MXPA97010059A - Surface- treated organic pigments - Google Patents

Abstract

This invention relates to a process for preparing pigment compositions comprising (a) treating an organic pigment with (1) about 0.1 to about 100 percent by weight, relative to the organic pigment, of a tertiary alkyl primary amine having the formula (1) (see formula) wherein R1 is a C5-C30 (cyclo)aliphatic group, and R2 and R3 are independently C1-C6 alkyl, (2) 0 to about 100 percent by weight, relative to the organic pigment, of a surfactant, and (3) about 5 to about 15 parts by weight per part by weight of the organic pigment of a liquid in which the organic pigment is substantially insoluble, thereby forming a suspension of the surface-treated pigment composition in the liquid;and collecting the pigment composition.

Description

ORGANIC PIGMENTS TREATED ON THE SURFACE BACKGROUND OF THE INVENTION This invention relates to a process for preparing pigment compositions having a better dispersibility, for example in plastics and other macromolecular materials, by surface treatment of organic pigments with certain primary alkyl tertiary amines and eventual dispersants. The surface treatment is a type of finish in which certain auxiliary agents, such as rosin or other resins, are applied to the pigments to influence their surface structure and, thus, their physical and coloristic properties. For example, . Herbst and K. Hunger, Industrial Organic Pigments (New York: VCH Publishers, Inc., 1993), pages 205-207. Surface treatment is a particularly useful method to improve the dispersibility of pigments in inks, toners, paints, coatings and plastics. It is known to use amines or amine derivatives in the preparation of pigment dispersions. For example, Czech Patent 227,779 describes a two-stage process for dispersing organic pigments in inks by first dispersing the pigments in the presence of ampholytic sulfonates of C 12 -C 24 fatty acids and then coagulating the dispersed pigments with hydrophobic alkylamines or ethoxylated C 12 -C 24 fatty acids. . European Patent Application 544,441 describes dispersions of organic pigments in which the pigment is treated with a non-polar additive and dispersed in a solution containing a polar additive, including certain amines of rosin or multifunctional amines. However, these two patents, in addition to requiring two-step treatments using two different types of dispersants, do not disclose the use of primary alkyl-tertiary amines, a critical feature of the present invention. Japanese Patent 63 / 305,172 describes the dispersion of organic pigments in inks in the presence of certain surfactants, including stearylamine and stearyl propyleneamine. This patent, however, does not disclose the treatment of organic pigments with primary alkyl-tertiary amines, a critical feature of the present invention. U.S. Pat. No. 4,929,279 discloses aqueous dispersions prepared by adding certain surfactants to an aqueous suspension of the pigment and then subjecting the treated pigment to ultrasonic irradiation. The surfactants include closely defined groups of diamines having two tertiary amino groups, two quaternary ammonium groups or a combination of a secondary amino group with a primary amino group. This patent, however, does not disclose the treatment of organic pigments with primary alkyl-tertiary amines, a critical feature of the present invention. The use of alkyl tertiary-primary amines according to the present invention provided pigment compositions having better dispersibility, as well as better storage stability when used in pigmented systems such as inks or paints. The presence of about 2% or more of a primary alkyl tertiary amine according to the invention also serves to reduce the viscosity of dispersions containing the pigment compositions of the invention. COMPENDIUM OF THE INVENTION This invention relates to a process for the preparation of pigment compositions consisting of (a) treating an organic pigment with (1) about 0.1 to about 100% by weight (preferably, 2 to 1). 