AU622499B2 - Condensation products based on colophonium maleic imides - Google Patents

Description

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BERNHARD HRANTL, ERICH FRANK, WALTER.KH GERD LOEBBERT,.....

4. The basic application referred to in paragraph 2 of this Declaration was t feirst application made in a (Convention country in respect of the invention the subject of the application.

DECLARED MM_ tH da4t of 9 BASF Lacke Farben Akteingesellschaft

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t6 2 1I DATE 28/05/90 APPLN. ID 45141 89 0 OJP DATE 05/07/90 PCT NUMBER PCT/EP89/01297 PcT INTERNATIONALZ iN iviLU UINU V nKUrrLhN I Lit41 1- At-WA-i UrJV! L/K I KAUJ Ubt U11rv INTERNATIONALE ZUSAMMENARBEIT AUF DEM GFBIET DES PATENTWESENS (PCT) (51) Internationale Patentklassiflaton 5 CPSG 73/16, C09F 1/04 C09D 11/10 Internationales Aktenzeichen: (11) Internationale Veroffentlichungsnummer: ,WO090/05159 Al (43) Intemnationales Veroffentlichungsdatum: 17. Mai 1990 (17.05.90) PCT/EP89/012971 (22) Internationales Anmeldedatuin: 3 1. Oktober 1989 (31.10,89) Prionitatsdaten: P 38 37 5 18.4 November 1988 (04.11.88) DE (74) Anwalt:,KARAU, Wolfgang; BASF Aktiengesellschaft, Patentabteilung ZSP-C 6, D-6700 Ludwigshafen (DE).

(81) Bestimniungsstaaten: AT (europ~isches Patent), AU, BE (europliisches Patent), Cl- (europliisches Patent), DE (europ~isches Patent), FR (europaisches Patent), GB (europlisches Patent), IT (europliisches Patent), JP, LU .europdisches Patent), NL (europliisches Patent), SE (europilisches Patent), US.

Veroffentlicht Mi:t intemnationalem Recherchenberich.

(71) Anmelder (fuir alle Bestimmungssaten ausser US), BASF LACKE FARBEN AG [DE/DE]; Max- Winkelmann- Strage 80, D-4400 MOnster (DE).

(72) fifinder; und Erfloder/Anmelder (nurflir US) :PRANTL, Bernhard [DE/ bEJ; Landgrafenstrage 37, D-6520 Worms I I (DE).

FRANK, Erich [DE/DE]; Landskronenweg 12, D-7320 G6ppingen KOCH-, Walter [DE/DE]: Winterlinger Weg 6, D-7000 Stuttgart 80 LOBBERT. Gerd [DE/DE]; Im Sch6nblick 15, D-7400 Tilbingen (54)Title: CONDENSATION PRODUCTS BASED ON COLOPHONIUM MALEIC IMIDES (54) Bezeichnung: KONDENSATIONSPRODUKTE AUF BASIS VON KOLOPHONIUM-MALEINIMI DEN (57) Abstract Condensadon products based on colophonium maleic imides are obtained by A) reaction of 100 parts by weight of cciophonium with I to 20 parts by weight of maleic anhydride at a temperature between .150 and 2501C; B) reaction of the adduct (A) formed in step A with an amino alcohol containing a primary amine group at temperatrues of 130 to 250 in a molar ratio of anhydride groups to amino groups of 0,8 to 1.2:1; C) if necessary, further condensation of the condensation product at a temperature between 180 and 300 0 C and/or D) if necessary, furlfher reaction of the condensation product or formed in step B or C with a dimeric and/or trimeric fatty acid at temperatures between 150 and 300*C, in a molar ratio of hydroxyl groups of the condensation product or to earboxylic groups of th~e fatty acid from 0. 1 to 1.2:1 and E) reaction of the condensation prov duct or formed in stop B, C or D with a polyalcohol of functionality 3 to, 6 at temperatures between 230 and 300 0 C, in a molar ratio of carboxylic group§ to hydroxyl groups of 0.7 to 1.5:1.

