Title of Invention

"FORMULATION FOR PROTECTING ANIMAL HIDES AND LEATHER FROM MICROBIAL ATTACK"

Abstract The invention relates to the use of combinations of active ingredients, containing phenolic and fungicidal active ingredients, for preserving animal skins and leather.,
Full Text The present application relates to the use of active compound combinations containing phenolic active compounds and fungicidal active compounds for preserving animal hides and leather.
It is known that phenol derivatives and mixtures or formulations thereof can be used as compositions for the protection of materials in leather manufacture. However, it has emerged that these compounds, when employed alone or' in combination, do not offer sufficient protection of stored hides and leath-er against microbial attack after some time.
It is furthermore known that benzirnidazoles, imidazoles, triazoles and/or morpholine derivatives in combination with phenolic compounds make possible a protection of the animal hides and leather during manufacture and storage (US 5 888 415). The use of 2-mercaptopyridine N-oxide and its salts for preserving leather is also known (WO 98/56959).
Surprisingly, it has now been found that combinations of certain fungicidal reactive active compounds such as m'ercaptobenzothiazble, methylene bisthiocyanate, thiocyanomethylthiobenzothiazole (TCMTB), benzisothiazolinone (BIT), octylisothiazolinone (OIT), dichlorooctylisothiazolinone (DCOIT), chlorothalonil, iodopropinyl butylcarbamate (TPBC), di-iodomethyl p-tolyl sulphone, . N-cyclohexylben20thiophene-2-carboxamide 5,5-dioxide and dithio-2,2"-bisbenzylmethylamide and specific phenolic active compounds are outstandingly suitable for the preservation of animal hides and leather.
Suitable phenolic active compounds are preferably phenol derivatives such as
tribromophenol, trichlorophenol, nitrophenol, 3 -methyl -4-chlorophenol,
3,5-dimethyl-4-chloraphenol, phenoxyethanol, dichlorophene, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4-chlorophenol (chlorophene),
2.4-dichloro-3,5-dimethylphenol. 4-chlorothymol, triclosan, fentichlor and their amirionium, alkali metal and alkaline earth metal salts, and mixtures of these.
Preferred are combinations containing 3,5-dirnethyl-4-chloxophenol, 2-benzyi-4-chlorophenol (BP), 3-methyl-4-chlorophenol (CMK) and/or o-phenylphenol (OPP) as phenolic constituents and one or more of the abovementioned fungicides.
The following combinations may be mentioned in particular': •
CME7mercaptobenzothiazole CMK/Anethylene bisthiocyanate CMK/thiocyanomethylthiobenzothiazole (TCMTB) CMK/benzisothiazolinone (BIT) CMK/octylisothiazolinone (OIT) CMK/dichlorooctylisothiazolinone (DCOIT) CMK/iodopropinyl butylcarbamate (IPBC) CMK/di-iodomethyl p-tolyl sulphone CMK/N-cyclohexylbenzothiophene-2-carboxarnide S,S-dioxide
OPP/mercaptobenzotbiazo le OPP/methylene bisthiocyanate OPP/thiocyanomethylthiobenzothiazole (TCMTB) OPP/benzisothiazolinone (BIT) OPP/octylisothiazolinone (OIT) OPP/dichl oroo ctyli so thi azolinone (DCOIT) OPP/iodopropinyl butylcarbamate (IPBC) OFP/di-iodomethyl p-tolyl sulphone OPP/N-cyclohexylbenzothiophene-2-carboxamide S,S-dioxide
CMK/OPP/mercaptobeirzothiazole CMK/OPP/methylene bisthiocyanate CMK/OPP/thiocyanomethylthiobenzothiazole- (TCMTB) CMK/OPP/benzisothiazolinone (BIT)
CMK/OPP/octylisothiazolinone (OIT) CMK/OPP/dichlorooctylisothiazolinone(DCOIT) CMX/OPP/iodopropinyl butylcarbamate (IPBC) CMK/OPP/di-iodomethyl p-tolyl sulphone CMK/OPP/N-cycIohexylbenzothiophene-2-carboxamide S,S-dioxide
CMK/BP/mercaptob enzo thiazo le
CMK/BP/methylene bisthiocyanate
CMK/BP/thiocyanomethyltbiobeiizothiazole(TCMTB)
CMK/BP/benzisothiazolinone (BIT) CMK/BP/octylisothiazolinone (OIT) CMK/BP/dicMorooctylisothiazolmone (DCOIT) CMK/BP/iodopropinyl butylcarbamate-(IPBC) CMK/BP/di-iodomethyl p-tolyl sulphone CMK/BP/N-cyclohexyIbenzothiophene-2-earboxairLide S,S-dioxide
The abovementioned fungicidal and phenolic compounds are known, see, for example, "Mi crobicides for the Protection of Materials, Chapmann & Hall, 1993".
