CZ2000360A3 - Compounds controlling growth of pigment particles and/or crystalline phase rise, process of their preparation and their use - Google Patents

Abstract

The compound of formula I wherein M is a metal cation, the quaternary nitrogen or hydrogen; Y 1 is a sulfone group or a carboxyl group an acid or a salt thereof; Q 1 is a pigment group; X1 is an aromatic group, a cycloheteroaliphatic group containing at least one five or six membered ring or a heteroaromatic group containing at least one a six membered ring which is not a phthalimido group; m1 and n1 are independently of one another from 0 to 2.5; and o1 is 0.05 to 4 or a compound of formula II wherein Q 2 is 6,13-dihydroquinacridone a group of formula III wherein A and Dj are independently of one another substituents selected from the group consisting of hydrogen, a fluorine atom, a chlorine atom, an alkyl group containing 1 to 3 carbon atoms and alkoxy having 1 to 3 carbon atoms, M is a metal cation, a quaternary nitrogen cation or an atom hydrogen; Y 2 is a sulfonic or carboxylic acid or other salt; X 2 is an aromatic group, a cycloheteroaliphatic group containing at least one five or six membered ring or a heteroaromatic group containing at least one a five- or six-membered ring that is not phthalimido; m2 and n2 are independently 0 to 2.5; and o 1 is a number 0 to 4 and a method for preparing and using these compounds.

Description

Technical field

The present invention relates to novel compounds which can control and control the growth and / or formation of the crystal phase of pigment particles. It is particularly preferred that these compounds are present during pigment synthesis.

Prior art s.Lav techniques

Many patents disclose a process for the direct synthesis of pigments in a pigment form in order to avoid expensive and often environmentally unfavorable final processing of the pigment (for example, a method for reducing particle size and / or modifying the crystal form). For example, EP 643,110 and US 5,424,429 describe direct synthesis of a solid solution of quinacridone and 2,9-dichloroquinacridone in pigment form in the presence of phthalimidomethylquinacridone derivatives. EP 685,530 discloses a process for the direct synthesis of pigmentazone-appropriate particle size dioxazines in the presence of dioxazine derivatives.

It is also known that sulfonic acid derivatives of certain pigments can effectively reduce crystal growth during the recovery of the pigment from the reaction mixture. Such sulfonic acid derivatives are described, for example, in US 3,386,843. Other patents disclose the use of sulfonic acid-derived pigments for stabilization against recrystallization and alteration of crystal modification, for example GB 1,544,839, which targets phthalocyanine pigments.

U.S. Patent No. 5,755,873 describes a process for the preparation of quinacridone pigments, wherein the chonacridone derivative is added during the synthesis, and the pending application Serial No. 60 / 087,773 describes the direct synthesis of pigment diketopyrrolo. 9 9 9 »· 9 99 99

999 9,999 9,999

9 9 9 9 9

9 9 9 9 9 9 9.9 9

9 9 9 9 9 9

9 999 999 99 99 99 99 β pyrrole pigments in the presence of quinacridone or diketopyrrolopyrrole derivatives.

Japanese Patent No. 061 45 546 discloses phthalimidomethyldihydroquinacridones and their use as pigment dispersants.

Known particle size growth inhibitors that are derived from pigment derivatives are often strongly colored and may behave as impurities.

It was not expected from the prior art that non-planar molecules can act as inhibitors of particle growth and crystal phase controlling agents of a pigment consisting of planar pigment molecules.

Although the addition of these known pigment derivatives may be advantageous, the synthesis of pigments in the presence of these derivatives does not in many cases provide an advantageous size, shape or crystal modification of the pigment crystals. Therefore, many pigments synthesized in this way may require additional steps to obtain pigments of advantageous color characteristics.

The present invention is based on the discovery that new selected pigment derivatives in which a specific aromatic or heteroaromatic group is attached via a methylene group to a pigment molecule are particularly effective for controlling and controlling the growth and / or crystal modification of pigment particles when they are present during the synthesis step.

These pigment particle size control agents can be prepared by a simple synthetic process and provide pigment manufacturers with a process for preparing pigments having advantageous color characteristics without the need for an additional pigment treatment step.

• 4 · 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 · ® ® ® ® ® ®

The compounds of the present invention allow manufacturers to prepare highly effective organic pigments in an economical and environmentally friendly manner, which is of particular commercial importance.

The subject invention

The present invention relates to novel compounds of formula I (MO 3 S) -Q ¹ - (CH ² - (X ¹ ) - (Y ¹ ) n ¹ ) o ¹ (I) wherein:

M is a metal cation, a quaternary nitrogen cation or a hydrogen atom;

Y ¹ is a sulfonic or carboxylic acid or a salt thereof;

Q ¹ is a pigment group;

X ¹ is an aromatic group, a cycloheteroaliphatic group containing at least one five or six membered ring, or a heteroaromatic group containing at least one six membered ring and which is not a phthalimido group;

m ^{1 and} n ¹ are independently from 0 to 2.5; and o ¹ is a number of 0.05 to 4 or or compounds of formula II (MO 3 S) _m ² -Q ² - (CH ² - (X ² ) - (Y ² ) n ² ) _o ² (II) wherein:

Q ² is a 6,13-dihydroquinacridone group of formula III HO

H (lil) · · «· · · (((((((((((((((

4 · kde kde kde kde::::: where:

A and D are independently selected from the group consisting of hydrogen, fluorine, chlorine, (C 1 -C 3) alkyl and (C 1 -C 3) alkoxy,

M 'is a metal cation, a quaternary nitrogen cation or a hydrogen atom;

Y ² is a sulfonic or carboxylic acid or a salt thereof;

X ² is an aromatic group, a cycloheteroaliphatic group containing at least one five or six membered ring, or a heteroaromatic group containing at least one five or six membered ring and which is not a phthalimido group;

m ² and ^{n 2} are independently from 0 to 2.5; and ¹ is ^an integer of 0 to 4.

The present invention further relates to a process for the preparation and use of these compounds.

Generally, the pigment group Q ¹ in formula I is selected from the group consisting of anthraquinone, phthalocyanine, perinone, perylene, diketopyrrolopyrrole, thioindigo, iminoisoindoline, iminoisoindolinone, quinacridone, flavanthron, dioxazine, indathronine, anthrapyrimidone and anthrapyrimidone.

The pigment group Q ¹ is preferably a quinacridone or diketopyrrolopyrrole pigment. Particularly preferably, the pigment group Q ^{1 is a} quinacridone of formula IV:

HIM

I JÍ

JOL ^(IV) - - - - - - - - - - - - - - - - - - - - - -

Or a 6,13-dihydroquinacridone of formula III wherein A and D are independently 1 or 2 substituents selected from the group consisting of: is selected from the group consisting of hydrogen, fluorine, chlorine, (C 1 -C 3) alkyl and (C 1 -C 3) alkoxy. Most preferably, the pigment group Q ^{1 is an} unsubstituted quinacridone and Q ² is a 6,13-dihydroquinacridone group.

Preferably, m ¹ in formula I is 0 to 0.5, most preferably 0 to 0.1; n ¹ is a number of 0 to 2, most preferably 0 to 1.2; and o is a number of 0.1 to 2, most preferably 0.2 to 1.5.

Preferably, m ² in formula II is 0 to 2, most preferably 0 to 1; n ² is a number of 0 to 2, most preferably 0 to 1.2; and o is a number of 0 to 2, most preferably 0 to 1.5.

The metal cation M in formula I is preferably an atom. sodium, potassium, calcium, magnesium or aluminum. The quaternary nitrogen cation in Formula I is an ammonium group or an alkylammonium group.

Typically, the group X ¹ in formula I and X ² in formula II is an aromatic group selected from a five or six carbon ring or a polycyclic group containing two to six fused five or six carbon rings or a cycloheteroaliphatic group containing at least one five or six ring atom or X ² and / or six-atom rings or X ¹ is a heteroaromatic group that is not a phthalimido group containing a six-atom ring or fused five and / or six-atom rings, and wherein said heteroaromatic group contains 1 to 4 heteroatoms selected from the group consisting of nitrogen, sulfur and and / or an oxygen atom, and wherein said heteroaromatic group of group X ² , which is not a phthalimido group, comprises a five or six ring atom or a fused five and / or six ring atom and

· «·« · · · · 9 9 9 · · ·

It contains 1 to 4 heteroatoms selected from the group consisting of nitrogen, sulfur and / or oxygen.