20% by weight, more preferably 5 to 20% by weight), in relation to the organic pigment, of a primary alkyl tertiary amine having the formula (I) R2 where R1 is a C5-C30 aliphatic (cyclo) group (preferably a C5-C22 aliphatic group) and R2 and R3 are independently C? -C6 alkyl (preferably methyl), (2) 0 to about 100% by weight, in relation to the organic pigment, of a surfactant and (3) about 5 to about 15 parts by weight (preferably, 6 to 12 parts by weight) per part by weight of the organic pigment of a liquid in which the organic pigment is substantially insoluble, thereby forming a suspension of the pigment composition surface treated in the liquid and (b) collecting the composition of pigment. This invention is further related to pigment compositions prepared by the process of this invention and to the use of said pigment compositions in the pigmentation of plastics, coatings, fibers, printing inks (including inkjet inks) and Similar. DETAILED DESCRIPTION OF THE INVENTION Suitable organic pigments for the process of the present invention include quinacridone, phthalocyanine and perylene pigments, as well as other known organic pigments. Mixtures, including solid solutions, of such pigments are also suitable. Quinacridone pigments are particularly suitable organic pigments. Quinacridones (including unsubstituted quinacridone, quinacridone derivatives and solid solutions thereof) can be prepared by methods known in the art, but are preferably prepared by thermal ring closure of various precursors of 2,5-dianilinoterephthalic acid. For example, S.S. Labana and L.L. Labana, "Quinacridones", in Chemical Review, 67, 1-18 (1967), and US Patents. 3,157,659, 3,256,285 and 3,317,539. Suitable quinacridone pigments can be unsubstituted or substituted (for example, with one or more alkyl, alkoxy, halogens such as chlorine or other typical quinacridone pigment substituents). The metal phthalocyanine pigments are also suitable organic pigments. Although copper phthalocyanines are preferred, other phthalocyanine pigments containing metals, such as those based on zinc, cobalt, iron, nickel and other metals of this type, can also be used. Suitable phthalocyanine pigments can be unsubstituted or partially substituted (for example, with one or more of alkyl, alkoxy, halogens such as chlorine or other typical phthalocyanine pigment substituents). The perylenes, particularly the diimides and dianhydrides of perylene-3, 4, 9, 10-tetracarboxylic acid, are also suitable organic pigments. Suitable perylene pigments may be unsubstituted or substituted (for example, with one or more alkyl, alkoxy, halogens such as chlorine or other typical perylene pigment substituents). Other suitable organic pigments include dioxazines (ie, triphenoxazoins), 1-diketopyrropyrroles, anthrapyrimidines, antantrones, flavantrones, indantrones, isoindolines, isoindolinones, perinones, pyrantrones, thioindigos, 4,4'-diamino-1, 1'- diantraquinonyl and azo compounds, as well as substituted derivatives. The organic pigment is first mixed in step (a) with a primary alkyl tertiary-amine and any eventual surfactant in a liquid in which the organic pigment is substantially insoluble. Suitable primary alkyl tertiary-amines (a) (1) are amines having the formula (I) R ~ * where R1, R2 and R3 have the meanings given above. The term "C ^ Cg alkyl" refers to straight or branched chain aliphatic hydrocarbon groups having from 1 to 6 carbon atoms. Examples of C ^ Cg alkyl are methyl, ethyl, propyl, butyl, pentyl, hexyl and their isomeric forms. The groups R2 and R3, however, should not be branched at the carbon atom attached to the C-NH2 moiety. The term "(C5-C30 aliphatic) cycle" as used herein refers to branched and unbranched, saturated and unsaturated aliphatic groups, as well as to groups consisting of or containing cycloaliphatic groups, having from 5 to 30 carbon atoms. The R1 group, however, is preferably unbranched or unsaturated at the carbon atom directly attached to the C-NH2 moiety. Examples of suitable C5-C30 aliphatic (cyclo) groups include C5-C30 alkyl, C5-C30 alkenyl, C5-C30 alkadienyl, C5-C30 alkanthienyl, as well as their isomeric branched forms, and C5-C8 cycloalkyl, C5- cycloalkenyl C8 and C5-C8 cycloalkalienyl. Examples of suitable C5-C30 aliphatic groups (cyclo) include alkyl, alkenyl, alkadienyl and alktrienyl groups in which the main chain is interrupted by one or more C5-C8 cycloalkylene groups, C5-C8 cycloalkenylene or C5-C8 cycloalkadienylene. , provided that the number of carbon atoms totals no more than 30 carbon atoms. Although, in general, it is not preferred, it is