In general, 5 to 200, preferably 10 to 100 and especially preferably 12 to 50 parts by weight of one or more of the abovementioned phenolic compounds are employed per part by weight of one or more of the abovementioned fungicides in the combinations.
If two or more phenolic compounds are present in the combinations according to the invention, their ratio to each other can be varied within wide limits. Advantageous
ratios can be determined in a simple fashion by conventional experiments which are
known to the skilled worker.
As a rule, the weight ratio between two phenolic compounds is between 1:1 and 1:10.
If, for example, OPP is present in addition to CMK in a combination according to the invention, the preferred weight ratio OPP:CMK is between 1:1 and 1:5.
Surprisingly, the combinations according to the invention have a synergistic action, that is to say the action of the combination exceeds the action of the individual active compounds.
In general, the combinations according to the invention of the active compounds are employed, in the form of formulations. The use concentration is preferably 0.1 to 1% of active compound or active compound mixture based on the hides or leather to be protected.
The compositions arising from the formulation contain the active compound mixture preferably in an amount of 10 to 50%. In general, the compositions" contain the following as further constituents: 0 to 30% alkali metal and/or alkaline earth metal hydroxides; 0 to 20% ionic and/or nonionic emulsifiers; 5 to 60% organic solvents such as, in particular, glycols, ketones, glycol ethers, alcohols such as ethanol, methanol, 1,2-propanediol, n-propanol and 0 to 0.5% of odoriferous substances and fragrances. The remainder to 100% is water or organic solvent, such as, for example, 1,2-propanediol. The percentages stated are by weight.
The active compound mixtures and the compositions which can be prepared from them are used in accordance with the invention by generally customary application, methods in leather manufacture for the protection of animal hides against attack and damage by microorganisms. It is of particular interest in this context that representatives of the species Aspergillus niger, Aspergillus repens, Hormoconis resinae, Penicillium glaucum and Trichoderma viride, Penicilliurh species such as P. citrinum or P. glaucum, Paecilomyces variotii, Cladosporium species and Mucor species such as Mucor mucedo, Rhizopus species such as Rhizopus oryzae, Thizopus rouxii are suppressed fully and permanent])'.
The examples which follow are intended to illustrate the invention and are not limited thereto.
Example 1
Agar plates axe inoculated with, conidia of the species Aspergillus niger, Aspergillus repens, Peniciffium glaucum, Trichoderma viride and Hormoconis resinae. Wet blue samples treated -with, mixture I, H and mixture HI are then placed on the agar plates and incubated for 28 days at 20 to 30° C and a relative atmospheric hurxndity of 95%.
Mixture I Mixture H
3 0 parts by weight of p-chloro-m-cresol 10 parts by weight of octylisothiazolinone 13 parts by weight of o-phenylphenol
Mixture III
30 parts by weight of p-chloro-m-cresol 10 parts by weight of 2-benzyl-4-chlorophenol 2 parts by weight of octyfeotbiazolinone
Mould growth is observed on the test pieces after an incubation time of as little as 10 days in the case of the wet blues preserved with mixture I and mixture II No" growth is observed after an incubation time of 20'days in the case of roixture HI. .
Example 2
Formulation I Formulation II
30 parts by weight of p-chloro-m-creso] 27 parts by weight of p-chloro-m-cresol
13 parts by weight of o-phenylphenol 12 parts by weight of 2-benzyi-4-
chlorophenol
2 parts by weight of octyhsorhiazolinone 1 part by weight of ocryhsothiazolinone
12 parts by weight of NaOH Remainder to 100 parts by weight:
1,2-propanediol
14 parts by weight of 1,2-propanediol Remainder to 100 parts by weight: water

