WO1999023172A1

WO1999023172A1 - Thermal storage stabilized pigment compositions comprising disproportionated and fumarated or maleinated rosin

Info

Publication number: WO1999023172A1
Application number: PCT/US1997/019805
Authority: WO
Inventors: Arne Vinther; Steffen C. Olsen; Knud R. BJØRNSON
Original assignee: Sun Chemical Corp
Current assignee: Sun Chemical Corp
Priority date: 1997-10-30
Filing date: 1997-10-30
Publication date: 1999-05-14
Anticipated expiration: 2000-04-30

Abstract

A pigment composition comprising one or more organic pigments and a rosin derivative made of a partially maleinated/fumarated and disproportionated rosin, wherein the pigment composition has improved thermal storage stability.

Description

THERMAL STORAGE STABILIZED PIGMENT COMPOSITIONS COMPRISING DISPROPORTIONATED AND FUMARATED OR MALEINATED

ROSIN

Field of the Invention

The present invention relates to pigment compositions comprising disproportionated and fumarated or aleinated rosin, and which have improved thermal storage stability. The present invention also relates to the preparation and use of such pigment compositions, as well as to pigment pastes comprising such pigment compositions.

Background of the Invention Many solid materials are unstable under certain conditions and may slowly decompose or oxidize. This can result in liberation of heat which, in the case of materials having good insulating character and held in bulk, may lead to significant temperature rise and in extreme cases spontaneous combustion. This occurs when the rate of heat production exceeds the rate of heat loss and the self-heating (i.e. self-initiation or auto- oxidation) temperature is reached. Such behavior offers potentially dangerous situations during transportation or storage of these solid materials and special packaging precautions are required to be taken under specific legislation directed to substances liable to spontaneous combustion which specifies transportation criteria in terms of packaging volume and materials of fabrication of the packaging. The technical requirement of pigments used in modern printing inks, e.g. those used in lithographic processes, has led to development of rosinated pigments. The incorporation of natural rosin and rosin derivatives into pigments is desirable in order to optimize and balance the properties of the pigment such as color strength, ease of dispersion and transparency. In such pigments, the mean particle size of the color component needs to be very small, and as a consequence the rosin, which is believed to coat the individual color particles, has a high surface area which, in the case of dry pigments, is exposed to air. These products therefore are prone to self-heating even at temperatures used in manufacture and storage. A result of this combination of instability in air and high surface area is that the products have a tendency to decompose slowly on storage which leads to self-heating and eventually under special conditions may result in ignition.

European Patent 0671443 Al describes one method for reducing the tendency of a rosinated pigment product to self-heat, wherein a multi-valent metal or metalloid is used.

Other methods to reduce the tendency to self-heating includes the use of hydrogenated or disproportionated gum rosin. However, there is a need for further and less expensive pigment compositions having a reduced tendency to self-heat.

Summary of the Invention The invention relates to pigment compositions having a reduced tendency to self-heat, and which furthermore have excellent physical and colouristic properties comprising an organic pigment and a rosin derivative, wherein the rosin derivative has a partially maleinated or fumarated and disproportionated rosin. Brief Description of Drawings

The invention will become apparent in the following description taken in connection with the drawings, in which:

Figure 1 illustrates the results of a self-heating test for Pigment Yellow 13 without rosin as prepared in Example 3.

Figure 2 illustrates the results of a self-heating test for Pigment Yellow 13 with Resin 731D^® as prepared in Example 4.

Figure 3 illustrates the results of a self-heating test for Pigment Yellow 13 with Recol^® as prepared in Example 5. Figure 4 illustrates the results of a self-heating test for Pigment Yellow 13 with Recol^® as prepared in Example 1.

Figure 5 illustrates the results of a self-heating test for Pigment Red 57:1 with Recol^® as prepared in Example 8.

Figure 6 illustrates the results of a self-heating test for Pigment Blue 15:3 with Recol^® as prepared in Example 6.