also possible to include (cyclo) aliphatic groups in which one or more of the (cyclo) aliphatic carbon atoms are substituted with halogen (such as fluorine or chlorine), CX-C6 alkoxy or C6-C10 aromatic hydrocarbon (preferably phenyl or naphthyl), which may in turn be optionally substituted. It is also possible, although much less preferred, to replace one or more non-adjacent aliphatic carbon (cyclo) atoms with an oxygen or sulfur atom or a NRa group (where Ra is alkyl or C6-C10 aryl). It is even possible to substitute one or more non-adjacent aliphatic chain carbon atoms of the R1 group with an aromatic ring, such as a benzene ring (although the resulting group would not be, in a formal sense, an "aliphatic" group). In general, the preferred primary alkyl tertiary amines are those in which the R 1 group is an acyclic aliphatic group having from 5 to 22 carbon atoms. The term "C5-C30 alkyl", as used for the group R1, refers to alkyl groups having from 5 to 30 carbon atoms, such as pentyl, hexyl, lauryl (ie, dodecyl), myristyl (is say, tetradecyl), cetyl (ie, hexadecyl), stearyl (ie, octadecyl), eicosanyl, docosanil and their isomeric forms. The terms "C5-C30 alkenyl", "C5-C3o alkadienyl" and "C5-C30 alkanthienyl" refer to corresponding unsaturated groups having one, two and three carbon-carbon double bonds, respectively. The term "C5-C8 cycloalkyl" refers to cycloaliphatic hydrocarbon groups having from 5 to 8 carbon atoms. Examples of C5-C8 cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. The terms "C5-C8 cycloalkenyl" and "C5-C8 cycloalkdienyl" refer to corresponding unsaturated cyclic groups having one and two carbon-carbon double bonds, respectively. The terms "C5-C8 cycloalkylene", "C5-C8 cycloalkenylene" and "C5-C8 cycloalkadienylene" refer to the corresponding difunctional cycloaliphatic groups. The term "Cj-Cg alkoxy" refers to straight or branched chain alkyloxy groups having from 1 to 6 carbon atoms. Examples of C] -C6 alkoxy methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy and its isomeric forms are examples. The term "C6-C10 aromatic hydrocarbon" refers to phenyl and 1- or 2-naphthyl, as well as to phenyl and naphthyl groups substituted with alkyl or halogen. Examples of suitable halogen are fluorine, chlorine and bromine. The primary alkyl tertiary-amines suitable for use as component (a) (1) can be purchased commercially under the name PRIMENE from Rohm and Haas Company (Philadelphia, Pennsylvania). Suitable surfactants (a) (2) include nonionic, cationic, positive and negative charged, amphoteric and anionic surfactants known in the art. Preferred surfactants are anionic surfactants containing carboxylate, sulfonate, phosphate or phosphonate groups, either as free acids or as the salts of alkali metals, alkaline earth metals or ammonium salts (especially sodium or potassium salts) . Particularly preferred anionic surfactants are sulfosuccinates, sulfosuccinamates and their derivatives. Examples of suitable sulfosuccinates are sodium disodium sulfosuccinate, sodium diamyl sulfosuccinate, sodium dibutylsulphosuccinate, sodium diisobutylsulfosuccinate, dihexyl sulfosuccinate, sodium dihexylsulfosuccinate, dioctyl sulfosuccinate, sodium dioctyl sulfosuccinate, sodium diisooctylsulfosuccinate, disodium isodecylsulfosuccinate, bis (tridecyl) sulfosuccinate. ), bis (tridecyl) sodium sulfosuccinate, lauric sulfosuccinate, disodium lauryl sulfosuccinate, diammonium lauryl sulphosuccinate, sodium dicyclohexylsulfosuccinate, other sodium alkylsulfosuccinates and (cyclo) alkylsulfosuccinates disodium, laureth disodium sulfosuccinate, lauryl ether sulfosuccinate, lauramidoethanolamine disodium sulfosuccinate, lauric diethanolamide sodium sulfosuccinate ester, lauramidoisopropanolamine disodium sulfosuccinate, oleic sulfosuccinate, ricinoleic sulfosuccinate, disodium oleth-3-sulfosuccinate, disodium oleamidoethanolamine sulfosuccinate, oleam idoisopropanolamine disodium sulfosuccinate, monooleamido PEG-2 disodium sulfosuccinate, coconut sulfosuccinate, cocamidoisopropanolamine disodium sulfosuccinate, the ethoxylated alcohol ester medium of disodium sulfosuccinate, disodium nonoxynol-10-sulfosuccinate and disodium mono- and didodecyldiphenyloxide disulfonate. Examples of suitable sulfosuccinamates are disodium N-octadecylsulfosuccinamate