AU626954B2

AU626954B2 - Phosphate-free liquid washing agent with high alkalinity

Info

Publication number: AU626954B2
Application number: AU46260/89A
Authority: AU
Inventors: Uwe Trabitzsch
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1988-12-07
Filing date: 1989-11-15
Publication date: 1992-08-13
Anticipated expiration: 2009-11-15
Also published as: CA2004895A1; EP0377807B1; EP0447413A1; DK101291D0; JPH04502337A; ES2061894T3; PT92396A; EP0377807A1; DE58906948D1; DK101291A; AU4626089A; WO1990006353A1

Description

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OPI DATE 26/06/90 AO.IP DATE 2f6fl7/qf APPLN. ID 46260 89 PClT MIIMnrD PflT/PRq/fl1 7f Pcr INTERNATIONALE ANMELDUNG VEROFFENTLIGHT NACH DEM VERTRAG OJBER DIE INTERNATIONALE ZUSAMMENARBEIT AUF DEM GEBIET DES PATEN ESENS (PCT) (51) Internationale Patentlassiflkation 5(1)tatoV et n er WO9/65 CI ID 1/66, 1/825, 3/08 Al Ia i C11D 3/33 Ve fetI pgsurmm:5 14. Juni 1990 (14.06.90) (21) Internationales Akitenzeichen: PCT/EP89/0 1370 Veriffentlicht Mit internationalem Recherchenberich.

(22) Internationales Anmeliledatum: Vor Ablauif der far Anderungen der Ansprtiche zugelasse- November 1989 (15.11.89) nen Frist. Veriiffenzlichung wird wiedecholt falls Anderungen elntreffen.

Priori tiitsdaten: P 38 41 129.6 7. Dezember 1988 (07.12.88) DE P 39 06 766.1 3. Milrz 1989 (03.03.89) DE (71) Anmelder (ftir alle Bestirnmungsstaaten ausser US): HEN- KEL KOM MAN DITGESELLSCHAFT AUF AKTIEN [DE/DE]; Henkelstra~e 67, D-4000 Diisseldorf-Holthausen (DE).

(72) Erfinder; und Erfinder/Anmelder (nur far US) TRABITZSCH, Uwe [DE/DE]; Rosendalstra&~ 79, D-4030 Ratingen 8 (DE).

(81) Bestimmungsstaaten: AT (europaisches Patent), AU, BE (europdisches Patent), BR, CH (europiiisches Patent), DE (europiiisches Patent), DK, Fl, FR (europ~isches Patent), GB (europiiisches Patent), IT (europaisches Patent), JP, LU (europiiisches Patent), NL (europ~isches Patent), SE (europiiisches Patent), US.

(54)Thite: PHOSPHATE-FREE LIQUID WASHING AGENT WITH HIGH ALKALINITY (54) Bezeichnung: PHOSPHATFREIES, FLOSSIGES WASCHMITI'EL MIT HOHER ALKALITAT (57) Abstract A washing agent concentrate suitable for preparing liquid concentrated stock solutions contains 5 to 20 wt. of nonionic tensides, including (Al1) 4 to 20 of alkyiglucosides of formula and (A2) 0 to 2 wt.% Of C 12 18 alkyl polyglycol ether with 5 to 9 ethylene glycol ether groups, (BI1) 4 to 20 wt. of sodium hydroxyde, (132) 0.5 to 12 wt. of sodium silicate NaO:Si0 2 I:1I to 1:3.4, (113) 2 to 12 wt. of sod~ium nitrilotriacetate and 0 to 3 wt. of at least one phosphonic acid in the form of the sodium salt. In the formula R-O-GX, R denotes a C 8 14 alkyl residue, G a glucose residue and the index x numbers between 1.2 and 5. The sum of the constituents (B3) and (134) is between 3 and 12 wt. (57) Zusammenfassung Ein zur Herstellung von flossigen, konzentrierten Vorratsl~sungen geeignetes Waschmittelkonzentrat enthalt 5 bis Gew.-% an nichtionischen Tensiden, wovon (Al1) 4 bis 20 auf Alkylglucoside der Formel R-O-G 5 und (A2) 0 bis 2 auf

