AU630126B2 - Condensation products based on colophonium maleic imides - Google Patents

Description

OPI VDATE 28/05/90 (A0JP DATE 05/07/90 APPLN. I D 45118 89 PCT NUMBER PCT/EP89/01298 INTERNATIONALE ANMELDUNG VEROFFENTLiCHT NACH DEM VERTRAG OJBER DIE INTERNATIONALE ZUSAMMENARBEIT AUF DEM GEBIET DES PATENTWESENS (,OCT) (51) Intermationale Patenticlassifikation 5 (11) Internationale Veroffentlichiingsnurnmer: WO 90/05158 C08G 73/14, C09F 1/04 C09D 11/101 Al (43) Internationales Veroffentlichungsdatzm:I 7. Mai 1990 (17.05,90) (21) Internationaies Aktenzeichen: PCT/EP89/0 1298 (22) Internationales Anmeldedatumn: 3 1. Oktober 1989 (31.10.89) Priorititsdaten: P 38 37520.6 4. November 1988 (04.11.88) DE (7 1) Anmelder (fir alle Besfimmungssiaaten ausser US): BASF LACKE FARBEN AG [DE/DE; Max- Winkelmann- Stralle 80, D-4400 Milnster (DE).

(72) E~fider, und Erfinder/Anmelder (.ar/ar US): PRANTL, Bernhard [DE,' DEJ; Landgrafenstrale 37, D-6520 Worms I I (DE).

FRANK, Erich [DE/DE]; Landskronen~veg 12, D-7320 Gdppingen KOCH, Walter Winterlinger Weg 6, D-7000 Stuttgart 80 LOBBERT, Gerd [DE/DE); Im Sch~nbhck 15, D-7400 T~bingen (DE), (74) Anwalt: *KARA'%U, Wolf,'dng; BASF Aktiengesellschaft, Patentabteiluzig ZSP-C 116, D-6700 Ludwigshafen (DE).

(81) Bestimmungsstaaten: AT (europ~isches Patenit), AU, BE (europ~isches Patent), CH (europtiisches Patent), DE (europdisches Patent), DK, FR (europliisches Patent), GB (europ~isches Patent), IT (europdisches Patent), JP, LU (europdisches Patent), NL (eurongisches Patent), SE (europ~isches Patent), US.

Ver~iffentlicht Alit internationalern Reclierchenberich.

(54)Title: CONDENSATION PRODUCTS BASED ON COLOPHONIUM MALEIC IMIDES (54) Bezeichnung: KONDENSATIONSPRODUKTE AUF BASIS VON KOLOPHONIUM-MALEINIMIDEN (57) Abstract Condensation products based on colophonium maleic imides are obtained by A) reaction of 100 parts by weight of color phonium with I to 20 parts by weight of maleic anhydride at a temperature between 150 and 2500'C; B) reaction or the adduct (A) rormed in step A with an organic diprimary amine at temperatures between 130 and 2500'C, in a molar ratio or anhydride groups to amino groups of 0,8 to 1,2:1 C) reaction or the condensation product formed in step B with a polyalcohol of functionality 3 to 6 at temperatures between 230 and~ 300'C, in a molar rat; or carboxylic groups to hydroxyl groups of 0.7 to 1,50,.

(57) Zusarnnfassung Die vorliegende Erfindung betrirrt Kondensationsprodukte auf Basis von Kolophonium-Maleinimiden, erhltlich durch A) Umsetzung von 100 Gew.-Teilen Kolophonium mit I bis 20 Gew.-Teilen Maleinstiureanbydrid bei einer Temperatur von 150 bis 250'C, B) weitere Umsetzung des in Sture A gebildeten Adduktes mit einem organischen diprimdren Diamin bei Temperaturen von 130 bis 250*C und mit einem Molverhilltnis Anhydridgruppen:Aminogi-uppen von 0,8 bis 1,2:1 und C) weiterer Um-.

s.uung des in Stufe B gebildeten Kondensationsproduktes mit einem Polyalkohol der Funktionalitfit 3 bis 6 bei 7TJmperatu.

r -n von 230 bis 300*C mit einem Molverh~ltnis von Carboxylgruppen:.Hydroxylgruppen von 0,7 bis 1,5:1.

VERFiED TRhANSLATKON C O.Z. 0062/90002 Condensation products based on rosin-maleimides The present invention relates to condensation products based on rosin-maleimides obtainable by reaction of an excess of rosin with maleic anhydride, subsequent condensation with organic diprimary diamines and esterification with polyalcohols of functionality 3 6, to a process for preparing the same and to the use thereof in printing inks.

