KR20070018878A - Fungicidal detergent composition - Google Patents

Abstract

The use of the compounds of formula (1) for the fungicidal treatment of hard surfaces and textile fibers is described:

(1)

(One)

In the formula,

R ₁ is hydrogen; Or C ₁ -C ₅ alkyl.

Compounds of formula (1) impart antifungal properties to the washed textile material. Bacteria on the fabric material are destroyed during wear.

Hard Surfaces, Fabrics, Fungicidal Treatments, Caetomium globosum

Description

Fungicidal Detergent compositions

The present invention relates to fungicidal detergent compositions and to the use of such compositions for the fungicidal treatment of hard surfaces and textile fibers.

Under high humidity conditions and mild temperatures, fungi cause moist moisture and unpleasant odors to the fabric. Some fungal species, such as Chaetomium globosum , are known to produce geosmin, a volatile organic compound with a pronounced coarse odor.

Some discoloration may occur due to the formation of colored spore masses. The color change of the fabric can be caused by the acid and other substances produced by the fungus.

The fungal zone changes from green to brown and dark black hues. Tomyum Globo breath (Chaetomium globosum) to be a very common fungal car associated with mildew occurs on the fabric creates a dark gray, light green pollution on the fabric. Pigmentation is also caused by acids produced by the action of Downy mildew on cellulose, soil and other food substances on fabrics.

The enzymes that the fungus produces can cause fabric contamination and rot. This species is known as a cellulose catcher, such as Chaetomium globosum .

Cleaning and disinfecting compositions comprising fungicidal active ingredients, such as hand-washing and dishwashing formulations, hard surface cleaning and disinfecting formulations and liquid and solid fabric laundry formulations, are increasingly being used. Fungicidal action and dust mite growth control are increasingly required in such formulations.

Surprisingly, detergent compositions comprising a compound of formula (1) as a fungicidal active ingredient have been found to exhibit a strong fungicidal effect on hard surfaces and textile materials:

In the formula,

R ₁ is hydrogen; Or C ₁ -C ₅ alkyl.

The present invention therefore also relates to the use of the compounds of formula (1) for the fungicidal treatment of hard surfaces and textile fibres.

Preferably, in formula (1), R ₁ is hydrogen (1H-benzimidazole, 2- (4-thiazolyl)-; thibendazole).

The present invention therefore relates to a detergent composition comprising:

(a) 0.01 to 90% by weight of compound of formula (1);

(b) 1 to 80% by weight of one or more synthetic detergents or soaps or combinations of the above components;

(c) 0 to 75% by weight builder;

(d) 0-30% by weight of peroxide;

(e) 0-10% by weight of a bleach activator;

(f) 0 to 50% by weight of one or more oysters;

(g) 0-50% by weight of alcohol;

(h) 0 to 80 weight percent of fabric softening component; And

(i) Add tap water or deionized water and add up to 100% by weight of all components.

Preferably, the present invention relates to a detergent composition comprising:

(a) 0.01 to 10% by weight of compound of formula (1);

(b) 5 to 70% by weight of one or more synthetic detergents or soaps or combinations of the above components and / or salts of saturated and / or unsaturated C ₈ -C ₂₂ fatty acids;

(f) 0 to 50% by weight of one or more oysters;

(g) 0-50% by weight of alcohol;

(h) 0 to 80 weight percent of fabric softening component; And in some cases

(i) Add tap water or deionized water and make up 100% by weight of all components.

As component (b), anionic, nonionic, or zwitterionic and amphoteric synthetic detergents are suitable.

Suitable anionic detergents are as follows:

Sulfates, such as fatty alcohol sulfates whose alkyl chains have from 8 to 18 carbon atoms, such as sulfated lauryl alcohol;

Acid esters or salts thereof of fatty alcohol ether sulfates, such as the polyaddition product of 2 to 30 moles of ethylene oxide with 1 mole of C ₈ -C ₂₂ fatty alcohols;

Alkali metal, ammonium or amine salts (called soap) of C ₈ -C ₂₀ fatty acids, such as coconut fatty acids;

Alkylamide sulfates;

Alkylamine sulfates such as monoethanolamine lauryl sulfate;

Alkylamide ether sulfates;

Alkylaryl polyether sulfates;

Monoglyceride sulfate;

Alkanesulfonates whose alkyl chains have from 8 to 20 carbon atoms, such as dodecyl sulfonate;

Alkylamide sulfonates;

Alkylaryl sulfonates;

α-olefin sulfonates;

Sulfosuccinic acid derivatives such as alkyl sulfosuccinates, alkyl ether sulfosuccinates or alkyl sulfosuccinamide derivatives;

N- [alkylamidoalkyl] amino acids of the formula:

In the food,

X is hydrogen, C ₁ -C ₄ alkyl or -COO ^- M ⁺ ,

Y is hydrogen or C ₁ -C ₄ alkyl,

Z _is- (CH ₂ ) _{m1- 1} ,

m ₁ is 1 to 5,

n ₁ is an integer of 6 to 18, and

M is an alkali metal cation or an amine cation,

Alkyl and alkylaryl ether carboxylates of formula (13):

CH ₃ -XYA (13)

In the food,

또는

이며, X _is- (CH ₂ ) _5-19 -O-,

or

Is,

R is hydrogen or C ₁ -C ₄ alkyl,

Y is - (CHCHO) _1-50 -, and

이고, A is (CH ₂ ) _{m 2-1} -COO ^- M ⁺ or

ego,

m ₂ is 1 to 6,

M is an alkali metal cation or an amine cation.