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12 18 Alkylpolyglykolether mit 5 bis 9 Ethyl englykoleth er- Gru ppen entfallen, (BI) 4 bis 20 Gew.-% Natriumhydroxid, (132) bis 12 Natriumsilikat Na 2 O:Si0 2 1:1 bis 1:3,4, (113) 2 bis 12 Gew.-% Natriumnitrilotriacetat und 0 bis 3 Gew.-% mindestens einer Phosphonsaure in Form des Natriumsalzes. In der Formel R-O-G, bedeutet R einen C 8 14 -AlkyIrest, G einen Glucoserest und der Index x Zahlen von 1,2 bis 5. Die Sumnme der Bestandteile (113) und (B14) betrAgt 3 bis 12 Gew.-%.

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ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. EP 8901370 SA 32402 This annex lists the patent family members relating to the Patent documents cited in the above-mentioned international gearch report.

The members are as Contained in the European Patent Office EDP ile on HENKEL KGaA Dr. Wa/Sk 07.07.1989 Patent Application D 7813-1 EP A licuid non-phosphate deterQent of high alkalinity Laundry detergents for institutional laundries differ considerably in their composition from those typically used in the home. On the one hand, softened water, i.e. Ca- and Mg-free water, is generally used in institutional laundries. On the other hand, institutional laundry detergents often contain highly alkaline builder salts and alkalis, such as sodium metasilicate and sodium hydroxide, which although they can be safely handled by the expert are unadvisable in the home for safety reasons. These highly alkaline constituents can in turn interact with the surfactants typically present, particularly nonionics of the alkyl polyglycol ether type, and can decompose them to a greater or lesser extent in the event of prolonged storage together. These problems exist in particular in the case of liquid concentrates and products which are intended for the preparation of concentrated stock solutions and in whose case the decomposing effect is particularly intensive through lack of spatial separation between surfactant and alkali component. Highly alkaline liquid products and stock solutions have the advantage over powder-form preparations of the same composition that they are dust free and, in particular, can be automatically dispensed and hence pose no operating problems.

Another aspect is the almost exclusive use of surfactants which can be obtained from natural, i.e. renewable, "I V ir D 7813-1 EP 2 raw materials and which are distinguished by complete and rapid biodegradability in the wastewater.

In addition, detergents of the type in question should not produce troublesome quantities of foam either in the main wash cycle or in the final rinse cycle. Since standard foam inhibitors, such as polysiloxanes and paraffin hydrocarbons, undergo losses of effect when dispersed in liquid detergents or, in the case of polysiloxanes, are decomposed by alkali, the surfactant component must itself be low-foaming.

The present invention, by which these problems; are solved, relates to a liquid, aqueous, non-phosphate detergent concentrate containing 5 to 20% by weight of a nonionic surfactant component 15 to 40% by weight of a builder component up to 3% by weight of other nonsurfactant and non-builder detergent constituents and water (balance to 100% by weight), characterized in that the components have the following composition, based on the detergent: Al) 4 to 20% by weight of an alkyl glucoside corresponding to formula I

R-O-G

x

(I)

where R a alkyl radical, G a glucose residue and x a number of 1.2 to A2) 0 to 2% by weight of at least one nonionic surfactant from the class of alkyl polyglycol ethers containing

C

1 2 18 alkyl groups and 5 toA-y ethylene glycol ether groups, Bl) 4 to 20% by weight sodium hydroxide, B2) 0.5 to 12% by weight sodium silicate having the composition Na 2 O SiO 2 1:1 to 1:3.4, B3) 2 to 12% by weight sodium nitrilotriacetate, B4) 0 to 3 by weight of the sodium salt of at least one phosphonic acid, with the proviso that the content of ANHANG ZUM INTERNATIONALEN

RECHERCHENBERICHT

OBER DIE INTERNATIONALE PATENTANMELDUNG NR. EP 890137 SA 32402 In ditem Anhang sind die Mitglieder der Patentfamilien der im obengenannten internationalen Recherchenhericht angerdhrt4en Patentdokumente angegeben.

Die Angben her die Familiemitglieder entsrechen dem Stand der Datei de Fmrnnchn D 7813-1 EP 3 constituents (B3 B4) is from 3 to 12% by weight.