(57) Zusamnienfassung Die vorliegende Erfindung betrifft Kondensationsprodukte auf Basis von Kolophonium-Maleinimiden, erhltlich durch A) Umsetzung von 100 Gew.-Teilen Kolophoniurn mit I bis 20 Gew.-Teilen Maleinsliureanhydrid bei einer !Thmperatur von 150 bis 250'C und B) weitere Umsetzung des in Stufs. A gebildeten Adduktes mit einem Aminoalkohol mit einer primliren Arnin t )gruppe be! Temperaturen von 130 bis 250'C und mit einem Molverhiltnis Anhydridgruppen zu Aminogruppen vor 0,8 bis 1,2:1 und C) gegebenenfalls weitere Kondensation des Kondensationsproduktes bei einer Temperatur von 180 bis 300'C und/oder D) gegebenenfalls weitere Umsetzung des in Stufe B oder C gebildeten Kondensatiorisproduktes oder mit einer dimeren und/oder trimeren Fettsilure bei Temperaturen von 150 bis 3000 C und mit einem Molverhilltnis von Hydroxyigruppen des kon densationsproduktes oder zu Carboxylgruppen der Fettsllure von 0, 1 bis 1,2:1 und E) weitere Umsetzung des in Stufe B, C oder D gebildeten Kondens ations prod uktes oder mit einem Polyalkohol der Funktionalit~t 3 bis 6 bei Temperaturen von 230 bis 300*C mit einem Molverhilltnis von Carboxyigruppen zu Hydroxyigruppen von 0,7 bis 1,5:1.

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I i O.Z. 0062/90003 K Condensation products based on rosin malel.ides The present invention relates to condensation products which are based on rosin maleimides and are obtainable by reaction of an excess of rosin with maleic anhydride, subsequent condensation with an amino alcohol having a primary amino group with possible further condensation to more highly condensed products, possible further reaction with a dimeric and/or trimeric fatty acid and esterificetion with a polyalcohol of functionality of 3-6, to a process for preparing them and also to the use thereof in printing inks.

Offset printing inks are prepared using highboiling mineral oils, i.e. apolar substances, as solvents. Polar solvents, which are customary in intaglio printing, would emulsify the ink on contact with the water which is always present in offset printing as dampening agent. Resins (condensation products) for offset printing inks must thus be soluble in apolar mineral oils; that is, the resins must not have too many polar groups.

Commercial resins for offset printing inks are for the most part rosin-modified phenolic resins esterifiod with polyalcohols.

JP-A-7111354-R, J-61264014-A and US-A-4 643 848 disclose condensation products of rosin, maleic anhydride and phenolic resins that are recommended for use as binders for printing inks. However, the disadvantage with these resins is that they do not dry rapidly enough and in some cases are not sufficiently glossy either.

US 3 554 982 discloses polyamide-imides prepared by reaction of a rosin/maleic anhydride adduct with organic diamines, sui:able for preparing intaglio printing inks. However, these resins, having polar groups, are insoluble in apolar solvents such as mineral oils and therefore unsuitable for offset printing inks.

US 3 554 981 describes polyester-imides obtainable by reaction of a rosin/maleic acid adduct with /f P J l

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2 O.Z. 0062/90003 i amino alcohols and subsequent condensation. Jut these resins too are insoluble in apolar solvents such as mineral oils and therefore unsuitable for offset printing inks.

It is an object of the present invention to develop condensation products which are soluble in apolar solvents and with which it is possible to prepare printing inks which exhibit good printability, rapid drying and hence rapid nontackiness, high gloss and minimal odor nuisance.

We have found that this object is achieved by rosin/maleic anhydride adducts condensed with amino alcohols and optionally also dimeric and/or trimeric fatty acids and esterified with polyalcohols of functionality 3-6.

The present invention accordingly provides a condensation product based on a rosin maleimide, obtainable by A) reacting 100 parts by weight of rosin with from 1 to 20 parts by weight of maleic anhydride at from 150 to 250 C, B) further reacting the stage A adduct with an amino alcohol having a primary amino group at from 130 to 250°C in a molar ratio of anhydride groups to amino groups of from 0.8 to 1.2:1 and C) optionally further condensing the condensation product at from 180 to 300"C or D) optionally further reacting the stage B or C condensation product or with a dimeric or trimeric fatty acid in a molayp ratio of hydroxyl groups of condensation product or to carboxyl groups of fatty acid of from 0.1 to 1.2:1 and 1 3 O.Z. 0062/90003 further reacting the stage B or C or D condensation product or with a polyalcohol of functionality 3-6 at from 230 to 300"C in a molar ratio of carboxyl groups to hydroxyl groups of from 0.7 to 1.5:1.

