Fungicidal Detergent Compositions

Abstract

Disclosed is the use of the compound of formula

Description

Example 1

Preparation of a liquid washing formulations (1)-(5)

Liquid formulations having the following compositions are prepared:

Formulation	1	2	3	4	5
Compound of formula (101)(Thiabendazol)	0.6	0.6	0.6	0.6	0.6
sodium dodecylbenzenesulfonate	6	6	6	6	6
sodium lauryl sulfate	8	8	8	8	8
Pareth 45-7 (Dobanol 45-7)	4	4	4	4	4
ethanol	9	9	9	9	9
sodium cumenesulfonate	5	—	5	5	—
soap noodles (Mettler)	5	7	7	5	7
trisodium citrate dihydrate	2	2	2	2	2
triethanolamine	5	5	5	5	5
fluorescent whitening agents	0.3	0.3	0.3	0.3	0.3
water to	100	100	100	100	100

Example 2

Determination of the anti-fungal efficacy of fabric washed with liquid detergents containing the compound of formula (101)

Test Formulations/liquid detergent:

Placebo, with 0,2% and 0.3% of the compound of formula (101) Before test begin the detergent is dissolved in 25° C. water.

Linitest with liquid detergent:

Liquor ratio: 1:20
Fabric:       15 g Cotton Tricot
Temperature:  25° C.
Duration:     10 Minutes
Rinsing:      twice for 30 seconds (each 1 liter water)
Drying:       until totally dry at room temperature

Concentrations:

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 the compound of formula (101): 0.40 g detergent/300 ml tap water (=0.2%)
• 3. Cotton tricot treated with liquid detergent +0.2% of the compound of formula (101): 0.60 g detergent/300 ml tap water (=0.3%)

Test strain: Chaetomium globosum ATCC 6105 (washed up agar slant) Diluted 1:10 in sterile 0.85% saline solution+50% Sabouraud−2% glucose broth. Each sample (4 cm discs) is inoculated with 0.5 ml fungal suspension (=final concentration on the sample: ˜10⁵ spores) and placed in a dessiccator (>90% humidity) and incubated at 28° C.

Test time: Visual evaluation after 1, 2, 3 and 4 weeks.

• • 1.1.1.1.1.1 Principle:
  • 1.1.1.1.1.2 Discs with a diameter of 4 cm are cut from the washed fabric and inoculated with 0.5 ml of the fungal suspension prepared above, given in sterile petri dishes and placed in dessiccator at 28° C. and ˜90% -95% humidity. After 1, 2, 3 and 4 weeks all samples are observed on visual growth on each sample (“black spots”) and the observations written in a table.

Results (visual observations)

	Chaetomium globosum
	ATCC 6205 (103-104
	spores/sample)
2. Evaluation on “black spots”	After 1	After 2	After 3	After 4
2.1.1.1 Samples	week	weeks	weeks	weeks
1) Placebo liquid detergent	++	+++	+++	+++
2) Liquid detergent + 0.2% of the	−	−	(+)	(+)
compound of formula (101)
3) Liquid detergent + 0.3% of the	−	−	−	−
compound of formula (101)
− = no visual growth
(+) = “single spots”
++ = strong growth
+++ = very strong growth

Example 3

Determination of the anti-fungal efficacy of fabric washed with detergent bars containing the compound of formula (101)

Test samples: (natural soap base)

• • 1. Placebo detergent without the compound of formula (101)
  • 2. Detergent bar soap containing 0.1% the compound of formula (101)
  • 3. Detergent bar soap containing 0.05% the compound of formula (101)

Hand washing test with the detergent bar soaps: Textile material: 10 g Cotton Tricot

Washing protocol: The detergent bar is rubbed by hand on the wet fabric 5 times on each side during 1 minute. Afterwards the fabric sample is soaked and kneaded for 10 minutes, rinsed under tap water for 1 minute. Drying until totally dry at room temperature

Test strain: Chaetomium globosum ATCC 6105*

A washed up agar slant is diluted: 1:10 in sterile 0.85% saline solution+0.05% Sabouraud−2% glucose broth. Each sample (4 cm disc) is inoculated with 0.5 ml of the fungal suspension (=final concentration on the sample: ˜105 cfu) and placed in a dessiccator (>90% humidity).

Test time: Visual evaluation after 1, 2, 3 and 4 weeks.

