EP1478336A1

EP1478336A1 - Perfume preparation containing 2- methyl-1, 3- propanediol

Info

Publication number: EP1478336A1
Application number: EP03708084A
Authority: EP
Inventors: Rainer Kröpke; Jens Nielsen
Original assignee: Beiersdorf AG
Current assignee: Beiersdorf AG
Priority date: 2002-02-08
Filing date: 2003-02-07
Publication date: 2004-11-24
Also published as: JP2005517692A; WO2003066011A1; DE10205192A1; US20050064000A1

Abstract

Disclosed is an aqueous and/or alcoholic cosmetic and/or dermatological preparation containing a) 2-methyl-1,3-propanediol at a concentration of 0.5 to 10 percent by weight, b) perfume oil at a concentration of 0.01 to 10.0 percent by weight, the respective percentage by weight being in relation to the total weight of the preparation, and the difference of the refraction indices of the dispersed phase and the external phase being larger than 0.003.

Description

PERFUME PREPARATION CONTAINING 2 -METHYL- l, 3-PROPANDIOL

The present invention relates to aqueous and / or alcoholic cosmetic and / or dermatological preparations containing 2-methyl-1, 3-propanediol and perfume oil with a difference in the refractive index of the dispersed phase and the outer phase of greater than 0.003, the process for the preparation and their use.

Fragrances and perfumes have been used by people to influence their environment since time immemorial. It can be assumed that a multitude of natural fragrance sources already existed in the environment of early humans, which he also used in connection with the satisfaction of primitive needs. With the discovery of fire, the use of fragrances received strong impulses and a new dimension in human life. The smoke offering is the oldest form of worshiping the gods, and the burning of certain parts of plants is one of the oldest methods of producing fragrance. The fragrance unfolds "per fumum" through the smoke.

Perfuming the human body has also been known for ages. Egyptians, Persians and Scythians used resins and fragrant vegetable oils to embalm their dead. In the Old Testament, a complete formulation for an anointing oil can be found in Exodus 30 in the second book of Moses.

Today, perfumes are made from natural plant and animal fragrances and from chemically synthesized compounds.

Herbal fragrances are usually obtained by steam distillation in the form of essential oils. One example is the eugenol obtained from clove oil. With volatile, temperature-sensitive fragrances, for example the oil from jasmine flowers, enfleurage has been used since ancient times as an extraction process to obtain the "Absolu de Chassis". Sensitive citrus oils are obtained by squeezing fruit peels. for example for the production of resinoids from balsams and resins or benzoin from certain types of lichen and moss, use.

Animal fragrances are mainly obtained from glandular excretions of certain animal species such as musk, civet or beaver. Due to their strong smell, these glandular secretions, which are mainly used by animals to mark territory, are only used in diluted form.

Due to the nature and species protection as well as the high price, many natural fragrances are made semi or fully synthetic. Chemical synthesis also enables the development of new, unknown fragrance notes.

Fragrances and the perfume oils made from them are used in almost all cosmetic preparations as well as in detergents and household cleaners. They serve to mask the intrinsic odor of components of these preparations and, in the case of cosmetics and detergents, the intrinsic odor of their users [W. Umbach (ed.): Cosmetics, development, manufacture and application of cosmetic products, 2nd edition, Thieme Verlag, Stuttgart, 1995].

Fragrances and the perfume oils made from them are mostly non-polar, oil-soluble compounds and mixtures that are difficult or not soluble in water, alcohol or aqueous-alcoholic solutions. In order to be able to incorporate and stabilize perfume oils in such polar preparations, these solubilizers are added. These usually have an amphiphilic structure and are similar to emulsifiers and tesides. As a rule, ethoxylated carbohydrates or fatty acid derivatives, for example polyoxyethylene (20) sorbitan monolaurate (Tween 20) or polyoxyethylene oxypropylene monostearate (Atlas G-2162), are used to impart perfume oils.

As such, the use of solubilizers in cosmetic or dermatological preparations is harmless. Nevertheless, solubilizers, like ultimately every chemical substance, can cause allergic or hypersensitive reactions in individual cases. Skin irritation, for example, can occur as an undesirable side effect in sensitive people. Therefore their concentration in cosmetic or dermatological preparations should be kept as low as possible or avoided entirely.

