DK146888B - PROCEDURE FOR IMPROVING THE PIGMENT FEATURES OF A COPPER PHTHALOCYAN PIGMENT - Google Patents

Description

(19) DENMARK \ WJ

| p (12) PUBLICATION MANUAL od 146888 B

DIRECTORATE OF THE PATENT AND TRADEMARKET SYSTEM

(21) Patent Application No .: 1989/77 (51) Int.CI.3: C 09 B 67/20 (22) Filing Date: 05 May 1977 (41) Alm. available: 08 Nov 1977 (44) Submitted: 30 Jan 1984 (86) International Application No: - (30) Priority: 07 May 1976 GB18736 / 76 (71) Applicant: 'CIBA-GEIGY AG; 4002 Basef, CH.

(72) Inventor: lan Robert * Wheeler; GB, George Heddie 'Robertson; GB.

(74) Plenipotentiary: Dansk Patent Kontor ApS

(54) Method for improving the pigment properties of a copper phththa-locyanin pigment

The present invention relates to a method of improving the pigmentation properties of a copper phthalocyanine pigment by contacting the pigmented copper phthalocyanine pigment in a polar aliphatic solvent which is at least partially miscible with water and separating the solvent from the treated pigment. the pigment before contacting the solvent or during this contact sets 1-12 weight-Q

percent of a sulfonated copper phthalocyanine amine derivative, calculated on

Q

0 the copper phthalocyanine pigment.

British Patent No. 1,263,684 discloses a process for treating a pigment which comprises contacting a dry pigmentary metal phthalocyanine pigment with a polar aliphatic solvent which is at least partially May be miscible with water and separation of the solvent from the treated pigment by which a small amount of the metalphthalocyanine blue pigment is contacted prior to contacting the solvent during this contact or after it is separated from the solvent. a copper phthalocyanine derivative of formula (SOJRE1) / 27

CuPc N 1 (SO 3 + H2 + NRRL) x wherein CuPc means the copper phthalocyanine group either chlorinated or non-chlorinated, R a cyclic or acyclic alkyl group of 1 to 20 carbon atoms or an aryl group and R 2 hydrogen or a cyclic or acyclic alkyl group of 1 to 20 carbon atoms or an aryl group, the alkyl or aryl groups being either unsubstituted or substituted by hydroxyl, amino, alkylamino or amide substituents, and x and y each mean 1, 2 or 3 with the proviso that the sum of x and y are 2, 3 or 4.

The pigment thus treated shows improved clarity when taken in color.

Surprisingly, it has now been found that by adding another phthalocyanine derivative to a copper phthalocyanine pigment by a similar treatment method before or during contact with a polar aliphatic solvent, a pigment composition which gives these substantially better properties in gloss is obtained. color strength and flow properties in comparison to the pigment composition disclosed in British Patent Specification No. 1,263,684. This is illustrated in more detail below.

Accordingly, the process of the invention is peculiar in that the sulfonated redox phthalocyanine amine derivative has the formula I - +

Cu-Pc SO, -R · * (I)

\) X

Wherein Pc is a phthalocyanine group, R, R and R are each independently alkyl or alkenyl, R 3 is hydrogen, alkyl, alkenyl or aralkyl, wherein the total number of carbon atoms in the groups R-R can be 2 4 5 is 20-60 and at least one of the groups R, R, R and R has a chain length of at least 12 carbon atoms and x is a number of 1-4,

Compounds of formula I can be formed by reacting a copper phthalocyanine of the formula

Cu-Pc (SO3M) x (II) wherein Pc and x have the meanings given in formula I and M is hydrogen or an alkali metal, with a tertiary amine of the general formula R2 - N - R3 (III) 1 or a quaternary ammonium salt of formula R6 (+) R2 - N - R3 B (IV) b wherein R 2, R 3 and R 4 have the meanings given in formula I, R 1 is an alkyl, alkenyl or aralkyl group, and B wherein the total number of carbon atoms in the tertiary amine or cationic portion of the quaternary ammonium salt is from 20 to 60, and at least one of the groups R

If the dye of formula II is reacted with a tertiary amine of formula III, in formula I is hydrogen and if the dye of formula II is reacted with the quaternary ammonium salt of formula IV, then R3 in formula I cannot be hydrogen. Preferably, two of the groups R 2, R 2, R 2 and R 2 have a skeleton having at least 12 contiguous carbon atoms, and the total number of carbon atoms on the nitrogen atom is preferably from 25 to 45. The anions are preferably halide, acetate or hydroxide.