• • 2.1.1.1.1.1 Principle Discs with a diameter of 4 cm are cut from the washed fabric and inoculated with 0.5 ml of the fungal suspension prepared above, given in a sterile petri dishes and placed in dessiccator at 28° C. and ˜90%-95% humidity.

After 1, 2, 3 and 4 weeks all samples are observed on visual growth on each sample (“black spots”) and the observations written in a table.

3. Evaluation on “black spots”
	Chaetomium globosum ATCC 6205
	(104 spores/sample)
4.	After 1	After 2	After 3	After 4
4.1.1.1 Samples	week	weeks	weeks	weeks
1) Placebo detergent	++	+++	+++	+++
2) Detergent bar with 0.1% of the	−	(+)	(+)	(+)
compound of formula (101)
3) Detergent bar with 0.05% of the	−	(+)	(+)	(+)
compound of formula (101)
− = no visual growth
(+) = “single spots”
++ = strong growth
+++ = very strong growth

Example 4

Determination of the anti-ungal efficacy of fabric washed with an ECE powder detergent containing the compound of formula (101)

Test samples:

• 1. Placebo =ECE Detergent powder (Color Fastness Detergent 77)
• 2. ECE Detergent powder containing 0.2% of the compound of formula (101) (*) (*) Incorporation via slurry of 0.2% of the compound of formula (101) in ECE Color Fastness Test.

Linitest with Detergent powder

Detergent concentration: 0.4 g/300 ml tap water
Liquor ratio:            1:20
Fabric:                  15 g Cotton Tricot
Temperature:             25° C.
Duration:                10 minutes
Rinsing:                 twice for 30 seconds (each in 1 liter water)
Drying:                  until totally dry at room temperature

Test strain: Chaetomium globosum ATCC 6105

Washed up agar slant is diluted 1:5 in sterile 0.85% saline solution +0.05% Sabouraud-2% glucose broth. Each sample (discs with 4 cm diameter) is inoculated with 0.5 ml of the bacterial mixture or fungal suspension (- final concentration on the sample: ˜105 cfu) and placed in a dessiccator (>90% humidity).

Material:

• Sterile Petri dishes (Ø55 mm)
• Humid chamber
• Sterile plastic Stomacher bags
• Sterile forceps
• Incubator 28° C. +/−1° C.

Contact times: Immediately, 1, 2, 3 and 4 weeks after inoculation at 28° C.

Principle Discs with a diameter of 4 cm are cut from the washed fabric and inoculated with 0.5 ml of the fungal suspension prepared above, given in sterile petri dishes and placed in dessiccator at 28° C. and ˜90%-95% humidity. After 1, 2, 3 and 4 weeks all samples will be observed on visual growth on each sample (“black spots”) and the observations written in a table.

• • 4.1.1.1.1.1.1.1

5. Evaluation on “black spots”
	Chaetomium globosum ATCC 6205
	(104 spores/sample)
6.	After 1	After 2	After 3	After 4
6.1.1.1 Samples	week	weeks	weeks	weeks
1) Placebo Detergent Powder	++	++	+++	+++
2) Detergent Powder with 0.2% of	−	−	(+)	(+)
the compound of formula (101)
− = no visual growth
(+) = “single spots”
++ = strong growth
+++ = very strong growth

Example 5

Determination of the fungicidal efficacy of fabric treated with a fabric conditioner containing the compound of formula (101)

The growth of Chaetomium globosum, a cause of “spots” is inhibited and even eliminated by time. On the cotton fabric rinsed with the original fabric conditioner, the growth of the mould was significant.

Test Formulations: 0.1% of the compound of formula (101) is suspended in the fabric conditioner. The market product fabric conditioner is tested in comparison.

Treatment:

Concentration: 0.75 g fabric conditioner 180 ml tap water
Liquor ratio:  1:6
Fabric:        30 g Cotton Tricot
Temperature:   20° C.
Duration:      5 Minutes
Drying:        Until totally dry at room temperature

Determination of the bactericidal activity according to AATCC test method 100-1998 (Assessment of the antibacterial finishes on textile materials)

Samples:

• 1) Cotton tricot treated with fabric conditioner (placebo)
• 2) Cotton tricot treated with fabric conditioner +0.1% of the compound of formula (101)

Test strain: Chaetomium globosum ATCC 6105 (washed up agar slant)

Dilution: 1:5 in sterile 0.85% saline solution +0.05% Sabouraud−2% glucose broth. Each sample is inoculated with 0.3 ml fungal suspension (=final concentration on the sample: ˜10⁵ cfu) and placed in a dessiccator.