The invention also concerns the preparation of this condensation product and its use in printing inks.

Following are observations concerning the individual stages and components: The stage A reaction of r din with maleic anhydride is known and is carried out at 150 to 250"C, preferably at from 180 to 230°C. The rosin is used in a molar excess in that from 1 to 20, preferably from 5 to 13, parts by weight of maleic anhydride are used per 100 parts by weight of rosin. Excess rosin is esterified with a polyalcohol in stage E.

The mixture of rosin and rosin/maleic anhydride adduct is condensed in stage B with an amino alcohol having a primary amino group at from 130 to 250 0

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preferably at from 140 to 210 0 C. The molar ratio of anhydride groups to amino groups is set hers within tbe range from 0.8 to 2.1:1, preferably from 0.9 to 1.1:1.

The result is a rosin maleimide with hydroxyl and carboxyl groups which is capable of condensing with itself at from 180 to 300°C, preferably at from 230 to 280"C, as in the optional stage C, to give higher molecular weight products.

•i |The stage B condensation product can also be prepared by reacting a rosin/maleic anhydride adduct with an amino alcohol having a primary amino group in the above-indicated molar ratio and dissolving the product in an appropriate excess of molten rosin, or by reacting a maleimide prepared from maleic anhydride and an amino alcohol having a primary amino group in the above-indi- i cated molar ratio with a molar excess of rosin or with an equimolar amount of rosin and dissolving the product in ir7't 2 4 o.Z. U062/90003 an excess of rosin, but the first method is preferred.

Suitable amino alcohols having a prmary amino group are aliphatic amino alcohols such as ethaielamine, isopropanolamine, 3-aminopropanol, neopentanolamine, 2amino-l-butanol, aliphatic amino ether alcohols such as 2,2'-aminoethoxyethanol and amino polyalcohols such as trishydroxymethylaminomethane. Preference is given to using ethanolamine, isopropanolamine and 2,2'-aminoethoxyethanol.

The optional further condensation of stage C may be followed by an optional esterification in stage D of condensation product or with a dimeric or trimeric fatty acid at from 150 to 300"C, preferably at from 170 to 230 0 C, in a molar ratio of hydroxyl groups of condensation product or to carboxyl groups of the fatty acid within the range from 0.1 to 1.2:1, preferably from 0.8 to 1.1:1. Dimeric and/or trimeric fatty acids are obtainable by dimerizing or trimerizing unsaturated predominantly C 16 -Cl.-carboxylic acid (Pripol® from Unichema) Preference is given to using a dimeric fatty acid. The condensation product or is esterified in stage E with a polyalcohol of functionality 3-6 at from 230 to 300°C, preferably at from 250 to 280 0 C, in the absence or presence of customary esterification catalysts, in a molar ratio of carboxyl groups of the reaction mixture or to hydroxyl groups of the polyalcohol within the range from 0.7 to 1.5:1, preferably from 0.8 to 1.1:1. Suitable polyols are aliphatic polyols having a functionality of from 3 to 6 such as trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol or sorbitol or amino alcohols such as triethanolamine and triisopropanolamine or reaction products of these polyalcohols with ethylene oxide and/or propylene oxide c. mixtures thereof. Preference is given to using trimethylpropane, glycerol, pentaerythritol and mixtures thereof.

The resulting resins are products which are solid 5 O.Z. 0062/90003 at room temperature and have melting points, depending on the resin structure, of within the range of eibout 160 0 C. In general they have acid numbers of from 5 to mg of KOH/g, preferably from 10 to 25 mg of KOH/g. The resins dissolve in mineral oil, which may contain further apolar solvents, to give clear mineral oil varnishes. By adding pigments and customary auxiliaries to these varnishes it is possible to formulate printing inks which are stable to storage, i.e. which do not increase in viscosity, which have gooc printing properties and which dry rapidly to give nontacky prints of high gloss.