Suitable aromatic groups include, for example, phenylene, naphthalene, acenaphthylene, anthracene, phenanthrene, naphthacene, chrasene, pyrene or perylene. Preferably, the aromatic group is a phenylene group, a naphthalene group, anthracene group, a phenanthrene group, a perylene group or a pyrene group, and most preferably the aromatic group is a phenylene group or a naphthalene group.

Cycloheteroaliphatic groups are, for example, pyrrolidine, imidazolidine, piperidine, piperazine or morpholine, preferably barbituric acid.

Suitable heteroaromatic groups X ¹ are, for example, pyridine group, pyrazine group, pyrimidine group, pyridazine group, indole group, isoindole group, quinoline group, isoquinoline group, carbazole group, phenothiazine group, benzimidazolone group or benzothiazole group, with preferred heteroaromatic groups X ¹ is a pyridine group or a carbazole group.

Suitable heteroaromatic groups X ² are, for example, pyridine, pyrazine, pyrimidine, pyridazine, isoindole, quinoline, isoquinoline, carbazole, phenothiazine, benzimidazolone,. benzothiazole, pyrrole, imidazole or pyrazole, with the preferred heteroaromatic X ² groups being pyridine, quinoline, pyrrole, imidazole or pyrazole.

· · * · · 7 7 · · · · · · · · · 7 7 7 7 7 7 · · · · ·

Z ·· · · ·> 0 0 0 ° C

The aforementioned aromatic, cycloheteroaliphatic and heteroaromatic groups may be optionally substituted by one or more halogen atoms, oxy, imino, amino and / or C 1 -C 18 alkyl groups or C 1 -C 18 alkoxy groups, preferably C 1 -C 18 alkyl groups C 3 -C 3 alkoxy groups or C 1 -C 3 alkoxy groups.

Examples of many such substituted aromatic, cycloheteroaliphatic or heteroaromatic groups are, for example, toluene, ortho-, meta- or para-xylene, chlorobenzene, 1- or 2-methylnaphthalene or anthraquinohal, barbitur. acid, melamine group. 1,3,7-trimethylxanthine, hydantoin, 2-methylbenzimidazole, 2,6,8-trihydroxypurine, 1,8-naphthosultamic, o-sulfimido benzoic acid or 2,4-dihydroxyprimidine.

Preferably, the aromatic groups are toluene, ortho-, meta- or para-xylene, chlorobenzene, 1- or 2-methylnaphthalene or anthraquinone.

The heteroaromatic group is preferably a melamine group,

1,3,7-trimethylxanthine, hydantoin, 2-methylbenzimidazole, 2,6,8-trihydroxypurine, 1,8-naphthosultamic, o-benzoic acid sulfimide or 2,4-dihydroxyprimidine.

Generally, Y ¹ or Y ^{2 are a} carboxylic acid or sulfonic acid or a free sulfonic acid or its sodium, potassium, magnesium, calcium or aluminum salt or Y ² is a quaternary ammonium group or an alkylammonium salt thereof. Most preferably, groups Ύ ¹ and Y ^{2 are} their sodium, potassium, magnesium, calcium or aluminum salts.

• 4 β 4 4 9 ·· 4 4 9 4 94 94 4 44 ·

4,494 4,444 «

4 4 44 9 4 4 44 4 + 4 4 4 4 9 4 95 4

444 4 444 4 «44

Another embodiment of the present invention relates to a process for the preparation of compounds of formula I or II, wherein:

(a) dissolve pigment pigment group Q ¹ or Q ² in concentrated sulfuric acid;

(b) intermediate X ¹ or X ² is added to the solution and dissolved at a temperature below 50 ° C;

(c) paraformaldehyde is added at a temperature below 50 ° C;

d). and then heated to 50-100 ° C;

e) and then isolated.

The pigment group Q ¹ or Q ² and the intermediate X ¹ or X ² , the basic part of which is the group X ¹ or X ² , are reacted with formaldehyde according to the new process.

The reaction is preferably carried out in concentrated (95 to 98%) sulfuric acid. In one preferred method, the pigment group Q ¹ or Q ^{2 is} dissolved in concentrated sulfuric acid at a concentration of 5 to 30% by weight, most preferably 10 to 20% by weight, at a temperature below 50 ° C, preferably at 35 to 45%. Deň: 32 ° C. Intermediate X ¹ or X ² is added to the pigment solution at a temperature below 50 ° C, preferably at a temperature of 35 to 45 ° C, and also dissolved. Finally, formaldehyde, preferably in the form of paraformaldehyde, is added at a temperature below 50 ° C, preferably at a temperature of 35 to 45 ° C. The reaction mixture is heated to 50 to 100 ° C and stirred at this temperature until the reaction is complete, preferably 30 minutes to 6 hours, most preferably 30 to 90 minutes, and poured into ice water. The suspension is stirred for 5 minutes to six hours, preferably 30 minutes to 3 hours, at a temperature of 0 to 50 ° C, preferably 10 to 25 ° C. The reaction mixture was poured into water to obtain a precipitate. Then, the compounds of the present invention are isolated by filtration or centrifugation and preferably washed with water. The filter cake is dried or can be used as an aqueous filter cake as an additive in pigment synthesis.

* · · · · • «· • · ♦ • · • · · · • * · * • · * • «· · * · · • · · • «· · · * * ·· »E · «· * · Generally use e stoichiometric amount pigment , dktu X ¹ or X ² and formaldehyde; To earned required

product, however, an excess of intermediate X ¹ or X ² may be used. Preferably the molar ratio pigment: intermediate X ¹ or X ² : formaldehyde is 1: Ϊ to 1.2: 1 to 2.

If desired, a high degree of sulfonation, the reaction mixture. is stirred at a higher temperature, for example greater than 60 ° C. If a low degree of sulfonation is desired, the reaction mixture is maintained at a lower temperature, for example below 60 ° C.

Isolated samples can be analyzed by known methods, for example, elemental analysis or mass spectroscopy, such as LCMS, GCMS or Matrix Laser Desorption Ionization (MALDI) techniques, or by high pressure liquid chromatography (HPLC), all of which are known to those skilled in the art. . Using the preferred preparation method described above, which does not involve purification steps, the purity of the isolated product is not usually 100% and contains, depending on the starting materials and reaction temperature, residues of some starting materials or other by-products which are tolerated and may optionally provide other preferred effects if their concentration has no negative impact on particle size and crystal phase. By known methods, such as solvent treatment, recrystallization or precipitation from solutions of basic polar solvents, for example basic dimethylsulfoxide or dimethylformamide, the products can be further purified if desired.

In general, the pigment particle growth control compounds and the crystal phase of the invention are added at a concentration of 0.1 to 15%, preferably 0.3 to 10%, and most preferably 0.5 to 8%, relative to the pigment to be synthesized, before or during the last steps of pigment synthesis.

9 9 ·

9 9 9 • 9 9 9

The pigment and / or crystal phase growth control agents of the present invention are useful as additives in the synthesis of pigments of various classes of pigments, including pigments of the anthraquinone, phthalocyanine, perinone _or perylene, diketopyrrolopyrrole, thioindigo, iminoisoindoline, iminoisoindolinone, quinacridone, flavathrone, indathron, anthrapyrimidine and quinophthalone. Preferably, the pigments used in the Q ¹ group of the present invention belong to the same pigment class as the pigments to be synthesized, but this is not a requirement.

The compounds of the present invention are particularly suitable for the direct synthesis of pigmented diketopyrrolopyrrols and quinacridones and / or their resolved solid solutions with a resized particle size and the 6,13-dihydroquinacridones of formula II are particularly suitable for the direct synthesis of pigmented diketopyrrolopyrrols and quinacridones and / or their solid solutions. adjusted particle size. Said compounds of formulas I and II are very suitable for the synthesis of quinacridone pigments in a specific crystal modification such as alpha, beta or gamma quinacridone, 2,9-dichloroquinacridone, 2,9-dimethylquinacridone, 4,11-dichloroquinacridone and their solid solutions. The pigment particle size control agents of the present invention are particularly effective when fully or partially soluble in the reaction medium. in which the pigment is synthesized.

Another embodiment of the present invention relates to a method for the direct synthesis of pigmented anthraquinones, phthalocyanines, perinones, perylenes, diketopyrrolopyrroles, thioindigo, iminoisoindolines, iminoisoindolinones, quinacridones, flavathroriins, dioxazines, indathrons, anthrapyrimonimides in size, 0.1 to 25% by weight of the pigment particle growth control compound and / or crystal phase of the formula

9 «9 ·

9 9 9 9 9 9 9 9 9 9999 9 9 9 9 9 99 99 9

1,999 ·, 9 9 9 9 99

A. J- 999 99 999 9 · 99

I or II according to claim 1, based on the weight of the pigment to be synthesized.