Offset printing inks contain high-boiling mineral oils, ie. apolar substances, as solvent. Polar solvents of tha type which are customary in intaglio printing would on contact with the obligatory offset printing dampening agent water lead to undesirable emulsification.

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 mostly rosin-modified phenolic resins which have been esterified with polyalcohols.

J-61264-014A, JA-7111 354-R 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, these resins have the disadvantage that they are slow to dry (become non-tacky) and in some instances exhibit low gloss.

US 3 554 982 describes polyamide-imides which were prepared by reaction of a rosin-maleic anhydride adduct with organic diamines and which are suitable for producing 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.

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 produce printing inks which exhibit good printability, rapid drying and hence rapid non-tackiness and hi h gloss and do not I_ ~1 2 O,Z. 0062/90002 constitute an odor nuisance.

We have found that this object is achieved by rosin-maleimides which have been esterified with alcohols of functionality 3 6 in a mixture with rosin.

The present invention accordingly provides condensation products based on rosin-maleimides, obtainable by A) reacting 100 parts by weight of rosin with from 1 to parts by weight of maleic anhydride at from 150 to 250 0

C,

B) further reacting the stage A adduct with an organic diprimary diamine at from 130 to 250 0 C in a molar ratio of anhydride groups amino groups of from 0.8 1 to 1.2 1, and C) further reacting the stage B condensation product with a polyalcohol of functionality 3 6 at from 230 to 300 0 C in a molar ratio of carboxyl groups hydroxyl groups of from 0.7 1 to 1.5 1.

The present invention also concerns the preparation of these condensation products and their use in printing inks.

The following remarks concern the individual stages and formative components: The stage A reaction of rosin with maleic anhydride is known and is carried out at from 150 to 250 0

C,

preferably at from 180 to 230°C. The rosin is used in a molar excess, the ratio being from 1 to 20 parts by weight, preferably 5 to 12 parts by weight, of maleic anhydride per 100 parts by weight of rosin. Excess rosin is esterified in stage C with a polyalcohol.

The mixture of the rosin-maleic anhydride adduct and rosin is condensed in stage B with an organic diamine at from 130 to 250 C, preferably at from 140 to 200"C.

The reaction is carried out with a molar ratio of anhydride groups amino groups of from 0.8 1 to 1.2 1, preferably from 0.9 1 to 1.1 1. The product is a bisrosin-maleimide in excess rosin.

I i i i i' 3 O.Z. 0062/90002 Stage B can also be prepared by reacting a rosinmaleic acid adduct with an organic diprimary diamine in the above-stated molar ratio and dissolving the product in an appropriate excess of molten rosin, or by condensing maleic anhydride with an organic diprimary diamine in the abovementioned molar ratio to give a bismaleimide, which is reacted with a more than twice the molar amount of rosin or with approximately twice the molar amount of rosin with the resulting rosin-maleimide being dissolved in excess molten rosin but the first method is preferred.

Suitable organic diprimary diamines are aliphatic diamines such as ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, neopentanediamine, 1,4-butanediamine, hexamethylenediamine and 9-aminomethylstea ylamine, cycloaliphatic diamines such as 1,6-cyclohexanediamine, 4,4 '-diaminodicyclohexylmethane and 3,3'-dimethyl- 4,4'-diaminodicyclohexylmethane, etherdiamines such as 4,7-dioxadodecane-1,10-diamine, 4,9-dioxadodecane-1,12diamine and 4,7,10-trioxatridecane-l,13-diamine, and diaminoamines such as bisaminopropylmethylamine and 1,4bis(3-aminopropyl)piperazine.

In addition to such polyamines of a low defined molecular weight it is also possible to use oligomeric or polymeric polyamines having an average molecular weight Mn of up to 3000. Examples of such polyamines are diamines which are preparable by reductive cyanoethylation of polyols, such as polytetrahydrofuran. Such products contain terminal primary amino groups in the form of aminopropoxy groups.

According to the present invention, it is also possible to use diamines having additional amide groups, as obtained for example by condensation of primary aliphatic or cycloaliphatic diamines with dicarboxylic acids such as adipic acid, sebacic acid or dimeric fatty acid. The above-described amines can be used alone or mixed with one another.

.*R^I

^^x i i I 4 0.Z. 0062/90002 Preference is given to using hexamethylenediamine, 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl- 4,4'-diaminodicyclohexylmethane and reaction products of dicarboxylic acids with diamines.