It is also a disadvantage of the prior art that complex mixtures of solubilizers often have to be used in order to achieve stable cosmetic preparations. The suitable compositions of these mixtures can usually only be found out by trial and error, which makes the development of these preparations lengthy and expensive. In addition, a large number of solubilizers are not pure substances but, due to the manufacturing process, mixtures, which further increases the problems with product compatibility and product stability.

It was therefore the object of the present invention to eliminate the disadvantages of the prior art and to develop new solubilizers with which stable, well-tolerated, aqueous and / or alcoholic cosmetic perfume preparations can be produced in a simple manner.

Many aqueous and / or alcoholic cosmetic preparations are transparent. However, consumers often associate water-clear, transparent solutions with products with a low active ingredient content. Slightly cloudy products, on the other hand, are associated with a high active ingredient content and high cosmetic or dermatological performance.

It was therefore a further object of the present invention to give the cosmetic preparations according to the invention a cloudy, translucent appearance.

The objects are surprisingly achieved by aqueous and / or alcoholic cosmetic and / or dermatological preparations containing a) 2-methyl-1,3-propanediol in a concentration of 0.5 to 30% by weight, b) perfume oil in a concentration of 0 , 01 to 10.0% by weight, based in each case on the total weight of the preparation, with a difference in the refractive indices of the dispersed phase and the outer phase of greater than 0.003. These preparations are characterized by a high tolerance and care performance. They can also be used to easily formulate a large number of extremely stable cosmetic and / or dermatological preparations.

Although WO 00/33804 also describes perfume compositions, which may also contain 2-methyl-1,3-propanediol, this document could not point the way to the present invention, since it describes only transparent and no cloudy, translucent preparations.

It is particularly advantageous if the preparations according to the invention a) 2-methyl-1,3-propanediol in a concentration of 2 to 10% by weight, b) perfume oil in a concentration of 0.1 to 3.0% by weight, in each case based on the total weight of the preparation included.

It is also advantageous according to the invention if the difference in the refractive indices of the dispersed phase and the outer phase is greater than 0.01.

The weight ratio of 2-methyl-1,3-propanediol to perfume oil in the preparations according to the invention is advantageously from 1: 1 to 100: 1 and particularly preferably from 5: 1 to 50: 1.

The alcohol which is particularly preferred according to the invention is ethanol.

Of course, the aqueous and / or alcoholic cosmetic and / or dermatological preparations according to the invention can, depending on the application, contain further cosmetic and / or dermatological active ingredients, auxiliaries and / or additives. The use of the preparations according to the invention for purposes other than cosmetic or dermatological purposes, for example as detergents, cleaning agents, household cleaners or disinfectants, is also in accordance with the invention in the compositions customary for these compositions, the list of these uses being in no way intended to be limiting. In addition to water, an aqueous solution according to the invention can also contain other ingredients according to the invention, for example alcohols, diols or polyols of low C number, and their ethers, preferably ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, diethylene glycol monomethyl or monoethyl ether and similar products, furthermore alcohols with a low C number, for example ethanol, isopropanol, 1, 2-propanediol and glycerol.

The preparations according to the invention can advantageously contain thickeners. These thickeners can advantageously be selected from the group of gums, polysaccharides, cellulose derivatives, layered silicates, polyacrylates and / or other polymers.

Gums include plant or tree sap that harden in the air and form resins or extracts from aquatic plants. Gum arabic, locust bean gum, tragacanth, karaya, guar gum, pectin, gellan gum, carrageenan, agar, algine, chondrus, xanthan gum can advantageously be selected from this group for the purposes of the present invention.

The use of derivatized gums such as e.g. Hydroxy-propyl guar (Jaguar® HP 8).

Among the polysaccharides and derivatives are e.g. Hyaluronic acid, chitin and chitosan, chondroitin sulfates, starch and starch derivatives.

Among the cellulose derivatives are e.g. Methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose.

Layered silicates contain naturally occurring and synthetic clays such as Montmorillonite, bentonite, hectorite, laponite, magnesium aluminum silicates such as Veegum®. These can be used as such or in a modified form such as e.g. Stearylalkonium hektorite.