146888 4

The phthalocyanine dye of formula II can be prepared by any of the commonly used methods, e.g. by reacting the phthalocyanine with chlorosulfonic acid or fuming sulfuric acid at elevated temperature for several hours, after which the mixture is poured into an aqueous solution of sodium chloride before the product is recovered as a filter cake by filtration.

The copper phthalocyanine pigment can contain up to 50% by weight of chlorine. The preferred pigment is a copper phthalocyanine which may be in either α- or β-crystalline form or a mixture of these two.

The weight ratio of phthalocyanine pigment to phthalocyanine dye of formula II can be from 88:12 to 99: 1, but is preferably from 92: 8 to 96: 4.

While x may be from 1 to 4, compounds of formula I in which x is 1 to 2.5 are preferred.

Compounds of formulas III and IV may be based on specific alkyl or alkenylamines, but are more conveniently derived from mixtures of hydrocarbon groups from naturally occurring oils and fats such as tallow, corn oil, fish oil or whale oil.

Among such suitable tertiary amines are dimethyl tallow, dimethyl hydrogenated tallow, dimethyl soya, dimethyloctadecyl, dimethyl eicosanyl, dimethyldocosanyl, monomethyl diicosanyl, monomethyl di (dodecyl), monomethyl di (hydrogen) -, monomethyl-didecosanyl, tridodecyl and trioctadecylamines or mixtures thereof.

The quaternary ammonium salts are conveniently formed by such tertiary amines by reaction with methyl chloride or dimethyl sulfate to form the methyl quaternary ammonium salt or with benzyl chloride to form the benzyl quaternary ammonium salt.

The sulfonated copper phthalocyanine amine derivatives of formula I formed by combining compounds of formula II with a compound of formula III and / or IV may e.g. is prepared by reacting a phthalocyanine compound containing x sulfonic acid groups with a sufficient amount of one or more amines and / or quaternary ammonium salts to substantially neutralize the free sulfonic acid groups.

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The sulfonated copper phthalocyanine titin derivatives of formula I can be prepared in aqueous solution provided that the nitrogen compounds of formulas III and IV are water soluble or capable of forming a solution in aqueous mineral acids or aqueous organic acids. Alternatively, the derivative may be prepared in a suitable solvent and recovered by precipitation, e.g. with water or by removing the solvent by distillation, if desired, with the addition of water. Such a solvent preparation is particularly useful for compounds of formulas III and IV which do not readily form solutions in water or in aqueous acidic media. Suitable solvents include acetone, ethyl methyl ketone, ethanol and methanol, but 2-propanol is particularly preferred.

The polar aliphatic solvent with which the pigment is treated is one which is at least partially miscible with water. Suitable solvents are described in British Patent Specification No. 1,140,836 and include alkanols having 1 to 4 carbon atoms in the alkyl chain, e.g. methanol, ethanol, n-propanol, 2-propanol and n-butanol; alkyl monocarboxylates having from 1 to 4 carbon atoms in the alkyl chain, e.g. alkyl esters of alkanoic acids, especially ethyl acetate; dialkyl ketones having from 1 to 4 carbon atoms in each alkyl chain, e.g. acetone, methyl ethyl ketone or diethyl ketone; alkoxyalkanols having from 1 to 4 carbon atoms in each of the alkyl chains of the alkoxy and alkanol moieties, e.g.

2-methoxyethanol or 2-ethoxyethanol; or alkylene glycols having from 2 to 6 carbon atoms in the alkylene chain, e.g. ethylene glycol or diethylene glycol.

The solvent may, if desired, contain dissolved water in an amount which is insufficient to cause two-phase separation, and thus may e.g. for example, aqueous ethanol (e.g., industrial methylated spirits), an azeotropic mixture of ethanol and water, or an azeotropic mixture of 2-propanol and water, the alkanol being the main constituent in each case.

The pigment to be contacted with the dye / amine derivative can be added to the solvent as a powder or aqueous filter cake. The pigment may be in a completely pigmentary state or in a highly aggregated state formed by a dry milling process.

