DE19958997A1 - Binder resin, used for pigment concentrates for e.g. printing ink, is made by reacting rosin with divalent metal compound and then reacting the resinate with unsaturated hydrocarbon resin and unsaturated acid or anhydride - Google Patents

Abstract

Binder resins (I), obtained using a multi-stage reaction at 100-300 deg C with separation of water, comprise (A) natural resin (acid), (B) divalent metal compound, (C) unsaturated hydrocarbon resin, (D) unsaturated acid or anhydride and optionally other modifiers. Binder resins (I) (mainly modified with hydrocarbon resin) obtained by the reaction of components comprising (wt.%): (A) natural resin and/or resin acid (1-50); (B) divalent metal compound (0.1-5) (based on the corresponding metal oxide and the weight of the reaction mixture); (C) unsaturated hydrocarbon resins (30-90); (D) alpha , beta -unsaturated carboxylic acid or anhydride (0.1-15); (E) optionally phenol-aldehyde condensation products (0-20); (F) optionally fatty acids and/or esters (0-20); and (G) optionally alcohols (0-10). An Independent claim is also included a method of production of (I), using a multi-stage reaction at 100-300 deg C with separation of water, comprising: (i) reaction of (A) with (B) to form a resinate; (ii) reaction of this resinate with (C) and (D); and (iii) optionally with addition of (E), (F) and (G) for further modification.

Description

The invention relates to modified binder resins containing units of natural resins or natural resin acids, divalent metal compounds, a predominant proportion ethylenically unsaturated hydrocarbon resins, α, β-unsaturated carboxylic acids and their Anhydrides and optionally phenol-aldehyde condensation products, fatty acids or Fatty acid esters and alcohols, a process for their preparation and their use as binder resins in printing inks for toluol gravure printing.

Mostly for the production of these printing inks, preferably the bright colors red and Blue, used as binder resins natural resins and natural resin esters, with Phenol resin and compounds of divalent metals are modified. You have one excellent dispersing performance for the polar pigments used in toluene gravure printing on. Among them, such binder resins are particularly interesting with which pigment rich Aasreibungen produce, in which thus the ratio of the masses of Pigments and binder resins is as large as possible. Such pigment concentrates are not only economically advantageous, but also application technology, since they by adding Toluene and other dissolved in toluene binder systems, eg. B. high molecular weight blend resins, diluted and can be adjusted relatively easily to printing conditions. On the other hand, asperities, which are already diluted, are difficult to continue modify.

For economic reasons and to reduce dependence on natural products, whose quality is subject to fluctuations, has already been proposed, the proportion of Natural resins and natural resin acids in the binder resins in favor of petrochemical Reduce raw materials. As raw materials are usually reactive ethylenically unsaturated  Hydrocarbon resins used, but before their usability only by Reaction at the double bonds must be modified accordingly.

For example, modified natural resins have become known for their production used minor amounts of ethylenically unsaturated hydrocarbon resins become.

Thus, in EP-B 0 548 506 and the German patent application DE-A 43 35 426 products which are prepared by reacting natural resins with α, β-unsaturated Dicarboxylic acids, phenol-aldehyde condensation products, magnesium compounds, Alcohols, fatty acids and fatty acid compounds and the mass fractions in the mixture of up to 30% of ethylenically unsaturated hydrocarbon resins. These However, products are only suitable for colors for offset printing.

Mass fractions of up to 30% of ethylenically unsaturated hydrocarbon resins can also contain phenolic resin and calcium compounds modified natural resin esters, but without the co-use of α, β-unsaturated dicarboxylic acids are produced (German patent application DE-A 43 08 108). With phenolic resin and magnesium compounds modified natural resin esters, the mass fractions of up to 30% of fatty acid components, but contain no α, β-unsaturated dicarboxylic acids, and only for colors are suitable for offset printing, are known from German patent application DE-A 43 08 109 known. State of the art are also with phenolic resin and lithium compounds modified natural resin esters (German Patent Application DE-A 44 03 547), with Phenolic resin and compounds of divalent metals modified natural resin esters (German patent application DE-A 195 20 530), as well as rosin-formaldehyde Adducts produced modified natural resin esters (German patent applications DE-A 195 38 954 and 195 38 161).

Higher mass fractions than 30% of hydrocarbon resins are possible by processes in which first natural resins with polymerized hydrocarbons based on C ₅ , which may also be present as copolymers with maleic anhydride or natural resin acids are reacted; the resulting addition products are then reacted further with .alpha.,. beta.-unsaturated dicarboxylic acids and calcium compounds in the presence of acetic acid to form binder resins, which can also be optionally modified with phenolic resins (US Pat. No. 4,528,036 and US Pat. No. 4,552,592).

Other modified binder resins, in the production of which prior to further modification first natural resins and natural resin acids with ethylenically unsaturated hydrocarbon resins are converted to C ₅ -based, have become known from the German patent application DE-A 196 26 726, in the implementation of polymers from Natural resins or fatty acids and fatty acid esters with dicyclopentadiene or cyclopentadiene with natural resin acids is described, the resulting addition products are reacted after modification with α, β-unsaturated dicarboxylic acids with compounds of divalent metals and alcohols, and from the German patent application DE-A 196 26 723, according to the first fatty acids and fatty acid esters are polymerized with dicyclopentadiene or cyclopentadiene and then the resulting polymers are reacted with N uric acid, wherein the resulting adducts with α, β-unsaturated dicarboxylic acids and compounds zweiwer tiger metals are further reacted, and from the German patent application DE-A 196 26 724, according to the copolymers of natural resins with dicyclopentadiene or cyclopentadiene, also in the form of adducts with further natural resin, with α, β-unsaturated dicarboxylic acids, carboxylic acids, divalent metals and fatty acids or fatty acid compounds are converted to binder resins for gravure inks.

Likewise known are reaction products of polymers of natural resins with Dicyclopentadiene or cyclopentadiene with α, β-unsaturated dicarboxylic acids, wherein the formed compounds with divalent metals and optionally phenolic resins be reacted (German Patent Application DE-A 196 26 725).