Furthermore, silica gels can also advantageously be used. The polymers according to the invention include, for example, polyacrylamides (Seppigel 305), polyvinyl alcohols, PVP, PVP / VA copolymers, polyglycols. Polyacrylates which are advantageous according to the invention are polymers of acrylic acid, in particular those selected from the group of the so-called carbomers or carbopols (Carbopol® is actually a registered trademark of the Noveon Company). Polyacrylates are compounds of the general structural formula

whose molecular weight can be between approximately 400,000 and more than 4,000,000. The group of polyacrylates also includes acrylate-alkyl acrylate copolymers, for example those which are distinguished by the following structure:

R 'represents a long-chain alkyl radical and x and y numbers which symbolize the respective stoichiometric proportion of the respective comonomers. These polyacrylates are also advantageous for the purposes of the present invention.

Examples of advantageous carbopoles are types 907, 910, 934, 940, 941, 951, 954, 980, 981, 1342, 1382, 2984 and 5984 or types ETD (Easy-to-disperse) 2001, 2020, 2050, where these compounds can be present individually or in any combination with one another.

Carbopol 981, 1382 and ETD 2020 (both individually and in combination) are particularly preferred. Also advantageous for the purposes of the present invention, the alkyl acrylate to acrylate copolymers, copolymers of comparable C _10-3 o-alkyl acrylates and one or more monomers of acrylic acid, methacrylic acid or esters thereof. The INCI name for such compounds is "Acrylates / C 10-30 Alkyl Acrylate Crosspolymer". Particularly advantageous are those available under the trade names Pemulen TR1 and Pemulen TR2 from the BF Goodrich Company.

Terpolymers, for example made from vinylpyrrolidone, dimethylaminopropyl methacrylamide and quaternized alkyldimethylaminopropyl methacrylamide, can also be used advantageously according to the invention.

In addition to the aforementioned substances, the compositions optionally contain the additives customary in cosmetics, for example perfume, dyes, antimicrobial substances, refatting agents, complexing and sequestering agents, pearlescent agents, further plant extracts, vitamins, active ingredients, preservatives, bactericides, self-tanning agents , Depigmenting agents, pigments that have a coloring effect, softening, moisturizing and / or moisturizing substances, or other customary components of a cosmetic or dermatological formulation such as polymers, foam stabilizers, electrolytes, organic solvents or silicone derivatives.

An additional level of antioxidants is generally preferred. According to the invention, all the antioxidants suitable or customary for cosmetic and / or dermatological applications can be used as favorable antioxidants.

According to the invention, the preparations according to the invention can advantageously contain small amounts of preservatives approved for food. Preservatives approved in food technology, which can also be used advantageously for the purposes of the present invention, are listed below with their E number.

Also useful in cosmetics are preservatives or preservatives, such as dibromodicyanobutane (2-bromo-2-bromomethylglutarodinitrile), phenoxyethanol, 3-iodo-2-propynylbutylcarbamate, 2-bromo-2-nitro-propane-1, 3-diol , Imidazolidinyl urea, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-chloroacetamide, benzalkonium chloride, benzyl alcohol.

The preparations according to the invention can advantageously contain one or more wash-active anionic, cationic, amphoteric and / or non-ionic surfactants. It is particularly advantageous to choose the wash-active surfactant or surfactants according to the invention from the group of surfactants which have an HLB value of more than 25, very particularly advantageous are those which have an HLB value of more than 35.

Particularly advantageous wash-active anionic surfactants in the sense of the present

Are invention

Acylamino acids and their salts, such as

^■ acylglutamates, especially sodium acylglutamate

^■ sarcosinates, roylsarcosinat for example myristoyl sarcosine, TEA-lauroyl sarcosinate, sodium and sodium,

Sulfonic acids and their salts, such as

^■ acyl isethionates, eg sodium / Ammoniumcocoyl isethionate, Sulfosuccinates, for example dioctyl sodium sulfosuccinate, disodium laureth sulfosuccinate, disodium lauryl sulfosuccinate and disodium undecylenamido MEA sulfosuccinate

as well as sulfuric acid esters, such as

■ Alkyl ether sulfate, for example sodium, ammonium, magnesium, MIPA, TIPA laureth sulfate, sodium myreth sulfate and sodium C ₁₂ . ₁₃ pareth sulfate,

■ Alkyl sulfates, for example sodium, ammonium and TEA lauryl sulfate.

