AU661125B2 - Process for stuffing, fulling and waterproofing leathers and pelts - Google Patents

Abstract

A process is disclosed for stuffing, fulling and waterproofing leathers and pelts by using en-adducts of maleic acid anhydride to either unsaturated fatty acids containing 12-24 C atoms, their C1?-C20? alkyl ester or C2?-C20? alkenyl esters, triglycerides, amides, mono- or di-(C2?-C4? alkanol) amides, mono- or dipolyetehr amides or polyether esters; or by using en-adducts derivatized partially or completely by conversion into amides or esters with amines or alcohols.

Description

OPI DATE 21/10/93 APPLN. ID 36321/93 IN~l 1111li ii111II AOJP DATE 23/12/93 PCI NUMBER PCT/EP93/00543 Illt~lIii IiI, 1111111lii 1 lul1l I N AU9336321 (51) Internationale Patentklassifikation 5 (11) Internationale Veriiffentlichungsnummer: WVO 93/19210 Veriiffentlichungsdatum: 30. September 1993 (30.09.93) (21) Yntcrnationales Aktenzelchen: PCT/EP93/00543 (74) Cemneinsamer Verireter: BASF AKTIENGESELL- SCHAFT'; Carl-Boschi-Strasse 38, D-67056 Ludwigsha- (22) Internationales Anmeldedatum: 10. Miirz 1993 (10.03.93) fen (DE).

Priori tfitsdaten: (81) Bcstimmungsstaaten: AU, JP, US, europdis-hes Patent P 42 09243.4 21. Miirz 1992 (21.03.92) DE (AT, BE, CH, DE, DK, ES, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE).

(71) Anmelder (fir alle Bestimmungssraaten ausser US): BASF AKTIENGESELLSCHAFT [DE/DE]; Carl-Bosch- Veriiffentlicht Strasse 38, D-67056 Ludvigshafen Mil internationalem RecIherclhenbericht.

(72) Erfinder; und Erfinder/Anmelder (nurflir US) BIRKHOFER, H-ermafnn12 [DE/DE]; Berner Weg 26, D-6700 Ludwigshafen (DE).

DANISCH, Peter rDE/DE]; An der Mittagsweide 123, D-6700 Ludwigshafen GREIF, Norbert [DE/DE]; Im Woogtal 3, D-6719 Bobenheimn OPPENLAEN- DER, Knut [DE/DE]; Otto-Dill-Strasse 23, D-6700 Ludwigshafen (DE).

(54) Title: PROCESS FOR STUFFING, FULLING AND WATERPROOFING LEATHERS AND PELTS (54) Bezeichnniag: VERFAHREN ZUM FETTEN, FOLLEN UND HYDROPHOBIEREN VON LEDERN UND PELZEN (57) Abstract A process is disclosed for stuffing, fulling and waterproofing leathers and pelts by using en-adducts of maleic acid anhydride to either unsaturated fatty acids containing 12-24 C atoms, their C 1 0 alkyl ester or C 2

'-C

20 alkenyl esters, triglycerides, amuides, mono- or di-(C 2

-C

4 alkanol) amides, mono- or dipolyetehr amides or polyether esters; or by using en-adducts denyvatized partially or completely by conversion into amides or esters with amines or alcohols.

(57) Zusammenfassung Verfahren zumn Fetten, Ffillen und Hydrophobieren von Ledern und Peizen unter Verwendung von En-Addukten des Maleinsitureanhydrids an ungesdttigte Fettsiiuren mit 12 bis 24 C-Atomen, deren C 1 bis C 2 o-Alkyl- oder C 2 bis C, 0 -Alkenylester.

deren Triglyceride, deren Amide, deren Mono-oder Di(C 2 bis C 4 -alkanol)amide, deren Mono- oder Dipolyetheramide oder deren Polyetherester oder von partiell oder vollstlindig durch Umsetzung mit Aminen oder Alkoholen zu Amiden bzw.

Estem derivatisierten En-Addukte.

O.Z. 0050/43110 Fatliquorin, filli.,q and hydrophobicizinq leathers and furs The present invention relates to an improved process for fatliquoring, filling and hydrophobicizing leathers and furs and to an improved fatliquoring agent for leathers and furs.