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Thus, the pigment may take the form of a mixture of phthalocyanine with a salt, in particular a mixture which results from the preparation of the dye in pigmentary form upon grinding with the salt; the mixture of the organic solvent and the pigment is then preferably treated by mixing it with a quantity of water sufficient to dissolve the salt present.

As noted in British Patent No. 1,140,836, such solvent mixtures lead to products of improved rheology, clarity and dispersibility. The present process provides improvements in properties beyond those obtained by such solvent treatment of the pigment alone. Therefore, the process of contacting the dye / amine derivative with the pigment can be combined with such a solvent treatment method. Such solvent treatments of the pigment can, as noted in British Patent Specification No. I4O.836, be carried out under numerous different conditions, the temperature and pressure at which the treatment is carried out, and the time during which the pigment and solvent are in contact, depending upon the nature of the pigment. the pigment and of the solvent to ensure the optimal improvement of the pigmentary properties.

Although it is preferred that the pigment be contacted with the solvent at a temperature in the range of from 10 ° C to the boiling point of the solvent at the pressure used, a temperature of from 50 ° C to the boiling point is particularly preferred if the treatment is carried out at atmospheric pressure. Although a pressure higher than atmospheric if desired can be used, e.g. if the solvent used is highly volatile at the selected treatment temperature, it is generally convenient to treat the pigment with the solvent at atmospheric or near atmospheric pressure.

The amount of the solvent by which the pigment is treated in this process relative to the pigment is preferably in the range of 0.5 to 20 parts by weight of solvent per liter. weight ratio of pigment, with a ratio of 1 to 15 and especially 5 to 10 parts by weight of solvent per liter. part by weight of pigment is particularly preferred. When the solvent to pigment ratio is above the preferred, no significant further improvement of the pigmentary properties of the treated pigment is achieved. When the ratio of solvent to pigment is below the preferred range, the strength and clarity of the treated pigment is inferior to that of the same pigment treated with a solvent amount within the preferred range.

Sulfonated copper phthalocyanine amine derivative may be added at any time during this treatment, but it is preferred that pigment and derivative be contacted for at least 10 minutes at the reflux temperature of the preferred solvent, i.e. 2-propanol or the azeotropic water / 2-propanol mixture. Although the sulfonated phthalocyanine amine derivative can be formed, as in the above case, and then contacted with the pigment, it is a further advantage of this process that the derivative can be formed in the selected solvent in the presence of the pigment. In such a process, separation of dye / amine composition is avoided. This is particularly advantageous when using the preferred dialkylamine derivatives which are essentially water insoluble but which readily react with sulfonated phthalocyanine dye in such solvents.

The pigment preparation can be isolated from the solvent by filtration, preferably after dilution with water. The more volatile solvents can be removed by direct distillation, but it is preferable to add water and to remove the solvent by distillation, after which the pigment is found dispersed in a substantially aqueous phase; isolation from the water is then done by conventional filtration and drying techniques. In all cases, the compositions are washed free of inorganic salts.

The pigment compositions prepared by the present process can be used for pigmentation of various media.

They can be used in decorative paints, in ink, nitrocellulose, alkyd M / F and acrylic M / F systems, but are especially useful in those media containing a large amount of hydrocarbon in the solvent.

Belgian Patent Specification No. $ 33 * 51 $ discloses a composition comprising: i) a finely divided solid having a mean grain size of less than 20 microns ii) a polymer or resin dispersing agent iii) a fluidizing agent which is an ammonium salt substituted by an acidic dye wherein 16 to 60 carbon atoms are contained in at least three chains attached to the nitrogen atom of the substituted ammonium ion; and iv) an organic liquid.

It has been found that phthalocyanine pigment compositions prepared by the process in which the pigment and dye derivative are contacted with a polar aliphatic solvent have better properties in strength and rheology when absorbed in color and paint media than the pigment preparations. , which is described in Belgian Patent Specification 333-513 and which has not been in contact with a polar aliphatic solvent.

It can be seen in the following examples that the sulfonated derivatives promote good fluidity and fluidity stability in systems that would otherwise be viscous and / or thixotropic and that they also accelerate the rate of dispersion.

Three samples are prepared: IRW A: Prepared according to Example 3.

IRW B: Prepared according to Example 1 of the specification of GB Patent No. 1,263,684.

IRW C: Prepared by treating pigmentary (3-copper phthalocyanine with sulfonated phthalocyanine dye alone, i.e. without using the amine used in the following Example 3. This pigment product is washed as little as possible to avoid significant loss of the water-soluble dye.