14 parts by weight of 1,2-propanediol Remainder to 100 parts by weight: water







WE CLAIM:
1. Formulation for protecting animal hides and leather from microbial attack containing in percentages by weight
a) an active compound mixture in an amount of 10 to 50%
b) 0 to 30% of an alkali metal hydroxide, an alkaline earth metal hydroxides or mixtures thereof;
c) 0 to 20% ionic or nonionic emulsifiers or mixtures thereof;
d) 5 to 60% organic solvents and
e) 0 to 0.5% of odoriferous substances and fragrances and
f) the remainder to 100% water and
wherein the active compound mixture is a mixture of
• at least one fungicide selected from the group consisting of mercaptobenzothiazole, methylene bisthiocyanate, thiocyano-methylthiobenzothiazole (TCMTB), benzisothiazolinone (BIT), octylisothiazolinone (OIT), dichlorooctylisothiazolinone (DCOIT), chlorothalonil, iodopropinyl butylcarbamate (IPBC), di-iodomethyl p-tolyl sulphone, N-cyclohexylbenzothiophene-2-carboxamide 5,5-dioxide and dithio-2,2--bisbenzylmethylamide and
• at least one phenolic compound selected from the group consisting of nitrophenol, 3-methyl-4-chlorophenol (CMK), 3,5-dimethyl-4-chlorophenol, phenoxyethanol, dichlorophene, o-phenylphenol (OPP), m-phenylphenol, p-phenylphenol, 2-benzyl-4-chlorophenol (BP), (chlorophene), 2,4-dichloro-3,5-dimethylphenol, 4-chlorothymol, triclosan and fentichlor and the ammonium, alkali metal and alkaline earth metal salts of the aforementioned phenols, and wherein 5 to 200 parts by weight of one or more of the above mentioned phenolic compounds are employed per part by weight of one or more of the abovementioned fungicides.
2. Formulation as claimed in claim 1, wherein the active compound mixture are those selected from the combinations of
CMK / mercaptobenzothiazole
CMK/methylene bisthiocyanate
CMK/ thiocyanomethylthiobenzothiazole (TCMTB)
CMK/benzisothiazolinone (BIT)
CMK/octylisothiazolinone (OIT)
CMK/dichlorooctylisothiazolinone (DCOIT) CMK/iodopropinyl butylcarbamate (IPBC) CMK/di-iodomethyl p-tolyl sulphone
CMK/N-cyclohexylbenzothiophene-2-carboxamide S,S-dioxide OPP/ mercaptobenzothiazole OPP/methylene bisthiocyanate OPP/thiocyanomethylthiobenzothiazole (TCMTB) OPP/benzisothiazolinone (BIT)
OPP/octylisothiazolinone (OIT)
OPP/dichlorooctylisothiazolinone (DCOIT)
OPP/iodopropinyl butylcarbamate (IPBC)
OPP/di-iodomethyl p-tolyl sulphone
OPP/N-cyclohexylbenzothiophene-2-carboxamide S,S-dioxide
CMK/ OPP/ mercaptobenzothiazole
CMK/OPP/methylene bisthiocyanate
CMK/ OPP/ thiocyanomethylthiobenzothiazole (TCMTB)
CMK/OPP/benzisothiazolinone (BIT)
CMK/OPP/octylisothiazolinone (OIT)
CMK/OPP/dichlorooctylisothiazolinone (DCOIT)
CMK/OPP/iodopropinyl butylcarbamate (IPBC)
CMK/OPP/di-iodomethyl p-tolyl sulphone
CMK/OPP/N-cyclohexylbenzothiophene-2-carboxamideS,S-
dioxide
CMK/ BP/ mercaptobenzothiazole
CMK/BP/methylene bisthiocyanate
CMK/BP/thiocyanomethylthiobenzothiazole (TCMTB)
CMK/BP/benzisothiazolinone (BIT)
CMK/BP/octylisothiazolinone (OIT)
CMK/BP/dichlorooctylisothiazolinone (DCOIT)
CMK/BP/iodopropinyl butylcarbamate (IPBC)
CMK/BP/di-iodomethyl p-tolyl sulphone
CMK/BP/N-cyclohexylbenzothiophene-2-carboxamide S,S-dioxide

Documents:

333-delnp-2003-abstract.pdf

333-delnp-2003-assignment.pdf

333-delnp-2003-claims.pdf

333-delnp-2003-complete specification(granted).pdf

333-DELNP-2003-Correspondence-Others-(10-09-2009).pdf

333-delnp-2003-correspondence-others.pdf

333-delnp-2003-correspondence-po.pdf

333-delnp-2003-description (complete).pdf

333-delnp-2003-form-1.pdf

333-delnp-2003-form-18.pdf

333-delnp-2003-form-2.pdf

333-DELNP-2003-Form-3-(10-09-2009).pdf

333-delnp-2003-form-3.pdf

333-delnp-2003-form-5.pdf

333-delnp-2003-form-6.pdf

333-delnp-2003-gpa.pdf

333-delnp-2003-pct-210.pdf

333-delnp-2003-pct-304.pdf

333-delnp-2003-pct-409.pdf

333-delnp-2003-petition-137.pdf


Patent Number 237251
Indian Patent Application Number 333/DELNP/2003
PG Journal Number 51/2009
Publication Date 18-Dec-2009
Grant Date 11-Dec-2009
Date of Filing 10-Mar-2003
Name of Patentee LANXESS DEUTSCHLAND GMBH
Applicant Address D-51369 LEVERKUSEN, GERMANY.
Inventors:
# Inventor's Name Inventor's Address
1 HEINZ-JOACHIM ROTHER DAHLERDYK 124 E, D-47803 KREFELD, GERMANY.
2 HARTMUT REHBEIN BUCHENWEG 95, D-47447 MOERS, GERMANY.
3 MARTIN KUGLER AM KLOSTER 47, D-42799 LEICHLINGEN, GERMANY.
PCT International Classification Number A01N 31/08
PCT International Application Number PCT/EP01/10303
PCT International Filing date 2001-09-07
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 100 46 265.0 2000-09-19 Germany