and other N-alkyl- and N-dialkylsulfosuccinamates' and N- (1,2-dicarboxyethyl) -N-octadecylsulfosuccinamate tetrasodium. These and other surfactants can be purchased commercially, example under the names AEROSOL and SOLUSOL (Cytec Industries, Inc., West Paterson, New Jersey), ARYLENE (Huntsman Corp., Houston, Texas), ASTROMID and ASTROWET (Aleo Chemical Corp.). , Chattanooga, Tennessee), EMCOL and VARSULF (Witco Corp., Greenwich, Connecticut), ERINAL and IRGASOL (Ciba-Geigy Corp., Greensboro, North Carolina), FOAMPOL (Alzo Inc., Matawan, New Jersey), GEMTEX (Finetex Inc., Elmwood Park :, New Jersey), GEROPON (Rhone-Poulenc Inc., Cranbury, New Jersey), HAROL (Graden Corp., Havertown, Pennsylvania), INCROSUL (Croda, Inc., Parsippany, New Jersey), MACKANATE (Mclntyre Chemical, University Park, Illinois), MONAMATE and MONAWET (Mona Industries, Inc., Paterson, New Jersey), NAXAF (Ruetgers-Nease Corp., State College, Pennsylvania), PROTOWET (Sybron Chemical Inc., Well, South Carolina), TEXAPON (Henkel Corp., Cincinna-ti, Ohio), TRITON (Union Carbide Corp., Danbury, Connecti-cut) and VULTAMOL (BASF Corpora Mount Olive, New Jersey). Other suitable anionic dispersants include neodecanoic acid (Exxon Chemical, Baton Rouge, Louisiana), sodium N-methyl-N-oleoyltaurate (Finetex Inc., Elmwood Park, New Jersey), sulfonated aliphatic polyesters and an aromatic sulfonate dispersant that can be purchased as a K-Sperse dispersant (King Industries, Norwalk, Connecticut). Suitable nonionic surfactants include fatty acids and ethoxylated amides, ethoxylated alcohols, ethoxylated alkylphenols and glycol esters. Suitable cationic surfactants include ethoxylated and / or propoxylated amines, diamines and quaternary ammonium salts. Amphoteric surfactants and having suitable positive and negative charges include amine oxides and betaine derivatives. Mixtures of surfactants are also, of course, suitable. The stage of the surface treatment (a) is carried out in a liquid (a) (3) in which the organic pigment is substantially insoluble, preferably water, an organic liquid miscible with water (such as methanol or other lower aliphatic alcohols) or mixtures thereof. It is desirable, although not necessary, that the primary alkyl tertiary amines (a) (1) be at least partially insoluble in liquid (a) (3). Surfactants (a) (2) are frequently soluble in liquid (a) (3), but solubility is not an essential characteristic. Suitable liquids include water and / or organic liquids miscible in water, including, for example, lower aliphatic alcohols, such as methanol.; ketones and ketoalcohols, such as acetone, methyl ethyl ketone and diacetone alcohol; amides, such as dimethylformamide and dimethylacetamide; ethers, such as tetrahydrofuran and dioxane; alkylene glycols and triols, such as ethylene glycol and glycerol, and other such organic liquids known in the art. Other organic liquids may be used, but are generally less preferred. The temperature at which the surface treatment is carried out is not critical in general, but is normally maintained between about 5 ° C and about 200 ° C. In general, temperatures between 5 ° C and the boiling point of the mixture (which may be under pressure) are preferred. During, or immediately following, step (a), the pigment composition may optionally be subjected to cavitation conditions using any known method (preferably using ultrasound). For example, US Pat. 4,588,576 and 4,929,279. Ultrasonic irradiation can be obtained by any conventional system in which an appropriate container is equipped with a source of high frequency vibrations, such as a piezoelectric, mechanical or magnetorestrictive acoustic generator, at sound frequencies varying between approximately 15 and approximately 20,000 kilohertz. The temperatures are not critical in general, but are usually between about 5 ° C and about 80 ° C, and, for safety reasons, are preferably kept well below the boiling point of the liquid medium. The resulting pigment is collected in the stage (b) by methods known in the art, but is preferably collected by filtration, followed by washing to remove residual acid. Other collection methods known in the art, such as centrifugation or even simple decanting, are suitable, but generally less preferred. The pigment is then dried for use or for further handling before use. The