The detergent preferably contains the individual components in the following quantities: Al) 5 to 12 by weight A2) 0.5 to 1.5 by weight Bl) 6 to 15 by weight B2) 0.5 to 3 by weight B3) 3 to 10 by weight B4) 0.2 to 2 by weight Component (Al) consists of alkyl glucosides or alkyl oligoglucosides of the type described, for example, in US- PSS 3,547,828, 3,772,269 and 3,839,318. They are obtainable by reaction of glucose or depolymerized starch and alcohols containing C 8 alkyl groups in the presence or absence of lower alcohols or glycols, such as butanol or propylene glycol, and acidic acetalization catalysts.

Alcohols or mixtures of alcohols obtained from native fats, such as coconut oil or palm kernel oil, are preferably used as the fatty alcohols. Examples are octyl, decyl, lauryl and myristyl alcohol and also mixtures thereof. Alternatively, it is also possible to use alkyl glucosides which are derived from oxoalcohols and which, in addition to linear alcohols, also contain alcohols methyl-branched in the 2-position in admixture or an even and/or odd number of i C atoms in the alkyl chain.

Examples are octyl, nonyl, decyl, undecyl, dodecyl and tridecyl alcohol and also mixtures thereof. R is preferably a C 812 alkyl group and more especially a 0 alkyl group. In the reaction of the glucose or glucose-containing starch degradation products with the alcohols, the glucose is partly oligomerized in the presence of acidic acetalization catalysts, resulting in the formation of mixtures of alkyl monoglucosides and alkylol oligoglucosides. The parameter x in formula I thus represents an average degree of oligomerization and is preferably from Z 4,V D 7813-1 EP 4 1.3 to 3. Mixtures such as these are meant where alkyl glucosides are mentioned generally in the context of the invention.

From their production, the alkyl glucosides still contain small quantities of free fatty alcohol and glucose.

Alkyl glucosides containing less than 5% by weight and, more especially, less than 2% by weight fatty alcohols (based on alkyl glucoside) are preferably used.

In addition to the alkyl glucosides, the detergents may optionally contain nonionic surfactants of the ethoxylated fatty alcohol and oxoalcohol type containing 12 to 18 C atoms and 5 to 10 ethylene polyglycol ether groups (EO) as component Suitable nonionic surfactants of this type are, for example, ethoxylates derived from coconut oil, tallow or palm kernel oil fatty alcohols having an HLB or ym-iove..

value of mur= than 121 for example from 13 to 18, and corresponding ethoxylates of oxoalcohols containing 12 to 16 C atoms and 6 to 8 EO groups.

The builder component consists of sodium hydroxide (constituent Bl), sodium silicate (constituent B2) and sequestering polyanionic salts derived from nitrilotriacetic acid (NTA) and, optionally, phosphonic acids (constituent B3 and B4).

In the sodium silicate, the ratio of Na 2 O to SiO 2 4 may be from 1:1 (metasilicate) to 1:3.4 (waterglass). In detergents containing relatively small amounts of sodium hydroxide, metasilicate is preferably used in the interests of high alkalinity whereas, in detergents having relatively high contents of sodium hydroxide, the sodium silicate may consist predominantly or completely of waterglass.

The NTA is present in the form of the trisodium salt, the quantitative calculation also being based on this form.

The NTA content is preferably from 5 to 10% by weight.

The phosphonate is primarily the sodium salt of 1hydroxyethane-1,1-diphosphonic acid (HEDP). The quantita- -os- 'N

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D 7813-1 EP tive calculation is based on the tetrasodium salt. It is also possible to use the sodium salts of aminotrimethylene phosphonic acid (ATMP), ethylenediamine tetramethylene phosphonic acid (EDTMP), diethylenetriamine pentamethylene phosphonic acid (DTPMP) and higher homologs thereof, although EDTMP is less preferred on account of its as yet unclear function in the wastewater. Their quantitative calculation is based on neutrally reacting sodium salts (Na 3 salt in the case of ATMP, Na 5 salt in the case of EDTMP, Na 6 salt in the case of DTPMP). The sum of components B3 B4 is from 3 to 12% by weight and preferably from 6 to 11% by weight.