Quaternary surfactants are particularly advantageous washing-active cationic surfactants for the purposes of the present invention. Quaternary surfactants contain at least one N atom which is covalently linked to 4 alkyl or aryl groups. Benzalkonium chloride, alkyl betaine, alkyl amidopropyl betaine and alkyl amidopropyl hydroxysultain are advantageous.

Particularly advantageous wash-active amphoteric surfactants in the sense of the present invention are

^■ acyl / dialkylethylenediamines, for example sodium, Dinatriumacyl- amphodipropionat, disodium, Natriumacylamphohydroxypropyl- sulfonate, and sodium acyl Dinatriumacylamphodiacetat,

Particularly advantageous washing-active nonionic surfactants in the sense of the present invention are

^■ alkanolamides, such as cocamides MEA DEA / MIPA, ^■ esters formed by esterification of carboxylic acids with ethylene oxide, glycerol, sorbitan or other alcohols,

^■ ethers, for example ethoxylated alcohols, ethoxylated lanolin, ethoxylated polysiloxanes, propoxylated POE ethers and alkyl polyglycosides such as lauryl glucoside, decyl glycoside and cocoglycoside.

Other advantageous anionic surfactants are

^■ taurates, for example sodium lauroyl taurate and sodium methyl cocoyl taurate,

^■ ether carboxylic acids, for example sodium laureth-13 carboxylate and sodium PEG-6 cocamide carboxylate, Phosphoric acid esters and salts, such as DEA-Oleth-10 phosphate and dilaureth-4 phosphate,

■ Alkyl sulfonates, for example sodium coconut monoglyceride sulfate, sodium C _12- , ₄ olefin sulfonate, sodium lauryl sulfoacetate and magnesium PEG-3 cocamide sulfate.

Other advantageous amphoteric surfactants are

■ N-alkylamino acids, for example aminopropylalkylglutamide, alkylaminopropionic acid, sodium alkylimidodipropionate and lauroamphocarboxyglycinate.

Further advantageous non-ionic surfactants are alcohols.

Other suitable anionic surfactants for the purposes of the present invention are also

^■ glutamates, such as di-TEA-palmitoyl aspartate and sodium caprylic / capric glutamate,

^■ Acyl peptides, for example palmitoyl hydrolyzed milk protein, sodium cocoyl hydrolyzed soy protein and sodium / potassium cocoyl hydrolyzed collagen

as well as carboxylic acids and derivatives, such as

^■ for example lauric acid, cylenat aluminum stearate, magnesium and Zinkunde-, ^■ ester carboxylic acids, for example calcium stearoyl lactylate, laureth-6 citrate and sodium PEG-4 lauramide carboxylate,

^■ alkylarylsulfonates.

Further suitable cationic surfactants for the purposes of the present invention are also ^■ alkylamines,

^■ Alkylimidazoles and

^■ ethoxylated amines.

Other suitable nonionic surfactants for the purposes of the present invention are also amine oxides, such as cocoamidopropylamine oxide.

Preparations in the sense of the present invention can preferably contain at least one UV-A, UV-B and / or broadband filter substance Advantageous UV filter substances for the purposes of the present invention are, for example, sulfonated, water-soluble UV filters, such as:

• Phenylene-1,4-bis (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid and its salts, especially the corresponding sodium, potassium or triethanolammonium salts, in particular phenylene-1 , 4-bis- (2-benzimidazyl) -3,3'-5,5'-tetrasulfonic acid-bis-sodium salt with the INCI name bisimidazylate (CAS no .: 180898-37-7), which, for example, under the trade name Neo Heliopan AP is available from Haarmann &Reimer;

• Salts of 2-phenylbenzimidazole-5-sulfonic acid, such as its sodium, potassium or triethanolammonium salt, and the sulfonic acid itself with the INCI name phenylbenzimidazole sulfonic acid (CAS No. 27503-81-7), which is available, for example, under the trade name Eusolex 232 from Merck or under Neo Heliopan Hydro from Haarmann &Reimer;

1,4-di (2-oxo-10-sulfo-3-bomylidenemethyl) benzene (also: 3,3 '- (1,4-phenylenedimethylene)) bis- (7,7-dimethyl-2- oxo-bicyclo- [2.2.1] hept-1-ylmethanesulfonic acid) and its