Used as anionic surfactants are fatty acid methyl taurids, alkyl isothionates, fatty acid polypeptide condensation products and fatty alcohol phosphate esters. The alkyl radicals present in these compounds preferably have 8 to 24 carbon atoms.

Anionic surfactants are generally in the form of water soluble salts such as alkali metal, aluminum or amine salts. Examples of such salts include lithium, sodium, potassium, ammonium, triethylamine, ethanolamine, diethanolamine and triethanolamine salts. Sodium, potassium or ammonium (NR ₁ R ₂ R ₃ ) salts wherein R ₁ , R ₂ and R ₃ are independently hydrogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ hydroxyalkyl.

Particularly preferred anionic surfactants in the compositions according to the invention are alkali metal salts of monoethanolamine lauryl sulphate or fatty alcohol sulphates, in particular sodium lauryl sulphate and 2 to 4 moles of ethylene oxide and sodium lauyl ether sulphate. Reaction product.

Suitable zwitterionic and amphoteric surfactants include C ₈ -C ₁₈ betaine, C ₈ -C ₁₈ sulfobetaine, C ₈ -C ₂₄ alkylamido-C ₁ -C ₄ alkylenebetaine, imidazoline carbine Carboxylates, alkyl ampocarboxylic acids, alkyl ampocarboxylic acids (such as lauroampoglycinate) and N-alkyl-β-aminopropionate or -iminodipropionate, and C ₁₀ -C ₂₀ alkylamido-C Preference is given to _1- C ₄ alkylenebetaines, particular preference to coconut fatty acid amide propylbetaines.

Illustrative nonionic surfactants include, for example, derivatives of adducts of propylene oxide / ethylene oxide of molecular weights 1000 to 15 000, fatty alcohol ethoxylates (1-50 EO), alkylphenol polyglycol ethers (1-50 EO) , Polyglucosides, ethoxylated hydrocarbons, fatty acid glycol partial esters such as diethyl glycol monostearate, fatty acid alkanolamides and dialkanolamides, fatty acid alkanolamide ethoxylates and fatty amine oxides.

As component (b) it is possible to use salts of saturated and unsaturated C ₈ -C ₂₂ fatty acids alone or mixtures of these with each other or with other detergents mentioned as component (b). Examples of such fatty acids are, for example, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, caprolein acid, dodecenoic acid, tetradecenoic acid, octadecenoic acid, oleic acid, Icosenoic and eruccinic acids and commercial mixtures of such acids, such as coconut fatty acids. Such acids exist in salt form, and cations include cationic alkali metal cations, sodium and potassium cations, metal atoms such as zinc and aluminum atoms, and nitrogen containing organic compounds having sufficient alkalinity such as amines and ethoxylated amines. . Such salts can be prepared in situ.

Laundry adjuvant component (c) comprises alkali metal phosphates, in particular tripolyphosphate; Carbonates or bicarbonates, especially sodium salts thereof; Silicates or disilicates; Aluminosilicates; Polycarboxylates; Polycarboxylic acids; Organic phosphonates; Or aminoalkylene poly (alkylene phosphonates); Or mixtures thereof. Preferred silicates are the crystalline layer sodium silicates of the formula NaHSi _m O _{2m +1} · pH ₂ O or Na ₂ Si _m O _{2m +1} · pH ₂ O, where m is a number from 1.9 to 4 and p is from 0 to 20 . Preferred aluminosilicates are commercially available synthetic materials represented as zeolites A, B, X and HS or mixtures thereof. Zeolite A is preferred. Preferred polycarboxylates include hydroxypolycarboxylates, in particular copolymers of citrate, polyacrylates and maleic anhydrides thereof.

Preferred polycarboxylic acids include nitrilotriacetic acid and ethylene diamine tetra-acetic acid.

Preferred organic phosphonates or aminoalkylene poly (alkylene phosphonates) include alkali metal ethane 1-hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine tetra methylene phosphonates and diethylene triamine penta Methylene phosphonate.

The amount of laundry aid is preferably 5 to 70% by weight, preferably 5 to 60% by weight, more preferably 10 to 60% by weight. The lower limit for the laundry aid is preferably 15% by weight, in particular 20% by weight.

Suitable peroxide components (d) include, for example, commercially available organic and inorganic peroxides (such as sodium peroxide) which bleach the fabric at ordinary washing temperatures, such as from 5 to 95 ° C. In particular, the organic peroxide is for example a monoperoxide or polyperoxide having at least 3, preferably 6 to 20 carbon atoms; Of particular importance are diperoxydicarboxylates having 6 to 12 carbon atoms, in particular their corresponding free acids, such as diperoxyperazate, diperoxypercebacate, diperoxyphthalate and / or diperoxydodecanedioate . However, preference is given to applying active inorganic peroxides such as persulfate, perborate and / or percarbonate. It is of course also possible to use mixtures of organic and / or inorganic peroxides.