In addition to the constituents mentioned above, the detergents may contain other non-surfactant and non-builder constituents, including optical brighteners in quantities of up to 1% by weight and preferably from 0.05 to 0.3% by weight. Examples of optical brighteners are derivatives of bis-(triazinylamino)-sti'bene disulfonic acid, for example the sodium salt of 4,4'-bis-(2-anilino-4-morpholino-l,3,5triazin-6-ylamino)-stilbene-2,2'-disulfonic acid and of the chlorinated diphenyl distyryl sulfonic acids.

Other optional constituents are enzymes, fragrances, dyes, hydrotropes and water-miscible solvents. Suitable hydrotropes are, for example, toluenesulfonate, xylenesulfonate and cumenesulfonate, in each case in the form of the sodium salts. Suitable solvents are, for example, ethanol, propanol, isopropanol and also ether alcohols, such as diglycol, and C1.

3 monoalkyl ethers of C2- 4 diols. The hydrotropes may be present in quantities of up to 6% by weight while the alcohols or ether alcohols may be present in quantities of up to 10% by weight. The detergents may also contain neutral salts, such as sodium sulfate and sodium chloride, in small quantities as impurities of the raw materials used. Thebalance to 100% by weight consists essentially of water.

7 lit 1.

§11 11 V -i-L _LIIC D 7813-1 EP The detergents are storable, pourable liquids which are suitable both for automatic dispensing and also for the preparation of stock solutions. The concentrates remain liquid and stable to separation at temperatures of down to Their in-use concentration is generally from 2 to g/l and preferably from 3 to 7 g/l.

EXAMPLES

Detergents were prepared from the following constituents. In the alkyl glucoside, R was a mixture of C8_i 0 groups and X 1.8, prepared by the direct synthesis method.

Table 1 Example Constituent 1 2 3 4 (quantities in by weight) Alkyl glucoside 6 6 8 6 7

C

1 15 alcohol 7 EO 1 1 1 1 NaOH 10 12.5 15 6 13 Naz-SiO 3 1:3.3 2 2 2 0.7 NTA (Na3 salt) 8 8 8 6 HEDP (Na salt) 2 1 1 2.

EDTMP (Na salt) 1 DTPMP (Na salt) 1 1 Optical brightener 0.1 0.1 0.1 0.1 0.1 Na cumenesuifonate 4 Isopropanol Water bal- bal- bal- bal- balance ance ance ance ance A washing machine (of the Frista(R) type) was loaded with lightly soiled washing (bed and table linen which had Iiii' i D 7813-1 EP 7 been used once) and test cloths soiled as follows: Al dust-wool grease on cotton A2 blood-milk-indian ink on cotton A3 blood on cotton A4 milk cocoa on cotton dust-sebum on crease-resistant cotton A6 dust-sebum on crease-resistant cotton/polyester blend A7 dust-wool grease on blended fabric (as A6).

The quantity of washing amounted to 7.5 kg, the water hardness was 0°Gh, normal program (no prewash), detergent concentration 4 g/l, 5 minutes at 40*C and 15 minutes at three rinses, low foaming.

The percentage remission (against a white standard) was photometrically evaluated. The figures represent averages of three parallel determinations (scattering The results are shown in Table 2 below. A commercially available detergent of similar composition (without glucoside) was used for comparison Equally good washing results were also obtained when alkyl glucosides in which x 1.4 and x 2.2 were used instead of the alkyl glucoside with x 1.8.

Table 2 Remission Soil 1 2 3 5 C Al 75.9 73.2 73.1 73.8 71.5 A2 40.2 37.8 37.6 39.2 35.2 A3 83.5 82.4 82.6 82.7 78.2 A4 75.7 72.5 77.9 78.1 74.4 58.6 54.6 52.0 53.8 48.1 A6 72.0 69.1 69.7 71.0 64.5 A7 58.9 56.0 53.6 58.1 49.3 4 1: i i;N __i i