Detailed Description of the Invention

Fumarated or maleinated rosins give very good colouristic properties when used in pigments. It is believed that fully maleinated/fumarated rosins should be substantially unable to self-heat. However, the softening point of such rosin qualities would be to high for practical applications in the pigment industry. It has now been found that if the rosin derivative is only partially maleinated/fumarated and at the same time is disproportionated, it is possible to obtain products that give good colouristic properties and have a greatly reduced tendency to self-heat.

In the present context the term, "partially maleinated/fumarated", used in conjunction with rosin derivative, means a rosin derivative modified so that 1-25 wt.%, and more preferably 2-20 wt.%, and even more preferably 3-15 wt.%, of the rosin derivative comprises maleic acid, maleic anhydride, and/or fumaric acid moieties . Maleination and fumaration of natural or modified rosin is performed by methods known to persons of ordinary skill in the art, e.g. by Diels-Alder reactions between the natural or modified rosin (the levopimaric acid constituent of natural or modified rosin, or isomeric constituents which can isomerise to levopimaric acid at elevated temperatures, e.g. abietic acid, palustric acid and neoabietic acid and maleic acid, maleic anhydride, and/or fumaric acid. It should be understood that a mixture of maleic acid, maleic anhydride and fumaric acid can be used to obtain a mixed product. In the present context "disproportionated", used in conjunction with rosin, means that at least some of the rosin constituents (which typically comprise two (conjugated) double bonds; e.g. abietic acid, levopimaric acid, neoabietic acid and palastric acid) have been treated under catalytic conditions to yield rosin constituents having no double bonds or only single non- conjugated double bonds and rosin constituents having an aromatic ring. Disproportionation may be obtained by heating a natural or modified rosin under catalytic conditions known to a person of ordinary skill in the art.

It is preferred that the degree of disproportionation is so that the content of abietic acid-type constituents a range of from 0-50 wt.%, preferably 0-40 wt.%, more preferably 0-30 wt.% and most preferably 0-20 wt.%. The term "abietic acid-type preferably 0-20 wt.%. The term "abietic acid-type constituents" refers to constituents having two conjugated or non-conjugated double bonds. Examples of abietic acid-type constituents are albietic acid, levopimaric acid, neoabietic acid, palustric acid, pimaric acid, iso-pimaric acid, sandaracopimaric acid and elliotinoic acid.

In the present context, "partially maleinated/fumarated and disproportionated" means that the rosin in question comprises 1-25 wt.%, more preferably 2-20 wt.% of constituents carrying maleic acid, maleic anhydride, and/or fumaric acid moieties, while at the same time comprising 0-50 wt.% of abietic acid-type constituents. In order to obtain the excellent properties, the pigment compositions of the present invention preferably contain a rosin derivative comprising at least 2 wt.%, and preferably at least 3 wt.%, rosin constituents which include an anhydride moiety. Such rosin constituents may arise from maleination, e.g. formation of the maleic anhydride modified rosin constituent.

The rosin quality, i.e. the partially maleinated/fumarated and disproportionated rosin, may be obtained from a natural rosin or modified rosin. Thus, the rosin derivatives included in the pigment compositions of the present invention comprise natural or modified rosins which have been partially maleinated or fumarated and subsequently disproportionated. Alternatively, the natural or modified rosins may be disproportionated prior to maleination or fumaration.

Preferably maleination/fumaration is performed prior to disproportionation.

Many natural rosin qualities are commercially available. Examples hereof are wood rosin, gum rosin and tall oil rosin. Furthermore, a wide range of modified rosin qualities are also available, e.g. natural rosins which have been chemically modified by for example hydrogenation, disproportionation, polymerisation, maleination, fumaration and esterification.

In the present context, "rosin constituent" refers to all of the individual chemical compounds (having the abietic acid skeleton or modifications thereof) found in natural and modified rosin qualities. Examples of such rosin constituents are abietic acid, levopimaric acid, neoabietic acid, palustric acid, pimaric acid, isopimaric acid, dihydroabietic acid, tetrahydroabietic acid, sandaracopimaric acid, dehydroabietic acid and elliotinoic acid.