EXAMPLE 1 2,338 g of rosin were reacted with 294 g of maleic anhydride at 200 0 C under nitrogen in the course of 2 hours. 183 g of ethanolamine were then added at 145°C over 15 minutes. After 30 minutes the temperature was increased to 200°C over 2 hours with distillative removal of the water of reaction and then 147 g of pentaerythritol and 3 g of magnesium oxide were added.

The temperature was increased to 265°C in the course of 2 hours. At 265°C the water of reaction was distilled off until an acid number of 27 had been reached and then the pressure was reduced to about 50 mmHg for 2 hours.

Thereafter the reaction was continued until the acid number was 22. The resin had a melting point of 137"C and a viscosity of 750 mPas at 23°C in a 50% strength by weight solution in butyldiglycol.

A mineral oil varnish prepared from 45 g of the resin, 40 g of a mineral oil of boiling range 260 to 290 C and 15 g of alkyd resin based on linseed oil, phthalic anhydride and glycerol was clear with minimal tack and had a viscosity of 25 Pas (23°C).

72 g of this varnish, 13 g of blue pigment (Pigment Blue 15), 5 g of a plasticizer (dioctyl adipate), 5 g of an alkyd resin based on linseed oil, phthalic anhydride and glycerol and 5 g of vaselin were used to formulate the offset printing ink. The ink had a *1P J I 6 O.Z. 0062/90003 viscosity of 12 Pas (23 0 C) with medium tack. It was very quick-drying at elevated temperature and, compared with inks based on rosin-modified phenolic resins, became tack-free much more rapidly.

In a test print on aluminum foil at 40 0 C the printing ink was tack-free after only 120 seconds, while a standard ink based on rosin-modified phenolic resin took 300 seconds.

EXAMPLE 2 1,616 g of rosin were reacted with 204 g of maleic anhydride at 200 0 C under nitrogen over 2 hours.

127 g of ethanolamine were then added at 145 0 C over minutes. After 30 minutes' stirring at 145 0 C the temperature was raised to 200°C over 2 hours while the water of reaction was removed by distillation. After 30 minutes' stirring at 200°C 435 g of a C 36 dimeric fatty acid were added over 1 hour. The reaction was allowed to proceed at 225 0 C for 4 hours with distillative removal of the water of reaction, 178 g of pentaerythritol and 2.5 g of zinc oxide were then added, and the temperature was raised to 265"C. This temperature was maintained with distillative removal of the water of reaction until the acid number had dropped to 15. The resin had a melting point of 105°C.

A varnish formed from 46 g of the resin, 21 g of linseed oil and 33 g of a mineral oil of boiling range 260 to 2909C had a viscosity of 45 Pas at 23 0 C and a very low level of tack, 44.5 g of the resin, 40 g of a mineral oil of boiling range 260 to 290°C, 15 g Jf an alkyd resin based on linseed oil, phthalic anhydride and glycerol, and 0.5 g of a gelling agent (aluminum alcoholate) were used to prepare a clear varnish which had a viscosity of 31 Pas (23°C) coupled with low tack.

67 g of this varnish, 19 g of a red pigment (Pigment Red 57), 4 g of a plasticizer (dioctyl adipate), g of an alkyd reain based on linseed oil, phthalic anhydride and glycerol, and 5 g of vaselin were used to 7 O.Z. 0062/90003 formulate an offset printing ink. The ink had a viscosity of 15 Pas and a medium tack. The ink, which was readily printable, gave gloss increases of up to 10% compared with inks based on rosin-modified phenolic resins.

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Claims (8)

1. A condensation product based on a rosin maleimide, obtainable by A) reacting 100 parts by weight of rosin with from 1 to 20 parts by weight of maleic anhydride at from 150 to 250"C, B) further reacting the stage A adduct with an amino alcohol having a primary amino group at from 130 to 250 0 C in a molar ratio of anhydride groups to amino groups of from 0.8 to 1.2:1 and C) optionally further condensing the condensation product at from 180 to 300 0 C or D) optionally further reacting the stage B or C condensation product or with a dimeric or trimeric fatty acid at from 150 to 300 0 C in a molar ratio of hydroxyl groups of condensation product or to carboxyl groups of fatty acid of from 0.1 to 1.2:1 and further reacting the stage B or C or D conden- sation product or with a polyalcohol of functionality 3 -o at from 230 to 300 0 C in a molar ratio of carboxyl groups to hydroxyl groups of from 0.7 to 1.5:1.