To control the mechanical properties of leather such as softness, flexibility or suppleness it is common to use fat liquors, aqueous emulsions of in general petrochemically produced or natural oils and fats rendered water-emulsifiable by partial sulfonation or by means of emulsifiers or solubilizers.

This class of fat liquor ingredients has the disadvantages of incomplete liquor exhaustion, lack of resistance to extraction by solvents or water, migratory phenomena and unsatisfactory fastness profiles.

For instance, DE-A-39 09 614 concerns a process for fatliquoring and hydrophobicizing leathers and furs by using sulfonated compounds of succinic acid with unsaturated fatty acids or esters, amides or alkanolamides, for example, the product of reacting oleic acid or an oleic acid derivative with maleic anhydride in the presence of a free radical initiator and subsequently sulfonating with sulfuric acid.

US-A-3 656 881 discloses that alkenylsubstituted saturated dibasic acids such as isooctadecenylsuccinic acid are suitable for softening leather.

Here adequate solubility or emulsifiability is achieved using organic solvents as solubilizers. Since organic solvents are in general not bound by leather, this gives rise to ecological problems, in particular contamination of the waste water by residual liquors and of the air through evaporation during the drying process.

It is an object of the present invention to provide an improved product for fatliquoring, filling and hydrophobicizing leathers and furs that is free of the prior art disadvantages.

2 O.Z. 0050/43110 We have found that this object is achieved by a process for fatliquoring, filling and hydrophobicizing leathers and furs, which comprises using ene adducts of maleic anhydride with unsaturated fatty acids of from 12 to 24 carbon atoms or their C 1 to C 20 -alkyl or C 2 to

C

20 -alkenyl esters, triglycerides, amides, mono- or di(C,to C 4 -alkanol)amides, mono- or dipolyetheramides or polyetheresters, or ene adducts partially or completely derivatized by reaction with amines or alcohols to form amides or esters, respectively.

The ene adducts mentioned are known in principle from and from DE-C-27 54 831 In they are mentioned as intermediates in the synthesis of the sulfonated fatliquoring agents claimed therein, but are not recommended for use as leather treatment assistants in their own right. In they are claimed as solubilizers for nonionic surfactants in alkaline aqueous solution.

The ene adducts are prepared in a conventional manner by a thermal addition of maleic anhydride to unsaturated fatty acids or derivatives thereof in which the unsaturated fatty acid, irrespective of its number of preferacbTly double bonds adds per mole about 0.4 2 mol, preferably from 0.7 to 1 mol, of maleic anhydride. The addition can be carried out for example in boiling toluene or without a solvent at from 100 to 200 0 C, preferably in the presence of catalytic amounts of iodine. The unsaturated fatty acids have from 12 to 24, preferably from 14 to 18, carbon atoms and one or more olefinic double bonds. The amount of maleic anhydride added per double bond is preferably not more than one mole, although more could be added, since only the double bond from maleic anhydride is used up in the addition and not that of the fatty acid. Examples of suitable unsaturated fatty acids [are] in particular oleic acid (cis-9,10-octadecenoic acid), but also the corresponding transisomer elaidic acid, lauroleic acid (9,10-eicosenoic acid), erucic acid 3 O.Z. 0050/43110 (13,14-docosenoic acid) and selacholeic acid (15,16-hexadecenoic acid). Examples of suitable fatty acids having two or mere olefinic double bonds are in particular linoleic acid (9,10-12,13-octadecadienoic acid) and linolenic acid (9,10-12,13-15,16-octadecatrienoic acid).

It is also possible to use the circumscribed esters of the unsaturated fatty acids mentioned, eg.

methyl, ethyl, propyl, butyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl, hexadecyl, stearyl, hexadecenyl, oleyl, linoleyl and linolenyl esters.

In addition to the circun.dcribed monoesters it is also possible to use the triglycerides of the unsaturated fatty acids, ie. especially natural fats and in particular oils, which contain predominant proportions, ie. more than 50 mol%, preferably more than 75 mol%, based on the fatty acid total present in the mixture, of the aforementioned unsaturated fatty acids as esters. Suitable examples are linseed oil, olive oil, castor oil, groundnut oil, sesame seed oil, corn seed oil, sunflower oil, soybean oil, poppy seed oil, cotton seed oil, hemp seed oil and palm kernel oil and also the various animal fats and in particular oils such as fish oil, whale oil and sperm oil. The last one contains not only glycerides but also appreciable amounts of esters with wax alcohols, including unsaturated alcohols.