The rosin derivative used in the pigment compositions of the present invention comprises as an important feature the maleinated/fumarated rosin and disproportionated rosin constituents as defined above.

It should be understood that even if the amount of rosin derivative is supplemented with an amount of natural or modified rosins not having the special features of the rosin derivative defined above, the amount of rosin constituents carrying maleic acid, maleic anhydride, and/or fumaric acid moieties, and the amount of abietic acid-type constituents, should, relative to the total content of rosin derivative and natural or modified rosin, still be within the defined limits. Furthermore, natural or modified rosins supplements should be construed as being included in the meaning of rosin derivatives .

The rosin derivatives should preferably have a softening point ranging from 80-120°C and more preferably from 80-100°C.

The rosinated pigment composition of the present invention may comprise further constituents such as one or more additives which may be supplied to the pigment, pigment dispersion or product before or after drying. Examples of such additives include surfactants, such as long chain fatty acids and derivatives thereof, alcohols, and amines. Further additives which may be added the pigment include water soluble dyestuffs.

The surfactants used may be of the anionic type, such as fatty acids taurides, fatty acid N-methyltaurides, fatty acid isothionates, alkylbenzenesulphonates, alkylnaphthalene-sulphoneates, alkylphenol, polyglycol ether sulphates and fatty alcohol polyglycol ether sulphates; fatty acids, such as palmitic, stearic and oleic acids; soaps such as alkali metal salts of fatty acids and naphthenic acids; cationic surfactants including quaternary ammonium salts, and N-oxides of tertiary amines or salts thereof; and non- ionic surfactants including fatty alcohol polyglycol ethers (ethoxylated fatty alcohols) , fatty acid polyglycol ester, alkylphenol polyglycol ethers and dialkyl polyglycol ethers.

The alcohols used may be aliphatic alcohols, long chain primary alcohols such as stearly, oleyl or cetyl alcohols or mixtures of alcohols. The amines used may be aliphatic amines which may be added include long chain primary amines e.g. stearylamine; amine derivatives of wood rosin; N-long chain alkylalkylene diamines, polyamines, betaamines, polyamide/polyamine derivatives of ethoxylated fatty amines and diamines, and derivatives of these compounds. In the present invention the pigment compositions comprise 55-98 wt.%, and more preferably 60-98 wt.%, of one or more organic pigments, 2-45 wt.% and more preferably 2-40 wt.% of a rosin derivative comprising a partially maleinated/fumarated and disproportionated rosin and optionally one or more additives.

In the cases where one or more additives are desirable or necessary, such additives typically constitute 1-20 wt.%, and more preferably 1-15 wt.%, of the pigment composition. It is believed that the rosin derivative should constitute at least 50 wt.% of the total amount of rosin derivative and optional additives. According to the invention, the organic pigment may, for example, be selected from phthalocyanines, perinones, quinacridones, indanthrones, flavanthrones, pyranthrones, perylenes, thioindigos, dioxazines, isoindolines, diketopyrrolopyrroles, basic dye complexes, metal complexes, monoazo pigments, azo metal salts, and disazo pigments. The invention is particularly useful where the organic pigment is a disazo pigment, e.g. a diarylide pigment of the formula:

wherein Ar¹ and Ar² are phenyl groups which independently may be optionally substituted by one, two or three substituents selected from halogen (preferably chlorine) , methyl, and methoxy. Preferably Ar¹ and Ar² are independently selected from phenyl, 2, 4-dimethylphenyl, 2-methylphenyl, 4-chloro-2, 5-dimethylphenyl . Such pigments include CI Pigment Yellow 12 (Ar¹⁼Ar²=phenyl) , Pigment Yellow 13 (Ar¹⁼phenyl, Ar²=2, 4-diphenyl) , Pigment Yellow 14 (Ar¹=Ar²=methylphenyl) , Pigment Yellow 174