2. A condensation product as claimed in claim 1, obtainable using an aliphatic amino alcohol as primary amine in stage B.

3. A condensation product as claimed in either claim 1 or claim 2, obtainable using ethanolamine, isopropanol- amine, 3-aminopropanol, neopentanolamine or 2,2'-amino- ethoxyethanol or a mixture thereof as primary amine in stage B.

4. A condensation product as claimed in any one of claims 1 to 3, obtainable using an aliphatic polyalcohol I- S- 9 O.Z. 0062/90003 of functionality 3-6 in stage E. A condensation product as claimed in any one of claims 1 to 4, obtainable using glycerol, trimethylolpro- pane, pentaerythritol, dipentaerythritol or sorbitol in stage E.

6. A process for preparing a condensation product as claimed in any one of claims 1 to 5, which comprises preparing it by the measures specified in claim 1.

7. The use of a condensation product as claimed in any one of claims 1 to 5 for preparing a printing ink.

8. A printing ink obtainable using a condensation product as claimed in any one of claims 1 to P L \w 10 O.Z. 0062/90003 Abstract of the Disclosure: Rosin maleimide condensation products are obtainable by A) reacting 100 parts by weight of rosin with from 1 to 20 parts by weight of maleic anhydride at irom 150 to 250 0 C, 1j further reacting the stage A adduct with an amino alcohol having a primary amino group at from 130 to 250°C in a molar ratio of anhydride groups to amino groups of from 0.8 to 1.2:1 and C) optionally further condensing the condensation product at from 180 to 300°C or D) optionally further reacting the stage B or C condensation product or at with a dimeric or trimeric fatty acid at from 150 to 300 0 C in a molar ratio of hydroxyl groups of condensation product or to carboxyl groups of fatty acid of from 0.1 to 1.2:1 and further reacting the stage B or C or D conden- sation product or with a polyalcohol of functionality 3-6 at from 230 to 300°C in a molar ratio of carboxyl groups to hydroxyl groups of from 0.7 to 1.5:1. °L I~ 4 product or to carboxyl. groups of tatty acid of from 0.1 to 1.2:1 and f urther reacting the stage B or C or D conden- sati-on product or with a polyalcohol of functionality 3-6 at from 230 to 300 0 c in a molar ratio of carboxyl groups. to hydroxcyl groups of from 0.7 to 1.5:1. '*1 INTERNATIONAL SEARCH REPORT International Application No PCT/EP 89/01297 I. CLASSIFICATION OF SUSgJECT MATTER lit several classification symbolSipapily, Indicate &III According to lnternsku;naI Potent Classification (IPC) or to both National Clasification and IPC Int. Cl. C 08 G 73/16, C 09 F 1/04, C 09 D 11/10 II. FIELDS SEARCHED Minimum Documentation Searched 7 Classification System I Classification Symbol& Int. C1. 5 C08 G, C09 F, C09D Documentation Searched other than Minimum Documentation to the Extent that such Documents are Included In the Fields Searched