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Each of these pigment preparations is then formulated into a printing ink as follows:

To a pint ball mill the following steatite balls (10 mm) are added 400 parts phenolic lacquer * 96 parts toluene 80 parts pigment preparation 24 parts

The milling is carried out for 16 hours, after which phenol varnish * 72 parts toluene 28 parts are added to the 100 parts milling base with stirring.

The ink thus produced has a pigmentation of 6% and a pigment to binder ratio of 1: 5.

* The phenolic varnish consists of "Alsyno1 RL.30" 50 parts toluene 50 parts "Alsynol KEi.30" is a modified phenolic resin which is esterified with pentaerythritol.

With the printed inks, printing is done on both matte paper and glossy paper. The resulting prints show that the printing ink made with IRW A has a significantly better gloss and color strength than the other prints.

Furthermore, the pigment preparation IRW A has substantially better flow properties than the pigment preparation IRW B, as shown in the table below.

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Table.

Yield in% from ball mill Grinding Mill

For Beginning After continued fineness viscosity dripping stir Zahn beaker No. 2 IRW A 91 (13 sec.) No further- 8: 7 1/2: 7 10 sec.

re outflow IRW B 20 (23 sec) 88 (46 sec) 8: 7: 7 29 sec.

The process according to the invention is illustrated by the following examples, in which parts and percentages are parts by weight and percentages, unless otherwise stated.

Preparation Examples.

Example 1.

175 parts of raw copper phthalocyanine were ground with 23 parts of inorganic salts, 1.6 parts of diethylaniline and 0.8 parts of glycerol monooleate until the phthalocyanine was in pigmentary form. 103 parts of this mixture, corresponding to 90 parts of copper phthalocyanine, was added to 600 parts of 2-propanol and heated under reflux and thorough stirring for 5 1/2 hours. 4 parts of the compound of formula CuPc (SOgH) (v), wherein x is 2, in filter cake form were added and reflux continued. After 15 minutes, 6 parts of an amine (Kemamine T.) were added.

9701, Humko Chemical Products) of Formula III wherein is a methyl-2 3 group and R and R are hydrogenated tallow groups as a solution in hot 2-propanol. After a further 15 minutes, 600 parts of water were added and the 2-propanol was removed by distillation. Stirring was stopped and the pigment preparation filtered from the clear liquid, washed salt-free to neutral pH and dried at 50-60 ° C. The yield was 9R, 1 parts.

11 148888

Example 2.

Example 1 was repeated using 3.4 parts of the compound of formula CuPc (SO, H) (V) wherein x is 2.4 and 5.6 parts of the

J X

hydrogenated tallow amine

Example 3

A) 20 parts of the compound of formula CuPc (SO3H) x (V), wherein x is 2, in filter cake form was stirred in 200 parts of 2-propanol and the temperature was raised to reflux. 29.2 parts of the amine of formula R2-N-R3 (III) R4 4 2 3 wherein R is a methyl group and R and R are hydrated tallow groups were dissolved in 200 parts of hot 2-propanol and added over 5 minutes . After another 30 minutes under reflux, 400 parts of water was added over 60 minutes and the 2-propanol was simultaneously distilled off at the same rate. Stirring was stopped and the bluish-green product of the reaction was isolated by filtration from the clear liquid, washed with warm water and dried at 60 ° C to yield 48.1 parts.

B) 175 parts of raw copper phthalocyanine were ground by the procedure of Example 1. 103 parts of this mixture, corresponding to 90 parts of copper phthalocyanine, was added to 600 parts of 2-propanol and heated under reflux conditions for 5 1/2 hours with thorough stirring.10 parts of the product from part A of this example was added as a solution in hot 2-propanol and the reflux was continued for 30 minutes. 600 parts of water were added and the 2-propanol was removed by distillation, after which the stirring was stopped.

The pigment preparation was filtered from the clear liquid, washed salt-free to neutral pH and dried at 50-60 ° C. The yield was 99.3 parts.

Example 4

Example 3B was repeated using 108.6 parts of the ground mixture, corresponding to 95 parts of copper phthalocyanine, together with 5 parts of the product of Example 3A.