(Ar¹⁼2-methylphenyl, Ar²=2, 4-dimethylphenyL, ) , Pigment Yellow 176 (Ar¹=4-chloro-2, 5dimethylphenyl, Ar²=2, 4- dimethylphenyl) and Pigment Yellow 188 (A^phenyl, Ar²=2, -dimethylphenyl) . The invention is also particularly useful where the organic pigment is an azo metal salt of the formula:

wherein M²⁺ is a metal ion, preferably calcium, barium or strontium, and R¹, R², R³, and R⁴ are independently selected from hydrogen, halogen (preferably chlorine), and methyl. Preferably only one or two of R¹, R², R³, and R⁴ are different from hydrogen. Such pigments include CI Pigment Red 57:1 (Me²⁺=Ca²⁺, R⁴=Me) , Pigment Red 48:2 (Me²⁺=Ca²⁺ R=Me, R⁵=C1 and Pigment Red 53:1 (Me²+=Ba²⁺, R=Cl,R⁵=Me) . Furthermore, the present invention is also believed to be particularly useful for phthalocyanine pigments, of the formula:

wherein Me is a metal such as copper, nickel, or cobalt, while preferred is copper. Such pigments include CI Pigment Blue 15 (Me=Cu) , which in the β-crystal form (Pigment Blue 15:3) is a preferred example.

The invention further provides a method for preparing a pigment composition having one or more organic pigments and rosin derivative wherein the method comprises contacting an aqueous dispersion of the organic organic pigments and rosin derivative wherein the method comprises contacting an aqueous dispersion of the organic pigment (s) with a solution or dispersion of rosin derivative and wherein the rosin derivatives comprise (s) a partially maleinated/fumarated and disproportionate rosin.

The organic pigments are typically synthesized as a dispersion in an aqueous medium. The rosin derivatives are preferably added to the aqueous dispersion in the form of a dispersion or solution, preferably in an alkaline solution as the corresponding basic salt, e.g. the alkali metal salt such as the sodium salt prepared from the rosin component (comprising a free carboxylic acid group) and sodium hydroxide For example, the solution or dispersion of the rosin derivatives is added to the dispersion of the organic pigment. It should be understood that the contacting process is equally applicable in the case where the dispersion of the organic pigment is added to the dispersion/solution of the rosin derivatives) . After contacting the two liquid systems, the resulting mixture (also a dispersion) is preferably kept at an elevated temperature, preferably in the range of 50-120°C, for up to 24 hours, and then acidified or laked, for example, with a calcium salt form to sparingly soluble calcium salt in order to precipitate the pigment composition.

The product of the present invention may be isolated by any conventional technique, e.g. using a filter press or band filter. The isolated pigment composition is optionally washed and dried, e.g. in an oven such as a conventional or microwave oven, or by a non-static technique, e.g. by spray drying or in a fluidised bed. Since the pigment compositions obtained by the present invention have a reduced tendency to self-heat, they can be dried at higher temperatures than are normally used for pigment drying. This also means that they can be dried faster which can lead to increased throughput in pigment manufacturing.

The reduction in the tendency of the pigment composition to self-heat, achieved by the present invention, is particular useful in surface coating compositions such as paints or printing inks or in high molecular weight materials that employ the pigment. The pigment compositions of the invention have a high degree of compatibility with conventional surface coatings, especially printing inks, resulting in improved ease of incorporation and dispersibility, color strength, transparency and gloss, relative to surface coating media produced using conventional means. Thus, the present invention is ideal for providing pigments for plastic or textile use.

The pigment compositions of the present invention are preferably in the form of a powder or a press cake.