The process is advantageous for the direct synthesis of pigment quinacridone, 2,9-dichloroquinacridone, 4,11-dichloroquinacridone, 2,9-dimethylquinacridone of suitable particle size, wherein said pigment or solid solution thereof is synthesized in the presence of 0.1 to 25% by weight of the growth controlling compound pigment particle size and / or crystal phase of the general formula

I, based on the weight of the pigment to be synthesized.

Further, the present invention relates to a process for the preparation of pigment anthraquinones, phthalocyanines, perinones, perylenes, diketopyrrolopyrrols, thioindigo, iminoisoindolines, iminoisoindolinones, quinacridones, flavathrons, dioxazines, indathrons, anthrapyrimidines, quinophthalone ointment, quinophthalone o solvent or water or pre-grinding followed by an organic solvent treatment step, which is preferably related to a process for preparing pigmented diketopyrrolopyrrols, quinacridones of appropriate particle size, or comprises a pre-grinding step followed by an organic solvent treatment step, in the presence of 0.1 to 25% 6.13 of the dihydroquinacridone of formula I, based on the weight of the pigment to be treated.

Further, the present invention relates to a process for the direct preparation of pigmented diketopyrrolopyrrole pigments or solid solutions thereof, comprising the step of synthesizing said pigment or solid solution thereof in the presence of 0.1 to 25% by weight of at least one compound of formula I or. 0.5 to 8% by weight of the 6,13-dihydroquinacridone of the formula

II, relative to the pigment to be synthesized.

Without limiting the present invention to any theory, it is believed that the particle growth control molecule adheres to the synthesized pigment molecule and thereby controls growth.

99 ··

9

9

9

9

999 9 9 9 · crystal and crystal phase. The term crystal growth control means controlling the synthesis of pigment particles to have a particle size suitable for pigments as well as controlling crystal growth to produce particles of a specific desirable shape, such as platelet, needle, cubic, flake, prism and other geometric forms, in the desired crystal. stage. The effect can. by the chemical structure of the organic pigment, by selecting the reaction medium and the concentration and chemical structure of the particle size growth inhibitor according to the present invention.

In circumstances where the reaction medium of the pigment to be synthesized is an oxidizing compound, the 6,13-dihydroquinacridone derivative of the present invention may be partially or fully oxidized to the corresponding quinacridone derivative during pigment synthesis. Therefore, 6,13-dihydroquinacridone derivatives are particularly useful for the synthesis of quinacridone pigments when the quinacridone pigment is obtained by oxidation of the corresponding 6,13-dihydroquinacridone as described above, for example, in US Patent No. 5,840,901.

During the isolation of the pigment, for example in the filtration step, these compounds, if soluble in the reaction medium, can be washed out and, if appropriate, recovered from the filtrate or wash liquid. Typically these compounds partially remain on the surface of the pigment and may provide additional benefits. These advantages are, for example, improved pigment properties such as rheological properties, dispersibility and wetting behavior, flocculation resistance, and increased heat stability.

It has further been found that phthalimidomethyldihydroquinacridone, previously described as a pigment dispersant, can be an effective pigment particle size control agent and a pigment crystal phase controlling agent.

·················· 4 9 * 99 99 ··· 9 999 9 49 9 • 9 9 9 9 9499

999 9 9 49 99 9 ·· 4 49 4 9999 ·· 994 44 999 44 99 l

In certain cases, it is preferable to use the compounds of the present invention in admixture or combination with other additives, including known pigment particle size growth inhibitors such as phthalimidomethyl, imidazole methyl or pyrazolomethylquinacridone, pigment sulfonic acids or specific polymers; or optionally other ingredients such as wetting agents, surfactants, antifoams, antioxidants, UV absorbers, light stabilizers, emollients, or generally texture enhancers, and the like. Any such additional additives may be used as long as they are stable under the conditions of pigment synthesis and do not adversely affect the final properties of the pigment or the environment. In general, these additives can be used at a concentration of 0.1 to 25%, preferably 0.2 to 15%, and most preferably 0.5 to 8%, relative to the pigment to be synthesized. The resulting pigment / additive composition can be used in any conventional pigment application, such as the preparation of paints, inks, color filters, fibers, paper and textiles.

Suitable polymers are, for example, polyacrylic acid, polymethacrylic acid, polymaleic acid anhydride, polyurethane, polyvinyl ether, polyvinyl alcohol, polyalkylene glycol, polyethylene oxide, cellulose derivatives, polyimine, polyvinylpyridine, or copolymers such as acrylic acid with styrene, vinyl chloride, acrylonitrile, acrylonitrile , itaconic acid or maleic acid or mixtures thereof, or polymer derivatives such as ethoxylated or propoxylated fatty amines such as ethoxylated cocoalkyl, oleyl or soy alkylamines; ethoxylated or propoxylated fatty quaternary salts such as ethoxylated coconut alkyltrimethylammonium chloride; ethoxylated fatty amines such as ethoxylated oleamides; alkyl-, cycloalkyl- or alkylaryl-oxypoly (ethyleneoxy) ethanol, cycloalkyloxypoly (ethylenoxy) laurate or oleate, 9 «« «· * · 9 9 9 9 9 9 9 9 9 • 9 9 9 9 9999

9 - 99 9, 9 - 999 9 - 99 polyethylene glycol 400 laurate or oleate, alkyl, cycloalkyl or alkylaryl poly (ethyleneoxy) carboxylate or phosphonate.

Suitable surfactants include anionic surfactants such as alkylbenzene or alkylnaphthalene sulfonates, alkylsulfosuccinates or naphthalene-formaldehyde sulfonates; cationic surfactants, including, for example, quaternary salts such as benzyltributylammonium chloride; or nonionic or surfactant surfactants such as polyoxyethylene surfactants and alkyl or amidopropyl betaines.

Suitable texture-enhancing agents are, for example, fatty acids such as stearic or behenic acid and fatty amines such as laurylamine and stearylamine. Furthermore, fatty alcohols or ethoxylated fatty alcohols, polyols such as aliphatic 1,2-diols or epoxidized soybean oil, waxes, acidic resins, and acidic acid salts may be used for this purpose.

Suitable UV stabilizers are, for example, the benzotriazole derivatives known under the trade name TINUVIN or CIBA. Fast H liquid arylsulfonated benzotriazole, which are products of CI ^ A Specialty Chemicals Corporation.

Since the compounds of the present invention can act as anti-flocculating agents and are also excellent particle size growth inhibitors and crystal phase controlling agents, they can generally be used in pigment finishing, pigment processing or pigment application as additives during the pigment dispersion step in roller mills, extruders. , calenders and the like, and also during the synthesis of pigments. The compounds of the present invention are themselves strongly colored and can be used as coloring agents in, for example, paints, inks, color filters, plastics, fibers, and the paper or textile industry.

···· ··

4 4

4 4

The present invention relates to the use of a compound of formula I or II for enhancing the thermal stability, rheological and flocculation properties of pigment particles.

Further, the present invention relates to a method for improving the thermal stability, rheological and flocculating properties of pigment particles, the method comprising adding at least one compound of formula I to said pigment particles in an amount sufficient to reduce flocculation or increase thermal stability.

Methods of finishing pigments in which 6,13-dihydroquinacridone derivatives can be used are, for example, the known kneading, water or solvent grinding process.

Further, many of the compounds of the present invention provide physical properties that are similar to those of pigments; in particular, it is low solubility in organic solvents or application medium. Therefore, the compounds of the invention do not have bleaching properties and, for example, will not pass into foods when a pigment composition comprising a compound of the present invention is used as a colorant in food packaging materials.

Particularly effective are the 6,13-dihydroquinacridone derivatives of the present invention when present in a pigment finishing process in which the crude pigment is pretreated and then treated in an organic solvent, a process described, for example, in U.S. Patent Nos. 5,194,088 and 2,857,400.

Said 6,13-dihydroquinacridone derivatives are particularly suitable for pigments of different classes of pigments having different shades, since they are only slightly discolored by themselves and therefore the presence of the compounds of the present invention does not reduce the saturation or change the shade of the pigment.

········· «« · 9 · «« · 4 «<

• 9 · 9 · 9 ^{v v} * * * 94 94 94 94 94 «94 · 4

Further, 6,13-dihydroquinacridone derivatives are non-planar molecules. Based on the prior art, it has not been assumed that non-planar molecules can act as inhibitors of particle growth and crystal phase controlling agents of a pigment composed of planar organic pigment molecules.