Suitable fatty acid amides are in particular the compounds which are unsubstituted at the amide nitrogen.

Suitable mono- or di(C 2 to C 4 -alkanol)amides are in particular N-monoethanolamide, N,N-diethanolamide, N-monoisopropanolamide and N,N-diisopropanolamide.

Examples of suitable mono- or dipolyetheramides are compounds that are substituted at the amide nitrogen by polyoxyethylene groups having a respective degree of ethoxylation of from 1 to 30, in particular from 2 to Examples of suitable polyetheresters are the reaction products of unsaturated fatty acids with from 1 R> ~to 30 mol, in particular from 2 to 20 mol, of ethylene 4 O.Z. 0050/43110 oxide.

The preparation of the amide or ester derivatives is effected in a known manner by addition of the amine or alcohol to the anhydride group-containing ene adduct at temperatures between eGustomaar 20 nd 200 C, referably between 50 and 150 0 C. The addition can be catalyzed, for example with p-toluenesulfonic acid. Per mole of anhydride group it is preferable to use not more than one mole of amine or alcohol. The addition can be carried out for example in toluene or in the absence of a solvent, preferably in the same reaction medium as used in the preparation of the ene adduct. For instance, the alcohols used can be for example methyl, ethyl, propyl, butyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl, hexadecyl, stearyl, oleyl alcohol or alkoxylated fatty or oxo alcohols or carbohydrates such as, for example, glucose.

Preference is given to using straight-chain or branched Ci-C 20 -alkanols, in particular C 4

-C,

1 -alkanols, and also to

C.-C

18 -alkanols reacted with from 2 to 20 mol of ethylene oxide and/or propylene oxide per mole of alkanol. The amines used can be for example mono- or di-N-alkylamines such as n-butylamine, 2-ethylhexylamine, morpholine, piperidine or tallowamine or amino acids such as sarcosine, taurine or iminodiacetic acid or amino alcohols such as iminodiethanol or hydroxyethylamine.

Preference is given to using saturated or unsaturated secondary or in particular primary aliphatic amines having a total of from 1 to 30, in particular from 4 to 18, carbon atoms.

In a preferred embodiment the ene adducts used of maleic anhydride are with unsaturated fatty acids of from 14 to 18 carbon atoms or their C 14 to C 1 i-alkenyl esters or triglycerides, but in particular with oleic acid, oleyl oleate or a triglyceride containing more than 50 mol% of unsaturated fatty acids of from 14 to 18 carbon atoms, based on total fatty acid present in the mixture, as esters, or ene adducts derivatized partially IL u 4B 5 O.Z. 0050/43110 or completely by reaction with aliphatic amines having in total from 1 to 30 carbon atoms or with C 1

-C

20 -alkanols or with alkoxylated alcohols to form amides or esters, respectively.

On being dissolved in an aqueous alkaline medium, the anhydride groups still present on the added maleic anhydride hydrolyze to form carboxylate groups, which, together with original carboxyl groups of unsaturated fatty acids that are likewise still in the salt form, ensure the solubility of the products to be used according to the invention.

The ene adducts described make it possible to produce very soft leathers without conventional fat liquors. This advantage is reflected in simple and short application recipes.

In addition to improving the mechanical properties, for example the breakinq strength, these ene adducts bring about a distinct enhancement in the softness profile of the leather.

As well as improving the mechanical properties, for example the tensile strength, these ene adducts bring about a distinct enhancement in the fastness profile of the leather.

For instance, they have a very positive effect on the light fastness and the thermal yellowing resistance of such leathers. In addition to producing a virtually quantitative exhaustion of the liquor, the high yield of fixation in the leather results in resistance to extraction by solvent or water. This results in washable leathers, ie. leathers which on washing do not lose their properties such as softness, firmness and suppleness, unlike leathers fatliquored with conventional fat liquors.