In a preferred embodiment the pigment compositions, when tested in the self-heating test (10x10x10) at a temperature of at least 120°C, resulted in no self- heating. Preferably even testing at a temperature of 130°C or higher, or even at a temperature of 140°C or higher, in the self-heating test should result in no self-heating. The present invention provides for pigment compositions of:

Diarylide Pigments

60-95 wt.% of one or more diarylide pigments of formula I and 5-40 wt.% of a rosin derivative comprising a partially maleinated/fumarated and disproportionated rosin and optionally one or more additives;

Azo Metal Salt Pigments 80-90 wt.% of one or more azo metal salt pigments of formula II and 3-20 wt.% of a rosin derivative comprising a partially maleinated/fumarated and disproportionated rosin and optionally one or more additives;

Phthalocyanine Pigments 80-98 wt.% of one or more phthalocyanine pigments of formula III and 2-20 wt. % of rosin derivative comprising a partially maleinated/fumarated and disproportionated rosin and optionally one or more additives

In each case the pigment composition has been self heating tested at temperatures of at least 120°C and resulted in no self-heating.

Even though the pigment compositions according to the present invention are intended to solve the problem associated with the self-heating of dry pigment compositions, the excellent transparency properties of the pigment compositions make them equally applicable for other formulations. Thus, one particularly interesting use of the pigment compositions of the invention are in formulations obtained using the so-called "flush" technique. The underlying principle in the flush technique is that an organic pigment (here associated with rosin derivatives, and optionally with additives) which has a greater affinity for an oil phase than for an aqueous phase (e.g. the aqueous phase in which the organic pigment is synthesized) can be transferred from^' the aqueous phase into an appropriate oil phase, thereby forming a pigment paste comprising the pigment composition. The "dry flush" technique where granules or lumps of the dry pigment composition is used may also be applied. The use of the flushing technique avoids certain problems, e.g. prolonged drying times, grinding treatment and dusting, associated with conventional pigment powder production methods . The present invention also relates to a pigment paste comprising the pigment compositions herein together with one or more components such as components selected from alkyds, varnished, and mineral oils. Other useful components are known to persons of ordinary skill in the art and are described in detail by Herbst, W. and Hunger, K., Industrielle Organische Pigmente, VCH; Gomm, A.S. et al., J. Oil Color Chem. Assoc, 51, 5 (1968), pp. 143- 460 and in European Patent 0770648 A2. The pigment pastes according to the present invention are especially useful for the preparation of an ink. The following examples illustrate specific aspects of the present invention and are not intended to limit the scope thereof in any respect and should not be so construed.

Assessment of the thermal storage stability was carried out by comparing the level of the exotherm of the product of the invention with the level of the exotherms from products containing either fumarated rosin (Recol^® F-10, available from Granel Derivados, Spain) ; disproportionate rosin (Resin 731D^®, available from Hercules); or fumarated and disproportionated rosin (Recol^® F-3, available from Granel Derivados, Spain) .

Example 1 Preparation of Pigment Yellow 13 with Recol^® F-3

Solution A: A slurry of 25 g 3, 3 ' -dichlorobenzidine bishydrochloride in 50 mL 30 vol.% hydrochloric acid and 100 mL of water was cooled to 0 °C and a solution of 14.2 g sodium nitrite in 25 mL of water was added. The surplus of sodium nitrite was removed with the help of sulfamic acid.

Solution B: 45.3 g acetoacet-m-xylidide dissolved in 30 mL 28 vol.% sodium hydroxide and 200 mL water was acidified by addition of a solution of 8.0 mL acetic acid and 15.5 mL 30% hydrochloric acid in 80 mL of water during 15 minutes. The pH was adjusted to 8.5-9.0 and the temperature to 20 °C. 0.9 g 2, 2 ' -benzidinedisulfonic acid was diazotised as above under A using sodium nitrite and was added to Solution B.

To the resulting solution was added Solution A during 4 hours while maintaining the pH at 5.2 and the temperature at 5° C. After adding an aqueous solution of 30.2 g Recol^® F-3 rosin in 28 vol.% sodium hydroxide, the pigment slurry was heated to 95°C and stirred for 3 hours where after the pigment slurry was acidified to pH equal to 1, filtered and washed.