Salts (especially the corresponding 10-sulfato compounds, especially the corresponding sodium, potassium or triethanolammonium salt), which is also referred to as benzene-1, 4-di (2-oxo-3-bornylidenemethyl-10-sulfonic acid) , Benzene-1,4-di (2-oxo-3-bomylidenemethyl-10-sulfonic acid) has the INCI name Terephthalic Dicampher Sulfonic Acid (CAS No. 90457-82-2) and is, for example, under the trade name Mexoryl SX available from Chimex; Sulfonic acid derivatives of 3-benzylidene camphor, such as. B. 4- (2-oxo-3-bornylidene-methyl) benzenesulfonic acid, 2-methyl-5- (2-oxo-3-bornylidene-methyl) sulfonic acid and salts thereof.

The list of the UV filters mentioned, which can be used in the sense of the present invention, should of course not be limiting.

The preparations according to the invention advantageously contain the substances which absorb UV radiation in the UV-A and / or UV-B range in a total amount of, for. B. 0.1% by weight to 30% by weight, preferably 0.5 to 20% by weight, in particular 1.0 to 15.0% by weight, in each case based on the total weight of the emulsions, for cosmetic purposes To provide preparations that protect the hair or skin from the entire range of ultraviolet radiation.

According to the invention, large amounts of acidic aluminum and / or aluminum / zirconium salts can advantageously be incorporated stably into the preparation. 5 to 40% by weight, in particular 10 to 20% by weight, aluminum chlorohydrate and / or aluminum / zirconium chlorohydrate can be stably incorporated into the preparations according to the invention. The concentration ranges described here relate to the so-called active contents of the antiperspirant complexes: for the aluminum compounds to anhydrous complexes, for the aluminum / zirconium compounds to anhydrous and buffer-free complexes. Glycine is usually used here as a buffer.

The following list of antiperspirant active ingredients to be used advantageously is in no way intended to be restrictive:

Aluminum salts (the empirical empirical formula [AI ₂ (OH) _m Cl _n ], where m + n = 6):

• Aluminum salts such as aluminum chloride AICI ₃ , aluminum sulfate AI ₂ (S0) ₃

• Aluminum chlorohydrate [AI ₂ (OH) ₅ CI] x H ₂ 0 standard Al complexes: Locron L (Clariant), chlorohydrol (Reheis), ACH-303

(Summit), Aloxicoll L (Giulini). Activated AI complexes: Reach 501 (Reheis), AACH-324 (Summit)

• Aluminum _{sesquichlorohydrate} [AI ₂ (OH) _4ι5 CI _{1 5} ] x H ₂ O

Standard AI complexes: Aluminum Sesquichlorohydrate (Reheis), ACH-308 (Summit), Aloxicoll 31 L (Giulini)

Activated AI complexes: Reach 301 (Reheis)

Aluminum dichlorohydrate [AI ^ OH ^ CIJ x H ₂ 0

Aluminum-zirconium salts: • Aluminum / zirconium trichlorohydrex glycine [AI ₄ Zr (OH) ₁₃ CI ₃ ] x H ₂ O x Gly

Standard Al / Zr complexes: Rezal 33GP (Reheis), AZG-7164 (Summit), Zirkonal P3G (Giulini)

Activated Al / Zr complexes: Reach AZZ 902 (Reheis), AAZG-7160 (Summit), Zirkonal AP3G (Giulini) • Aluminum / zirconium tetrachlorohydrex glycine [AI ₄ Zr (OH) ₁₂ CI ₄ ] x H ₂ Ö x Gly

Standard Al / Zr complexes: Rezal 36G (Reheis), AZG-368 (Summit), Zirkonal

L435G (Giulini) Activated Al / Zr complexes: Reach AZP 855 (Reheis), AAZG-6313-15 (Summit), Zirkonal AP4G (Giulini)

• Aluminum / zirconium pentachlorohydrex glycine [AI ₈ Zr (OH) ₂₃ CI ₅ ] x H ₂ 0 x Gly Standard Al / Zr complexes: Rezal 67 (Reheis), Zirkonal L540 (Giulini) Activated Al / Zr complexes: Reach AZN 885 (Reheis)

• Aluminum / zirconium octachlorohydrex glycine [Al ₈ Zr (OH) ₂₀ CI ₈ ] x H ₂ 0 x Gly

However, glycine-free aluminum / zirconium salts can also be advantageous.