The amount of peroxide is preferably 0.5 to 30% by weight, preferably 1 to 20% by weight, more preferably 1 to 15% by weight. When using peroxides, the lower limit is 2% by weight, in particular 5% by weight.

의 화합물이며, 이때 R은 술포네이트 기, 카르복시산 기 또는 카르복실레이트 기이며, 또 R'는 직쇄 또는 측쇄 (C₇-C₁₅) 알킬이며; 또한 SNOBS, SLOBS, NOBS 및 DOBA로 공지된 활성화제, 아실화된 다가 알코올, 특히 트리아세틴, 에틸렌 글리콜 디아세테이트 및 2,5-디아세톡시-2,5-디히드로푸란 및 아세틸화된 소르비톨 및 만니톨 및 아실화된 당 유도체, 특히 펜타아세틸글루코오스(PAG), 수크로오스 폴리아세테이트 (SUPA), 펜타아세틸프럭토오스, 테트라아세틸크실로오스 및 옥타아세틸락토오스, 및 아세틸화된, 경우에 따라 N-알킬화된, 글루카민 및 글루코노락톤이다. 독일 특허출원 DE-A-44 43 177호에 기재된 통상의 표백 활성화제의 조합물도 사용할 수 있다. 퍼옥사이드와 함께 퍼옥시이미드산을 형성하는 니트릴 화합물이 표백 활성화제로서 적합하다. 테트라아세틸 에틸렌디아민 및 노노일옥시벤젠 술포네이트가 바람직하다. Peroxides, especially inorganic peroxides, are preferably activated by incorporating bleach activators (component (e)). Preference is given to compounds which give unsubstituted or substituted perbenzo- and / or peroxo-carboxylic acids having from 2 to 10 carbon atoms, in particular from 2 to 4 carbon atoms, under perhydrolysis conditions. Suitable compounds are compounds having O- and / or N-acyl groups having the aforementioned number of carbon atoms and / or unsubstituted or substituted benzoyl groups. Preference is given to polyacrylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N, N-diacetyl-N, N-dimethyl-urea ( DDU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT),

Wherein R is a sulfonate group, carboxylic acid group or carboxylate group, and R 'is straight or branched chain (C ₇ -C ₁₅ ) alkyl; Activators also known as SNOBS, SLOBS, NOBS and DOBA, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran and acetylated sorbitol and Mannitol and acylated sugar derivatives, in particular pentaacetylglucose (PAG), sucrose polyacetate (SUPA), pentaacetylfructose, tetraacetylxylose and octaacetyllactose, and acetylated, optionally N-alkylated Glucamine and gluconolactone. Combinations of conventional bleach activators described in German patent application DE-A-44 43 177 can also be used. Nitrile compounds that form peroxyimide acids with peroxides are suitable as bleach activators. Tetraacetyl ethylenediamine and nonnoyloxybenzene sulfonate are preferred.

The amount of bleach activator is 0 to 10% by weight, preferably 0 to 8% by weight. If a bleach activator is used, the lower limit is preferably 0.5% by weight, in particular 1% by weight.

Bleach catalysts that may be added include, for example, enzyme peroxide precursors and / or metal complexes. Preferred metal complexes are manganese, cobalt or iron complexes such as manganese or cobalt phthalocyanine or the complexes described in EP-A-0 509 787. If a bleach catalyst is used, the amount is preferably 0.005 to 2% by weight, more preferably 0.01 to 2% by weight, in particular 0.05 to 2% by weight. Especially preferably, it is 0.1-2 weight%.

Examples of bleach catalysts include:

WO-A-95 / 30681 (Reference, formula (I) and the definitions in lines 7-30 on page 1; in particular formula (I) and the definitions described on page 2, lines 29 to 11, line 11). Preferred ligands are described on page 13 line 12 to page 26 line 11.

WO-A01 / 09276 (references defined in formulas (1), (2) and (3) and pages 2-3).

-WO-A01 / 05925 (Reference, formula (1) and the definitions set out in the last paragraphs on page 1 to the first paragraphs on page 2. Preferred contents given for the metal complexes are given in formulas (2) on page 2 and on page 4) Also applies to (3)).

WO-A-02 / 088289 (reference, formula (1) and the definitions set forth on page 2. Preferred contents given for the metal complexes apply to the ligands of formula (3), page 3, paragraph 4 to page 4). Contents of the seventh paragraph are preferred).

The following compounds are suitable as component (f):

Sulfonates of terpenoids or sulfonates of mononuclear or dinuclear aromatic compounds, such as camphor, toluene, xylene, sulfonates of cumene or sulfonates of naphthol;

Saturated or unsaturated C ₃ -C ₁₂ di- or poly-carboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, undecane- and dodecane- Diacids, fumaric acid, maleic acid, tartaric acid and malic acid, and citric acid and aconic acid;

Aminocarboxylic acids such as ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetetraacetic acid and nitrilotriacetic acid;

Cycloaliphatic carboxylic acids, such as camphoric acid;

Aromatic carboxylic acids such as benzoic acid, phenylacetic acid, phenoxyacetic acid and cinnamic acid, 2-, 3- and 4-hydroxybenzoic acid, anilic acid and o-, m- and p-chlorophenylacetic acid and o-, m- and p-chlorophenoxy acetic acid;

Isethionic acid;

Tannic acid;