Example 2 Preparation of Pigment Yellow 13 and 174 with Recol^® F-3

The pigment press cake was made according to Example 1, except that instead of the 45.3 g acetoacet-m-xylidide used in Solution B, a mixture of 32 g acetoacet-m- xylidide and 12.5 g acetoacet-o-toluidide was used.

Example 3

Preparation of Pigment Yellow 13 without rosin

The pigment press cake was made according to Example 1 with the exception that no rosin was used.

Example 4 Preparation of Pigment Yellow 13 with Resin 731D^®

The pigment press cake was made according to Example 1 with the exception that the rosin used was Resin 731D^®.

Example 5 Preparation of Pigment Yellow 13 with Recol^® F-10

The pigment press cake was made according to Example 1 with the exception that the rosin used was Recol^® F-10. Example 6 Preparation of Pigment Yellow 13 with Recol^® F-3 and Resin 731D^®

The pigment press cake was made according to Example

1 with the exception that the rosin used was a mixture of Recol^® F-3 and Resin 731D^® in a 1:1 ratio.

Example 7

Preparation of Pigment Yellow 13 and 174

The pigment press cake was made according to Example

2 with the exception that the rosin used was a mixture of Recol^® F-3 and Resin 731D^® in a 1:1 ratio.

Example 8 Preparation of Pigment Red 57 : 1 with Recol^® F-3

61 g 3-hydroxynaphthalene-2-carboxylic acid were dissolved in 127 mL 28 vol.% sodium hydroxide and 250 mL of water and added to a diazotised mixture of 58.3 g 2- amino-5-methylbenzenesulfonic acid and 0.6 g 2-aminonaphthalene-l-sulfonic acid. After 30 min. a solution of 25 g of Recol^® F-3 in 15 mL of 28% sodium hydroxide and 300 mL of water was added at 8-10°C. After 30 min. a solution of 75 g of calcium chloride in 250 L of water was added and hydrochloric acid was added until pH reach 8.5 where after the pigment suspension was warmed to a temperature of 60 °C and stirred for another 30 min. The pigment suspension was filtered and washed.

Example 9 Preparation of Pigment Blue 15:3 with Recol^® F-3 A dough mixer was preheated to 80°C. 2800 g sodium chloride, 800 g of Blue Crude No 4s, 120 g of Recol^® F-3, 28 mL of sodium hydroxide and 208 g of calcium chloride were added to the mixer. 2800 g of sodium chloride was added together with 320 mL of diethyleneglycol . The product was mixed for several hours at 80°C. After mixing, the product was transferred to a bucket and 40000 L of water was added. The temperature was set to 80°C and pH was adjusted to 1. After 2 hours the product was filtered, washed and dried.

The washed press cake made according to Examples 1-9 may either be used as such (e.g. as in Example 10) or may be dried prior to use (e.g. as in Example 11) .

Example 10

Preparation of pigment pastes from wet press cakes

Each of the water containing press cakes produced according to Examples 1-2 and 4-8 were transferred to the flush machine and alkyd, varnish and mineral oil were added. When the pigment had been flushed into the oil, the water was poured off first and secondly the remaining water was evaporated from the concentrated pigment paste. When compared to the inks made from Pigment Yellow 13, mixtures of 20 Pigment Yellow 13 and Pigment Yellow 174 and Pigment Red 57:1 containing Resin 731D^®, inks prepared with the flushed pigment pastes containing Recol^® F-3 had a much higher color strength measured colormetrically.

Example 11 Preparation of pigment pastes from dry press cakes

Each of the dried press cakes produced according to Examples 1-2 and 4-7 were transferred to the flush machine and alkyd and varnish was added, see Example 10. After the pigments were fully dispersed, the concentrated pigment pastes were transformed into an ink. When compared to the inks made from Pigment Yellow 13, mixtures of Pigment Yellow 13 and Pigment Yellow 174 and Pigment Red 57:1 containing Resin 731D^®, inks prepared with the flushed pigment pastes containing Recol^® F-3 had much higher color strength measured colormetrically.