Furthermore, it has already been proposed, fatty acids and / or natural resins with a through Implement polymerization prepared hydrocarbon resin from cyclopentadiene, and  then with metal salts and optionally phenols or phenolic resins and To modify acrylic acid derivatives (DE-A 22 46 283); Natural resins together with Hydrocarbon resins containing α, β-unsaturated carboxylic acids and their anhydrides modified with resoles and alcohols to convert products for offset printing (DE-A 25 49 902); Tall oil fatty acid, rosin, styrene, dicyclopentadiene, Maleic anhydride and resoles in the presence of magnesium compounds simultaneously in to implement a one-step reaction at high temperatures and pressures (DE-A 35 31 242); a terpene-modified cyclopentadiene resin with natural resin, To implement tall oil fatty acid and zinc oxide (WO-A 94/18257); and copolymers Dicyclopentadiene and rosin with phenol-aldehyde condensation products, but without modification with α, β-unsaturated carboxylic acids and their anhydrides, in the presence to reactivate monovalent or divalent metal compounds to give binder resins, but which are only suitable for colors for offset printing (EP-A 0 580 954, US-A 5,376,719). Furthermore, it has also been proposed with phenolic modified natural resin acids with Dicyclopentadiene to polymerize binder resins for offset printing (US-A 5,403,391).

From the German patent application DE-A 25 27 719 is also already known Dicyclopentadiene with α, β-unsaturated carboxylic acids and their anhydrides too copolymerize and the products obtained with natural resins, divalent metal Implement connections and Veresterungsmitteln. It is also known to use dicyclopentadiene too polymerize, and the polymers with α, β-unsaturated carboxylic acids and phenolic To react formaldehyde resins (US-A 3,887,641).

With these products, as long as they are used as binder resins for toluol gravure colors are suitable, sometimes at relatively high binder resin and low Pigment contents achieved good dispersion performance for pigments for gravure printing with toluene become. None of the products described in the above references  however, suitable, with reduced binder resin content, a similarly good dispersing performance how to achieve modified natural resin esters.

It was therefore the task of hydrocarbon resin-rich binder resins for To provide printing inks for toluene gravure printing, which improved Have dispersing performance.

This problem could be solved by first using natural resins and Natural resin acids with compounds divalent metals converted into resinates and these then with ethylenically unsaturated hydrocarbon resins, α, β-unsaturated carboxylic acids and / or their anhydrides and optionally phenol-aldehyde condensation products, Fatty acids and / or fatty acid esters and alcohols brings to the reaction.

The improvement of processes and product properties over the prior art The measures taken were unpredictable and therefore surprising describe.

The invention therefore relates to binder resins modified predominantly with hydrocarbon resin, preparable by reaction of certain mass fractions of the compounds mentioned below, namely

• From 1% to 50% of component A selected from natural resins and natural resin acids,
• - 0.1 to 5% of divalent metal compounds B, wherein the mass fraction is calculated as the ratio of the mass of the corresponding oxide to the mass of Reaction mixture,
• From 30 to 90% of ethylenically unsaturated hydrocarbon resins C,
• - 0.1 to 15% of component D, selected from α, β-unsaturated carboxylic acids and their anhydrides,

and optionally

• 0 to 20% of phenol-aldehyde condensation products E,
• - 0 to 20% of component F selected from fatty acids and fatty acid esters, as well as  
• 0 to 10% of alcohols G,

where the sum of the mass fractions of the individual compounds from the individual groups in the reaction mixture gives 100%, characterized in that the reaction under Dehydration in the temperature range of 100 to 300 ° C in at least two successive running stages, wherein in the first stage, the compounds of group A with Compounds of group B are reacted with Resinatbildung, and the Resinate AB in the subsequent stage with at least one compound from each the groups C and D is reacted, optionally for further modification Compounds of substance classes E, F and G can be used. From each of the Groups A to D (and E to G, as far as they are used) will be at least one Connection used.

Preferably, the sum of the mass fractions of the individual compounds of the individual groups in the reaction mixture A 5 to 30%, B 0.2 to 3%, each calculated as oxide, C 45 to 80%, D 5 to 12%, E 0 to 15%, F 0 to 10%, and G 0 to 5%, wherein the Sum of mass fractions always gives 100%.

However, in particular binder resins can be prepared without additional Modifying E to 6 get along, and where the sum of the mass fractions of the Compounds of the individual groups in the reaction mixture for A 5 to 30%, for B 0.2 to 3%, for C 45 to 80%, and for D 5 to 12%.

Other preferred binder resins are those which are additionally modified only with phenolic resin, and in which the sum of the mass fractions of the individual compounds from the individual groups in the reaction mixture for A 5 to 30%, for B 0.2 to 3%, for C 45 to 80%, for D 5 to 12%, and for E 0.1 to 15,
further binder resins, which are additionally modified only with phenolic resin and fatty acids and fatty acid esters, and in which the sum of the mass fractions of the individual compounds from the individual groups in the reaction mixture for A 5 to 30%, for B 0.2 to 3%, for C 45 to 80%, for D 5 to 12%, for E 0.1 to 15%, and for F 0.1 to 10,
Binder resins, which are additionally modified with phenolic resin, fatty acids and fatty acid esters and alcohols, and in which the sum of the mass fractions of the individual compounds from the individual groups in the reaction mixture for A 5 to 30%, for B 0.2 to 3%, for C 45 to 80%, for D 5 to 12%, for E 0.1 to 15%, for F 0.1 to 10% and for G 0.1 to 5%,
Binder resins, which are additionally modified only with phenolic resin and alcohols, and in which the sum of the mass fractions of the individual compounds from the individual groups in the reaction mixture for A 5 to 30%, for B 0.2 to 3%, for C 45 to 80 %, D is 5 to 12%, E is 0.1 to 15% and G is 0.1 to 5%,
Binder resins, which are additionally modified only with fatty acids and fatty acid esters, and in which the sum of the mass fractions of the individual compounds from the individual groups in the reaction mixture for A 5 to 30%, for B 0.2 to 3%, for C 45 to 80 %, D is 5 to 12% and F is 0.1 to 10%,
Binder resins, which are additionally modified with fatty acids and fatty acid esters and alcohols, and in which the sum of the mass fractions of the individual compounds from the individual groups in the reaction mixture for A 5 to 30%, for B 0.2 to 3%, for C 45 to 80%, for D 5 to 12%, for F 0.1 to 10% and for G 0.1 to 5%,
and binder resins, which are additionally modified only with alcohols, and in which the sum of the mass fractions of the individual compounds from the individual groups in the reaction mixture for A 5 to 30%, for B 0.2 to 3%, for C 45 to 80% , for D is 5 to 12% and for G is 0.1 to 5%.