의 산 아미드, -Chemical formula

Acid amide,

Wherein R ₁ is hydrogen or C ₁ -C ₁₂ alkyl and

R ₂ and R ₃ are each independently hydrogen, C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₂ -C ₁₂ hydroxyalkenyl, C ₂ -C ₁₂ hydroxyalkyl or 1 to 30 A polyglycol ether chain having a CH ₂ -CH ₂ -O- or -CHY ₁ -CHY ₂ O- group, wherein one of the radicals Y ₁ and Y ₂ is hydrogen and the remainder is methyl, such as N-methylacetamide ;

의 우레아 유도체, -Chemical formula

Urea derivatives,

Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen, C ₁ -C ₈ alkyl, C ₂ -C ₈ alkenyl, C ₁ -C ₈ hydroxyalkyl or C ₂ -C ₈ hydroxyalke Neil.

All organic acids mentioned under (f) are their water-soluble salt forms, such as alkali metal salts, in particular sodium or potassium salts, or amine (NR ₁ R ₂ R ₃ ) salts,

Wherein R ₁ , R ₂ and R ₃ are each independently hydrogen, C ₁ -C ₈ alkyl, C ₂ -C ₈ alkenyl, C ₁ -C ₈ hydroxyalkyl, C ₅ -C ₈ cycloalkyl or polyalkylene oxy, or -C ₁ -C ₁₈ alkyl, or

R ₁ , R ₂ and R ₃ are unsubstituted or C ₁ -C ₄ alkyl-substituted morpholino combined with the nitrogen atom to which they are attached.

Component (f) may consist of a single compound or a plurality of different compounds.

Particular preference is given to combinations of cumenesulfonate and citric acid monohydrate.

Component (g) is a dihydric alcohol, in particular a compound having 2 to 6 carbon atoms in the alkylene moiety, such as ethylene glycol, 1,2- or 1,3-propanediol, 1,3-, 1,4- or 2 , 3-butanediol, 1,5-pentanediol and 1,6-hexanediol.

1,2-propanediol (propylene glycol) is preferred.

Preferred monohydric alcohols are ethanol, n-propanol and isopropanol and mixtures of these alcohols.

Preferred detergent compositions according to the invention which are particularly useful for the fungicidal treatment of textile fibers

(a) 0.01 to 5% by weight of compound of formula (1);

(b) 1 to 70 weight percent of anionic surfactant and / or nonionic surfactant;

(c) 0 to 75% by weight of laundry aids;

(d) 0-30% by weight of peroxide; And

(e) 0 to 10 weight percent of a peroxide activator;

Most preferably,

(a) 0.01 to 5% by weight of compound of formula (1);

(b) 5 to 70 weight percent of anionic surfactants and / or nonionic surfactants;

(c) 5 to 70% by weight of laundry aids;

(d) 0.5 to 30 weight percent of peroxide; And

(e) 0.5 to 10 weight percent peroxide activator and / or 0.1 to 2 weight percent bleach catalyst.

Detergents also optionally contain enzymes. Enzymes can be added to the detergent for decontamination. Enzymes often improve performance against protein- or starch-based contamination, such as contamination by blood, milk, grass or fruit juices. Preferred enzymes are cellulases, proteases, amylases and lipases. Preferred enzymes are cellulases and proteases, in particular proteases. Cellulase is an enzyme that acts on cellulose and its derivatives and hydrolyzes them to glucose, cellobiose, celloligosaccharides. Cellulase has the effect of removing dust and softening roughness. Examples of enzymes used include, but are not limited to:

Proteases described in US-B-6,242,405 column 14, lines 21-32;

Lipases described in US-B-6,242,405, columns 14, lines 33-46;

Amylases described in US-B-6,242,405, column 14, lines 47-56;

Cellulase as described in US-B-6,242,405, column 14, lines 57-64.

Enzymes may optionally be present in detergents. If used, the enzyme is present in an amount of from 0.01 to 5% by weight, preferably from 0.05 to 5% by weight, more preferably from 0.1 to 4% by weight, based on the total weight of the detergent.

The composition according to the invention may also further comprise an antimicrobial agent (k) selected from 2-hydroxy-diphenyl ethers of formula (2) and more particularly compounds of formula (3):

In the formula,

Y is chlorine or bromine,

Z is SO ₂ H, NO ₂ or C ₁ -C ₄ alkyl,

r is 0 to 3,

o is 0 to 3,

p is 0, 1 or 2,

m is 1 or 2, and

n is 0 or 1.

In the food,

Y is chlorine

r is 1 or 2.

Especially preferred are compounds of formula (4) or (5):

Therefore, the present invention preferably relates to a detergent composition comprising the following components for the fungicide treatment for hard surface treatment:

(a) 0.01 to 90% by weight of the compound of formula (1) according to claim 1;

(b) 1 to 80% by weight of one or more synthetic detergents or soaps or a combination of the foregoing;

(f) 0 to 50% by weight of one or more oysters;

(g) 0-50% by weight of alcohol;

(k) 0.00 to 50% by weight of an antimicrobial agent selected from 2-hydroxy-diphenyl ethers of formula (2); And

(i) Add tap water or deionized water and make up 100% of all ingredients.

Compounds of formula (1) are preferably used as fungicides in laundry compositions.