The following examples further describe some preferred embodiments of the present invention but do not limit the scope of the present invention. In these examples, all parts are by weight unless otherwise indicated.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

A 1 liter flask equipped with a stirrer, thermometer, condenser and drying tube was charged with 200 mL concentrated (95-98%) sulfuric acid. At a temperature below 45 ° C, 46.8 g (0.15 mol) of MONASTRAL Red Y RT-759-D, which is an unsubstituted quinacridone pigment from CIBA Specialty Chemicals Corporation, is added, and the mixture is stirred at 40-45 ° C for 20 minutes. C until the pigment is dissolved.

At a temperature below 45 ° C, 26.4 g (0.15 mol) of benzenesulfonic acid (90%) are added and the mixture is stirred for 20 minutes at 40 to 45 ° C, then 4.8 g (0.16) are added rapidly. mol) paraformaldehyde. The reaction mixture was stirred at 55-60 ° C for 1 hour, then poured into 2.5 L of water. The precipitate was stirred at room temperature for 2.5 hours, then filtered. Filter cake made. washed with water to pH 5 and dried to obtain a product which according to MALDI (matrix laser desorption ionization technique) contains methyl quinacridone benzenesulfonic acid having a molar mass of 482.

···· •

* 9 • 9 · 99 ·

9 9 9 9 9 9 * 99 9

9 9 9 9 9

999 99 99

Example 2

A 1 liter flask equipped with a stirrer, thermometer, condenser, and drying tube was charged with 200 mL concentrated (95-98%) sulfuric acid. Add at a temperature below 45 ° C. 31.2 g (0.1 mol) of MONASTRAL Red Y RT-759-D and the mixture is stirred at 40-45 ° C for 20 minutes until the pigment is dissolved.

At a temperature below 45 ° C, 41.4 g (0.1 mol) of naphthalene-1-sulfonic acid (50%) are added and the mixture is stirred for 20 minutes at 40-45 ° C and then quickly added 3.2. g (0.107 mol) of paraformaldehyde. The reaction mixture was stirred at 55-60 ° C for 1 hour, then poured into 2.5 liters of ice water. The precipitate was stirred at room temperature for 2.5 hours, then filtered. The filter cake was washed with water to pH 2.8 and kept as a press cake. The small sample is further washed to pH 5 and dried to give the product methyl quinacridonna phthalene-1-sulfonic acid of molar mass 532, as determined by MALDI.

Example 3

The procedure described in Example 2 was repeated using 0.1 mol of naphthalene-2-sulfonic acid instead of naphthalene-1-sulfonic acid to give the product, methyl quinacridone naphthalene-2-sulfonic acid, with a molar mass of 532 as determined by MALDI.

Example 4

The procedure described in Example 2 was repeated using 0.1 moles of anthraquinone-2-sulfonic acid instead of naphthalene-1-sulfonic acid to give the product, which is methyl quinacridone anthraquinone sulfonic acid having a molar mass of 614 as determined by MALDI.

· * * «« · · · · · · · · · · · · · · · · · · · · · · · · • ··· ·· ··· ··

Example 5

The procedure described in Example 2 was repeated using 18.4 g (0.1 mol) of the sodium salt of o-benzoic acid sulfimide instead of naphthalene-1-sulfonic acid to give the product, which is methyl quinacridone-o-benzoic acid sulfimide of 507 molar mass. is determined by MALDI.

Example 6

The procedure described in Example 2 was repeated using 20.4 g (0.1 mol) of Naxonate ST which is a commercially available sodium toluene sulfonate from Ruetgers-Naese (sodium toluene sulfonate of 93% content) instead of naphthalene-1-sulfonic acid. to give the product, which is methylquinacridone. toluenesulfonic acid of 496 molar mass, as determined by MALDI.

Example 7

A 1 liter flask equipped with a stirrer, thermometer, condenser, and drying tube was charged with 200 mL of concentrated (95-98%) sulfuric acid. IRGAZIN DPP Scarlet EK (0.1 mol of commercial 3,6-diphenyl-1,4-diketopyrrole- [3,4-c] -pyrrole pigment from CIBA Specialty Chemicals Corp.) was added at 40-45 ° C. and the mixture is stirred at 40-45 ° C for 20 minutes until the pigment is completely dissolved.

At a temperature below 45 ° C, 18.4 g (0.1 mol) of the sodium salt of o-benzoic acid sulfimide are added and the mixture is stirred at 40 to 45 ° C for 20 minutes and then 3.2 g ( 0.107 mol) paraformaldehyde. The reaction mixture was stirred at 45-50 ° C for 50 minutes, then poured into 2.5 liters of ice water. The precipitate was stirred at room temperature for 1.5 hours, then filtered. The filter cake is washed with neutral water and dried to give a reddish brown product in which methyl sulfide methyl 19 is detected. · ······ · · · · · 4 ··· · * ··· · »··· ··» ·

3,6-diphenyl-1,4-diketopyrrole- [3,4-c] pyrrole sulfonic acid, molar mass 483, by MALDI.

Example 8

A 1 liter flask equipped with a thermometer, stirrer and condenser was charged with 40 g of 6,13-dihydroquinacridone, 180 ml of methanol and 40.9 g of 50% aqueous sodium hydroxide solution. The mixture was stirred under slow nitrogen flow at 30-45 ° C for 5 minutes. 2.4 g of the pigment additive prepared according to example 4 are added, followed by 0.5 g of the anthraquinone monosulfonic acid sodium salt as a catalyst and the reaction mixture is heated to boiling for 1 hour to generate 6,13-dihydroquinacridone sodium salt. Using a peristaltic pump at a rate of 0.3 ml / min, 73.5 g of an aqueous 1.6.9% hydrogen peroxide solution are added while boiling at low nitrogen flow. The resulting red suspension was further stirred at boiling for 10 minutes, then diluted with 100 mL cold water and filtered. The filter cake is washed with hot water and then dried. recovery of 38.9 g of red quinacridone.

The product shows a purity of more than 98% quinacridone as determined by spectrophotometric methods. The X-ray of the pigment shows the characteristics of alpha quinacridone. Viewed from a microscope, the pigment shows crystals having a length of 1 to 6 µm and a width of 0.2 to 0.6 µπι. When added to the plastics or paints, the pigment lends them a bright yellow-red color that has excellent properties.

Example 9

A 1 liter flask equipped with a thermometer, stirrer and condenser was charged with 45 g of 2,9-dichloro-6,13-dihydroquinacridone, 3.0 g of pigment additive prepared according to Example 1, 280 ml of methanol and 136.8 g of 45% aqueous hydroxide solution. potassium and stir 5 ·· · ·

* Minutes at 30 to 40 ° C for 9 to 10 minutes. The mixture was stirred under gentle nitrogen flow, boiling for one hour, generating 2,9-dichloro-6,13-dihydroquinacridone potassium salt. 0.6 g of anthraquinone-2-sulfonic acid sodium salt is added. While boiling, 67.8 g of an aqueous solution of 16.9% hydrogen peroxide are added over a period of 3 hours 20 minutes by means of a pump set at a flow rate of 0.3 ml / min with slight nitrogen flow. The resulting fuchsin-colored suspension is kept at boiling point for a further 10 minutes, diluted with 100 ml of cold water, then filtered at 50-60 ° C. The filter cake was washed with hot water and dried to give 44 g of a fuchsin-colored 2,9-dichloroquinacridone pigment.

The x-ray pigment shows the gamma characteristics of 2,9-dichloroquinacridone. When the product is added to automotive paints, a transparent fuchsin-colored dispersion is obtained which has excellent rheological properties and which can be easily sprayed onto metal panels to produce a paint with excellent durability.

Example 10

The procedure described in Example 9 was repeated using 1.8 g instead of 3.0 g of the pigment additive prepared according to Example 1 and 80 g of a 50% sodium hydroxide solution instead of potassium hydroxide, to give a strongly fuchsin-colored 2,9-dichloroquinacridone.

When added to plastics, an intensely bluish fuchsin color product with excellent thermal and light stability is obtained.

Example 11

A 1 liter flask equipped with a thermometer, stirrer and condenser was charged with 40 g of 6,13-dihydroquinacridone, 180 ml of methanol and 42 g of a 50% aqueous sodium hydroxide solution and 14.6 g of a naphthalene-1-sulfonic acid methyl quinacridone aqueous filter cake.