As compounds of groups A to F are preferably used:

• 1. A: rosin, root resin, tau resin and disproportionated or partially hydrogenated or dimerized natural resin of any provenance, abietic acid, Levopimaric acid, pimaric acid, whereby the natural or natural resin acids also in minor amounts contain more terpenes or slightly, so z. Up to a mass fraction of preferably 10%, with α, β-unsaturated carboxylic acids and whose anhydrides, formaldehyde or phenolic resin may be modified;
• 2. B: compounds of divalent metals, preferably the oxides, hydroxides, formates, Acetates, Stearates, Oxalates, Carbonates, Hydrogencarbonates, Alcoholates of Magnesium, calcium; Zinc;
• 3. C: ethylenically unsaturated hydrocarbon resins, predominantly by polymerization of cyclopentadiene, dicyclopentadiene, their alkyl substitution products and their Oligomers, such as di-, tri- and tetramers available from Diels-Alder addition and the alkyl derivatives or cooligomers of these compounds, e.g. B. Methylcyclopentadiene, cyclopentadiene-isoprene dimers, cyclopentadiene-piperylene Dimers, as well as homopolymers and copolymers derived from these cyclic Derive connections, eg. As polymers of dicyclopentadiene, methylcyclo pentadiene, copolymers with styrene, α-methylstyrene, vinyltoluene, indene, Methyl indene or mixtures thereof, propylene, butene, butadiene, pentene, Cyclopentene, copolymers with natural resins and natural resin acids, as well as with Fatty acids and fatty acid compounds, such as. B. tall oil fatty acid, linseed oil. It is preferred that these ethylenically unsaturated hydrocarbon resins to more than 50% of cyclopentadiene units exist (these hydrocarbon resins are according to the known polymerization, the thermal, radical under Influence of catalysts or cationic under the action of catalysts can be carried out);  
• 4. D: α, β-ethylenically unsaturated carboxylic acids or their anhydrides, in particular Fumaric acid, maleic acid, maleic anhydride, itaconic acid, cinnamic acid, acrylic acid, methacrylic acid;
• 5. E: Phenol-aldehyde condensation products, preferably resols, which are prepared by the usual methods of Phenolharzchemie by reacting under basic conditions of mononuclear or polynuclear phenols, preferably alkylphenols, aryl or aralkylphenols, cresols, 1,3,5-xylenols , Isopropyl, p-tert-butyl, amyl, octyl, nonylphenols, diphenylol propane (bisphenol A), phenylphenol, cumylphenol and addition products of phenols and ethylenically unsaturated monomers, such. B. cyclopentadiene, with aldehydes or aldehyde acetals, preferably aliphatic (C ₁ -G ₇ ) aldehydes, especially formaldehyde in its various monomeric, oligomeric and polymeric forms, acetaldehyde, butyraldehyde, isobutyraldehyde, also benzaldehyde, furfurol, glyoxal;
• 6. F: animal, vegetable or refining derived fatty acids, and Fatty acid esters, in particular in the form of vegetable or animal fatty acids and olives, for example palmitic or stearic acid, unsaturated fatty acids such as oil and tall oil fatty acid, ricinoleic acid, dimerized and trimerized fatty acids, oils, For example, fatty acid glycerol esters such as cottonseed, soybean, linseed, wood, fish, Castor oil, hydrogenated castor oil, coconut oil, hydrogenated coconut oil and tall oil;
• 7. G: hydroxyl-containing esterification agents, for example methanol, ethanol, Propanol, n-butanol, secondary and tertiary butanol, isobutanol, allyl alcohol, 2- Ethylhexyl alcohol, nonyl alcohol, dodecyl alcohol, cyclohexanol, benzyl alcohol, Oleyl alcohol, preferably polyfunctional alcohols, especially bifunctional, for example, glycols, or trifunctional, for example trimethylolethane, Trimethylolpropane, glycerol, or tetrafunctional, for example pentaerythritol,  or pentafunctional, for example dimerized trimethylolpropane, or hexafunctional alcohols, for example dimerized pentaerythritol or sorbitol.

For the preparation of the binder resins according to the invention are those in natural resin chemistry usual equipment used. They usually consist of a steel boiler, with Heat transfer oil can be heated, with a dosing and distillation apparatus, a temperature sensor and a stirrer is equipped. At first this will be Apparatus charged with the natural resin and the natural resin acid from group A and the Boiler contents brought to a temperature above 100 ° C, so that the contents in molten Form is present. Then the metal compound of group B, which is also suspended in a inert volatile vehicle such. B. xylene can be present, registered and the Resinatbildung performed. This can easily occur at the resulting and from the reaction vessel distilling water, which also with a suitable entrainer, such. Xylene, can be distilled off azeotropically, and the slowly becoming homogeneous mixture followed become. To complete the reaction of this first stage, it is usually necessary to heat the kettle contents to temperatures of preferably 150 to 250 ° C. Become Oxides used as component B, so can be small to increase the reactivity Amounts of organic acids, such as. As acetic acid, benzoic acid or tartaric acid added become. At relatively high metal concentrations, it may also be advisable to To use natural resins and natural resin acids, with minor amounts of α, β unsaturated carboxylic acids and their anhydrides, formaldehyde or phenolic resin are modified to prevent crystallization of the resinate.

After the formation of the resin AB, in the second stage, preferably the first added ethylenically unsaturated hydrocarbon resin of group C. This can be done in solid, molten or dissolved form, e.g. In xylene. Distil volatile components thereby from the reaction mixture. In the temperature range of 150 to 250 ° C takes place the reaction of the resinate with the hydrocarbon resin within a few minutes. Then, the α, β-ethylenically unsaturated carboxylic acid or its anhydride from the Group D added. The reaction temperature is expediently at first  200 ° C held in order to keep the viscous mixture stirrable. higher Temperatures may be at relatively high levels of Group D compounds Distillation out of the reaction mixture cause. After about 30 to 60 min is also this implementation almost completely.