pigments of this invention are highly water resistant, oil resistant, acid resistant, lime resistant, alkali resistant, solvent resistant, overcoat stable, over spray stable, sublimation stable, heat resistant and resistant to vulcanization and still give a very good dyeing performance and are easily dispersible (for example, in plastic materials). Due to their light stability and migration properties, the pigments according to the present invention are suitable for many different pigment applications. For example, the pigments prepared according to the invention can be used as a colorant (or as one of two or more colorants) for photoresist pigmented systems. The pigments of the present invention are particularly suitable for use in macromolecular materials, especially macromolecular substances synthetically produced. Examples of synthetic macromolecular substances include plastics materials, such as polyvinyl chloride, polyvinyl acetate and polyvinyl propionate; polyolefins, such as polyethylene and polypropylene; high molecular weight polyamides; polymers and copolymers of acrylates, methacrylates, acrylonitrile, acrylamide, butadiene or styrene; polyurethanes, and polycarbonates. Other suitable macromolecular substances include those of natural origin, such as gum; those obtained by chemical modification, such as acetylcellulose, cellulose butyrate or viscose; or those produced synthetically, such as polymers, polyaddition products and polycondensates. The materials pigmented with the pigments of the invention can have any desired shape. The pigments of the present invention are also suitable for blends pigmented with other materials, pigment formulations, paints, printing ink and colored paper. It is understood that the term "mixtures with other materials" includes, for example, mixtures with inorganic white pigments, such as titanium dioxide (rutile) or cement, or other organic pigments. Examples of pigment formulations include pastes washed with organic liquids or pastes and dispersions with water, dispersants and, if appropriate, preservatives. Examples of paints in which the pigments of this invention may be used include, for example, physical or oxidative drying lacquers, hot enamels, reactive paints, two-component paints, solvent or water-based paints, emulsion for coatings to waterproof and tempered. Printing inks include those known for use in paper, textiles and tinplate printing. The following examples further illustrate the details for the process of this invention. The invention, which is set forth in the foregoing description, is not limited in spirit or scope by these examples. Those skilled in the art will readily understand that known variations of the conditions of the following procedures can be used. Unless stated otherwise, all temperatures are in degrees Celsius and all percentages are percentages by weight.

EXAMPLES Quinacridones The following quinacridone pigments were used as starting materials for the Examples: Quinacridone (beta form), 2,9-dimethylquinacridone and 2,9-dichloroquinacridone were prepared according to the method described in US Pat. 3,342,828 and were obtained in the form of crude cake from the filter press by drowning the reaction mixtures in methanol. The resulting raw pigments were collected, but not conditioned or treated on the surface. A solid solution containing 75% of 2,9-dimethylquinacridone and 25% of quinacridone was prepared in a similar manner using mixtures of the unsubstituted and methyl-substituted unsaturated 2,5-dianilinoterephthalic acid precursors. The resulting crude pigment solid solution was collected and finished by suspension in water / methanol at a pH of 9, heat treatment at 115-120 ° C and isolation of the finish. The solid solution of finished pigment was not treated on the surface. The following commercial pigments were used as comparative standards: Standard A: 2, 9-dimethylquinacridone, available as QUINDO® Magenta RV-6832 from Bayer Corporation. Pattern B: 75% solid solution of 2, 9-dimethylquina cridone and 25% quinacridone, available as QUINDO® Magenta RV-6825 from Bayer Corporation. Standard C: 2, 9-Dichloroquinacridone, available as QUINDO® Magenta RV-6863 from Bayer Corporation.

Pattern D: 2, 9-Dichloroquinacridone, available as MONASTRAL® Magenta RT-235-D from Ciba-Geigy Corp.