Materials:

• Sterile petri dishes (diameter 55 mm and 90 mm)
• Discs with a diameter of 4 cm
• Humid chamber
• Plastic bags sterile
• Stomacher 80
• Sterile forceps

Neutralizer: Sterile phosphate buffer 0.07 molar containing 1% Tween 80 and 0.3% lecithin (20 ml/Stomacher bag)

Dilution media: Sterile deionized water, pH 7.4

Media: Mycological agar for fungal numbers (Chaetomium globosum)

Contact times: Immediately after inoculation, after 1, 2 and 4 weeks at 28° C. and >90% humidity.

Incubation of the plates: ˜4-5 days at 28° C.

Principle Discs with a 4 cm diameter are prepared and placed into sterile petri dishes (55 mm). The test samples are then inoculated with 0.30 ml of the diluted fungal suspension (about 105 cfu/end concentration on each sample), placed in a dessiccator and incubated at 280C. Immediately after inoculation, after 1, 2 and 4 weeks at 28° C., the samples are placed into a sterile bag (Stomacher bag 80) containing 20 ml phosphate buffer, 0.07 molar, pH 7.4 containing 1% Tween 80 and 0.3% lecithin and treated in the Stomacher for 1 minute. After shaking 1:10 dilutions until 10-3 in sterile deionized water are made. From the un-diluted and from the dilutions, samples of 0.1 ml were given on 18 ml containing Mycological agar plates by the help of a spiral plater. All plates are placed in the incubator at 28° C. for about 4-5 days. After incubation the surviving colonies are counted and reported as cfu/sample in a table.

	7. Test strain
	Chaetomium globosum ATCC 6205
	(4.7 × 106/ml)
7.1.1.1 Samples	0′	1 week	2 weeks	4 weeks
1) Cotton tricot treated	2.4 × 104	No growth	3.9 × 104	6.1 × 105
with fabric conditioner	2.5 × 104	visible	1.3 × 104	8.5 × 104
(placebo)
2) Cotton tricot treated	—	No growth	<100*	<100*
with fabric	—	visible	<100*	<100*
conditioner + 0.1% of
the compound of
formula (101)

Chaetomium globosum ATCC 6205: 4,7×10⁶/ml

Conclusion Strong antifungal activity can be observed after 2 and 4 weeks contact time with the cotton sample treated with Market fabric conditioner containing 0.1% of the compound of formula (101) against Chaetomium globosum.

Example 6

Preparation of further liquid washing formulations

	Formulation
Components	12a	12b	12c	12d	12e	12f	12g	12h	12i	12k	12l
Composition comprising 30% of	0.6	0.6	0.6	0.6	0.6	0.6	0.6	0.6	0.6	0.6	0.6
the compound of formula (101)
and 70% of propylene glycol
compound of formula (102)	0.9	0.9	0.9	0.9	0.9	0.9	0.9	0.9	0.9	0.9	0.9
dodecylbenzenesulfonic acid	7.5							8.5
sodium		27	23.6	10	28				20	24	6
dodecylbenzenesulfonate
sodium laureth sulfate 3 EO	17	10
sodium lauryl sulfate						6					8
coconut acid	12.5			10	4	4	10			10
C12-13 Pareth-7	10							26.9	27.8	25	4
PEG-7 C13 oxoalcohol				20	9	14.5	12	29	26
PEG-8 C13-15 fatty alcohol							10
alkyl polyglucoside			5			1	2
laureth-10		5
PPG				2	3	8
sodium carbonate			2
sodium tripolyphosphate			20
potassium tripolyphosphate 50%		22
sodium cumenesulfonate 40%		25
trisodium citrate	5.5					2					2
lauryltrimonium chloride	0.7
polycarboxylate				13	18	15	10	23	16.2
2-propanol	6			7	3		4	9.5	8
ethanol	6										9
glycerol										20
propylene glycol										6
NaOH	3.2			2	1	2.3	1.8	1.1		1.8	4
fluorescent whitening agent	0.1	0.1	0.1	0.1	0.1	0.1	0.1				0.1
Tinopal CBS-x
fluorescent whitening agent								0.1	0.1	0.1
Tinopal CBS-CL
Soap											7
water to	100	100	100	100	100	100	100	100	100	100