Thereafter, to complete the reaction and to adjust the desired Polymerization or condensation degree to temperatures of about 250 to 260 ° C heated. The progress of the reaction can be conveniently determined by determining the Viscosity values in a solvent, such as toluene, determined and then at desired stage are terminated, with optional volatile components Brief application of reduced pressure to the batch kettle are removed.

The binder resins according to the invention initially fall after cooling the melt Solid on. The melt can, however, by adding solvents such as mineral oil or Also gasoline fractions, but preferably toluene, are converted into a varnish, wherein All transitions from a solid to a liquid execution are possible.

To determine the viscosities, solutions of the resin (50 g of resin in 100 g of toluene solution) with a conventional rotational viscometer at 23 ° C. The viscosities are preferably in a range of 30 to 1000 mPa.s. These areas however, they can also be exceeded or fallen short of.

The molar mass of the resins of the invention can be determined by gel permeation chromatography of the resin solutions in tetrahydrofuran (THF) on polystyrene gel in a Permeationsmeßgerät by known methods. The weight-average molar mass M _{w of} the resins according to the invention is, according to the results of the measurements obtained, preferably at values of M _w <500 g / mol and is not critically limited to the top. More preferably, the weight-average molar mass M _w , but in a range of 1000 to 50 000 g / mol.

The inventive (not further modified) resins ABCD from the Components A, B, C and D may also during or after the reaction of the second Stage can be processed by adding other substances, as in the production of Ink resins is known. So it is possible to optimize the solution viscosity the desired application phenol-aldehyde condensation products of group E admit. For reasons of handling, these are preferably in a Resolform used. The addition is carried out expediently after the addition of D.

Batches that have too high melt viscosities can be made by adding fatty acids or fatty acid esters from group F are brought into a manageable range. These However, they must be used well dosed, as they unfavorably lowering the Cause solution viscosities as well as the drying properties of the binder resins can slow down adversely. Surprisingly, however, provides the addition of Ricinoleic acid, castor oil and hydrogenated castor oil Melt viscosity without adversely lowering the solution viscosity. At the same time improves the printing properties of the binder resins. They show in particular excellent dispersing behavior for commonly used pigments. It It is possible to formulate easily flowable, pigment-rich aasings that are very colorful lead to good drying. The concomitant use of ricinoleic acid, castor oil and hydrogenated Castor oil is therefore particularly preferred.

An optimization of solution viscosities can also be achieved by adding alcohols G under Esterification of acid groups take place. By the monofunctional aliphatic Alcohols with more than 5 carbon atoms can be considered simultaneously the melt viscosity of Minimize resins. Is esterified with polyfunctional alcohols, the Solution viscosity of the resins raised. The amount and type of alcohol depends on the desired viscosity. The mass fraction of alcohols can be up to 10%, preferably up to 5% based on the sum of the mass of all reactants (= 100%). Too high Shares of higher quality alcohols lead to gelation. The esterification is in the generally carried out so that the alcohols are preferably in the melt with the  converts binder resins according to the invention. At esterification temperatures of over 220 ° C, as required in particular for high-melting binders for printing inks are, prove the good thermal resistance of the products. The esterification can be completed without unwanted thermal buildup reactions z. B. by Polymerization, which lead to less suitable resins, at the same time to a greater extent occur.

The procedure, first group A compounds with group B compounds react with Resinatbildung and only then with the compounds of groups C and D and optionally E, F and G continue to behave, compared to those in the state of Technique described first, before further modification of the To implement compounds of group A with compounds of group C, not only the Advantage of improved dispersibility, but also leads to products decreased heat reactivity, which is extremely advantageous. This is for the technical Manufacturing important because the products are easy to handle and maintain during the hours of discharge from the reaction vessel via a cooling belt in their quality so to change as little as possible.

The resins of the invention have excellent compatibility with others in the Production of printing inks conventional binder resins, for example with modified Natural resin acid esters of the prior art, resinates, hydrocarbon resins or Chlorinated rubber and Äthylhydroxyäthylcellulose, whereby they are widely used.

The resins of the invention have an excellent wetting behavior for in the Illustration gravure used pigments. Another object of the invention is therefore the Use of the resins of the invention as binder resins in Pigmentanreibungen and Pigment concentrates and in printing inks preferably for illustration gravure with Toluene. Very favorable in wetting behavior especially against red laked Azopigments have proven to be binder resins that are relatively high in Mass fraction of more than 5% (based on the total mass of the components used  = 100%) of α, β-unsaturated carboxylic acids and / or their anhydrides. To be particularly favorable, the additional modification with phenolic resins of Group E, with fatty acids or fatty acid esters of group F and alcohols of group G. proved. Such resins are therefore particularly preferred.

The gravure inks containing toluene are formulated by the usual methods. For this purpose, the appropriate binder resin is dissolved in toluene and this varnish is pigmented or dilute a previously prepared pigment slurry with toluene. As aggregates can For example, fillers such as calcium carbonate or surfactants for Improvement of the pigment dispersion such as lecithin or waxes to improve the Rub resistance, to be used.

The invention is further illustrated by the following examples, but without them limit. In the examples below, as in the preceding Text all information with the unit "%" mass proportions (quotient of the mass of the concerned Substance and the mass of the mixture), unless otherwise stated. "Parts" (abbreviated "Tle.") Are always mass shares. Concentration data in "%" are mass fractions of the solute in the solution (mass of solute divided by the mass of the solute) Solution, in g / 100 g).

example 1 [Use of Components from Groups A, B, C, D]

In a heatable 2 l kettle with stirrer, thermometer, dropping funnel, reflux condenser and filler tube were under a nitrogen atmosphere 210 g commercially available Rosin melted. In the 180 ° C hot melt 5 g of zinc acetate were added and the temperature increased to 200 ° C. This distilled off water and acetic acid, and the initially inhomogeneous melt became bright after 30 minutes. Thereafter, 700 g of a Dicyclopentadiene homopolymer (prepared by the usual methods thermal polymerization of dicyclopentadiene at about 260 ° C and a pressure of about 1 MPa) introduced into the melt. The mixture was then stirred for 1 h at 200 ° C and then gave 90 g of maleic anhydride. Then the melt was heated to 250 ° C. One was still stirring  4 h after and emptied the approach. After cooling, 936 g of a brittle resin with the softening point 147 ° C and the viscosity of 42 mPa.s (50 g of resin in 100 g of solution in toluene at 23 ° C).