As well as a softening effect, the products described also have a hydrophobicizing effect, ie.

leathers and furs which have been treated therewith are water-repellent and absorb only minimal amounts of water.

6 O.Z. 0050/43110 A further advantage of the aqueous ene adduct emulsions to be used according to the invention is that they do not contain additional emulsifiers. As will be known, leathers and furs treated with emulsifiercontaining products must afterwards be subjected to expensive processes, for example aftertreatment with polyvalent metal salts, in order to render the emulsifiers in the leather or fur skin, where they have a negative effect on the water repellency, ineffective.

The present invention also provides leather and fur fatliquoring, filling and hydrophobicizing compositions comprising the above-described ene adducts of maleic anhydride with unsaturated fatty acids or derivatives thereof.

The leather treatments of the invention are suitable for any conventional tanned hide. Tanned hides are customarily neutralized prior to the treatment. They may have already been dyed prior to the treatment.

However, dyeing may also be delayed until after the treatment according to the invention.

pre:eriby The tanned hides are advantaggq=sJLw treated with the aqueous emulsions of the ene adducts in an aqueous liquor obtainable by diluting the emulsions with water at pH 4 10, preferably pH 5 8, and 20 60 0 C, preferably 30 50 0 C, for 0.1 5 hours, in particular 0.5 2 hours. This treatment may take the form for example of drumming. The amount of emulsion required is, based on the shaved weight of the leather or the wet weight of the fur skin, from 0.1 to 30% by weight, preferably from 1 to 20% by weight.

The liquor length, ie. the percentage weight ratio of treatment liquor to goods, based on the shaved weight of the leather or the wet weight of the fur skin, is customarily from 10 to 1000%, preferably from 30 to 150% in the case of leathers and from 50 to 500% in the case of fur skins.

After the treatment with the above-described 7 O.Z. 0050/43110 aqueous liquor, the pH of the treatment liquor is adjusted with acids, preferably organic acids, eg. formic acid, to pH 3 5, preferably pH 3.5 4.

If customary retanning agents are additionally employed in the finishing of the leather or fur skin, the treatment with the aqueous emulsion of the ene adducts can be carried out before or after the retanning operation.

EXAMPLES

The percentages in the Examples are by weight, unless otherwise stated.

Preparation of aqueous ene adduct emulsions EXAMPLE 1 240 g of oleic acid (hydrogenation iodine number 90.1) and 108 g of maleic anhydride were heated together in a nitrogen atmosphere at 200°C for 4.5 hours. Unconverted maleic anhydride was then distilled off (25 g) under a water jet vacuum, leaving 320 g of product.

To 57 g of the oleic acid-ene adduct were added 12 g of 50% strength NaOH in 172 g of water to obtain a strength brown emulsion.

EXAMPLE 2 Example 1 was followed to react 348 g of ester oil (hydrogenation iodine number 112.6) with 166 g of maleic anhydride. This resulted in 535 g of product, leaving 13 g of unconverted maleic anhydride.

To prepare an emulsion 24 g of 50% strength NaOH in 295 g of water were added to 97 g of ene adduct.

EXAMPLE 3 Example 1 was followed to react 375 g of capellan oil (hydrogenation iodine number 122) with 176 g of maleic anhydride. This resulted in 540 g of product leaving 10 g of unconverted maleic anhydride.

To prepare an emulsion 92 g of the ene adduct were dissolved in 24 g of 50% strength NaOH in 279 g of water.

8 O.Z. 0050/43110 EXAMPLE 4 Example 1 was followed to react 266 g of oleyl oleate (hydrogenation iodine number 95.5) with 127 g of maleic anhydride. This resulted in 365 g of product, leaving 20 g of unconverted maleic anhydride.

To prepare an emulsion 66 g of the ene adduct were dissolved in 75 g of 50% strength NaOH in 197 g of water.

EXAMPLE To 114 g of the capellan oil-ene adduct of Example 3 were added 6.2 g of n-butylamine at from 70 to 120 g of product were obtained after three hours at 0

C.

To prepare an emulsion 100 g of product were added to 300 g of water and 16 g of 50% strength sodium hydroxide solution.

EXAMPLE 6 To 88 g of the capellan oil-ene adduct of Example 3 were added 33.2 g of n-tallowamine at from 70 to 80 0

C.