Claims

1. A liquid, aqueous, non-phosphate detergent concentrate containing 5 to 20% by weight of a nonionic surfactant component 15 to 40% by weight of a builder component up to 3% by weight of other non-surfactant and non- builder detergent constituents and water (balance to 100% by weight), characterized in that the components have the following composition, based on the detergent: Al) 4 to 20% by weight of an alkyl glucoside corresponding to formula I R-O-G, (I) where R a C- 14 alkyl radical, G a glucose residue and x a number of 1.2 to A2) 0 to 2% by weight of at least one nonionic surfactant from the class of alkyl polyglycol ethers containing C 12 iz. alkyl groups and 5 tof-W ethylene glycol ether groups, Bl) 4 to 20% by weight sodium hydroxide, B2) 0.5 to 12% by weight sodium silicate having the composition NaO0 SiO 2 1:1 to 1:3.4, B3) 2 to 12% by weight sodium nitrilotriacetate, B4) 0 to43 by weight of the sodium salt of at least one phosphonic acid, with the proviso that the content of constituents (B3 B4) is from 3 to 12% by weight.

2. A detergent as claimed in claim 1, characterized in that the individual components are present in the following quantities: Al) 5 to 12 by weight A2) 0.5 to 1.5 by weight Bl) 6 to 15 by weigb B2) 0.5 to 3 by weigl B3) 3 to 10 by weigh B4) 0.2 to 2 by wei,:

3. A detergent as claimed in claim 1 or 2, characterized I -9- r r c in that, in formula R C8 12 alkyl radicals and x a number of 1.3. to 3.

4. A detergent as claimed in any one of claims 1 to 3, characterized in that the nonionic surfactant of component (A2) has an HLB value of 12 or more. A detergent as claimed in any one of claims 1 to 4, characterized in that component (B4) consists of the sodium salt of l-hydroxyethane-l,1-diphosphonic acid.

6. A detergent as claimed in claim 5, characterized in that component (B4) additionally contains the sodium salt of diethylenetriamine pentamethylene phosphonic acid.

7. A detergent as claimed in any one of claims 1 to 6, characterized in that the content of component (B3) is from 5 to 10% by weight.

8. A detergent as claimed in any one of claims 5 to 7, characterized in that the sum of components (B3 B4) is from 6 to 11% by weight.

9. A liquid, aqueous, non-phosphate detergent concentrate substantially as hereinbefore described with reference to any one of Examples 1 to A method for preparing a liquid, aqueous, non-phosphate detergent concentrate, substantially as hereinbefore described with reference to the Examples.