The use of antiperspirants from the raw material classes aluminum and aluminum / zirconium salts should not affect the commercially available, mostly aqueous solutions, e.g. Locron L (Clahant), may be limited, but it may also be advantageous to use the commercially available anhydrous powders of the same raw materials by incorporating them into the claimed formulations, such as Locron P (Clariant).

Furthermore, it can also be advantageous to use special aluminum and aluminum / zirconium salts, which are offered as glycol complexes to improve solubility.

Other advantageous antiperspirants are based on other metals, such as e.g. aluminum or zirconium. Beryllium, titanium, hafnium.

However, the list of antiperspirant active ingredients that can be used should not be limited to metal-containing raw materials, but also compounds that contain non-metals such as boron and those that belong to the field of organic chemistry, such as e.g. Anticholinergics.

In this sense, polymers which can be both metal-containing and metal-free are also advantageous. The method for producing an aqueous and / or alcoholic cosmetic and / or dermatological preparation according to the invention is also according to the invention. This is characterized in that the perfume oil is first dissolved in 2-methyl-1,3-propanediol and then the remaining components of the preparation are added.

Furthermore, the use of 2-methyl-1,3-propanediol according to one of the preceding claims as a solubilizer in aqueous and / or alcoholic cosmetic and / or dermatological preparations is according to the invention.

The use of the aqueous and / or alcoholic cosmetic and / or dermatological preparations according to the invention as a facial tonic, fragrant water, aftershave, deodorant, antiperspirant, facial cleansing water, make-up remover, hair tonic, hair fixer and hair styling agent, bath additive, foam or shower bath is also in accordance with the invention. repellent, depigmenting agent.

The use of aqueous and / or alcoholic cosmetic and / or dermatological preparations according to one of the preceding claims as water, solution, impregnation, tincture or spray is also according to the invention.

The following examples are intended to illustrate the present invention without restricting it. Unless otherwise stated, all quantities, parts and percentages are based on the weight and the total amount or on the total weight of the preparations.

Aqueous and / or alcoholic preparation

(Facial toner, eye make-up remover, aftershave)

Claims

claims

1. Aqueous and / or alcoholic cosmetic and / or dermatological preparation containing a) 2-methyl-1,3-propanediol in a concentration of 0.5 to 30% by weight, b) perfume oil in a concentration of 0.01 to 10 , 0% by weight, based in each case on the total weight of the preparation, with a difference in the refractive indices of the dispersed phase and the outer phase of greater than 0.003.

2. Aqueous and / or alcoholic cosmetic and / or dermatological preparation according to claim 1, characterized in that it contains further cosmetic and / or dermatological active ingredients, auxiliaries and / or additives.

3. Aqueous and / or alcoholic cosmetic and / or dermatological preparation according to one of claims 1 or 2, characterized in that the weight ratio of 2-methyl-1, 3-propanediol to perfume oil is 1: 1 to 100: 1.

4. A method for producing an aqueous and / or alcoholic cosmetic and / or dermatological preparation according to one of claims 1 to 3, characterized in that the perfume oil is first dissolved in 2-methyl-1, 3-propanediol and then the other constituents of the Preparation to be added.

5. Use of 2-methyl-1, 3-propanediol according to one of the preceding

Claims as solubilizers in aqueous and / or alcoholic cosmetic and / or dermatological preparations.

6. Use of aqueous and / or alcoholic cosmetic and / or dermatological preparations according to one of the preceding claims as a facial toner, fragrance, aftershave, deodorant, antiperspirant,

Facial cleansing water, make-up remover, hair tonic, hair fixer and conditioner, bath additive, insect repellent (repellent), depigmenting agent.

7. Use of aqueous and / or alcoholic preparations according to one of the preceding claims as detergents, cleaning agents, household cleaners,

Disinfectant.

8. Use of aqueous and / or alcoholic cosmetic and / or dermatological preparations according to one of the preceding claims as water, solution, impregnation, tincture, spray.