121 g of product were obtained after three hours at 80 0

C,

To prepare an emulsion 100 g of product were added to 300 g of water and 10.5 g of 50% strength sodium hydroxide solution.

EXAMPLE 7 To 107 g of the capellan oil-ene adduct of Example 3 were added 0.6 g of p-toluenesulfonic acid at from 70 to 80°C. 14.1 g of isobutanol were added at from 120 to 130°C. 119 g of product were obtained after three hours at 130 0

C.

To prepare an emulsion 100 g of product were added to 300 g of water and 10 g of 50% strength sodium hydroxide solution.

EXAMPLE 8 To 40.5 g of the capellan oil-ene adduct of Example 3 were added 0.6 g of p-toluenesulfonic acid at from 70 to 80°C. 81.6 g of a commercial mixture of C,-C 15 alkanols which had been reacted with ethylene oxide and 9 O.Z. 0050/43110 propylene oxide (together about 9 mol per mole of alkanol) were added at from 120 to 1300C. 122 g of product were obtained after three hours at 130 0

C.

To prepare an emulsion 100 g of product were added to 300 g of water and 3.5 g of 50% strength sodium hydroxide solution.

Use in leathermaking EXAMPLE 9 Chrome tanned cattlehide leather which had a shaved thickness of 1.8 mm and had been adjusted to a pH of 5.0 was drummed at 40 0 C for 2 hours with an amount of the emulsion of Example 1 to correspond to 15% of active ingredient, based on the shaved weight. The total liquor length was 150%. The leather was then dyed with 1% by weight of a conventional anionic aniline dye. It was then adjusted to pH 3.8 with formic acid and finally washed, mechanically set out and dried.

The leather obtained was very soft, supple, highly filled and uniform in color.

EXAMPLE Chrome tannned cattlBhide leather which had a shaved thickness of 1.8 mm and had been adjusted to a pH of 5.0 and dyed with 0.7% by weight of a conventional anionic aniline dye was drummed at 40 0 C for 1.5 hours with an amount of the emulsion of Example 2 to correspond to 20% of active ingredient, based on shaved weight.

Thereafter the leather was adjusted with formic acid to pH 3.6 and finished in a conventional manner.

The leather thus obtained was very soft and pliable.

EXAMPLE 11 Chrome tanned cattlehide leather which had a shaved thickness of 1.8 mm and had been adjusted to pH 5.0 and dyed with 0.7% of a conventional anionic aniline dye was drummed at 40 0 C for 30 minutes with an amount of the emulsion of Example 3 corresponding to of active ingredient, based on shaved weight, and then 10 O.Z. 0050/43110 further treated with 3% of a conventional synthetic tanning agent for one hour. The leather was then adjusted with formic acid to pH 3.6 and finished in a conventional manner.

The leather thus obtained had a pleasantly soft and pliable feel.

EXAMPLE 12 The emulsion of Example 4 was used in the manner of Example 9.

The leather thus obtained had soft and round hand properties.

EXAMPLE 13 The emulsion of Example 5 was used in the manner af Example 9.

The leather thus obtained had soft and pleasant hand properties.

EXAMPLE 14 The emulsion of Example 6 was used in the manner of Example 9.

The leather obtained was soft with a slightly creamy hand. No water penetration occurred in the course of 12 hours in the penetrometer under 10% compression.

EXAMPLE The emulsion of Example 7 was used in the manner of Example 9.

The leather thus obtained was pleasantly soft and pliable.

EXAMPLE 16 The emulsion of Example 8 was used in the manner of Example 9.

The leather obtained had a pleasantly soft hand and a uniform coloring.

Claims (6)

1. A process for fatliquoring, filling and hydrophobicizing leathers and furs, which comprises using ene adducts of maleic anhydride with unsaturated fatty acids of from 12 to 24 carbon atoms or their C 1 to C 20 -alkyl or C2- to C 2 0 -alkenyl esters, triglycerides, amides, mono- or di(C 2 to C 4 -alkanol)amides, mono- or dipolyetheramides or polyetheresters, or ene adducts as prepared above partially or completely derivatized by reaction with amines or alcohols to form amides or esters, respectively.

