Claims
- 1. An oil soluble, phenolic resin modified natural resinic acid ester wherein the compounds from groups A) to H) used are
- A) at least one natural resin or natural resinic acid selected from the group consisting of colophony (tree resin), root resin, tall resin and natural resins which are partially hydrogenated, disproportionated or dimerized and have a bromine number in the range from 200 to 280 and an acid number in the range from 100 to 300 mg KOH/g of resin, and
- B) at least one phenol selected from the group consisting of monofunctional, difunctional phenols, trifunctional and tetrafunctional phenols, the proportion of trifunctional or tetrafunctional phenols of no more than 20% by weight, based on the total amount of the phenols employed,
- C) at least one aliphatic (C.sub.1 -C.sub.7)-aldehyde, the molar ratio of the phenol component from B) to the aldehyde component for the formation of a phenol resol being 1:0.9 to 1:3.5,
- D) at least one polyfunctional alcohol selected from the group consisting of glycerol, trimethylolpropane, pentaery-thriol and dimerized pentaerythritol,
- E) at least one condensation catalyst selected from the group consisting of magnesium oxide, magnesium hydroxide, magnesium salts of organic acids, magnesium carbonate and magnesium bicarbonate,
- F) optionally animal or vegetable fatty acids, the iodine number of which is in the range from 50 to 150 selected from the group consisting of semidrying and drying oils and fats, hydrogenated coconut fat, coconut fat, palm oil, shea butter, Japan wax, peanut oil, olive oil, sulfocarbon oil, caster oil, rice oil, cotton seed oil, maize oil, rape oil, soya bean oil, linseed oil, sunflower oil, wood oil, tallow, sperm oil, train oil, wool fat, refinery fatty acids, tall oil, dehydrated castor oil, polymerized oils, linseed oils and mixtures of these components,
- G) optionally ethylenically unsaturated hydrocarbon resins, the macromolecules of which contain units selected from the group consisting of cyclopentadiene, dicyclopentadiene, cumarone, indene and styrene,
- H) .alpha.,.beta.-ethylenically unsaturated aliphatic carboxylic acids having 3 to 22 carbon atoms or carboxylic acid anhydrides
- by reaction of the components in solution or in bulk at temperatures from 80.degree. to 300.degree. C., the entire mixture of all components being reacted together or individual components being initially introduced and the others being reacted by metering in, wherein,
- 1) natural resins or natural resinic acids from group A) are reacted at a temperature of between 90.degree. and 250.degree. C., with .alpha.,.beta.-ethylenically unsaturated carboxylic acids of 3 to 22 carbon atoms or their anhydrides from group H), the reaction product
- 2) is mixed with a condensation catalyst of group E) and the phenolic component from B) is added to the molten mixture at a temperature of between 100.degree. and 250.degree. C., the aldehyde component from group C) is then introduced at the same temperature and reacted with resol formation,
- 3) the polyol component from group D) is then added to the reaction product at a temperature of between 190.degree. and 280.degree. C., and optionally the fatty acid component from group F) and optionally the hydrocarbon resin component from group G) are admixed at one or more of the steps 3), 2) or 1), and
- 4) an inert organic solvent as entraining agent for the azeotropic distillation of water at the reaction temperature is added to the reaction mixture, at temperatures of between 200.degree. and 280.degree. C., the water of reaction formed is distilled continuously as an azeotrope and removed from the reaction mixture via a water separator, optionally circulating the entraining agent, the azeotropic distillation is continued until the formation of water of reaction has ended and the resin formed has an acid number of below 50 mg KOH/g of resin, the entraining agent is then removed by distillation, initially under normal pressure and at the end under vacuum at pressure of between 1000 and 0.1 mbar, and temperatures of up to 300.degree. C. and the reaction mixture is cooled to room temperature and the phenolic resin-modified natural resinic acid ester is obtained as solid resin, or
- 5) optionally, a small amount of a high-boiling mineral oil is dissolved in the resin melt free from entraining agent, before said melt has cooled, the solution is cooled to room temperature and the resin is obtained in solid, mineral oil-containing gel form.
- 2. An oil-soluble, phenolic resin-modified natural resinic acid ester, as claimed in claim 1, wherein resinic acid ester clear solutions prepared at 180.degree. C. in standardized mineral oil (boiling range 240.degree. to 270.degree. C., aniline point 72.degree. C.) show no turbidity or demixing after cooling to 23.degree. C. in the ratio range of 1 part by weight of resin to 3 to 10 parts by weight of mineral oil.
- 3. A printing ink for offset printing and letter press printing containing a resinic acid ester of claim 1 as a binder resin.
- 4. An oil-soluble, phenolic resin-modified natural resinic acid ester as claimed in claim 1, wherein 40% strength by weight solutions of the oil soluble, phenolic resin-modified natural resinic acid ester in standardized mineral oil (boiling range 240.degree. to 270.degree. C., aniline point 72.degree. C.) form viscoelastic gels which on measurement in an oscillation rotary viscometer at 23.degree. C. in the angular velocity range of .omega.=1 to 10 s.sup.-1 give tan .delta. values of <5.
- 5. An oil-soluble, phenolic resin-modified natural resinic acid ester as claimed in claim 1, wherein the molecular weight (weight-average M.sub.W) of the oil soluble, phenolic resin-modified natural resinic acid ester is in the range between 10,000 and 200,000.
- 6. The process for the preparation of oil-soluble, phenolic resin-modified natural resinic acid esters from natural resins, phenols, aldehydes, condensation catalyst, esterifying agents and modifiers as claimed in claim 1, wherein the reaction of the reactants is carried out as described in claim 1 and the process product is isolated, the combined use of process characteristics 2) and 4), the use of a magnesium compound as condensation catalyst and the continuous removal of the water of reaction during the condensation reaction by azeotropic distillation with co-use of an inert organic solvent at the reaction temperature as distillative entraining agent.
Priority Claims (1)
Number |
Date |
Country |
Kind |
41 36 316.7 |
Nov 1991 |
DEX |
|
PRIOR APPLICATION
This application is a continuation of U.S. patent application Ser. No. 970,264, filed Nov. 2, 1992, now abandoned.
Continuations (1)
|
Number |
Date |
Country |
Parent |
970264 |
Nov 1992 |
|