Example 2 [Use of Components from Groups A, B, C, D, E]

In a heatable 2 l kettle with stirrer, thermometer, dropping funnel, reflux condenser and filler tube were under a nitrogen atmosphere 210 g commercially available Rosin melted. In the 180 ° C hot melt 5 g of zinc acetate were added and the temperature increased to 200 ° C. This distilled off water and acetic acid, and the initially inhomogeneous melt became bright after 30 minutes. Thereafter, 700 g of the Dicyclopentadiene homopolymer of Example 1 introduced into the melt. One stirred then for 1 h at 200 ° C and then gave 90 g of maleic anhydride. Then 20 became g of an aqueous phenol-formaldehyde condensation product (70 g of resin in 100 g of solution in Water, viscosity 270 mPa.s) is added dropwise and the melt is heated to 250 ° C. One stirred 4 hours after and emptied the approach. After cooling, 950 g of a brittle resin with the softening point 148 ° C and the viscosity of 65 mPa.s (50 g of resin in 100 g Solution in toluene at 23 ° C).

Example 3 [Use of Components from Groups A, B, C, D, E, F]

In a heatable 2 l kettle with stirrer, thermometer, dropping funnel, reflux condenser and filler tube were under a nitrogen atmosphere 210 g commercially available Rosin melted. In the 180 ° C hot melt 5 g of zinc acetate were added and the temperature increased to 200 ° C. This distilled off water and acetic acid, and the initially inhomogeneous melt became bright after 30 minutes. Thereafter, 700 g of the Dicyclopentadiene homopolymer of Example 1 introduced into the melt. One stirred then for 1 h at 200 ° C and then gave 90 g of maleic anhydride. Then 50 g Castor oil and 20 g of an aqueous phenol-formaldehyde condensation product (70 g of resin in 100 g of solution in water, viscosity 270 mPa.s) was added dropwise and the melt to 250 ° C. heated. The mixture was stirred for 4 h and emptied the approach. After cooling, 995 g a brittle resin having a softening point of 143 ° C and a viscosity of 71 mPa.s.  (50 g of resin in 100 g of solution in toluene at 23 ° C).

Example 4 [Use of Components from Groups A, B, C, D, E, F, G]

In a heatable 2 l kettle with stirrer, thermometer, dropping funnel, reflux condenser and filler tube were under a nitrogen atmosphere 210 g commercially available Rosin melted. In the 180 ° C hot melt 5 g of zinc acetate were added and the temperature increased to 200 ° C. This distilled off water and acetic acid, and the initially inhomogeneous melt became bright after 30 minutes. Thereafter, 700 g of the Dicyclopentadiene homopolymer of Example 1 introduced into the melt. One stirred then for 1 h at 200 ° C and then gave 90 g of maleic anhydride. Then 50 g Castor oil, 20 g of an aqueous phenol-formaldehyde condensation product (70 g of resin in 100 g solution in VÜasser, viscosity 270 mPa.s) was added dropwise and 30 g of pentaerythritol added and the melt is heated to 250 ° C. The mixture was stirred for 4 h and emptied the approach. After cooling, 1027 g of a brittle resin having a softening point of 145 ° C and the viscosity of 220 mPa.s (50 g of resin in 100 g of solution in toluene at 23 ° C).

Example 5 [Use of Components from Groups A, B, C, D, E, G]

In a heatable 2 l kettle with stirrer, thermometer, dropping funnel, reflux condenser and filler tube were under a nitrogen atmosphere 210 g commercially available Rosin melted. In the 180 ° C hot melt 5 g of zinc acetate were added and the temperature increased to 200 ° C. This distilled off water and acetic acid, and the initially inhomogeneous melt became bright after 30 minutes. Thereafter, 700 g of the Dicyclopentadiene homopolymer of Example 1 introduced into the melt. One stirred then for 1 h at 200 ° C and then gave 90 g of maleic anhydride. Then 20 g of an aqueous phenol-formaldehyde condensation product (70 g of resin in 100 g of solution in Water, viscosity 270 mPa.s) was added dropwise, 60 g of pentaerythritol added and the melt on Heated to 250 ° C. The mixture was stirred for 4 h and emptied the approach. After cooling, were 1010 g of a brittle resin having a softening point of 152 ° C and a viscosity of 290 mPa.s. (50 g of resin in 100 g of solution in toluene at 23 ° C).  

Example 6 [Use of Components from Groups A, B, C, D, F]

In a heatable 2 l kettle with stirrer, thermometer, dropping funnel, reflux condenser and filler tube were under a nitrogen atmosphere 210 g commercially available Rosin melted. In the 180 ° C hot melt 5 g of zinc acetate were added and the temperature increased to 200 ° C. This distilled off water and acetic acid, and the initially inhomogeneous melt became bright after 30 minutes. Thereafter, 700 g of the Dicyclopentadiene homopolymer of Example 1 introduced into the melt. One stirred then for 1 h at 200 ° C and then gave 90 g of maleic anhydride. Then 20 g Castor oil added dropwise and the melt heated to 250 ° C. The mixture was stirred for another 4 h and emptied the approach. After cooling, 948 g of a brittle resin with the Softening point 141 ° C and the viscosity of 55 mPa.s (50 g of resin in 100 g of solution in Toluene at 23 ° C).