111. DOCUMENTS CONS5IDERED TO BE RELEVANT'I Category i~ Ion Document, 11 with Indication, wrer appropriate, of the relevant passages 'a Relevant to Claim No. 13 A 12B, A, 1232058 (HERCULES) 19 May 1971, US, A, 3554981 SLOAN) US, A, 3554982 ALDRICH) (cited inthe application) A Chemical Abstracts, vol. 106, No. 2, 12 January 1987, (Columbus, Ohio, US) S. Maiti et all: "Polymers from renewable resources: crosslinking and thermal behaviori, see page 6, abstract 5537x Polym. Sci. Technol. (Plenum), 1986, 33 (Renewable-Resour. Mater.) 18 7-203 A Chemical Abstracts, vol. 110, No. 2, 9 January 1989, (Columbus, Ohio, US) M. Maiti et al.: "Polymers from renewable resources.Part 6 Poly(ester imides) from rosin", see page 90, abstract 9945j, J. Polym. Mater, 1988, 201-7 *Special categories ot cited documents: it later document published slier the International filing date "A document def6Ing the general state of the art which in not er PrIoritv date andi not in conflict witri ins aroolication but considered to be ot Particular relevance cite,, to understand the principle or tneory unoerlying the "Ell nti *invention E"alier documeint but published on or otter the international o atctrrlvne h lie neto rilin datecannot be considered novel or cannot te considered to document which may throw do~ubts on priority clitife or Involve en inventive atop Which is cited to establish the Publication dote ot anot)her *,document of pniltr relevance: the Ciatmed invenion Citaionor Oherspeial easn ta spcifed)cannot be considered to involve an inventive stoo when the document referring to an Oral disclosure, use, eahibitiori or document is combined with one or more otnor such docu- Other means ments, such combination being obvious to ai person skilled document pubtished prior to the international filing dote but in the art, later than the Priority date claimed 6'document member of the orris patent familV IV. CERTIFICATION Date of the Actual Comoletion of the International Search JDate of Mailing of this international Search Report 9 February 1990 (09.02.90) 2 -ebruary 1990 (28.02.90) international Searching Authority Signature of Authorized Officer EUROPEAN PATENT OFFICEI Form PCTIISAI 2Io isecond sheet i anuary Iqesi dimeren und/oder trimeren Fettsaure bei Temperaturen von 150 bis 300' C und mit einemn Molverhdiltnis von Hydroxyigruppen des Kondensationsprodukles oder zu Carboxyigruppen der Fettsgiure Von 0,1 bis 1,2:1 und E) weitere Umnsetung des in Stufe B, C oder D gebildeten Kondensations prod uktes oder mit einemn Polyalkohol der Funktionalitlt 3 bis 6 bei Teruperaturen von 230 bis 3000'C mit einemn Molverhailtnis von Carboxyigruppen zu Hydroxylgruppen von 0,7 bis 1,5:1. ANNEX -16 THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. EP 8901297 SA 32226 TUhis annex lists the patent family members relating to the patent documents cited in 'die obovz=iti--:wd internationi search report. The members are as contained in the European Patent Office EDP filr on 21/02190 The European Patent Office is in no waI y liable for these particulars r ich are aw~rely given for the purpose of information. Patent document Publication Patent family Publication cited in search report date member(s) date GB-A- 1232058 19-05-71 US-A- 3554981 12-01-71 US-A- 3554982 12-01-71 wFor more details about this annez see Officiail Journal of the European Patent Office, No, 12182 LL1 jor unsuitanie tor off sec print .;ng inks.