9999 9 9 9 9

9

9 9 ·

999 acid, which is a pigment additive prepared according to the example

2. Stir the mixture under gentle nitrogen flow at 50-55 ° C for one hour. 0.5 g of anthraquinone monosulfonic acid sodium salt is added and the reaction mixture is heated to boiling for 1 hour, generating 6,13-dihydroquinacridone sodium salt. 67 g of an aqueous solution of 19.3% hydrogen peroxide are added to the reaction mixture at low nitrogen flow, while boiling, using a peristaltic pump set at an addition rate of 0.3 ml / min. 2 g of phthalimidomethylquinacridone and then, the addition of hydrogen peroxide is continued. The resulting purple suspension was further stirred for 10 minutes at boiling and then diluted with 100 ml of cold water and filtered. The filter cake was washed with hot water and then dried to give 38.9 g of violet quinacridone.

According to spectrophotometric analysis, the product shows high purity and contains only 0.3% - of the remaining 6,13-dihydroquinacridone. The X-ray of the pigment shows the characteristics of beta quinacridone.

Example 12

A 1 liter flask equipped with a thermometer, stirrer and condenser was charged with 50 g of 6,13-dihydroquinacridone, 310 ml of methanol and 66 grams of 50% aqueous sodium hydroxide solution, and 3.8 g of 50% benzyltributylammonium chloride solution and stirred at 35-40 for 5 minutes. Deň: 32 ° C. 0.9 g of methylquinacridone anthraquinone sulfonic acid is added as a pigment additive prepared according to Example 4, and then 0.5 g of anthraquinone monosulfonic acid sodium salt as catalyst is added. The mixture was stirred under gentle nitrogen flow and heated to boiling. Using a peristaltic pump, 66 g of an aqueous 17% hydrogen peroxide solution are added over a period of 3 hours 20 minutes while the pump is set at a flow rate of 0.3 ml / min while maintaining boiling and with a slight nitrogen flow. Obtained red • 444 4 ·· · 44 44

44 44 44

4,444 4,444 »• 444,444 44 4 ·· 4,444 4,444

The suspension is further stirred for 10 minutes at boiling point, then diluted with 100 ml of cold water and filtered. The filter cake was washed with hot water and then dried to give 48.9 g of red quinacridone.

The x-ray pigment shows the characteristics of gamma-III quinacridone as described in U.S. Patent No. 5,223,624. It can easily be added to paints and plastics to produce intensely red colored products.

Example 13

With nitrogen flowing, a 1 liter flask equipped with a thermometer, stirrer and condenser was charged with 100 ml of t-amyl alcohol, 34.6 g of potassium t-butylate and 144.4 g of benzonitrile and heated to 98 ° C. An almost anhydrous solution of 14.6 g of dimethylsulcinate in 10 ml of t-amyl alcohol and methanol was distilled off over 145 minutes at 98-99 ° C using a metering pump. After completion of the addition, the reaction mixture was stirred at 99 ° C for 2 hours. C and 0.5 g of methyl-3,6-diphenyl-1,4-diketopyrrole- [3,4-c] -pyrrole o-benzoic acid sulfimide prepared according to Example 8 is added, then cooled to 65 ° C, diluted with 100 g. ml of methanol, and then 100 ml of water are added. The mixture was filtered. The filter cake is washed neutral with water and dried to give 19 g of a red, direct, pigmented diketopyrrolopyrrole pigment having a high color intensity, high saturation and light stability when added to paints and plastics.

Example 14A

Crude beta-quinacridone having a particle size of 2 to 6 μιη, which is obtained, for example, by oxidation of 6,13-dihydroquinacridone with peroxide 9 9

995 99 ··. ·· • 9 9 <

• 100 9 • 100 9 ·

9 9 ·

9 · 99 of the hydrogen oxidizing agent of the US is ground according to the following procedure of Patent Number

5,840,901

1-SDG Attritor ™ Mill from Union Process, Inc. Akron, Ohio, which is provided with L-arms and contains 3.78 liters of 0.6 cm diameter ceramic grinding media, 7.5 MOH hardness, 60-65 Rockwell 45N hardness, 3.0 kg / cm impact strength, and compressive strength 8500 kg / cm. The mill is filled with 350 g of crude betachinacridone and the pigment is milled under nitrogen flow at 500 rpm for 50 minutes. Upon completion of the grinding cycle, the product is obtained by opening the flap at the bottom of the mill, rotating for 15 minutes to obtain a brown highly aggregated powder of very low crystallinity.

Example 14B

A 1 liter flask equipped with a thermometer, stirrer and condenser was charged with 0.3 g methyl quinacridone o-benzoic acid sulfimide, an additive prepared according to Example 5, and 250 ml dimethylformamide. The mixture was stirred at 50-55 ° C for 15 minutes to partially dissolve the additive in the solvent. 30 g of the pre-ground powder obtained according to Example 14A are added and the suspension is stirred at 50-55 ° C for 3 hours. The resulting purple suspension was filtered. The filter cake is washed with water and dried to give a violet pigment which exhibits excellent durability and high color saturation when added to plastics and paints. The radiograph shows the characteristics of beta quinacridone.

Example 15

63.0 g of polyvinyl chloride, 3.0 g of epoxidized soybean oil,

2.0 g of barium / cadmium temperature stabilizer, 32.0 g of dioctyl phthalate and 1.0 g of betachinacridone prepared according to Example 11 are mixed in a glass beaker using a glass beaker. · · · · · · · · · · · · · · · · · · · · · · · The mixture is formed into soft polyvinyl chloride sheets of about 0.4 mm thickness by rolling in a laboratory twin-roll mill for 8 minutes, at a temperature of 160 ° C, a roller speed of 25 rpm and a friction of 1: 1.2 at constant wrinkling, removal and filling. The obtained soft polyvinyl chloride slice is colored to an attractive violet shade, has excellent resistance to heat, light and migration.

Example 16

Five grams of fuchsine 2,9-dichloroquinacridone pigment prepared according to Example 10, 2.5 g hindered amine light stabilizer, 1.0 g benzotriazole UV absorber, 1.0 g hindered phenolic antioxidant and 1.0 g phosphate stabilizer process After melting, they are mixed together with 1000 g of high density polyethylene at a speed of 175 to 200 rpm for 30 seconds. The molten, pigmented resin is chopped when it is warm and malleable and then passed through a granulator. The resulting granules are injection molded at five minutes of rest and 30 second cycles at 260 ° C. Homogeneously colored chips show a clear whitish color with excellent light stability.

Example 17

Preparation of car paints ground vehicle:

A 1 liter vessel was charged with 66 grams of acrylic resin, 14.5 grams of AB dispersant and 58.1 grams of solvent (SOLVESSO 100 from American Chemical). 26.4 g of the quinacridone pigment obtained according to Example 12 and 980 g of 4 mm diameter diagonal iron bars. The mixture is ground in a container for 64 hours in a cylindrical »*

• · · · · • · · • · ·· 9 • «« · • · · * · · · «· · · 25 e · · · · » • · · •> » • · · ·

mill. The resulting milled composition contains 16.0% pigment at a pigment / binder ratio of 0.5 and a total nonvolatile content of 48.0%.

solid color:

Mix 47.3 g of the above milled formulation, 36.4 g clear solid solution containing melamine resin catalyst, non-aqueous resin dispersion and UV absorber and 16.3 g balanced clear solid solution containing polyesterurethane resin and dilute with a solvent mixture containing 76 parts xylene , 21 parts of butanol and 3 parts of methanol for a spray viscosity of 20 to 22 seconds, as measured by the # 2 Fisher Cup.

The resulting red resin / pigment dispersion is sprayed twice on the panel as a primer at 1.5 minute intervals. After 2 minutes, a clear resin coating is sprayed twice at 1.5 minute intervals onto the primer. The sprayed panel is then air dried in an oven for 10 minutes and then cured in an oven at 129 ° C for 30 minutes to give a red-colored panel of high color saturation, with excellent weathering resistance.

Example 18

1000 grams of polypropylene granules (DAPLEN PT-55®, from Chemie Linz) and 10 grams of the 2,9-dichloroquinacridone pigment obtained in Example 9 were mixed well in a mixing drum. The granules so obtained are melted and cast at 260-285 ° C into fuchsin-colored fibers with good light fastness and textile fiber properties.

···· · ·· ·; · · · · · »» · »» »..»... ♦ '· ♦ # · 9 9 · 99 99 · 99 99 999 999 · 999 999 ·

In addition to the embodiments described above, many variations of these embodiments are possible according to the present invention, the scope of which is limited only by the appended claims.