Accordingly, the present invention relates to a method for home washing and fungicidal treatment of textile fibers, wherein the textile fibers are contacted with an aqueous solution of a detergent composition comprising the compound of formula (1).

Preferably, the detergent composition comprises at least one enzyme selected from the group consisting of cellulase, amylase and lipase and the temperature of the solution is between 5 ° C. and 40 ° C., preferably between 5 ° C. and 30 ° C. during the method.

Another preferred additive for the detergent according to the invention is a polymer which inhibits the contamination caused by dyes (dye fixatives, dye transfer inhibitors) in the wash liquor released from the fabric under washing conditions during washing of the fabric. Such polymers are preferably polyvinylpyrrolidone, polyvinylimidazole or polyvinylpyridine N-oxides, which may be modified by the incorporation of anionic or cationic substituents, and are 5000 to 60 000, more particularly 10 000 To a molecular weight ranging from 50 000. Such polymers are used in amounts of 0.01 to 5% by weight, preferably 0.05 to 5% by weight, in particular 0.1 to 2% by weight, based on the total weight of the detergent. Preferred polymers are described in WO-A-02 / 02865 (see especially page 1, last paragraph and page 2, first paragraph).

Detergents used include suspending agents such as sodium carboxymethylcellulose; PH adjusting salts such as alkali or alkaline earth metal silicates; Bubble control agents such as soaps; Salts for adjusting spray drying and granulation properties such as sodium sulfate; perfume; And antistatic and softening agents, if necessary; Smectite clay; Photobleach; Pigments; And / or one or more adjuvants, such as colorants. These ingredients must be stable to the bleach system used. Such adjuvants may be present in amounts of 0.1 to 20% by weight, preferably 0.5 to 10% by weight, in particular 0.5 to 5% by weight, based on the total weight of the detergent.

Detergent compositions can take a variety of physical forms, including powder, granule, tablet, and liquid forms. Examples are tablets such as conventional powder heavy-duty detergents, compressed and ultra-compressed heavy duty detergents and heavy duty detergent tablets. One important physical form is in the form of so-called concentrated granules adapted to be added to the washing machine.

So-called compressed (or supercompressed) detergents are important. In the field of detergent manufacturing there is a tendency to produce compressed detergents containing increased amounts of active substances. In order to minimize energy consumption during the laundry process, the compressed detergent needs to work effectively at temperatures below 40 ° C., or at room temperature, such as 25 ° C. Such detergents usually contain small amounts of fillers or processing aids such as sodium sulfate or sodium chloride. The amount of such fillers is 0 to 10% by weight, preferably 0 to 5% by weight, in particular 0 to 1% by weight, based on the total weight of the detergent. The bulk density of such detergents is between 650 and 1000 g / l, preferably between 700 and 1000 g / l, in particular between 750 and 1000 g / l.

Detergents may also be present in the form of tablets. Features associated with tablets are ease of dispensing and ease of handling. Tablets are the most compressed delivery form of solid detergents and have a bulk density of 0.9 to 1.3 kg / liter. Laundry detergent tablets contain the following special disintegrants to expedite the decomposition:

Foaming agents such as carbonates / hydrocarbonates / citric acid;

Swelling agents such as cellulose, carboxymethyl cellulose, crosslinked poly (N-vinylpyrrolidone);

Quick dissolving materials such as Na (K) acetate, or Na (K) citrate;

Fast dissolving water soluble hard coatings, such as dicarboxylic acids.

Tablets may contain a combination of the disintegrants described above.

The detergent is also formulated as an aqueous liquid comprising 5-50% by weight, preferably 10-35% by weight water or as a non-aqueous liquid detergent containing up to 5% by weight, preferably 0-1% by weight of water. Can be. The non-aqueous liquid detergent composition may contain other solvents such as a carrier. Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol and isopropanol are suitable. Monohydric alcohols are preferred for solubilizing surfactants, but polyols containing 2 to about 6 carbon atoms and polyols containing 2 to about 6 hydroxy groups (such as 1,3-propanediol, ethylene glycol, glycerin and 1, 2-propanediol) can also be used. The composition may contain from 5% to 90% by weight, typically 10% to 50% by weight of the carrier. Detergents may be present in so-called "unit liquid dosage forms".

Detergent treatment of the fabric may be carried out as a home treatment in a normal washing machine.

The textile fibers treated by the process of the present invention may be natural or synthetic fibers or mixtures thereof. Examples of natural fibers are vegetable fibers such as cotton, viscose, flax, rayon or linen, preferably cotton and animal fibers such as wool, mohair, cashmere, angora and silk, preferably cotton. Synthetic fibers include polyester, polyamide and polyacrylonitrile fibers. Preferred textile fibers are cotton, polyamide and wool fibers, in particular cotton fibers. Preferably, the fabric fibers treated according to the method of the invention have a density of less than 200 g / m ² .

According to the method a compound of formula (1) is used in an amount of 0.01 to 3.0% by weight, in particular 0.05 to 3.0% by weight, based on the weight of the textile fiber material.

The process is usually carried out in a temperature range of 5 to 100 ° C., in particular 5 to 60 ° C. Preferably it is 5-40 degreeC temperature range, especially 5-35 degreeC, More preferably, it is 5-30 degreeC.