2. A process for fatliquoring, filling and hydrophobicizing leathers and furs as S claimed in claim 1, wherein the ene adducts of maleic anhydride used are with unsaturated fatty acids of from 14 to 18 carbon atoms or their C14- to C 18 -alkenyl esters or triglycerides or ene adducts derivatized partially or completely by reaction with aliphatic amines having in total from 1 to 30 carbon atoms or with C1-C20- alkanols or with alkoxylated alchohols to form amides or esters, respectively.

3. A process for fatliquoring, filling and hydrophobicizing leathers and furs as claimed in claim 1, wherein the ene adducts of maleic anhydride used are with :oleic acid, oleyl oleate or a triglyceride containing up to 50 mol% of unsaturated S fatty acids of from 14 to 18 carbon atoms, based on total fatty acid present in the mixture, as esters. consisting essentially of ene adducts of maleic wit unsaturated fatty acids or derivative set forth in claim 1 and other usually applied -mponents for sch a gents DATED this 19th day of December, 1994 BASF AKTIENGESELLSCHAFT WATERMARK PATENT TRADEMARK ATTORNEYS 290 BURWOOD ROAD HAWTHORN VICTORIA 3122 AUSTRALIA INTERNATIONAL SEARCH REPORT International application No. PCT/EP93/00543 A. CLASSIFICATION OF SUBJECT MATTER Int.Cl 5 C14C 9/00 According to International Patent Classification (IPC) or to both national classification and IPC B. FIELDS SEARCHED Minimum documentation searched (classification system followed by classification symbols) Int.Cl 5 C14C Docur.entation searched other than minimum documentation to the extent that such documents are included in the fields searched Electronic data base consulted during the international search (name of data base and, where practicable, search terms used) C. DOCUMENTS CONSIDERED TO BE RELEVANT Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No. X DE, A, 3909614 (ZSCHIMMER SCHWARZ GMBH CO CHEMISCHE FABRIKEN) 27 September 1990 (cited in the application) see page 2, line 31 line see example 1 SFurther documents are listed in the continuation of Box C. See patent family annex. Special categories of cited documents: later document publisbedafter the international filing dateor priority document deining the general stateof the art which is not considered da and non onflict with the application but cited to understand to be of particular relevance the principle or theory underlying the invention earlier document but published on or after the international filing date document of particular relevance: the claimed invention cannot be .considered novel or cannot be considered to involve an inventive document which may throw doubts on priority claim(s) or which is step when the docu.nent is taken alone cited to establish the publication 4 ate of another citation or other special reason (as specified) document of particular relevance; the claimed invention cannot be document referring to an oral disclosure, use, exhibition or other considered to involve an inventive step when the document is means combined with one or more other such documents, such combination document published prior to the international filing date but later than being obvious to a prson skilled in the art the priority date claimed document member of the same patent family Date of the actual completion of the international search Date of mailing of the international search report 08 June 1993 (08.06.93) 25 June 1993 (25.06.93) Name and mailing address of the ISA/ Authorized officer European Patent Office Facsimile No. Telephone No. Form PCT/ISA/210 (second sheet) (July 1992) ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. EP 9300543 SA 71034 This annex lists he patent family members relating to the patent documents cited in the above-mentioned international search report. The members are as contained in the European Patent Office EDP file on The European Patent Office is in no way liable for thixa particulars which ame merely given for the purpose of information. 08/06/93 cited in search report DE-A-3909614 Publicrtion dateI Patent family moember(s) Publication date

7-09-9" None 0 't For more details about this annex :sce Official Journal Q( the European Patent Office, No. 12192 INTERNATIONALER RECHERCHENBERICHT Internationales Aktoaxelchan PCT/EP 93/00543 I. KLASSIFIKATION DES ANNIEWJUNGSGEGENSTANDS (bel mebreren Kiassiflktatioassymbolei sind aile axtzugeben)' Nach der Internationaien Patentklassifikadon (TPC) oder nati der ngtionalin Klusslfkadon und der EPC Int.K1. 5 C14C9/00