- US 3 554 981 describes polyester- imides obtainable by reaction of a rosin/maleic acid adduct with K I I -A INTERNATIONALER RECHERCHENBERIC4IT Internationales Aktenzeichen P C11/ EP 8 9 0 129 7 1. KLASSIFIKATION DES ANMELDUNGSGEGENSTANOS (bel mehrwrt Klessitiketionslymboign sirwd all, anaugeoent 6 Nach der gnternatioflalef Patentkiassitikatiofl (IPC) oder nach der nationalen Kiassifikation und der IPC Int.C1 5 C 08 G 73/16, C-09 F 1/04, C 09 D 11/10 11. RECHERCHIERTE SACHGEBIETE Mindestpruifstoff 7 Klassifikationssystem Klassifiltationssymbole Int.CI 5C 08 G, C 09 F, C 09 D Recheu;hierto nicht zumn Mindestpnifstoht -ehirendle Veroffentlichungen, soweit diese unter die recherchiertln Sochgetbiote fallen 8 Ili. EINSCHLAGIGE VEROFFENTLICHUNGEN 9 Art* Kennzuichnuflg der Veroffentlichungl,soweit orforderlicli unter Angab~e der maflgeblichen Telle 12 j Betr. Anspruch Nr.13 A GB, A, 1232058 (HERCULES) 19. Mai 1971, US, 3554981 SLOAN) US, A, 3554982 ALDRICH) (In der Anmeldung erwdhnt) A chemical Abstracts, Band 106, Nr. 2, 12. Januar 1987, (Columbus, Ohio, US) S. Maiti et al.: "Polymers from renewable res'ourc, s: crosslinking and thermal behavior", Seite 6, Zusammenfassung 5537X Polym. Sci. Technol. (Plenu~m), 1986, 3 3(Renewabl.e -xesour. Mater.) 187-203 A Chemical Abstracts, Band 110, Nr. 2, 9. Januar 1989, (Columbus, Ohio, US) M. Maiti et al.: "Polymers from renewable resources. Part 6. Poly(ester imides) from rosin", siehe Seite 90, Zusarnmenfassung 9945j, J. Polym. Mater, 1988, 2,01-7 *Besondere Katogorien Von t4ngsgebenen'Verafentlichungen Verbffentlichung, die den ailgemelnen Stand der Technik Spiters Verbffentlichung, tiie nach demn internationmion An- diiniirt, abet nkcht al$ betonders bedeutuam anzuseoen ist meldedatumn oder dem Priorit~tsdatumr verotfentiicht warden Aiteres Doktument, des itdc~ch emrt n oder nach demrinterna- Ist und mit der Anmeidlung njcht kollidliert, sandemn nur zumn tinlnAmlesunver~ffenticht warden ist Vcindnis des der Erfindlung zugrundeliegenden Prlnzips tionien nmeledetm odr det 1hr zt.-rijndeliigenden Theorie angegeben int L~Veroffentlichung, die geeignat lit, omnen Priorititsanspruch Veroiffontichung von besonderer Bedleutung; die beanspruch. zweifolhaft viich,%inon zu lesson, oder durch die des Voral- to Erfindurgq kann.nlcht all neoJ oder auf erfindetrischer Tatig- fentlichungularim 0ee anderen Irn Rtcherchenberlcht kit beruhest1 be*t-ochtet warden narmien Whrifentlichung beielt werden soill oder die sin iewn anderon busonderen Gnund angegeben int (wit eusgefuhrt) Vfqffentiichung von besonderer Bedeutung; die beanspruch- 0Q~ erofen~chngdiesic cufein mudlihe ffebarng, to, Erfindung kann nicht ala auf erfinderischer Titigkoit be- On-. lenutzung, eine Austeliung odor andere Mal~nahmen wir ercttwren endeVrtetichung mit 6eight eit odor mehroren anderen Verotf entl ichu ngen diema Kate- gorne in Verbinering gebracht wird und dies@ Verbindlung Wru "ll' Veroffentlichung, die vot dem intermntionalen Animeideda- einen Fachmann naheliegend Ist turn aber nach deam beenspnwuhten Prlorititsdatumn veroffent- Ver~fentichtnrg, die Mitgiied derselben Patentfamilie ist iicht warden it IV. BESCHEINIGUNG Datum des Abschluses der internatiorlalen Recherche Absendledatumn des internationalen Recherchenber!Ohts 9. Februar 1990 b 02 g Internationale Recherchenbohnrdit Unescrf de tY~WA agi. Europijiches Patenillmt W !U For'macz PCWI/l821O (icas 2) (Januar 1985) carboxyl groups of fatty acid of from 0.1 to 1. 2:1 and I 4 L ANHANG ZUM INTERNATIONALEN RECHERCHENBERICHT' (JBER DIE INTERNATIONALE PATENTANMELDUNG NR. EP 8901297 SA 32226 In diesem Anhang sind die Mitgfieder der Patentfamilien der im obengenannienj internationalen Recbenbenberkht angefihen Patentdokurnente angegeben. Die Angaben ti~er die Familienmitglieder entsprechen demn Stand der Datai des Europisehien Patentamts am 21/02/90 Diese Augaben dienen nur zur Unterrichtung und erfolgen obne Gewihr. Im Rechercbenberkclt Da.tum der NMitIieder) der Datum der angefifhrtes Patentdokuiaent ver6ffentfichung Pawentlmmiie Vet Iffendtung GB-A- 1232058 19-05-71 US-A- 3554981 12-01-71 US-A- 3554982 12-01-71 Fuir nihere Einzelheitcn zu diesemn Anhang :siehe Amtsblatt des Europiisd1ien Patentamnts, Nr.1 2/82