The detergent composition is preferably formulated so that the pH of the wash water is from about 6.5 to about 11, preferably from about 7.5 to 11, during use in aqueous cleaning operations. The pH of the detergent product is typically 9-11. Techniques for controlling pH at recommended levels of use include the use of buffers, alkalis, acids, and the like, which are known to those skilled in the art.

Machine wash methods include treating contaminated laundry with an aqueous wash liquor in a washing machine having an effective amount of the machine laundry detergent composition according to the invention, typically dissolved or dispersed. An effective amount of detergent composition means 20 g to 300 g of a product dissolved or dispersed in 5 to 85 liters of wash liquor, which is the wash liquor volume and typical product dose commonly applied to conventional machine washing methods. An example is this:

A top-loading, vertical American automatic washing machine with about 45 to 83 liters of water in a washing tank, a washing cycle of about 10 to about 14 minutes and a washing water temperature of about 10 to about 50 ° C .;

A front-loading, horizontal European-type automatic washing machine with about 8 to 15 liters of water in a washing tank, a washing cycle of about 10 to about 60 minutes and a washing water temperature of about 30 to about 95 ° C .;

Top-loading, vertical Japanese-type automatic washing machine with about 26 to 52 liters of water in a washing tank, a washing cycle of about 8 to about 15 minutes and a washing water temperature of about 5 to about 25 ° C.

The liquid ratio is preferably 1: 4 to 1:40, in particular 1: 4 to 1:15. Very preferred is a liquid ratio of 1: 4 to 1:10, especially 1: 5 to 1: 9.

The composition according to the invention can be used to destroy fungi present on the laundry material in the dilution liquid during the washing process. At the same time, the washed textile material is endowed with antifungal properties, ie bacteria on the textile material are destroyed during wear.

The preparations according to the invention exhibit strong fungicidal activity.

The composition according to the invention is used as a solid soap, dishwashing preparation or universal detergent.

Detergents include, for example, the following composition:

0.01 to 5% by weight of compound of formula (1);

Octanol 4EO 3.0 wt%;

1.3% by weight fatty alcohol C ₈ -C ₁₀ polyglucoside;

Isopropanol 3.0 wt%; And

Water, added to achieve 100%.

The detergent composition of the present invention delivers fungal proliferation and fungicidal properties to the laundry to protect the fabric from fungi and mold. They prevent mold and fungi from growing on fabrics, prevent the odor of molds in clothing, prevent fibrotic damage, and prevent the formation of dark pigmented contamination by fungi. They also have a long lasting antifungal effect on the fabric during storage under moisture and warm conditions. Thus, the garment keeps fresh for much longer.

The compounds of formula (1) are also useful for dust mites.

The following examples illustrate the invention in detail. % And parts mean parts by weight.

Example  1: Preparation of Liquid Laundry Formulations (1) to (5)

A liquid formulation having the following composition was prepared:

Example  2: Determination of Antifungal Efficacy of Fabrics Washed with Liquid Detergent Containing Compound of Formula (101)

Test Formulation / Liquid Detergent:

Placebo, 0.2% and 0.3% of the compound of formula (101)

Prior to the start of the test, the detergent was dissolved in 25 ° C. water.

Shall using the liquid detergent test (Linitest):

Liquid ratio: 1:20

Fabric: 15g Cotton Tricot

Temperature: 25 ℃

Duration: 10 minutes

Rinse: 2 times for 30 seconds (1 liter of water each)

Drying: until full dry at room temperature

density:

1. Cotton tricot treated with liquid detergent placebo:

0.40 g detergent / 300 ml tap water

2. Cotton tricot treated with liquid detergent + 0.2% of compound of formula (101):

0.40 g detergent / 300 ml tap water (= 0.2%)

3. Cotton tricot treated with liquid detergent + 0.2% of compound of formula (101):

0.60 g detergent / 300 ml tap water (= 0.3%)

Test strain :

Chaetomium Globosum globosum ) ATCC 6105 (washed upper agar slant)

Dilute in sterile 0.85% saline solution + 50% Sabouraud-2% glucose gravy 1:10

Each sample (4 cm disc) was inoculated with 0.5 ml fungal suspension (= final concentration on sample: ˜10 ⁵ spores) and placed in a dryer (> 90% humidity) and incubated at 28 ° C.

Exam time :

Observational evaluation after 1, 2, 3 and 4 weeks.

1.1.1.1.1.1. Principle :

1.1.1.1.1.2. Discs 4 cm in diameter were cut from the laundry fabric and inoculated with the 0.5 ml fungal suspension prepared above, placed in a sterile petri dish and placed in a dryer at 28 ° C. and ˜90% to 95% humidity.

After 1, 2, 3 and 4 weeks all samples were visually assessed for growth on each sample (spot) and listed in Table 1.

result( Neck side  evaluation)

Example  3: Determination of Antifungal Efficacy of Fabrics Washed with Rod Detergent Containing Compound of Formula (101)

Trial sample: (natural soap system)

1. Placebo detergent without the compound of formula (101)

2. Detergent bar soap containing 0.1% of the compound of formula (101)

3. Detergent bar soap containing 0.05% of the compound of formula (101)

Hand washing test with detergent bar soap :

Fabric Material: 10g Cotton Tricot

Laundry order :

The detergent bar was rubbed five times per side for one minute on the wet fabric by hand. The sample was then immersed, immersed for 10 minutes, and then rinsed with tap water for 1 minute. Dry to room temperature at room temperature.