11. RECH-ERcHIERTE SACHGEBIET Recherchlertcr Mindestp.aMtoff 7 wlssfiaonsstem Klassifkationssymbole Int.K1. 5 C14C Recherchlerte nicit zum Mindstprttoff gdillrende Vertlffentlichungeo, sowelt diese unter die rediterchlerten Sacbg~bite fien Eal. EINSCHLAGIGE VEROFFENTUCHUNGEN 9 Art.' Kennzeicbnung der Verliffentlidwung 11 soweit erfordeulicb unter Angahe der mailgebiichen Telie L2 Retm Anpruch Nr.U X DE,A,3 909 614 (ZSCHIMMER SCHWARZ GMBH CO CHEMISCHE FABRIKEN)

27. September 1990 in der Animeldung erwdhnt siehe Seite 2, Zeile 31 Zeile siehe Beispiel 1 Dfesondem Kategorien von angegbenen Verliffentlicbungen' A' Verdffeatlichug, di.e den aliguenen Stand der Tedinik 'T Spt! ert= lffniicbun die nach dcm internatioaales An- defniert, abet &Ihtas besonders bedeatsam anniseben Ist r.eldedtm oe dem Prirlitstatum verdffentlidit worden 'V 1teres Dokumeu das jedoch erst am oder nadi dem intena- ist und mit der Anmeldung niclit koilidiert, sondern nut zum tionlenArnededtumver~fenlict wodenistVerstlindnis des der Erfindung zugnandefiegeden Prinzps tionlenAnmededtut verlffntlcht oodn ~oder der ihr zugrundeflienden Thenrie angegeben ist W" Verliffentlicbung, die geesret ist, einen Prioifltstt c X' Verldfentlidiung von besonderer fledeutung; die beansprucb- vweffelhaft erscbdinai zu lassen odcr durch die das t ridn mnndta~nuoe i rldrshrTtg fentliditingsdatum einer anderen Im Re chebnbelcbt go- kt b aidugkn ib aJ wede defnedce nanoten Vertlffentllchung beiegt werden soil oder die aus eioem etbradbtace wdn anid*=e besonderan Grund angeeben 1st (wit ausgefuhui) Y' Vrtiffentliciun von besondeie Bedeutung die bensruch- 0' Veatlffentlicbung, die sicl ald eine milndiiche Offabang, te Erfindungmno nidit uls auf edlindeulscher Titigk t be- em. enuzuo, de Austeiun 081 anete flnhzno nhend betuaclitet warden. wenD die Vertiffentllihung mit ein Beumug, ineAustelungode anereM~aj~heneinet ode: menhren anderen Verlifaxtllchungn di ee Kato- bezietgore In Vetbindung gebracht wird und dies d Veb un g tg qP Vatiffleitcung, die yor dem Internationalen Arneideda- einen Faclimano nab eliegend Ist tum, aber nacb dent beansptucbten Prioritillsdatuin verbifent- VerUffentflebung, die Mltgiied derselben Paceiitfamile 1st liclit worden 1st IV. BESCHEINIGUNG Datum dets Abschlusses der internationalen Recherche Absendedatum des Internationaieo Rediarchemberlcbts 08.JUNI 1993 Internationale Rechercheobeiirde Unterscbtlft des beolmlditigten Bediensteten IEUROPAISCHES PATENTAMIT GOERKE H.R. FarmiAt PCT/LSA4210 (Bltt 2) (Jamw Inn) ANHANG ZUM INTERNATIONALEN RECHERCHENBERICHT OBER DIE INTERNATIONALE PATENTANMELDUNG NL EP 9300543 SA 71034 In dicsetn Anhang sind die Mitglieder der Patentfamiin der im obengenanntca internationa"~ Rchbeschenbenicht angeftlhrtez Patentdokumente angegeben. Die Angahen fiber die Familenmitglicder entsprechen dean Stand der Datei des Europiischea Patentiumts am Diese Angaben dienen nur zr Unterrichtung und erfolgen obme Gewiihr. 08/06/93 Im edarvhiheichhung c tglied(er) der Datum der angcfilbtc Patentdokument Verfiffentlicbn PatentfamilcVwwfaiibn DE-A-3909614 27-09-90 Keine C6 Far niihere Einza~citen zu diesena Anhanii sicbe Amtsbtatt des Europiiscbcn Patentus,% Nr.I2/82