Example 7 [Use of Components from Groups A, B, C, D, F, G]

In a heatable 2 l kettle with stirrer, thermometer, dropping funnel, reflux condenser and filler tube were under a nitrogen atmosphere 210 g commercially available Rosin melted. In the 180 ° C hot melt 5 g of zinc acetate were added and the temperature increased to 200 ° C. This distilled off water and acetic acid, and the initially inhomogeneous melt became bright after 30 minutes. Thereafter, 700 g of the Dicyclopentadiene homopolymer of Example 1 introduced into the melt. One stirred then for 1 h at 200 ° C and then gave 90 g of maleic anhydride. Then 20 g Added dropwise castor oil and 45 g of pentaerythritol and the melt heated to 250 ° C. The mixture was stirred for 4 h and emptied the approach. After cooling, 995 g of a brittle resin with the softening point 151 ° C and the viscosity of 275 mPa.s (50 g Resin in 100 g solution in toluene at 23 ° C).

Example 8 [Use of Components from Groups A, B, C, D, G]

In a heatable 2 l kettle with stirrer, thermometer, dropping funnel, reflux condenser and filler tube were under a nitrogen atmosphere 210 g commercially available Rosin melted. In the 180 ° C hot melt 5 g of zinc acetate were added  and the temperature increased to 200 ° C. This distilled off water and acetic acid, and the initially inhomogeneous melt became bright after 30 minutes. Thereafter, 700 g of the Dicyclopentadiene homopolymer of Example 1 introduced into the melt. One stirred then for 1 h at 200 ° C and then gave 90 g of maleic anhydride. Then 65 g Added pentaerythritol and the melt heated to 250 ° C. The mixture was stirred for another 4 h and emptied the approach. After cooling, 985 g of a brittle resin with the Softening point 161 ° C and the viscosity of 320 mPa.s (50 g of resin in 100 g of solution in Toluene at 23 ° C).

Example 9 [Use of Components from Groups A, B, C, D, E]

In a heatable 2 l kettle with stirrer, thermometer, dropping funnel, reflux condenser and filler tube were under a nitrogen atmosphere 210 g commercially available Rosin melted. In the 180 ° C hot melt 2 g of calcium hydroxide and 1 g of magnesium oxide and 5 g of benzoic acid added and the temperature to 220 ° C. increased. This distilled off water, the initially inhomogeneous melt after 30 min was blank. Thereafter, 700 g of the dicyclopentadiene homopolymer of the Example 1 entered in the melt. The mixture was then stirred for 1 h at 200 ° C and gave then 90 g of maleic anhydride. Then 20 g of an aqueous phenol-formaldehyde Condensation product (70 g of the resin in 100 g of solution in water, viscosity 270 mPa.s) added dropwise and the melt heated to 250 ° C. The mixture was stirred for another 4 h and emptied Approach. After cooling, 951 g of a brittle resin with the softening point 148 ° C and the viscosity of 85 mPa.s (50 g of resin in 100 g of solution in toluene at 23 ° C) receive.

Example 10 [From group A use of rosin modified with MSA is, as well as components from the groups B, C, D]

In a heatable 2 l kettle with stirrer, thermometer, dropping funnel, reflux condenser and filler tube were under a nitrogen atmosphere, 210 g of rosin containing a 10% by mass of maleic anhydride was modified (produced by W. Sandermann, natural resins, Springer Verlag 1960, p. 239) melted. In the 180 ° C hot  Melt were 15 g of calcium hydroxide, 8 g of magnesium oxide and 5 g of benzoic acid registered and the temperature increased to 220 ° C. This distilled off water, the initially inhomogeneous melt after 30 min was blank. Thereafter, 700 g of the Dicyclopentadiene homopolymer of Example 1 introduced into the melt. One stirred then for 1 h at 200 ° C and then gave 90 g of maleic anhydride. Then the Melt heated to 250 ° C. The mixture was stirred for 4 h and emptied the approach. To Cooling was 956 g of a brittle resin with the softening point 147 ° C and the Viscosity of 278 mPa.s (50 g of resin in 100 g of solution in toluene at 23 ° C).

Example 11 [From Group A Use of Rosin Modified with MSA and components from groups B, C, D, E, F, G]

In a heatable 2 l kettle with stirrer, thermometer, dropping funnel, reflux condenser and fill tube were under a nitrogen atmosphere 210 g of the maleic anhydride modified rosin from Example 10 melted. In the 180 ° C hot melt were added 15 g of calcium hydroxide, 8 g of magnesium oxide and 5 g of benzoic acid and the Temperature increased to 220 ° C. This distilled off water, the initial Inhomogeneous melt after 30 min was blank. Thereafter, 700 g of a rosin Dicyclopentadiene copolymer (prepared by the usual methods by thermal Polymerization of a mixture with mass proportions of 90% dicyclopentadiene and 10 Rosin at 260 ° C and a pressure of 1 MPa) introduced into the melt. you The mixture was then stirred for 1 h at 200 ° C and then gave 90 g of maleic anhydride. After 1 h were 50 g of castor oil and 100 g of a nonylphenol-formaldehyde condensation product (70 g of the resin in 100 g of a solution in xylene, viscosity 480 mPa.s) was added dropwise and the Melt heated to 250 ° C. Then 20 g of pentaerythritol were added. The mixture was stirred for another 4 h and emptied the approach. After cooling, 1078 g of a brittle resin with the Softening point 158 ° C and the viscosity of 421 mPa.s (50 g of resin in 100 g of solution in Toluene at 23 ° C).  

Example 12 [From group A use of rosin modified with MSA and components from groups B, C, D, E, F, G]

In a heatable 2 l kettle with stirrer, thermometer, dropping funnel, reflux condenser and fill tube were under a nitrogen atmosphere 210 g of the maleic anhydride modified rosin from Example 10 melted. In the 180 ° C hot melt were added 15 g of calcium hydroxide, 8 g of magnesium oxide and 5 g of benzoic acid and the Temperature increased to 220 ° C. This distilled off water, the initial Inhomogeneous melt after 30 min was blank. Thereafter, 700 g of a tall oil fatty acid Dicyclopentadiene copolymer (prepared by the usual methods by thermal Polymerization of a mixture of mass fractions of 90% dicyclopentadiene and 10 Tall oil fatty acid at 260 ° C and a pressure of 1 MPa) added to the melt. you The mixture was then stirred for 1 h at 200 ° C and then gave 90 g of maleic anhydride. After 1 h were 50 g of castor oil and 100 g of the nonylphenol-formaldehyde condensation product from Example 6 is added dropwise and the melt is heated to 250 ° C. Then you gave 10 g Pentaerythritol too. The mixture was stirred for 4 h and emptied the approach. After cooling were 1069 g of a brittle resin having the softening point of 164 ° C and the viscosity of 456 mPa.s (50 g resin in 100 g solution in toluene at 23 ° C).