Test strain :

Chaetomium Globosum globosum ) ATCC 6105 *

The washed upper agar slant was diluted 1:10 with sterile 0.85% saline solution + 0.05% Sabouraud-2% glucose juice.

0.5 ml fungal suspension was inoculated into each sample (4 cm disc) (= final concentration on the sample: ˜10 ⁵ cfu) and placed in a dryer (> 90% humidity).

Exam time :

Observational evaluation after 1, 2, 3 and 4 weeks.

2.1.1.1.1.1. Principle :

Discs 4 cm in diameter were cut from the laundry fabric and inoculated with the 0.5 ml fungal suspension prepared above, placed in a sterile petri dish and placed in a dryer at 28 ° C. and ˜90% to 95% humidity.

After 1, 2, 3 and 4 weeks all samples were visually assessed for growth on each sample (spot) and listed in the table.

Example  4: containing a compound of formula (101) ECE  Determination of Antifungal Efficacy of Fabrics Washed with Powdered Detergent

Trial sample :

1. Placebo = ECE detergent powder (color fastness detergent 77)

2. ECE detergent powder containing 0.2% of compound of formula (101) (*)

(*) Incorporation through 0.2% slurry of the compound of formula (101) in ECE color fastness test.

With detergent powder Linni Exam

Detergent concentration: 0.4 g / 300 ml tap water

Liquid ratio: 1:20

Fabric: 15g Cotton Tricot

Temperature: 25 ℃

Duration: 10 minutes

Rinse: 2 times for 30 seconds (1 liter of water each)

Drying: Dry until all dry at room temperature

Test strain :

Chaetomium Globosum globosum ) ATCC 6105

The washed upper agar slant was diluted 1: 5 with sterile 0.85% saline solution + 0.05% Sabouraud-2% glucose gravy.

0.5 ml fungal suspension was inoculated into each sample (4 cm disc) (= final concentration on the sample: ˜10 ⁵ cfu) and placed in a dryer (> 90% humidity).

Substances :

Sterile Petri Dish (φ55 mm)

Humidity room

Sterile Plastic Stomacher Bag

Sterile forceps

Incubator 28 ℃ +/- 1 ℃

Contact time :

Immediately after incubation at 28 ° C., after 1, 2, 3 and 4 weeks

Principle :

Discs 4 cm in diameter were cut out of the laundry fabric and inoculated with 0.5 ml fungal suspension prepared above in a sterile petri dish and placed in a dryer at 28 ° C. and ˜90% to 95% humidity.

After 1, 2, 3 and 4 weeks all samples were visually assessed for growth on each sample (spot) and listed in the table.

Example  5: fabric containing a compound of formula (101) By conditioner  Of treated fabric Determination of Fungicidal Efficacy

The growth of Chaetomium globosum , which causes "spots", is inhibited and removed over time. Mold growth was remarkable on cotton fabrics rinsed with the original fabric conditioner.

Test formulation :

0.1% of the compound of formula (101) was suspended in a fabric conditioner. Commercially available product fabric conditioners were tested for control.

Processing :

Concentration: 0.75 g fabric conditioner 180 ml tap water

Liquid ratio: 1: 6

Fabric: 30g Cotton Tricot

Temperature: 20 ℃

Duration: 5 minutes

Drying: until all dry at room temperature

AATCC  Determination of Bacterial Activity According to Test Method 100-1998

( Evaluation of Antimicrobial Processing on Textile Material)

Sample :

1) Cotton tricot treated with fabric conditioner

2) Fabric conditioner + cotton tricoat treated with 0.1% compound of formula (101)

Test strain :

Chaetomium Globosum globosum ) ATCC 6105

Dilution :

1: 5 in sterile 0.85% saline solution + 0.05% Sabouraud-2% glucose gravy. Each sample was inoculated with 0.3 ml fungal suspension (= final concentration on sample: ˜10 ⁵ cfu) and left to dry.

Substances :

Sterile Petri Dishes (Diameter 55 mm and 90 mm)

4 cm diameter disc

Humidity room

Sterile plastic bags

Stomacher 80

Sterile forceps

Incubator 28 ℃ +/- 1 ℃

Heavy weapons :

0.97 moles of sterile phosphate buffer containing 1% Tween 80 and 0.3% Lecithin (20 ml / Stomach Bag)

Dilution medium :

 Sterile Deionized Water, pH 7.4

Badge :

Fungus ( Chaetomium globosum mycological agar for globosum ))

Contact time

Immediately after incubation, 1, 2, 3 and 4 weeks after incubation at 28 ° C and> 90% humidity

Incubation of the plate :

~ 4 to 5 days at 28 ℃

Principle :

Discs 4 cm in diameter were cut from the laundry fabric and placed on sterile petri dishes (55 mm). This test sample was inoculated with 0.30 ml of diluted fungal suspension (about ˜10 ⁵ cfu / final concentration on each sample) and placed in a dryer to incubate at 28 ° C.