Stage C comprises further condensation with a polyalcohol of functionality 3 6 at from 230 to 300 0

C,

preferably at from 250 to 280 0 C, in the presence or absence of customary esterification catalysts, in a molar ratio of carboxyl groups of reaction mixture B) hydroxyl groups of polyalcohol of from 0.7 1 to 1.5 1, preferably from 0.8 1 to 1.1 1.

Suitable polyalcohols are alipahtic polyalcohols having a functionality of from 3 to 6 such as trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol or sorbitol or amino alcohols such as triethanolamine or triisopropanolamine or reaction products of these polyalcohols with ethylene oxide and/or propylene oxide or mixtures thereof. Preference is given to trimethylolpropane, glycerol, pentaerythritol and mixtures thereof. The resulting resins are solid at room temperature and have melting points which, depending on the structure of the resin, range from about 80 to 160"C.

In general they have acid numbers of from 5 to 40 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 and additives it is possible to use these varnishes to formulate printing ink which have a long shelf life, ie. which do not increase in viscosity on storage for periods of several months, which are readily printable and dry quickly to become non-tacky, and which exhibit high gloss and very little odor.

EXAMPLE 1 334 g of rosin were reacted with 28.4 g of maleic anhydride at 200°C under nitrogen for 2 h, after which 16.8 g of hexamethylenediamine were added at 140 0 C. The i i. 5 O.Z. 0062/90002 temperature was increased to 200 0 C over 2 h while the water of reaction was distilled off. 36.7 g of pentaerythritol and 0.4 g of magnesium oxide were added and the temperature was increased to 260°C. This temperature was maintained and the water of reaction distilled off until the acid number had dropped to about 20. The resin had a melting point of 126°C and gave highly viscous, clear mineral oil varnishes.

A varnish prepared from 49.5 g of resin, 19.6 g of linseed oil and 30.9 g of mineral oil of the boiling range 260 290"C had a viscosity at 23 0 C of 100 Pas combined with low to medium tack.

62.7 g of this varnish were mixed with 13.7 g of phthalocyanine blue, 17.6 g of linseed oil alkyd resin, 1.0 g of polyethylene wax, 0.5 g of rice starch, 2.0 g of a siccative (manganese drier) and 2.5 g of linseed oil on a three-roll mill. This printing ink had a viscosity of Pas at 23 0 C coupled with medium to high tack. It exhibited very good printing characteristics, good print crispness and very high gloss (10% higher than prior art printing inks).

EXAMPLE 2 2050 g of rosin were reacted with 124 g of maleic anhydride at 200 0 C under nitrogen for 2 hours, after which 73.5 g of hexamethylenediamine and 1.2 g of butyl titanate were added at 140°C over 15 min. After one hour at 140 0 C the temperature was raised to 220"C over 2 hours while the water of reaction was distilled off. After stirring at 220*C for one hour, 203 g of glycerol and 2.4 g of butyl titanate were added at 200°C and the temperature was raised to 265 0 C over 5 hours. Water of reaction was distilled off at 265"C until the resin had an acid number of 16. Its melting point was 105 0 C. A strength by weight solution of the resin in toluene had a viscosity at 23 0 C of 20 mPas. A varnish prepared from g of the resin, 21 g of linseed oil and 29 g of mineral oil of boiling range 260 290"C had a viscosity 6 O.Z. 0062/90002 of 3 Pas at 23 0

C.

EXAMPLE 3 2021 g of rosin were reacted with 123 g of maleic anhydride at 200°C under nitrogen for 2 hours, after which 110 g of 4,7-dioxadodecane-l,10-dii mine and 1.2 g of butyl titanate were added at 140 0 C over 15 min. After one hour at 140 C the temperature was raised to 220 0

C

over 2 hours while the water of reaction was distilled off. After one hour at 220 0 C 223 g of pentaerythritol and 2.5 g of butyl titanate were added. The temperature was raised to 265"C over 2 hours and maintained until an acid number of 21 had been reached. The resin had a melting point of 120"C and the viscosity of a 50% strength by weight solution in toluene at 23"C was 25 mPas. A varnish prepared from 53 g of resin, 19 g of linseed oil and 28 g of mineral oil of boiling range 260 290 0 C had a viscosity of 16 Pas at 23 0

C.