Pattern E: Quinacridone, available as QUINDO® Magenta RV-6911 from Bayer Corporation. Primary alkyl tertiary-amines The following primary alkyl tertiary-amines according to the invention were used in Examples: t-Amin A: A tertiary C 16 -C 22 amine available as PRIMENE® JM-T from Rohm and Haas Company, Philadelphia, PA . t-Amin B: A tertiary C12-C14 amine available as PRIMENE® 81-R from Rohm and Haas Company, Philadelphia, PA. t-Amine C: A tertiary octylamine containing 99% of 1,1,3,3-tetramethylbutylamine (available as • PRIMENE® TOA from Rohm and Haas Company, Phila delphia, PA) Dispersibility in PVC Dispersibilities of prepared pigments according to the examples they were determined in polyvinyl chloride ("PVC") using untreated pigments and / or commercial pigments to be compared Dispersibility was evaluated by comparing the development of hot rolled and cold rolled color according to the following procedure. studied, a 50 g portion of flexible PVC was added to a two-roll hot mill (155 ° C) having a narrowing thickness of 25 mils (about 0.6 mm) and washed until uniform. a 0.050 g portion of the test pigment or the comparative pigment in the constriction over a period of about ten seconds, after which the washed material was cut and laminated in the mill for five minutes. The pigmented plate of the mill was then removed and placed on a clean flat surface to cool. A piece cut from the resulting sheet and which had been allowed to cool to room temperature as a "hot-rolled" sample for evaluation was used. A sample cut from the same sheet was placed while it was still hot on a cold mill (24 ° C) of two rollers having a narrowing thickness of 21 mils (approx, 0.5 mm), then it was folded and passed through the mill seven times. The cold rolled sheet was again washed in the hot mill until smooth. A sample cut from the resulting sheet was used as a "cold rolled" sample for evaluation. Color development was evaluated using a scale of 1 to 5 based on the difference between the development of hot rolled and cold rolled color, where 1 represents poor dispersibility (evidenced by extreme differences in color development) and 5 represents excellent dispersibility (evidenced by essentially no difference in color development). Studies of solvent-based paints Studies of solvent-based paints were carried out using a generic system of alkali melamine paints. Pigment dispersions were prepared using a 33% blend of AROPLAZ® 1453-X-50 alkyd resin (Reichhold Chemicals, Inc.), 63% xylene and 4% pigment, which gave a pigment-binding ratio of 4:33 and a total solids content of 37%. The pigment-to-binder ratio was reduced to 1:10 by the addition of 2.3% AROPLAZ® 1453-X-50 alkyd resin and 6.5% RESIMENE® 717 melamine resin (Monsanto Company), which gave a total solids content of 40%. Measurements of mass tone and transparency were made using films applied at 152 μm and 38 μm wet film thickness, respectively, and flashed at room temperature for 30 minutes and at 121 ° C for 30 minutes. Paints were prepared for surface printing from the dispersion described above, which had a pigment-to-binder ratio of 4:33, adding 31% of a dispersion prepared from 30% AROPLAZ® alkaline resin 1453- X-50, 20% xylene, 5% NUOSPERSE® 657 (Hüls America) and 50% Ti02 pigment TI-PURE® R-960 (DuPont); 21% AROPLAZ® alkaline resin 1453-X-50, and 7% RESIMENE® 717 melamine resin, which gave a pigment-to-binder ratio of 1: 2, a total solids content of 50% and a Ti02-a-pigment ratio of 90:10. Color measurements were made using films applied at 76 μm wet film thickness and flashed at room temperature for 30 minutes and at 121 ° C for 30 minutes. Metal paints were prepared from the dispersion described above, which had a pigment-to-binder ratio of 4:33, using an aluminum paste (which can be obtained as 5251 AR from Silberline Manufacturing Co., Inc.), resin AROPLAZ® 1453-X-50 alkyd and RESIMENE® 717 melamine resin in quantities that give rise to a pigment-to-binder ratio of 1: 9, an aluminum-to-pigment ratio of 20:80 and a total solids content of 41% Color measurements were made using films applied at a wet film thickness of 76 μm and flashed at room temperature for 30 minutes and at 121 ° C for 30 minutes. Water-based paints studies Water-based paints studies were carried out using a waterborne base coat / solvent-borne clear coat system. Aqueous dispersions were prepared using 12.4% acrylic resin AROLON® 559-G4-70 (Reichhold Chemicals, Inc.), 3.2% hyperdispersant SOLSPERSE® 27000 (Zeneca, Inc.), 1.6% of 2-amino-2-methyl-1-propanol (Angus Chemical) and 18% pigment, which gave a pigment-to-binder ratio of 18:12 and a total solids content of 30%. The pigment-to-binder ratio was then reduced to 10:40 with