11. A method of washing textiles or fabrics substantially as hereinbefore described with reference to any one of Examples 1 tlo 5 but excluding the Comparative Example. DATED this TWENTY-EIGHTH day of MAY 1992 Henkel Kommanditgesellschaft auf Aktien Patent Attorneys for the Applicant SPRUSON FERGUSON TMI1872R ~i's :1 I~ D 7813-1 EP ABSTRACT A liquid non-phosphate detergent of high alkalinity A detergent concentrate suitable for the preparation of liquid, concentrated stock solutions contains 5 to by weight nonionic surfactants, of which (Al) 4 to by weight consist of alkyl glucosides corresponding to the formula R-O-G, and (A2) 0 to 2% by weight C 12 18 alkyl polyglycol ethers containing 5 to 9 ethylene glycol ether groups, (Bl) 4 to 20% by weight sodium hydroxide, (B2) to 12% by weight sodium silicate Na 2 O SiO 2 1:1 to 1:3.4, (B3) 2 to 12% by weight sodium nitrilotriacetate and 0 to 3% by weight of at least one phosphonic acid in the form of the sodium salt, in the formula R is a C 8 alkyl radical, G is a glucose residue and the index x is a number of 1.2 to 5. The sum of the constituents (B3) and (B4) is 3 to 12% by weight. QI w i i N 1 1 0 I INTERNATIONAL SEARCH REPORT I. CLASSIFICATION OF SUBJECT MATTER (it several Classification symbols apply, Indicate $11) According to international Patent Classification (IPC) or to both National Classification and IPC int. Cl. 5 C 11 D 1/66; C 11 D 1/825; C 11 D 3/08; C 11 D 3/33 I1. FIELDS SEARCHED Minimum Documentation Searched Classification System Classification Symbois Int. Cl. C 11 D Documentation Seachild other than Minimum Documentation to the Extent that such Dacumnents are Included In the Fields Searched I Ill. DOCUMENTS CONSIDERED TO BE RELEVANT 5 Category Citation of Docunt,"1 with Indication, where appropriate, of the relevant passages It Relevant to Claim No, 11 Y WO, A, 8706949 STALEY) 19 November 1987 1 see the whole document Y EP, A, 0075995 (PROCTER GAMBLE) 6 April 1983 1 see claims 1-10 Y FR, A, 2540511 (HENKEL) 10 August 1984 1 see claims; examples Y US, A, 3721633 RANAUTO) 20 March 1973 1 see column 6, lines 68 75; claims Spc% categories of cited documents: Is later document publishedafethinraiolflngde ocuentdefnin thegenrslstae 0 theartwhih I no orpriority date and not in conflict with the application but ocumnt efinng he gnerl stte f th oi whih I ncite"d t0 understand the principle or theory underlying the consiloed to be of particular relevance invention earlier document but published on or after the International document of particular relevance: the claimed Invention filing date cannot be considered novel or cannot be considered to IL" document which may throw doubls on priority claimis) or involve an Inventive step which Is cited to establish the publication date of another document of particular relevance;' the claimed Invention citation or other special reason (as specified) cannot be considered to involve an inventive ase when the document referring to an orio disclosure, use, exhibition or document is combined with one or more other such docu- other means ments, such combinaltium being obvious to a person skilled "P'0 document published prior to the international filing date but In the an. later then the priority date claimed document member of the same patent family IV. CERTIFICATION_____________ Date, of ho Actual Completion of the International Search Date of Mailing of this International Search Report April 1990 (10.04.90) 22 May 1990 (22.05.90) international Searching Authority Signature of Authorized officer European Patent Office Form PCTjiSAf2IO (second Sheet) (January I- ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. EP EP 8901370 SA 32402 This annex lists the patent family members relating to the patent documents cited in the ahove-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 these particulars which are merely given for the purpose of information. 