Example 13

The procedure was as described in Example 11, except that 210 g of Maleic anhydride modified rosin from example 10, 26 g calcium hydroxide, 5 g Benzoic acid, 700 g of the rosin-dicyclopentadiene copolymer of Example 11, 90 g Maleic anhydride, 50 g of castor oil, 100 g of a nonylphenol-formaldehyde condensation product (70 g of the resin in 100 g of a solution in xylene, viscosity 480 mPa.s) and 20 g Pentaerythritol were used. After cooling, 1116 g of a brittle resin with the softening point 163 ° C and the viscosity of 475 mPa.s (50 g of resin in 100 g of solution in toluene at 23 ° C).  

Example 14

The procedure was as described in Example 11, with the modification that 210 g of Maleic anhydride modified rosin from example 10, 16 g magnesium oxide, 5 g Benzoic acid, 700 g of the rosin-dicyclopentadiene copolymer of Example 11, 90 g Maleic anhydride, 100 g of castor oil, 100 g of a nonylphenol-formaldehyde Condensation product (70 g of the resin in 100 g of a solution in xylene, viscosity 480 mPa.s) and 25 g of pentaerythritol were used. After cooling, 1158 g of a brittle resin with the softening point 163 ° C and the viscosity of 545 mPa.s (50 g Resin in 100 g solution in toluene at 23 ° C).

Example 15

The procedure was as described in Example 11, except that 210 g of Maleic anhydride modified rosin from example 10, 25 g zinc oxide, 5 g Benzoic acid, 700 g of the rosin-dicyclopentadiene copolymer of Example 11, 90 g Maleic anhydride, 100 g of castor oil, 100 g of a nonylphenol-formaldehyde Condensation product (70 g of the resin in 100 g of a solution in xylene, viscosity 480 mPa.s) and 25 g of pentaerythritol were used. After cooling, 1158 g of a brittle resin with the softening point 163 ° C and the viscosity of 545 mPa.s (50 g Resin in 100 g solution in toluene at 23 ° C).

Example 16 [From group A use of rosin containing formaldehyde modified, as well as components from groups B, C, D, E, F, G]

In a heatable 2 l kettle with stirrer, thermometer, dropping funnel, reflux condenser and filler tube were under a nitrogen atmosphere, 210 g of rosin containing a Mass fraction of 10% formaldehyde was modified (manufactured by W. Sandermann, Natural resins, Springer Verlag 1960, p. 247), melted. In the 180 ° C hot melt were added 15 g of calcium hydroxide, 8 g of magnesium oxide and 5 g of benzoic acid and the Temperature increased to 220 ° C. This distilled off water, the initial Inhomogeneous melt after 30 min was blank. Thereafter, 700 g of a rosin Dicyclopentadiene copolymer of Example 11 introduced into the melt. One stirred  then for 1 h at 200 ° C and then gave 90 g of maleic anhydride. After 1 h were 50 g of castor oil and 100 g of a nonylphenol-formaldehyde condensation product (70 g of the Resin in 100 g of a solution in xylene, viscosity 480 mPa.s) was added dropwise and the melt on Heated to 250 ° C. Then 20 g of pentaerythritol were added. The mixture was stirred for another 4 h and emptied the approach. After cooling, 1075 g of a brittle resin with the Softening point 163 ° C and the viscosity of 395 mPa.s (50 g of resin in 100 g of solution in Toluene at 23 ° C).

Example 17 [From group A use of rosin mixed with phenolic resin modified, as well as components from groups B, C, D, E, F, G]

In a heatable 2 l kettle with stirrer, thermometer, dropping funnel, reflux condenser and filler tube were under a nitrogen atmosphere, 210 g of rosin containing a 10% by mass of a phenolic resin was modified (manufactured by W. Sandermann, Natural resins, Springer Verlag 1960, p. 251), melted. In the 180 ° C hot melt were added 15 g of calcium hydroxide, 8 g of magnesium oxide and 5 g of benzoic acid and the Temperature increased to 220 ° C. This distilled off water, the initial Inhomogeneous melt after 30 min was blank. Thereafter, 700 g of the rosin Dicyclopentadiene copolymer of Example 11 introduced into the melt. One stirred then for 1 h at 200 ° C and then gave 90 g of maleic anhydride. After 1 h were 50 g of castor oil and 100 g of a nonylphenol-formaldehyde condensation product (70 g of the Resin in 100 g of a solution in xylene, viscosity 480 mPa.s) was added dropwise and the melt on Heated to 250 ° C. Then 20 g of pentaerythritol were added. The mixture was stirred for another 4 h and emptied the approach. After cooling, 1072 g of a brittle resin with the Softening point 169 ° C and the viscosity of 415 mPa.s (50 g of resin in 100 g of solution in Toluene at 23 ° C).

Comparative Example 1 (analogous to US-A 4,552,592)

525 g of rosin and 445 g of a dicyclopentadiene homopolymer were added for 1 h 160 ° C stirred. Then, 63 g of maleic anhydride was added. After half an hour Stirring was 70 g of an aqueous phenol-formaldehyde condensation product (70 g of the  Resin in 100 g of a solution in water, viscosity 270 mPa.s) was added dropwise. Subsequently The mixture was heated to 250 ° C, added 36 g of calcium oxide and after 1 h gradually 16 g of acetic acid was added dropwise. The melt was stirred for a further 3 hours and removed Volatile matter still kept under reduced pressure. There were 1075 g of a brittle Resin with a softening point of 165 ° C and a viscosity of 378 mPa.s (50 g of resin in 100 g Solution in toluene at 23 ° C).