Example 19

A 1 liter flask equipped with a thermometer, stirrer, condenser and drying tube was charged with 200 mL concentrated (95-98%) sulfuric acid. At a temperature below 45 ° C, 23.6 g (0.075 mol) of 6,13-dihydroquinacridone are added and the resulting solution is heated to 100 ° C and stirred at 100 ° C for 6 hours, then. pour into 2.5 liters of ice water. The precipitate was stirred at room temperature for 30 minutes, then filtered. The filter cake is washed with water to pH 5 and dried to give a product in which 6,13-dihydroquinacridone sulfonic acid of molar mass 394 is detected by MALDI.

Example 20

A 1 liter flask equipped with a thermometer, stirrer, condenser and drying tube was charged with 200 mL concentrated (95-98%) sulfuric acid. At a temperature below 45 ° C, 47.1 g (0.15 mol) of 6,13-dihydroquinacridone are added and the mixture is stirred at 40-45 ° C for 10 minutes until the 6,13-dihydroquinacridone is completely dissolved.

At a temperature below 45 ° C, 23.2 g (0.158 mol) of phthalimide are added and the mixture is stirred for 10 minutes at 40 to 45 ° C, then 4.9 g (0.163 mol) of paraformaldehyde are added rapidly. The reaction mixture was stirred at 55-60 ° C for one hour, then poured into 2.5 liters of water. The precipitate was stirred at room temperature for 2.5 hours, then filtered. The filter cake is washed with water to pH 6-7 and dried to give a product in which the phthalimidmethyl-6,13-dihydroquinacridone of 473 molar mass is detected by MALDI.

«» · · · · · · · · · · · ·

Example 21

The method described in Example 20 was repeated using 19.2 g (0.15 mpl) of barbituric acid instead of phthalimide to give a product in which methyl-6,13-dihydroquinacridone-barbituric acid of molar mass 454 was detected by MALDI.

Example 22

The procedure described in Example 20 was repeated using 18.9 g (0.15 mol) of melamine instead of phthalimide to give a product in which melamine methyl-6,13-dihydroquinacridone of 452 molar mass was detected by MALDI.

Example 23

The procedure described in Example 20 was repeated using 27.6 g (0.15 mol) of sodium salt of o-benzoic acid sulfimide instead of phthalimide to give the product in which methyl 6,13-dihydroquinacridone-o-benzoic acid sulfimide was used at molar mass. 509 detects using MALDI.

Example 24

The method described in Example 2 was repeated using 26.4. g of benzenesulfonic acid (0.15 mol containing 90%) instead of phthalimide to give a product in which methyl-6,13-dihydroquinacridone-p-benzenesulfonic acid of molar mass 486 is detected by MALDI.

Example 25

The method described in Example 21 was repeated using. 30.6 g of Naxonate ST, which is a commercially available sodium toluene sulphonate from Ruetgers-Naese (0.15 mol sodium toluene sulphonate containing 93%) instead of phthalimide to give a product in which (· 9 9

9 9 9

In 9 9 9

9

9 9 9 * * 9 9 acid and cooler

9 9 9 9 · »· · · • 9 9 9 9 9 _ _Λ · 9 9 · · · · · methyl-6,13-dihydrochinakridontoluensulfonová molecular weight of 500 is detected by MALDI ..

Example 26

A 1 liter flask equipped with a thermometer and stirrer was charged with 40 g of 6,13-dihydroquinacridone, 250 ml of methanol, 52.8 g of 50% aqueous sodium hydroxide solution and 3.0 g of 50% aqueous benzyltributylammonium chloride solution. The mixture was stirred under gentle nitrogen flow at 30-45 ° C for 5 minutes, warmed to 50-55 ° C and stirred at 50-55 ° C for one hour. 0.6 g of the pigment additive of melamine methylquinacridone prepared according to Example 22 is added, then 0.5 g of the anthraquinone monosulfonic acid sodium salt catalyst is added and the reaction mixture is heated to boiling. 73 g of an aqueous solution of 17% hydrogen peroxide are added to the reaction mixture using a peristaltic pump set at 0.3 ml / min while maintaining boiling and a low nitrogen flow. The resulting red suspension is further stirred at boiling point for 10 minutes, then diluted with 100 ml of cold water and filtered. The filter cake was washed with hot water and then dried to give 38.9 g of red quinacridone.

The product shows a purity of more than 98% quinacridone by spectrophotometric analysis. The X-ray of the pigment exhibits gamma quinacridone characteristics. When pigment is added to plastics or paints, it gives them a red color with excellent properties

Example 27

The procedure of Example 26 was repeated using 0.6 g of dihydroquinacridone sulfonic acid as an additive prepared according to Example 1 instead of 0.6 g of melamine methyldihydroquinacridone to give 39 g of blue-red quinacridone.

· · · 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9

OQ ♦ * * ··· 9 9 9 9

9,999 99,999 9 9 9 9 9

The product shows a purity of more than 99% quinacridone by spectrophotometric analysis. The X-ray of the pigment shows the characteristics of the quinacridone beta type. When pigment is added to plastic or paints, it gives them a violet-red color with excellent properties.

Example 28

A 1 liter flask equipped with a thermometer, stirrer and condenser is charged with 40 g of 6,13-dihydroquinacridone, 180 ml of methanol, 42.5 g of a 50% aqueous sodium hydroxide solution and 14.6 g of an aqueous filter cake containing 1.6 g of methylquinacridone naphthalene-1- sulfonic acids as pigment additives prepared according to Example 2. The mixture was stirred under gentle nitrogen flow at 50-55 ° C for one hour. 0.5 is added. g of the anthraquinone monosulfonic acid sodium salt catalyst and the reaction mixture is heated to reflux. 67 g of an aqueous 19.3% hydrogen peroxide solution are added by means of a peristaltic pump at a pumping rate of 0.3 ml / min. After 15 minutes, 1.2 g of the phthalimidomethyldihydroquinacridone obtained according to Example 20 are added to the reaction mixture and then after 45 minutes. an additional 0.8 g of phthalimidomethyldihydroquinacridone, while continuously adding hydrogen peroxide while maintaining the boiling and slow flow of nitrogen. The resulting violet suspension is stirred for a further 10 minutes at boiling, then diluted with 100 ml of cold water and filtered. The filter cake was washed with hot water then dried to give 38.9 g of violet quinacridone.

The product shows high purity and contains only 0.7% of 6.13 dihydroquinacridone as determined by spectrophotometric methods. The X-ray of the pigment shows the characteristics of beta quinacridone. The specific surface area measured by the BET method is 50 m ² / g.

· · E e e............ Fi · · · fi fi fi fi fi fi fi fi

When the product is added to automotive paints, an intense violet dispersion is obtained which has excellent theological properties and when coated onto a contrasting board, has a semi-transparent appearance and can be easily sprayed onto metal panels to give a violet paint that has excellent durability.

Example 29

A 1 liter flask equipped with a thermometer, stirrer and condenser was charged with 116.6 g of 45% aqueous potassium hydroxide, 20.0 ml of methanol and 0.8 g of phthalimidomethyldihydroquinacridone, as prepared according to Example 21. The mixture was stirred at 30-40 ° C for 5 minutes. 45 g of 2,9-dichloro-6,13-dihydroquinacridone and then 60 ml of methanol are added and the resulting suspension is stirred at low nitrogen flow, boiling for 1 hour, to give the potassium salt of 2,9-dichloro-6,13-dihydroquinacridone. . 0.6 g of anthraquinone-2-sulfonic acid sodium salt is added. 68 g of an aqueous solution of 16.9% hydrogen peroxide are added over a period of 3 hours 20 minutes using a pump set at 0.3 ml / min while maintaining boiling and a low nitrogen flow. The resulting fuchsin-colored suspension is stirred for a further 10 minutes at boiling, diluted with 100 ml of cold water, then filtered at 50-60 ° C. The filter cake was washed with hot water and dried to give 44 g of a fuchsin-colored 2,9-dichloroquinacridone pigment.

The X-ray of the pigment shows gamma characteristics of 2,9-dichloroquinacridone. The specific surface area measured by the BET method is 45.2 m ² / g. Addition to automotive paints results in an intense fuchsin paint dispersion having excellent rheological properties and which is easily sprayed onto metal panels to produce a fuchsin paint with excellent durability.