Immediately after incubation at 28 ° C., 1, 2, 3 and 4 weeks later, sterile bag containing 20 ml phosphate buffer containing 1% Tween 80 and 0.3% lecithin, 0.07 mol, pH 7.4 (Stomacher bag 80) In Stomacher for 1 minute. 10 of sterile deionized water, and then ^{shaking-up 3} made a 1:10 dilution. 0.1 ml of the sample, taken from the undiluted and diluted, was provided in 18 ml of agar plate with the help of a spiral plater. All plates were placed in an incubator at 28 ° C. and left for 4-5 days. The number of colonies surviving after incubation was counted and reported as cfu / sample in the table.

conclusion:

Strong antifungal activity against Chaetomium globosum was observed two and four weeks after contact with cotton samples treated with a commercially available fabric conditioner containing 0.1% of the compound of formula (101).

Example  6: Preparation of Liquid Detergent Formulations

Example  7: Preparation of different formulations

Claims (19)

Use of a compound of formula (1) for fungicidal treatment of hard surfaces and textile fibers:

(One) In the formula, R ₁ is hydrogen; Or C ₁ -C ₅ alkyl. The use according to claim 1, wherein R ₁ is hydrogen. (a) 0.01 to 90% by weight of the compound of formula (1) according to claim 1; (b) 1 to 80% by weight of one or more synthetic detergents or soaps or combinations of the above components; (c) 0 to 75% by weight builder; (d) 0-30% by weight of peroxide; (e) 0-10% by weight of a bleach activator; (f) 0 to 50% by weight of one or more oysters; (g) 0-50% by weight of alcohol; (h) 0 to 80 weight percent of fabric softening component; And (i) Detergent composition comprising tap water or deionized water added so that all the components are added up to 100% by weight. The method of claim 3, wherein (a) 0.01 to 10% by weight of a compound of formula (1) according to claim 1; (b) 5 to 70% by weight of one or more synthetic detergents or soaps or combinations of the above components and / or salts of saturated and / or unsaturated C ₈ -C ₂₂ fatty acids; (f) 0 to 50% by weight of one or more oysters; (g) 0-50% by weight of alcohol; (h) 0 to 80 weight percent of fabric softening component; And in some cases (i) a composition comprising tap water or deionized water which is added to add up to 100% by weight of all components. The acid according to any one of claims 2 to 4, wherein lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, caprolein acid, dodecenoic acid, tetradecenoic acid, octadecenoic acid , Wherein a salt of oleic acid, icosane acid and erucic acid is used as component (b). The method according to any one of claims 2 to 5, (a) 0.01 to 5% by weight of compound of formula (1); (b) 1 to 70 weight percent of anionic surfactant and / or nonionic surfactant; (c) 0 to 75% by weight of laundry aids; (d) 0-30% by weight of peroxide; And (e) 0-10% by weight of a bleach activator. The method of claim 6, (a) 0.01 to 5% by weight of compound of formula (1); (b) 5 to 70 weight percent of anionic surfactants and / or nonionic surfactants; (c) 5 to 70% by weight of laundry aids; (d) 0.5 to 30 weight percent of peroxide; And (e) 0.5 to 10% by weight of a bleach activator and / or 0.1 to 2% by weight of a bleach catalyst. 8. The composition of claim 3, wherein said detergent composition additionally comprises at least one enzyme, preferably a protease, selected from the group comprising cellulase, protease, amylase and lipase. The method according to any one of claims 3 to 8, A composition in which an antimicrobial agent (k) selected from 2-hydroxy-diphenyl ethers of formula (2) is additionally used:

(2) In the formula, Y is chlorine or bromine, Z is SO ₂ H, NO ₂ or C ₁ -C ₄ alkyl, r is 0 to 3, o is 0 to 3, p is 0, 1 or 2, m is 1 or 2, and n is 0 or 1. 10. Composition according to claim 9, wherein as component (k) 2-hydroxy-diphenyl ether of formula (4) or (5) is used:

(4)

(5) The method according to any one of claims 2 to 6, 9 and 10, (a) 0.01 to 90% by weight of the compound of formula (1) according to claim 1; (b) 1 to 80% by weight of one or more synthetic detergents or soaps or a combination of the foregoing; (f) 0 to 50% by weight of one or more oysters; (g) 0-50% by weight of alcohol; (k) 0-50% by weight of an antimicrobial agent selected from 2-hydroxy-diphenyl ethers of formula (2); And (i) a composition comprising tap water or deionized water which is added such that the total components add up to 100%. A method of home laundering and fungicidal treatment of woven fibrous material comprising contacting the woven fibrous material with an aqueous solution of a detergent composition comprising the compound of formula (1) according to claim 1. The method of claim 12 wherein the detergent composition contains at least one enzyme selected from the group comprising cellulase, protease, amylase and lipase and the temperature of the solution is between 5 ° C. and 40 ° C., preferably between 5 ° C. and during the process. 30 ° C. The method according to claim 12 or 13, wherein the textile material is polyamide, wool or cotton. The method of claim 12, wherein the composition is used as a powder laundry formulation, laundry paste, liquid laundry formulation, fabric softener or solid soap. Use of a composition according to any one of claims 3 to 12 for fungicidal treatment of hard surfaces. The use according to claim 16, wherein said composition is used in dishwashing formulations. The use according to claim 16, wherein said composition is used in a general purpose detergent. Use of a compound of formula (1) as an activator for dust mites.