Example 7

Preparation of different formulations:

	formulation
components	13a	13b	13c
combination of 30% of the compound of formula	0.6	0.6	0.3
(101) and 70% of propylene glycol
compound of formula (102)	0.9	0.9	0.45
sodium laureth sulfate	1.2
cocamidopropyl betaine	1
lauramine oxide	1
sodium Citrate	4
sodium carbonate	3
ethanol	3
sodium C14-17 alkyl sec. Sulfonate		16.6
sodium laurylsulfate		20
Laureth-09		3
sodium cumolsulfonate		5
sodium chloride		3
Quaternium 18 and iospropylalcohol			4
Pareth-25-7			0.5
water to	100	100	100

Claims

1. A method for the fungicidal treatment of hard surfaces and textile fiber material comprising contacting said hard surfaces and said textile fiber materials with a compound of formula

2. A method according to claim 1, wherein R1 is hydrogen.

3. A detergent composition comprising (a) 0.01 to 90% by weight of a compound of formula (1) according to claim 1;(b) 1 to 80% by weight of one or more synthetic detergents or of a soap or combinations thereof;(c) 0-75% of a builder;(d) 0-30% by weight of a peroxide;(e) 0-10% by weight of a bleach activator;(f) 0 to 50% by weight of one or more hydrotropic agents,(g) 0 to 50% by weight of an alcohol,(h) 0 to 80% by weight of a fabric softening component; and(i) tap water or deionised water ad 100%.

4. A composition according to claim 3 comprising (a) 0.01 to 10% by weight of a compound of formula (1);(b) 5 to 70% by weight of one or more synthetic detergents or of a soap or combinations thereof and/or of a salt of a saturated and/or unsaturated C8-C22 fatty acid,(f) 0 to 50% by weight of one or more hydrotropic agents,(g) 0 to 50% by weight of an alcohol,(h) 0 to 80% by weight of a fabric softening component; and(i) tap water or deionised water ad 100%.

5. A composition according to claim 3, wherein a salt of lauric, myristic, palmitic, stearic, arachidic, behenic, caproleic, dodecenoic, tetradecenoic, octadecenoic, oleic, eicosenoic or erucic acid is used as component (b).

6. A composition according to claim 3, comprising (a) 0.01-5% of a compound of formula (1);(b) 1-70% of an anionic surfactant and/or a nonionic surfactant;(c) 0-75% of a builder;(d) 0-30% of a peroxide; and(e) 0-10% of a bleach activator.

7. A composition according to claim 6, comprising (a) 0.01-5% of a compound of formula (1);(b) 5-70% of an anionic surfactant and/or a nonionic surfactant;(c) 5-70% of a builder;(d) 0.5-30% of a peroxide; and(e) 0.5-10% of a bleach activator and/or 0.1-2% of a bleaching catalyst.

8. A composition according to claim 3 in which the detergent composition additionally comprises at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase.

9. A composition according to claim 3, wherein additionally (k) an antimicrobial agent selected from 2-hydroxy-diphenyl ether of formula

10. A composition according to claim 9, wherein as component (k) 2-hydroxy-diphenyl ether of formula

11. A composition according to claim 9 comprising (a) 0.01 to 90% by weight of a compound of formula (1);(b) 1 to 80% by weight of one or more synthetic detergents or of a soap or combinations thereof;(f) 0 to 50% by weight of one or more hydrotropic agents,(g) 0 to 50% by weight of an alcohol,(k) 0 to 50% by weight of an antimicrobial agent selected from 2-hydroxy-diphenyl ether of formula (2); and(i) tap water or deionised water ad 100%.

12. A process for the domestic washing and fungicidal treatment of a textile fibre material wherein the textile fibre material is contacted with an aqueous solution of a detergent composition comprising a compound of formula (1) according to claim 1.

13. A process according to claim 12, wherein the detergent composition contains at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase, and wherein the temperature of the solution is between 5° C. and 40° C. throughout the process.

14. A process according to claim 12 in which the textile materials are polyamides, wool or cotton.

15. A process according to claim 12, wherein the composition is used in powder washing formulations, washing pastes, liquid washing formulations, fabric softeners or solid soaps.

16. A method for the fungicidal treatment of hard surfaces comprising contacting said hard surface with a composition according to claim 3.

17. A method according to claim 16, wherein the composition is used in dishwashing formulations.

18. A method according to claim 16, wherein the composition is used in all-purpose cleaners.

19. (canceled)