Example 12 Determining tendency towards self-heating

The assessment of the thermal storage stability was carried out at an elevated temperature (e.g. at 120°C) which results in acceleration of the decomposition and greater ease of measurement. Decomposition at elevated temperature is indicative for the tendency for a pigment composition to self-heat at temperatures normally used for storage.

Fine mesh basket made of stainless steel in the shape of a cube of size 1000 mL was packed with dry milled product with gentle tapping. The basket was placed in the middle of another net of side lengths 15 cm and height 25 cm, to reduce cooling. A thermocouple was then placed in the middle of the pigment mass, and the temperature recorded by computer. The pigment composition sample (dried and pulverised) and nets were placed in a thermostatic air oven held at 120 °C and the temperature in the center of the pigment was recorded throughout the heating period. The heating period was not less than 24 hours, unless the temperature in the center of the pigment exceeded 200°C during this period. The results for pigment compositions tested in the self-heating test as described above (i.e. center temperature <y-axis> versus time <x-axis>) are shown in Figures 1-6. Example 13

Hydrolysis of the acid anhydride moiety of maleinated/fumarated rosin

64 g of a Recol^® F-3 rosin were mixed with 171 mL of 28% sodium hydroxide. The mixture was heated with steam, so that the rosin was dissolved to an emulsion. The emulsion was placed in an oven at 85°C for 24 hours.

A) Half of the emulsion was poured into 150 mL of water, then cooled to 20°C. An IR spectrum of the emulsion was recorded. The emulsion was then filtered and an IR spectrum of the remanence was recorded.

B) The other half of the emulsion was cooled to 20°C and 100 mL of 33% hydrochloric acid was poured into the emulsion under stirring. An IR spectrum of the emulsion was recorded. The emulsion was then filtered and an IR spectrum of the remanence was recorded.

Looking at the unfiltered emulsions from A and B, emulsion A showed that the anhydride was degraded to acid as there only was absorption at the COO^' region of the spectrum.

Looking at the filtered products, product A showed no anhydride absorption, but large absorption for COO^". The spectrum of product B showed traces of anhydride.

Example 14

Hydrolysis of the acid anhydride moiety of maleinated/fumarated rosin

As Example 9, modified to 36 mL of 28% sodium hydroxide and 200 mL of water.

The solution was cooled to 20°C and crystallized by adding hydrochloric acid until pH below 0. The crystals were broken into small pieces and washed with water, then dried in an oven at 95°C for 12 hours. The rosin mass was cooled to 20°C. An IR spectrum was recorded. Comparison of the IR spectra of the starting material Recol^® F-3 and the treated material showed no significant differences.

The present invention has been described in detail, including the preferred embodiments thereof. However, it will be appreciated that those skilled in the art, upon consideration of the present disclosure, may make modifications and/or improvements to this invention as set forth in the following claims.

Claims

What is claimed is:

1. A pigment composition comprising one or more organic pigments and a rosin derivative, wherein the rosin derivative is made of a partially maleinated/fumarated and disproportionated rosin.

2. The pigment composition of claim 1, wherein the rosin derivative comprises a natural or modified rosin which has been partially maleinated/fumarated and disproportionated.

3. The pigment composition of claim 2, wherein the rosin constituents of the rosin derivative make up 1-25 wt.% of the rosin constituent and are selected from maleic acid, maleic anhydride, and/or fumaric acid moieties .

4. The pigment composition of claim 1, wherein the degree of disproportionation of the rosin derivative is so that the content of abietic acid-type constituents ranges from 0-50 wt.%.

5. The pigment composition of claim 3, wherein the rosin derivative is made up of at least 2 wt.% of rosin constituents that include an anhydride moiety.

6. The pigment composition of claim 1, wherein the rosin derivative has a softening point ranging from 80-120°C.

7. The pigment composition of claim 1, further comprising one or more additives.

8. The pigment composition of claim 7, wherein the additives are selected from surfactants, aliphatic alcohols, and aliphatic amines.