I. f t,

Claims (4)

1. 7- THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS: 1. A condensation product based on a rosin-maleimide, obtained by A) reacting 100 parts by weight of rosin with from 1 to 20 parts by weight of maleic anhydride at from 150 to 2500C. B) further reacting the stage A adduct with an organic diprimary diamine at from 130 to 2500C in a molar ratio of anhydride groups: amino groups of from 0.8 1 to 1.2 1, and C) further reacting the stage B condensation product with a polyalcohol of functionality 3 6 at from 230 to 300oC in a molar ratio of carboxyl groups: hydroxyl groups of from 0.7 1 to 1.5 1. 2. A condensation product as claimed in claim 1, obtainable using an aliphatic polyalcohol of functionality 3 6 in stage C. 3. A condensation product as claimed in claim 1 or 2, obtainable using glycerol, S trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol or a mixture thereof in stage C. 4. A process for preparing a condensation product as claimed in claim 1, which comprises the process steps defined in claim 1. 5. The use of a condensation product as claimed in claim 1 or 2 or 3 for preparing -printing inks. 6. A printing ink, obtained using a condensation product as claimed in claim 1 or 2 or 3. DATED THIS 24TH DAYOF APRIL 1992. BASFLACKE FARBEN AKTIENGESELLSCHAFT WATERMARK PATENT TRADEMARK ATTORNEYS 2ND FLOOR, "THE ATRIUM" 290 BURWOOD ROAD .,HAWTHORN VIC 3122 INTERNATIONAL SEARCH REPORT International Application No PCT/EF 89/01298 1. CLASSIFICATION OF SUBJECT MATTER (if several classification symbol@ apply. indicate all) According to international Patent Classification (IPC) or to both National Classification and IPC Int. Cl. 5C 08 G 73/14, C 09 F 1/04, C 09 D 11/10 It. FIELDS SEARCHED Minimum Documentation Seayched 7 Classification System I Classification Synbols 5 Int. C1. *C08G, C09 F,CO09 D Documentation Searched other than Minimum Documentation to the Extent thiat such Documents are Inciuded In the Fields Searched
2. 111. DOCUMENTS CONSIDERED TO ME RELEVANT' Category *I Citation of Document, It with indication, where appropriate, of the relevant passages 12 Relevant to Claim 1No. 13 A GB, A, 1232058 (HERCULES) 19 May 1971 US, A, 3554982 ALDRICH) (cited in the application) A Chemical Abstracts, vol. 106, No. 2, 12 January 1987, (Columbus, Ohio, US) S. Maiti et al.: "Polymers from renewable resources: crosslinking and thermal behavior", see page 6, abstract 5537(x Polym. Sci. Technol. (Plenum) 1986, 33 (Renewable-Resour. Mater.),
3. 187-203 A Chemical Abstracts, vol. 109, No. 26, 26 December 1988, (Columbus, Ohio, US) s.s. Ray et al.: iPolymers from renewable resources. XII. Structure-property relation in poly(amide imides) from rosin", see page 6, abstract 232'05Ox,&J. Appl. Polym. Sci. 1988, 26(6),
4. 1283-93 *Special categories ot cited documents: 10 later document oublished altear the international filing dte document defining the oeneral state of the art which is not or priority date ano not in conflict with the apolication but considered to be of Psaricular relevance cited to understand tneI princitple or theory underlying the invention fiealier docuen bu ulse no ftrteitrairl X' document of oarticular relevancei the claimed invention filin datecannot be considered novel or cannot be considered to document which may throw doubts on ariority claimlel or involve an inventive alts) which is cited to establish the publication date of another document of Particular relevehc@-: 'he claimed invention citation or other epecial reason le specified) cannot ois considered to involve an inventive stab when the document referring to an oral disclosure, use, exhibition or document is combined witn one or i'lore otner such docii. other means rrenta, such combination being obvious to a Person skilled vP" document published prior to the international filing date but in the art. later than the Priority date claimed 'W document memberof the same patent family IV. CERTIFICATION Date of the Actual Completion of the Interoational Searc, Date of Mailing of Inis International Search Reoort 9 February 1990 (09.02.90) 28 February 1990 (28.02.90) International Searching Auithority Signature of Autnorized Officer EUROPEAN PATENT OFFICE Ffom PCT1ISAI2io 'aecona eneet) IJanuerv 19W5 I I ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. EP 8901298 SA 32227 This annex lists the 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 23/02/90 The European Patent Office is in no way liable for these particulars which are merely given for the purpose of informatioi. Patent documer t Publication Patent family Publication cited in search rrport date member(s) dale GB-A- 1232058 19-05-71 US-A- 3554981 12-01-71 US-A- 3554982 12-01-71 I For more details about this annex see Official Journal of the European Patent Office, No. 12/82