• 4 • »« • 4 «. 4

4 ·· * «

C 4 4 4

4 4 4

4 44

Example 30

A 1 liter flask equipped with a thermometer, stirrer and condenser was charged with 40 g of 6,13-dihydroquinacridone, 185 ml of methanol, 42 g of 50% aqueous sodium hydroxide solution and 1.2 g of methyl dihydroquinacridone barbituric acid as prepared according to Example 21. The mixture was stirred with a low nitrogen flow at 50-55 ° C for one hour. 0.5 g of anthraquinone monosulfonic acid sodium salt as catalyst is added and the reaction mixture is heated to boiling. 67 g of an aqueous solution of 19.3% are added using a peristaltic pump set at 0.3 ml / min while maintaining boiling and with a low nitrogen flow. hydrogen peroxide. The resulting violet suspension is stirred for a further 10 minutes at the boiling point, diluted with 100 ml of cold water, then filtered. The filter cake was washed with hot water and dried to give 38.9 g of purple red quinacridone.

The product is of high purity and is determined to contain only 0.1% of 6,13-dihydroquinacridone by spectrophotometric methods. The X-ray of the pigment shows the characteristics of beta quinacridone. The BET specific surface area is 8 m ² / g.

Addition to automotive paints results in an intense violet-red dispersion having excellent rheological properties when applied to a contrasting carton, opaque and also easily sprayed onto metal panels to produce a violet-red color with excellent durability.

Example 31

A 1 liter flask equipped with a thermometer, stirrer and condenser was charged with 45 g of 2,9-dichloro-6,13-dihydroquinacridone, 136.8 g

45% aqueous potassium hydroxide, 280 mL of methanol, 0.3 g of methyldihydroquinacridone o-benzoic acid sulfimide, such as &lt; tb &gt;

4 ingredients prepared according to Example 23 and 3.4 g of a 50% aqueous solution of benzyltributylammonium chloride. The mixture was stirred at 30-40 ° C for 5 minutes, then heated to boiling and stirred at low reflux for one hour to give the potassium salt of 2,9-dichloro-6,13-dihydroquinacridone. 0.6 g of anthraquinone-2-sulfonic acid sodium salt is added. Using a peristaltic pump set to 0.3 ml / min while maintaining boiling and a low nitrogen flow, 66 g of an aqueous solution of 17% hydrogen peroxide are added over 3 hours 20 minutes. The resulting fuchsin-colored suspension is stirred for a further 10 minutes at boiling, diluted with 100 ml of cold water, then filtered at 50-60 ° C. The filter cake was washed with hot water and dried to give 44 g of a fuchsin-colored 2,9-dichloroquinacridone pigment.

The x-ray pigment shows the gamma characteristics of 2,9-dichloroquinacridone. The specific surface area measured by the BET method is 20 rm / g. When added to car paints, a dispersion with an intense fuchsin paint is obtained which has excellent theological properties and which is easily sprayed onto metal panels behind. formation of fuchsin-colored paint with excellent durability.

Example 32

Crude beta chiriacridone having a particle size of 2 to 6. For example, the oxidation of 6,13-dihydroquinacridone by hydrogen peroxide as the oxidizing agent according to U.S. Patent No. 5,840,901 is carried out as follows:.

The 1-SDG Attritor ™ mill from Union Process, Inc.Akron, Ohio, which is provided with L-arms and contains 3.78 liters of ceramic grinding media with a diameter. 0.6 cm with 7.5 MOH hardness, 60-65 Rockwell 45N hardness, 3.0 kg / cm impact strength and 8500 kg / cm compressive strength. The mill is filled with 350 grams of raw betachinacridone and pigment. Pigment pigment pigment pigment pigment pigment pigment pigment pigment pigment pigment pigment pigment pigment pigment pigment pigment pigment pigment pigment pigment ··· ♦♦ · ··· * · · ·. 4 is milled under nitrogen flow at 500 rpm for 50 minutes. Upon completion of the grinding cycle, the product is obtained by opening the flap at the bottom of the mill, rotating for 15 minutes to obtain a brown highly aggregated powder of very low crystallinity.

Example 33

A 1 liter flask equipped with a thermometer, stirrer and condenser was charged with 0.3 g of methyldihydroquinacridone o-benzoic acid sulfimide, an additive prepared according to Example 23, and 250 ml of dimethylformamide. The mixture was stirred at 50-55 ° C for 15 minutes to partially dissolve the additive in the solvent. 30 g of the pre-ground powder obtained according to the above example are added and the suspension is stirred for 3 hours at 50 to 50 ° C. High: 55 ° C. The resulting purple suspension was filtered. The filter cake is washed with water and dried to give a violet pigment which exhibits excellent durability and high color saturation when added to plastics and dyes. The radiograph shows the characteristics of beta quinacridone.

Example 34A

The process described in Example 32 was repeated using crude 3, β-diphenyl-1,4-diketopyrrole- [3,4-c] -pyrrole instead of betachinacridone to give a brown, highly aggregated powder of very low crystallinity.

Example 34B

A 1 liter flask equipped with a thermometer, stirrer and condenser was charged with 0.5 g of methyldihydroquinacridontoluenesulfonic acid as prepared according to Example 25 and 230 ml of dimethylsulfoxide. The mixture is stirred at 50-55 ° C for 15 minutes, while the additive is partially dissolved in the solvent. Add 20 g ··········· 99 99 99

9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 99 99 99 of the powder prepared according to Example 34A, and the suspension was stirred at 2-3-25 ° C for 2 hours. The resulting red suspension is filtered. The filter cake is washed with water and dried to give a red pigment which, when added to paints and plastics, has a very intense color, high opacity, as well as excellent durability and high color saturation.

Example 35A

The procedure of Example 32 was repeated using perylene 3,4,4,10,10-tetracarboxylic acid diimide instead of betachinacridone to give a highly aggregated powder of very low crystallinity.

Example 35B

A 1 liter flask equipped with a thermometer, stirrer and condenser was charged with 0.2 g of methyldihydroquinacridone-benzenesulfonic acid as prepared according to Example 25 and 250 ml of dimethyl sulfoxide. The mixture is stirred at 50-55 ° C for 15 minutes, while the additive is partially dissolved in the solvent. 20 g of the pre-ground powder prepared according to Example 35A were added and the suspension was stirred at 80-90 ° C for 2 hours. The resulting purple suspension is filtered. The filter cake is washed with water and dried to give a violet pigment which, when added to paints and plastics, has a very intense color, excellent durability and high transparency.

Example 36

With a nitrogen flow, a 1 liter flask equipped with a thermometer, stirrer and condenser was charged with 100 ml of t-amyl alcohol, 34.6 g of potassium t-butyrate, and 144.4 g of benzonitrile and heated to 98 ° C. Using a metering pump, a nearly anhydrous solution of 14.6 g of dimethyl succinate in 10 ml of t-amyl alcohol was added over a period of 145 minutes at 98-99 ° C and methanol was added.

999

99

9 9 9 t · · «· · · ·

9 9 9

9 9 9 distills. After the addition was complete, the reaction mixture was stirred at 99 ° C for 2 hours and 0.5 g of methyldihydroquinacridone-benzenesulfonic acid added as described in Example 24 was added, then the mixture was cooled to 65 ° C, diluted with 100 mL of methanol and 250 mL of water was added. . The mixture was filtered. The filter cake is washed with water until neutral to give 19 g of a red diketopyrrolopyrrole pigment of high color intensity, high saturation and good light stability when added to paints and plastics.

Example 37

63.0 g of polyvinyl chloride, 3.0 g of epoxidized soybean oil, 2.0 g of barium / cadmium heat stabilizer, 32.0 g of dioctyl phthalate and 1.0 g of betachinacridone prepared according to Example 28 are mixed in a glass beaker using a stir bar. The mixture is formed into soft 0.4 mm thick polyvinyl chloride sheets by 8 minutes rolling in a laboratory rolling mill at 160 ° C, a roller speed of 25 rpm and a fraction of 1: 1.2 at constant, wrinkling, removal and filling. The obtained soft polyvinyl chloride sheets have an attractive violet shade, they are very resistant to heat, light and migration.

Example 38 grams of fuchsine 2,9-dichloroquinacridone pigment prepared according to Example 31, 2.5 g hindered amine light stabilizer, 1.0 g benzotriazole UV absorber, 1.0 g hindered phenolic antioxidant and 1.0 g phosphite stabilizer after melting, it is mixed with 1000 g of high density polyethylene at a speed of 175 to 200 rpm for 30 seconds. The molten, pigmented resin is chopped when it is warm and malleable and then passed through. 9 9 9 9 9 9 9 9 9 9 9

99 99 .9 99 99 9 9 granulator. The resulting granules are injection molded at five minutes of rest and 30 second cycles at 260 ° C. The obtained homogeneously colored flakes show a bright fuchsin color with excellent light stability.