9. The pigment composition of claim 1 comprising

55-98 wt.% of one or more organic pigments and 2-45 wt.% of a rosin derivative comprising a partially maleinated/fumarated and disproportionated rosin and optionally one or more additives.

10. A pigment composition of claim 9 comprising

1-20 wt.% additives.

11. The pigment composition of claim 1, wherein when subjected to self heating at a temperature of at least 120°C results in no self-heating.

12. The pigment composition of claim 1, wherein the organic pigment is selected from phthalocyanines, perinones, quinacridones, indanthrones, flavanthrones, pyranthrones, pervlenes, thinindigos, dioxazines, isoindolines,diketopyrrolopyrroles, basic dye complexes, metal complexes, monoazo pigments, azo metal salts, and disazo pigments.

13. The pigment composition of claim 12, wherein the organic pigment comprises a disazo pigment.

14. The pigment composition of claim 13 wherein the disazo pigment is a diarylide pigment of formula:

where Ar and Ar are phenyl group which may be optionally independently substituted by one, two or three substituents selected from halogen, methyl, and methoxy.

15. The pigment composition of claim 14, wherein the diarylide pigment is selected from CI Pigment Yellow 12, Pigment Yellow 13, Pigment Yellow 14, Pigment Yellow 174, Pigment Yellow 176, and Pigment Yellow 188.

16. The pigment composition of claim 14 comprising 60-95 wt.% diarylide pigments and 5-40 wt.% of a rosin derivative having a partially maleinated/fumarated and disproportionated rosin and optionally one or more additives, and wherein the pigment composition, when subjected to self heating at a temperature of at least 120°C, results in no self-heating.

17. The pigment composition of claim 12, wherein the pigment is an azo metal salt of the formula:

where M², is a metal ion selected from calcium, barium, and strontium, and R¹, R², R³ and R⁴ independently selected from hydrogen, halogen, and methyl.

18. The pigment composition of claim 17, wherein the azo metal salt pigment is selected from CI Pigment Red 57:1 and Pigment Red 48:2 and Pigment Red 53:1.

19. The pigment composition of claim 17 comprising 80-97 wt.% of one or more azo metal salt pigments and 3- 20 wt.% a rosin derivative having a partially maleinated/fumarated and disproportionated rosin and optionally one or more additives, and wherein the pigment composition, when subjected to self heating at a temperature of at least 120°C, results in no self- heating.

20. The pigment composition of claim 12, which is a phthalocyanine pigment of the formula:

wherein Me is a metal selected from copper, nickel, and cobalt.

21. The pigment composition of claim 20, wherein the pigment is Pigment Blue 15:3.

22. The pigment composition of claim 20 having 80-98 wt.% phthalocyanine pigments and 2-20 wt.%. of a rosin derivative having a partially maleinated/fumarated and disproportionated rosin and optionally one or more additives, and wherein the pigment composition, when subjected to self heating at a temperature of at least 120°C, results in no self-heating.

23. The pigment composition of claim 1 in the form of a powder.

24. The pigment composition of claim 1 in the form of a dry press cake.

25. The pigment composition of claim 1 in the form of a paste and having a component selected from alkyds, varnishes, and mineral oils.

26. A method of preparing a pigment composition having one or more organic pigments and a rosin derivative comprising: contacting an aqueous dispersion of organic pigment (s) with a solution or dispersion of rosin derivative (s) , wherein the rosin derivative (s) comprise (s) a partially maleinated/fumarated and disproportionated rosin.

27. The method of claim 26, wherein the solution or dispersion of the rosin derivative is an alkaline aqueous solution or dispersion.

28. The method of claim 26, wherein the organic pigment is as described in claim 12.

29. The use of the pigment composition in claim 1 for preparing a printing ink, paint, plastic, or textile.

30. The use of a pigment composition in claim 1 for preparing a printing ink.