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Example 5

A) 90 parts of a copper phthalocyanine, substantially in α form containing 1.8% by weight peripherally bound chlorine, was added to 500 parts of 2-propanol as a 30% aqueous filter cake and heated to reflux with stirring. 4.8 parts of the compound of formula CuPc (SO 2 H) (V), wherein x is 2, in filter cake form, were added and the reflux continued for 15 minutes. 5.1 parts of technical di (dodecyl) methylamine were then added as a solution in 2-propanol.

After 15 minutes, 500 parts of water were added and the 2-propanol removed by distillation. Stirring was stopped and the pigment preparation filtered from the clear liquid, washed salt-free to neutral pH with warm water and dried at 50-60 ° C. The yield was 99.1 parts.

Example 6

A) A copper phthalocyanine derivative was prepared by the process of Example 3A using 21.7 parts of the amine of formula R2-N-R3 (III) R4 L2 3 wherein R * is a methyl group and R and R are dodecyl groups.

B) The procedure of Example 5 was repeated with the addition of 10 parts of the product from Part A of this example instead of the separate additions of dye and amine.

Example 7, A) A copper phthalocyanine derivative was prepared by the method of Example 3A using 32.6 parts of the amine of formula R2-N-R3 (III) i4 2 3 wherein the groups R and R are each eicosanyl or docosanyl groups and 4 R is a methyl group.

B) 150 parts of a pigmentary phthalocyanine green pigment powder with a chlorine content of $ 47.1 was added with effective stirring to SOO parts of acetone and the temperature was raised to reflux. After 10 minutes, 15 parts of the product of part A in this example were added as a slurry in acetone, and the reflux was continued for an additional 15 minutes, after which 800 parts of water were added and the acetone was removed by distillation. A mixture of 15 parts of concentrated hydrochloric acid and 15 parts of water was then added evenly over 2 minutes. After 30 minutes, stirring was stopped and the product isolated by filtration from the clear liquid, washed with warm water and dried at 50-60 ° C. The yield was 163.2 parts.

Example 8.

95.2 parts of the α-form of the copper phthalocyanine in Example 5 was added to 900 parts of ethyl acetate as an aqueous filter cake and heated to reflux with stirring. After 30 minutes, 7.5 parts of the product of Example 3A were added and stirring at reflux was continued. A further 15 minutes later, 1000 parts of water were added and the ethyl acetate was removed by distillation. The mixture was acidified with 15 parts of 25 $ aqueous hydrochloric acid and stirred for 15 minutes. Stirring was then stopped and the pigment preparation was filtered from the clear liquid, washed to neutral pH with warm water and dried at 50-60 ° C. The yield was 98 parts.

Example 9

The procedure of Example 8 was repeated using 91.5 parts of the α-form of copper phthalocyanine, 8.5 parts of the product of Example 3A and with methanol as solvent. 98 parts of pigment preparation were obtained.

Example 10.

The procedure of Example 8 was repeated using 90.5 parts of the α-form of copper phthalocyanine, 9.5 parts of the product of Example 3A and with ethanol as the solvent. The resulting pigment composition was obtained in 99 parts yield.

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Example 11.

89 parts of ground copper phthalocyanine were stirred in 500 parts of n-butanol. The temperature was raised to reflux and kept there for 5 hours.

Eleven parts of the product of Example 3 A were added and the reflux continued for 15 minutes. 1000 parts of water at 55 ° C were poured in and the n-butanol removed by distillation. The mixture was acidified with 15 parts of 2% Ts aqueous hydrochloric acid. 15 minutes later, stirring was stopped and the pigment preparation filtered from the clear liquid, washed to neutral pH with warm water and dried at 50-60 ° C. The yield was 9 $ parts.

Example 12.

The procedure of Example 11 was repeated using 87.5 parts of ground copper phthalocyanine, 12.5 parts of the product of Example 3A and with ethyl methyl ketone as the solvent. The pigment composition was obtained in 97 parts yield.

Example 13

A) 59 parts of the amine of formula R2-N-R3 (III) i4 3 4 2 wherein R and R are methyl groups and R is a soy oil group commercially available as "Kemamine T. 9972.D", (Humko Chemical Products) was added to 1800 parts of boiling water containing 13 parts of glacial vinegar and stirred until a solution was obtained. The solution was allowed to cool and diluted to 2000 parts with water.