16/05/90 Patent document Publication Patent family Publication cited in search report date memher(s) date WO-A-8706949 19-11-87 EP-A- 0270600 15-06-88 JP-T- 63503389 08-12-88 US-A- 4780234 25-10-88 EP-A-0075995 06-04-83 CA-A- 1200171 04-02-86 JP-A- 58132094 06-08-83 US-A- 4483780 20-11-84 FR-A-2540511 10-08-84 None US-A-3721633 20-03-73 None r more d abot this annex :s OiciJ the ro Patn o. 1 For more details about this annex see Official Journal of the European Patent Office, No. 12/82 INIERNATIONALER RECI-ERCI-ENBERICHT PCT/EP 89/01370 lnternationales Akten~eichen 1. KL.ASSIIKA1 ION DES ANNMELDUJNGSCEGENSTUNDS (bei melsrerco Klassifikatlonssymbnlen sind alle anZUgeben) 6 Nach der Internatitinalen Patent klassifi katlsn (IPC) oder nacls der nationalen K12agifiliation und der IrC IInt.Kl. 5 C1l1/66 C11O1/825 C1103/08 C1103/33 II. RECIIFRCIIIERTF SA(:IIGEFtIETE Recherchierter Mindestprdfstoff 7 Klassifikationssuiem K1a2sifilsatonssyrmbole Int.Kl. 5 C11D Reciserchiefle nlcht zumn Nindestprlifstoff gehdrendc Veroffentlichunien. nwril dims unter die recherchicrirn Sachtehlit falen Ill. EINSCI L.AGIGF. NERO171ENTI.ICI UNGEN q Art.' KennzeichnunR der Veriffentlichungi, snweit erfordetlich unter Arlguhe der mrifleblichen *re lctr. Anspruch \r, 1 3 Y WO,A,8706949 STALEY) 19 November 19871 1 siehe das ganze IDokument Y I EP,A,0075995 (PROCTER GAMBLE) 06 April 1983 1 siehe AnsprUche 1-10 Y FR,A,2540511 (HENKEL) 10 August 19841 siehe AnsprUche; Beispiele Y US,A,3721633 (HJ. RANAUTO) 20 M~rz 19731 siehe Spalte 6, Zeilen 68 -75; AnsprUche flcondere Kasceorien von angeehenen Veriiffentlichungen In Y Verdffentlichung, die den ailgemteinen Stand der Technik '1 Stere Verfiffentlichungt, die nach demn Internationalen An- definiert. aher nlcht als hesonders Weest~rm an,.usehen 1st meldedatum oder dent I'rlrit~tSdatumn verdiffcntlicht wnrden Mteres IDokument, das ledocls erst am oder nach demn interna- 1st und mit der Anmeldun g nicht kollidiert, snndern nur zorn tirinalen~~~~~~~~~ Anedattsvrfetlh rdn Vrst~n iss des der Erfindusng zuarundelieenden I'rinzip tionlenAntnldeatur vetifentlchtwordn It rder der il~r Zu~rssndelteienden 1 heorie angeeben Ist Vertiffefltllchung, die geelgnct ist, einen Prlorlt~tsanspruch ''Vrifnlcugvnbsnce ldu~g i enpuh Zweifelhaft erscheinen isi lassen, Ode! durch die das Verof. elfctl-ugvnbsnerrfeet'g i enpuh fentlichungsdatutn ci anderen im Rcchet'chenbcrlcht ge*. te Erfindung kann nicht alt neu oder auf orfinderiocher Tlig. nannten Veroffentllchung bec werden toll oder die aus elnern keit beru h end betrachc- werden andefen besonderen Grund angeeen is (wie auogefuhni) Vertiffenillchupt; von besonderer Fledeutting;, die beanmproch. Verfiffentlichung, die sich auf edoe mudih febrnte Erfindungi kansn nlcht als auf erflnderscher ltlikeit bo- mlldlch Ofebastgru hend beirachte~ "erden, weno die Verliffentlichungi mit eloe Denutzng. eine Ausstellung oder andere NIalInaismen ere oder sncnrerm andcren Veroffeotliclsuntien dieser Kate- hoizlelt gonle In Verbinduon gcbracho wird stod dimre Verlsindungt for IP' VernffentlichunR, die von dern Internatlonalen Anmeldeda- eloen Fachmsann naholietend kt turn, abet nach demn beanspruchten Priorili~sdatumn verliffent- Ver~frenslichunR, die Miltiled dennelben Patentfamllle iot licht worden it IV. HIESCIIEINIGCNG Ipatunm des Ahochiusses der internatlonalen Recherche Absendedattirn dms internatinnalen Rechenclsenberlchs 1990 22. 05. Internationale Ikecherchenlsehdnde Untrshritt des beolm~tcht !glen Ileslenteten EUROPAISCIIES I'ATENTANIT 7 Ts- Fwrbjtl 'C1 /SA/2tO 11111t 21 iJ2mner 19951 I 4 e. B I V ANHANG ZUM INTERNATIONALEN RECHERCHENBERJCHT CBER DIE INTERNATIONALE PATENTANMELDUNG NR. EP 890i370 SA 32402 In diesem Anhang sind die Mitglieder der Patentfamilien der tnt obengenannten intenaionalen Rechcrchenhericht angel~hrten, Patentdokuntente angegeben. Die Angoben fiher die Funtilienmitglieder entsprechen dem Stand der Datei des Europiischen Patentomtq anm Diese Angsbeti dienen nur zur Unterrichtung mid erfolgen obtie Gewihr. 16/05/90 Imn Recberchenbericht Datum der Mitglaed(er) der Datum der aneihrtes Patentdokcument VrfenlhngPetfaie Verlifientichung WO-A-8706949 19-11-87 EP-A- 0270600 15-06-88 JP-T- 63503389 08-12-88 US-A- 4780234 25-10-88 EP-A-0075995 06-04-83 CA-A- 1200171 04-02-86 JP-A- 58132094 06-08-83 US-A- 4483780 20-11-84 FR-A-2540511 10-08-84 Keine US-A-3721633 20-03-73 Keine FOr nihere Einzelheiten 7ai diesem Anhang :Mehe Awtshlatt des Europlisehen fPatentamits, Nr.12/82