Comparative Example 2 (analogous to German patent application DE-A 196 26 725)

Analogously to Example 5 given there was a copolymer of 195 g of rosin and 455 g of dicyclopentadiene at 260 ° C first with a further 210 g of rosin and then with 45 g of maleic anhydride reacts and the intermediate obtained finally with 40 g Calcium hydroxide and 50 g of tall oil fatty acid reacted. There were 760 g of a brittle resin the viscosity 65 mPa.s (50 g of resin in 100 g of solution in toluene at 23 ° C).

Comparative Example 3 (analogous to the German patent application DE-A 196 26 724)

Analogously to Example 1 given there was a copolymer of 215 g of rosin and 430 g of dicyclopentadiene at 260 ° C first with another 210 g of rosin and then with 45 g of maleic anhydride reacts and the resulting intermediate finally with 36 g Calcium hydroxide, 30 g of wood oil and 10 g of acetic acid reacted. It became a brittle resin of Viscosity 80 mPa.s (50 g of resin in 100 g of solution in toluene at 23 ° C).

Application example

By conventional methods, dispersing a mixture of 48 g of a solution of the respective binder resin in toluene (50 g of resin in 100 g of solution in toluene), 13 g Pigment ® Litholubin D 4250 (red pigment, BASF AG) and 39 g of toluene anhydrides or pigment concentrates produced. These pigment concentrates containing resin and pigment in a mass ratio of 1.84: 1 were then added by the addition of 30 g of toluene and another 20 g of a solution of a high molecular weight rosin (40 g of resin in 100 g of solution in toluene) in toluene in ready-to-print colors. These then existed each from mass fractions of 21.3% resin, 8.7% pigment and 70.0% toluene and meadows  a mass ratio of resin to pigment of 2.4: 1.

These colors were used to print coated paper by gravure printing. The splendor of Proofs that should be as high as possible for a good printing result then with the laboratory reflectometer according to Lange at an angle of incidence of 60 ° measured.

As a standard, a commercial phenol resin-modified natural resin ester, the after analysis contained a mass fraction of 1.8% Zn and its solution (50 g of resin in 100 g solution in toluene at 23 ° C) had a viscosity of 320 mPa.s used.

table Gloss of proofs

Paint with resin Gloss of carrion pressure in% default 68 Example 4 67 Example 5 67 Example 7 69 Example 8 66 Example 10 66 Example 11 70 Example 12 71 Example 13 72 Example 14 72 Example 16 73 Example 17 72 Comparative Example 1 59 Comparative Example 2 55 Comparative Example 3 53

Compared to conventional natural acid esters could with the new according to the invention with hydrocarbon resin modified binder resins similarly good or improved colors are formulated.

Claims (14)

1. Primarily with hydrocarbon resin modified binder resins obtainable by reaction of mass fractions of

• From 1% to 50% of component A selected from natural resins and natural resin acids,
• 0.1 to 5% of divalent metal compounds B, the mass fraction being calculated as the ratio of the mass of the corresponding oxide to the mass of the reaction mixture,
• From 30 to 90% of ethylenically unsaturated hydrocarbon resins C,
• - 0.1 to 15% of component D selected from α, β-unsaturated carboxylic acids and their anhydrides, and optionally
• 0 to 20% of phenol-aldehyde condensation products E,
• - 0 to 20% of component F selected from fatty acids and fatty acid esters, as well as
• 0 to 10% of alcohols G,

wherein the sum of the mass fractions of the individual compounds from the individual groups in the reaction mixture gives 100%, characterized in that the reaction takes place with elimination of water in the temperature range of 100 to 300 ° C in at least two successive stages, wherein in the first stage, the compounds the group A with compounds of group B are reacted with resination, and the resinate is reacted in the subsequent step with at least one compound from each of groups C and D, wherein for further modification, if appropriate, compounds of the substance classes E, F and G. can be used. 2. binder resins modified primarily with hydrocarbon resin according to claim 1, characterized in that the sum of the mass fractions of the individual compounds the individual groups in the reaction mixture A 5 to 30%, B 0.2 to 3%, respectively calculated as oxide, C 45 to 80%, D 5 to 12%, E 0 to 15%, F 0 to 10%, and G 0 to 5% is, where the sum of the mass fractions always gives 100%.   3. Primarily with hydrocarbon resin modified binder resins after Claim 1, characterized in that for their synthesis compounds of group E be used, and that their mass fraction in the reaction mixture 0.1 to 15% is. 4. Primarily with hydrocarbon resin modified binder resins after Claim 1, characterized in that for their synthesis compounds of group F be used, and that their mass fraction in the reaction mixture 0.1 to 10% is. 5. Primarily modified with hydrocarbon resin binder resins Claim 1, characterized in that for the synthesis of compounds of the group G. be used, and that their mass fraction in the reaction mixture 0.1 to 5% is. 6. Primarily with hydrocarbon resin modified binder resins after Claim 1, characterized in that the natural resins or the natural resin acids of the Group A partially with maleic anhydride and / or phenolic resin and / or formaldehyde are implemented. 7. Primarily with hydrocarbon resin modified binder resins after Claim 1, characterized in that the fatty acids or fatty acid esters of group F selected from ricinoleic acid, castor oil and hydrogenated castor oil. 8. Primarily with hydrocarbon resin modified binder resins after Claim 1, characterized in that as divalent metal compounds B calcium, Magnesium or zinc compounds can be used, alone or in a mixture. 9. Process for the preparation of predominantly hydrocarbon resin modified binder resins according to claim 1, characterized in that in the first  Stage, the conversion of components A and B to Resinaten takes place, and in the second Stage the resinate first with the component C and then reacted with the component D. 10. Process for the preparation of predominantly hydrocarbon resin Modified binder resins according to claim 9, characterized in that in second stage additionally at least one compound selected from the components E, F. and G is used. 11. binder resin mainly modified with hydrocarbon resin according to claim 1, characterized in that their determined by gel permeation chromatography on polystyrene gel weight average molar mass M _{w is} 500 to 50,000 g / mol. 12. Use of the binder mainly modified with hydrocarbon resin Resins according to Claim 1 in pigment concentrates. 13. Use of predominantly modified with hydrocarbon resin Binder resins according to claim 1 in printing inks. 14. Use of predominantly modified with hydrocarbon resin Binder resins according to Claim 1 in printing inks for toluol gravure printing.