60 parts of the compound of formula CuPc (SO-H) (V) wherein x = 2, i

J X

form of an aqueous filter cake containing inorganic salts was dissolved in 4000 parts of water with stirring. The pH was adjusted to 5.0 with aqueous sodium hydroxide solution and 1650 parts of the above amine acetate solution was added evenly over 30 minutes with stirring. The mixture was stirred for an additional hour and then filtered, washed free of inorganic residue with hot water and recovered as a filter cake.

B) The procedure of Example 11 was repeated using 86.5 parts of ground copper phthalocyanine in the form of an aqueous filter cake, 13.5 parts of the product of part A of this example, also in filter cake form, and with 2-propanol as solvent. . The pigment composition, which had properties similar to the pigment composition of Example 11, was recovered in a yield of 97 parts.

Example 14

Example 1 was repeated except that the 6 parts of the amine used in that example were replaced by 8.6 parts of an amine of formula r2-n-r3 (III) Å4 2 3 4 wherein R, R and R is hydrogenated tallow groups ("Adogen 340" from Ashland Chemicals).

Example 15

Example 1 was repeated except that the 6 parts of the amine used in that example were replaced by 4.0 parts of an amine of formula r2-n-r3 (III) wherein R, R and R is isoctyl groups ("Adogen 381" from Ashland Chemicals).

Example 16.

A) The procedure of Example 1 was repeated except that the 6 parts of amine were replaced by 6.6 parts of an ammonium salt of formula r6 2 in 3 (_) R -N-R B '1 (IV)> 4

R

2 3 4 6 with R = RJ = methyl and R and R ° = hydrogenated tallow and B = Cl. ("Kemamine Q. 9702.C").

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Example 17 ·

The procedure of Example 16A was repeated except that the 6.5 parts of ammonium salt were replaced by 4.0 parts of an ammonium salt with R 2 = R 2 = methyl, R 2 = dodecyl and R 4 = benzyl ("Kemamine BQ .6502.C ").

Example 18.

2143 parts of crude copper phthalocyanine with a slight chlorination rate of 1.8% by weight were milled for approx. 14 hours with 6857 parts of inorganic salts. 4200 parts of this mixture, corresponding to 1000 parts of pigment, were stirred in 1900 parts of 2-propanol-water azeotrope containing 25 parts of the copper phthalocyanine derivative of Example 6 A. The mixture was heated at reflux for 2 hours with stirring. Twenty-five parts of diethylaniline was added and heated under reflux and stirring for 30 minutes.

With continued stirring, 2500 parts of water were added in portions of 500 parts, while 2-propanol-water azeotrope was removed by distillation to a steam temperature of 84 ° C. The mixture was acidified by adding 800 parts of 1: 1 concentrated hydrochloric acid water over 10 minutes and then stirred for one hour, filtered warm, washed salt-free to neutral pH with hot water and dried at 60 ° C.

Example 19.

A pigmentary α-form of copper phthalocyanine prepared by forming, under acid addition, a paste of crude copper phthalocyanine was treated with the product of Example 6A in 2-propanol-water azeotrope and then recovered from water by the method of the previous example.

application examples

Example 20

An ink of 6% pigmentation and a pigment binder ratio of 1: 5 was made by milling in a ball mill of the pigment preparation of Example 1 in a phenolic resin lacquer with toluene as the solvent according to the procedure of Example 10 in British Patent Application No. 37,106 / 75 . Compared to a similar ink made of untreated β-copper phthalocyanine, the ink produced from the product of Example 1 had a more fluid flowing base and was 15¾ stronger, cleaner and clearer.

Example 21.

A printing ink prepared from the pigment composition of Example 2 using the method of Example 20 was about 10% stronger than the corresponding ink produced from untreated β-copper phthalocyanine and had a more fluid flow grinding base.

Example 22.

A printing ink made from the product of Part B of Example 3 by the method of Example 20 had similar properties to the ink derived from the product of Example 1.

Example 23

The pigment preparation obtained according to Example 4, when taken up in the ink medium of Example 20, was 10-15% stronger than the corresponding ink derived from untreated β-copper phthalocyanine.

Example 24.

