingredients of the composition include:

- thickening polymers,

- hydrophilizing polymers, - soil-release polymers,

- deposition agents or deposition aid agents, for example deposition polymers, such as silicones,

- anti-foaming agents, - foaming agents, - foam stabilizing and/or enhancing agents,

- perfumes or fragrances, - builders (detergency adjuvants), including organic builders and inorganic builders,

- buffers, - salts or fillers,

- chelatants, - colorants,

- preservatives,

- enzymes,

- corrosion inhibitors,

- scale inhibitors, - dyes,

- optical bighteners,

- soiling suspending agents, - freezing-thawing stabilizers,

- solvents, - opacifiers,

- pearlescence agents,

- mixtures or associations thereof.

Products and Process of use of the products According to some advantageous embodiments, the product and/or supported composition is:

- a softening and/or antiwrinkling and/or easy-ironing composition and/or product,

- a wipe product to be used in automatic laundry drying,

- a glass cleaning composition and/or product, including a window cleaning composition and/or product or a car windshield composition and/or product,

- a floor cleaning composition and/or product,

- a versatile cleaning hard surface cleaning composition and/or product,

- a kitchen cleaning composition and/or product,

- a bathroom cleaning composition and/or product, - a toilet bowl cleaning composition and/or product,

- a wood treatment composition and/or product,

- a shower rinse (daily shower) composition and/or product,

- a car cleaning composition and/or product, or

- a tile or plastic floor cleaning composition and/or product.

Examples of products include home-care wet wipes, being: - a wipe or pad for glass, shiny surfaces, floors, counters, walls, kitchen cleaning, bathroom cleaning and/or toilets cleaning,

- a wipe or pad for daily shower.

In such wipes, the composition typically comprises a liquid medium preferably an aqueous medium, an alcoholic medium, or a hydroxyalcoholic medium, the hop extract, and optionally a surfactant.

Other examples of products can be personal-care wet wipes or pads or puffs, wherein the composition comprises: - a liquid medium, preferably an aqueous medium, an alcoholic medium, or a hydroxyalcoholic medium,

- the hop extract,

- optionally at least one surfactant.

Such personal-care products for example:

- an antiperspirant product,

- an after shaving product, or

- a product for removing make-up.

The product can be used for treating a surface against proliferation of bacteria.

Accordingly, the composition can be used in a process of treating a surface against bacteria proliferation, comprising the step of applying onto surface the product comprising a hop extract. The process (or treatment or use) can provide cleaning, disinfection, suppression of odors, and/or prevention of malodors. The surface can be for example a hard surface, or skin, or hair. Applying can be performed for example by wiping the product on the surface.

In one embodiment the surface is a hard surface. The surface in this embodiment can be: - glass, for example comprised in windows, or cars windshields,

- tile or ceramic, for example comprised in kitchens, bathrooms, toilet bowls, showers, china, dishware, floors,

- metal, for example comprised in silverware, car body parts, window frames, or floors,

- plastic, for example comprised in dishware, silverware, cars, windows, furniture, or floors,

- wood or leather, optionally waxed, for example comprised in furniture or floor, - concrete, optionally waxed , for example comprised in floors.

Claims

1. A product comprising a fibrous support and a composition to be released from the support, wherein said composition comprises a hop extract.

2. A product according to one of the preceding claims, wherein the hop extract comprises an active matter having

- alpha hop acid, isomers thereof, or reduced derivatives thereof,

- beta hop acid, isomers thereof, or reduced derivatives thereof, or - mixtures thereof.

3. A product according to one of the preceding claims, wherein the hop extract comprises at least 5% by weight the active matter.

4. A product according to one of the preceding claims, wherein the amount of hop extract in the composition is of lower than 5% by weight, and preferably of higher than 100 ppm by weight.

5. A product according to one of the preceding claims, wherein the amount of active matter in the composition is of lower than 5% by weight, and preferably of higher than

100 ppm by weight.

6. A product according to claim one of the preceding claims, wherein the fibrous support is a woven or non woven fiber web.

7. A product according to one of the preceding claims, being a wipe, a pad, or a diaper.

8. A product according to one of the preceding claims, being a substantially dry wipe or pad, the composition being substantially dry.

9. A product according any of claims 1-7, being a wet wipe or pad, the composition comprising an aqueous, alcoholic or hydroxyalcoholic medium.

10. A product according to one of the preceding claims being a personal-care wipe or pad, a home-care wipe or pad, a personal-care wipe or pad or a baby-care wipe or pad.

11. A product according to any of claims 1-8 and 10, being:

- or a diaper, wherein the hop extract is released onto skin when a liquid such as urine is contacted to the diaper.

12. A product according to any of claims 1-7 or 9-10, being a home-care wet wipe wherein the composition comprises:

- a liquid medium, preferably an aqueous medium, an alcoholic medium, or a hydroxyalcoholic medium,

- the hop extract,

- optionally at least one surfactant.

13. A product according to the preceding claim, wherein the composition further comprises at least one deposition agent or deposition-aid agent, preferably at least one deposition polymer.

14. A product according to any of claims 12 or 13, being:

- a wipe or pad for glass, shiny surfaces, floors, counters, walls, kitchen cleaning, bathroom cleaning and/or toilets cleaning,

- a wipe or pad for daily shower.

15. A product according to any of claims 1 to 7 or 9 or 10, being a personal-care wet wipe or pad, wherein the composition comprises: - a liquid medium, preferably an aqueous medium, an alcoholic medium, or a hydroxyalcoholic medium,

- the hop extract,

- optionally at least one surfactant.

16. A product according to the preceding claim, being:

- an antiperspirant product,

- an after shaving product, or

- a product for removing make-up.

17. A process of treating a surface for preventing bacteria proliferation, cleaning, disinfecting, suppressing odors, and/or preventing malodors, comprising the step of applying onto surface a product according to one of the preceding claims.

18. A process according to the preceding claim, wherein the surface is: - skin,

- hair, or

- a hard surface.

19. A process according to the preceding claim, wherein the surface is a hard surface being:

- glass, for example comprised in windows, or cars windshields,

- tile or ceramic, for example comprised in kitchens, bathrooms, toilet bowls, showers, china, dishware, - metal, for example comprised in silverware, car body parts, or window frames,

- plastic, for example comprised in dishware, silverware, cars, windows, or furniture, or

- wood or leather for example comprised in furniture.