Example 39

Preparation of car paints ground vehicle:

A 1 liter vessel was charged with 66 grams of acrylic resin, 14.5 grams of AB dispersant and 58.1 grams of solvent (SOLVESSO 100 from American Chemical), 26.4 grams of the quinacridone pigment obtained according to Example 31 and 980 grams of iron diagonal bars were added. diameter 4 mm. The mixture is ground in a roller mill for 64 hours. The resulting milled composition contains 16.0% pigment at a pigment / binder ratio of 0.5 and a total nonvolatile content of 48.0%.

solid color:

Mix 47.3 g of the above milled formulation, 36.4 g clear solid solution containing melamine resin catalyst, non-aqueous resin dispersion and UV absorber, and 16.3 g balanced clear solid solution containing polyesterurethane resin and dilute with a solvent mixture containing 76 parts xylene , 21 parts of butanol and 3 parts of methanol for a spraying viscosity of 20 to 22 seconds as measured by the # 2 Fisher Cup.

The resulting purple resin / pigment dispersion is sprayed twice at 1.5 minute intervals as a primer on the panel. After minutes, a clear resin coating is sprayed twice at 1.5 minute intervals onto the primer. Sprayed panel with

9 999 9999 99 9 999 9999 9 9 9 99 99 9 * - * 9 9 9 9 9 99 9 '99999 99999 9999 then air dried in the oven for 10 minutes and then cured in the oven at 129 ° C for 30 minutes, giving a violet-red panel with excellent weather resistance.

Example 40

1000 grams of polypropylene granules (DAPLEN PT-55®, from Chemie Linz) and 10 grams of the 2,9-dichloroquinacridone pigment obtained in Example 29 were mixed well in a mixing drum. The granules so obtained are melted and cast at 260-285 ° C into fuchsin-colored fibers with good light fastness and textile fiber properties.

In addition to the embodiments described above, many variations of these embodiments are possible according to the present invention, the scope of which is limited only by the appended claims.

»999 9 • · 9 • 9% - £> (? £> ~ ^ Ο ·· 9 98 99 • 9 9 9 9 9 9 9

9 9 9 9 9 9 • 9 9 9 9 9 9999 ·· 999 99,999 · 9,99

Claims (12)

FURTHER CLAIMS A compound of formula I (MO 5 S ¹ -Q ¹ - (CH ₂ - (X ¹ ) - (Y Jn ¹ )) (I), wherein: M is a metal cation, a quaternary nitrogen cation or a hydrogen atom; Y ¹ is a sulfonic or carboxylic acid or a salt thereof; Q ¹ is a pigment group; X ¹ is an aromatic group, a cycloheteroaliphatic group containing at least one five or six membered ring, or a heteroaromatic group containing at least one six membered ring and which is not a phthalimido group; m ^{1 and} n ¹ are independently from 0 to 2.5; o ¹ is a number of 0.05 to 4 or or a compound of formula II (MO ₃ S) _m ² -Q ² - (CH ² - (X ² ) - (Y ² ) n ² ) _o ² (II) Q ² is a 6,13-dihydroquinacridone group of formula III (III) A and D are, independently of one another, a substituent selected from the group consisting of hydrogen, fluorine, chlorine, alkyl · 9 · 99 99 9 9 9 99 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 99 99 99 99 Group (C 1 -C 3) and (C 1 -C 3) alkoxy; M is a metal cation, a quaternary nitrogen cation or a hydrogen atom; Y ² is a sulfonic or carboxylic acid; or. a salt thereof; X ² is an aromatic group, a cycloheteroaliphatic group containing at least one five or six membered ring, or a heteroaromatic group containing at least one five or six membered ring and which is not a phthalimido group; m ² and ^{n 2} are independently from 0 to 2.5; and ¹ is ^an integer of 0 to 4. The compound of claim 1, wherein said pigmented group Q ¹ in formula ¹ is a pigment selected from the group consisting of anthraquinone, phthalocyanine, perinone, perylene, diketopyrrolopyrrole, thioindigo, iminoisoindoline, imino ispindolinone, quinacridone, flavanthrone, dioxazine. , indathron, anthrapyrimidine and quinophthalone pigments. A compound according to any one of claims 1 or 2, wherein the pigment group in the formula is a pigment selected from the group of quinacridone or diketopyrrolopyrrole pigments. A compound according to any one of claims 1 or 3, wherein the pigment of formula I is a quinacridone of formula IV: or a 6,13-dihydroquinacridone of formula III, wherein A and D are independently selected from the group consisting of hydrogen, fluorine, chlorine, · * «· · · · · · · ί · · ······ 4 0 · · · ··· An alkyl group having 1 to 3 carbon atoms and an alkoxy group having 1 to 3 carbon atoms. A compound according to claim 1, wherein X ¹ and X ² is an aromatic group selected from a pentagonal or hexagonal ring or a polycyclic group containing two to six fused pentagonal and / or hexagonal rings or a cycloheteroaliphatic group containing at least one pentatomic or hexatomic ring or X ² are fused five and / or six-atom rings, or X ¹ is a non-phthalimido heteroaromatic group containing a six-atom ring or fused five and / or six-atom rings, and wherein said heteroaromatic group contains 1 to 4 heteroatoms selected from the group consisting of nitrogen; a sulfur atom and / or an oxygen atom, and wherein said heteroaromatic group X ² is not a phthalimido group and contains a five or six-atom ring or a fused five and / or six-atom ring and contains 1 to 4 heteroatoms selected from nitrogen, sulfur and /No or an oxygen atom. Process for the preparation of compounds of formula I or II according to claim 1, characterized in that: (a) dissolve pigment pigment group Q ¹ or Q ² in concentrated sulfuric acid; (b) intermediate X ¹ or X ² is added to the solution and dissolved at a temperature below 50 ° C; (c) paraformaldehyde is added at a temperature below 50 ° C; d) and then heated to 50-100 ° C; e) and then isolated. 7. Process for the direct synthesis of anthraquinone, phthalocyanine, perinone, perylene, diketopyrrolopyrrole, thioin. particle size, characterized in that said pigment or solid solution thereof is synthesized in the presence of 0.1 to 25% by weight - relative to the weight of the pigment to be synthesized - of the compound of formula I controlling the particle growth of the pigment and / or the crystal phase. 8. A process for the direct preparation of a diketopyrrolopyrrole or quinacridone pigment or a solid solution thereof, comprising the step of synthesizing said pigment or solid solution in the presence of 0.1 to 25% by weight, relative to the weight of the pigment to be synthesized, of at least one. of the compound of formula I or 0.5 to 8% by weight of the 6,13-dihydroquinacridone according to claim 1, based on the weight of the pigment to be synthesized. 9. A process for the preparation of anthraquinone, phthalocyanine, perinone, perylene, diketopyrrolopyrrole, thioindigo, iminoisoindoline, iminoisoindolinone, quinacridone, flavanthron, dioxazine, indathron, anthrapyrimidine and quinophthalone particles of the following sizes: a kneading step, a step of grinding in solvent or water, or a step of pre-grinding followed by treatment in an organic solvent, in the presence of 0.1 to 25% by weight of the 6,13-dihydroquinacridone according to claim 1, based on the weight of the pigment to be treated. 10. Process for the direct preparation of quinacridone, 2,9-dichloroquinacridone, 4,11-dichloroquinacridone, 2,9-dimethylquinacridone or diketopyrrolopyrrole or quinakri. . • · ··· ···· · ··· » 49 of the orifice pigment or solid solution thereof, characterized in that, in the case of quinacridone, 2,9-dichloroquinacridone, The 4,11-dichloroquinacridone, 2,9-dimethylquinacridone pigment comprises the step of synthesizing said pigment or a solid solution thereof in the presence of 0.5 to 8% by weight of the 6,13-dihydroquinacridone of formula II according to claim 1 or in the case of diketopyrrolopyrrole or quinacridone pigment said pigment or a solid solution thereof in the presence of 0.1 to 25% by weight of the compound of formula I according to claim 1, based on the weight of the pigment to be synthesized. 11. A method of improving the thermal stability, rheological and flocculation properties of pigment particles, comprising adding at least one compound of claim 1 to said pigment particles in an amount sufficient to reduce flocculation or increase thermal stability. Use of compounds of formula I or II according to claim 1 for improving the thermal stability, rheological and flocculation properties of pigment particles.