The pigment composition of Example 5 was taken up in a glycerol coconut oil alkyd resin in xylene / n-butanol as solvent by ball milling and then reduced to 6o pigmentation and a 1: 6.6 pigment binder ratio with an unmodified isobutylated melamine / formaldehyde. (M / F) -harpiksopløsning. The original milling base dispersion from the mill was light-flowing, in contrast to a similar dispersion made of a-copper phthalocyanine pigment which was not treated with dye and amine, which dispersion was thixotropic and could only be poured after stirring. Blue-tinted alkyd M / F paints were prepared from the reduced dispersions by mixing with white alkyd M / F paints and oven drying. The paint which was derived from the pigment from this example was approx. 10-15% stronger than the paint derived from a pigment not treated in this way.

If this pigment composition was dispersed in a long-chain soybean oil paint by Red DevilM technique and then reduced in a white-based paint in a 1:25 reduction, i.e. ratio of phthalocyanine pigment preparation to titanium dioxide, this product was 20% stronger than the untreated α-copper phthalocyanine, which was dispersed and evaluated by an identical technique. The initial dispersion of the treated pigment in the alkyd medium had better flow properties than the dispersion of the untreated pigments.

Example 25

A paint made with the pigment composition of Example 6 using the method of Example 24 had application properties similar to the properties of the paint derived from the pigment composition of Example 5.

Example 26

The pigment composition of Example 7 was taken up in a nitrocellulose varnish by ball milling and then reduced to 11.7% pigmentation at a 1: 1.38 pigment binder ratio by adding a mixture of nitrocellulose and maleic acid condensate lacquers. The resulting dispersion had ash color properties but a distinct superior fluidity of the grinding base as compared to a similar dispersion made from untreated phthalocyanine green.

Example 27

The pigment composition of Example 8 was taken up in an alkyd M / F paint medium by the method of Example 24. The grinding base was very light-flowing and the corresponding blue-tinted paint was 15-20% stronger and cleaner and slightly redder than the paint derived. of the α-form of the copper phthalocyanine starting material.

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Example 28.

The alkyd M / F paint produced by the pigment composition of Example 9 was similar to that of Example 27 in that it was 10-15% stronger, cleaner and slightly redder than the corresponding paint made from the α-form of the copper phthalocyanine starting material.

Example 29.

The pigment composition of Example 10 was also taken up in a long-chain soybean oil-pentaalkyd-based decorative paint medium by milling in a ball mill. A 1:25 reduction made by mixing the grinding base with white decorative alkyd paint was approx. 20% stronger than the corresponding reduction made from the untreated α-form of the copper phthalocyanine starting material and additionally had a significantly improved flocculation resistance.

The milling base containing the pigment preparation from this example was also much more fluid than the milling base which was derived from the untreated α-copper phthalocyanine starting material.

Example 30.

The ink produced from the product of Example 11 by the method of Example 20 was 15-20% stronger and slightly greener than the corresponding ink produced from the ground copper phthalocyanine starting material, and was further derived from a significantly more fluid liquid formalin base.

Example 31.

The printing ink produced from the pigment composition of Example 12 by the method of Example 20 was similar to that of Example 30 in that it was 15% stronger than the corresponding ink produced from the ground copper phthalocyanine starting material.

Examples 32-34.

Inks made from the pigment compositions of Examples 14-16 at

Claims (2)

20 146888 by the method of Example 20 was similar to those obtained with the product of Example 1. Example 35. The ink produced from the pigment composition of Example 17 by the method of Example 20 was similar to that produced by the product of Example 16A. Example 36. The product of Example 18 was taken up in a decorative alkyd paint medium, 15% stronger and clearer than a pigment prepared in a similar manner, but from which the dye amine derivative was omitted. Example 37. The product of Example 19 was taken up in a hydroxy-acrylic resin in 4: 1-xylene-n-butanol solvent by ball milling and then reduced to 6% pigmentation and 1: 5 pigment-binder ratio with an unmodified isobutylated melamine. formaldehyde resin in n-butanol. The resulting dispersion was significantly more fluid than a similar dispersion made from the α-form of the copper phthalocyanine starting material. Blue-tinted acrylic paints were made from these dispersions by mixing with white acrylic paint and oven drying. The paint containing the dye-treated pigment was 15% stronger, more red and clearer than the paint derived from the untreated α-form of the copper phthalocyanine starting material. Claims. A process for improving the pigment properties of a copper phthalocyanine pigment, by contacting the pigmented copper phthalocyanine pigment with a polar aliphatic solvent which is at least partially miscible with water, and separating the solvent from the treated pigment before contacting the solvent or below