additional AROLON® 559-G4-70 acrylic resin (total amount, 26%) and 25% CYMEL® 325 melamine / for-maldehyde resin (Cytec Industries ), which gave a total solids content of 50%. Measurements of mass tone and transparency were made using films applied at 76 μm and 38 μm wet film thickness, respectively, and allowed to stand at room temperature for fifteen minutes and at 100 ° C for five minutes. Transparent layers were then applied containing a mixture of 80% AROPLAZ® 1453-X-50 alkyd resin (Reichhold Chemicals, Inc.) and 20% CYMEL® 325 melamine / formaldehyde resin to a total solids level of 57% on the base layer at a wet film thickness of 76 μm, allowed to stand at room temperature for fifteen minutes and at 121 ° C for fifteen minutes. Paints for surface printing were prepared from the reduced aqueous dispersions described above, which had a pigment-aligner ratio of 10:40 by addition of additional acrylic resin AROLON® 559-G4-70, melamine resin / formaldehyde CYMEL® 325 and 35% white dispersion of TINT-AYD® CW-5003 (Daniel Products Company), which gave a pigment-to-binder ratio of 1: 1.1, a total solids content of 55% and a Ti02 ratio -a-pigment of 90:10. Color measurements were made using films applied at a wet film thickness of 38 μm and allowed to stand at room temperature for fifteen minutes and at 100 ° C for five minutes. Transparent layers were then applied and baked as described above. Metal paints were prepared from the dispersion described above, which had a pigment-to-binder ratio of 18:12, using a water-dispersible aluminum pigment (which can be purchased as HYDRO-PASTE® 8726 from Silberline Manufacturing Co. , Inc.), AROLON® 559-G4-70 acrylic resin and CYMEL® 325 melamine / for-maldehyde resin in amounts that gave a pigment-to-binder ratio of 1: 2, an aluminum-to-pigment ratio of 20 : 80 and a total solids content of 43%. Color measurements were made using films applied at a wet film thickness of 38 μm and baked as described above. Transparent layers were then applied and baked as described above. Example 1 (comparative) Crude cake was resuspended from the filter press of 2, 9-dimethylquinacridone (120.0 g, corresponding to 25.0 g of 100% strength pigment) in 155.0 g of water. The suspension was heated at 140-145 ° C for two hours in a laboratory Parr reactor. The mixture was allowed to cool to room temperature and the pH was adjusted to 3.4. The suspension was stirred at 60 ° C for 30 minutes, after which the resulting suspension was filtered and washed with water. The wet cake of the filter press was dried in the oven at 60 ° C overnight to give 25.0 g of a magenta pigment (i.e., red-violet) that had no surface treatment.

Example 2 Crude cake was resuspended from the filter press of 2,9-dimethylquinacridone (120.0 g, corresponding to 25.0 g of 100% strength pigment) in 155.0 g of water and 5.0 g of t-Amina A. The suspension was heated at 140-145PC for two hours in a laboratory Parr reactor. The mixture was allowed to cool to room temperature and the pH was adjusted to 3.4. The suspension was stirred at 60 ° C for 30 minutes, after which the resulting suspension was filtered and washed with water. The wet cake was dried from the filter press in the oven at 60 ° C overnight to obtain 27.8 g of a magenta pigment having good dispersibility in PVC, as shown in Table 1.

TABLE 1 PVC Dispersibilities for the 2, 9-dimethylquinacridone pigments of Comparative Example 1 and of Example 2 Test sample Dispersibility Example 1 (comparative) 1 Example 2 2-3 Example 3 Crude cake was resuspended from filter press 2 , 9-dimethylquinacridone (120.0 g, corresponding to 25.0 g of 100% strength pigment) in 155.0 g of water and 5.0 g of t-Amine A. The suspension was heated to 140-145. ° C for two hours in a laboratory Parr reactor. The mixture was allowed to cool to room temperature and the pH was adjusted to 3.4. An emulsion of 0.9 g of an anionic sulfosuccinate surfactant and 13.1 g of petroleum distillate in water was added and the mixture was stirred at 50 ° C for three hours. The resulting suspension was filtered and washed with water. The wet cake was dried from the filter press in the oven at 60 ° C overnight to give 29.3 g of a magenta pigment having good dispersibility in PVC, as shown in Table 2. TABLE 2 Dispersibility in PVC for the 2,9-dimethylquinacridone pigment of Example 3 Test sample Dispersibility Example 3 3 Standard A 1-2 Example 4 Crude cake was resuspended from the filter press of 2,9-dimethylquinacridone (120.0 g, corresponding to 25.0 g of 100% strength pigment) in 155.0 g of water and 2.5 g of t-Amine-A. The suspension was heated at 140-145 ° C for two hours in a laboratory Parr reactor and allowed to cool to room temperature. After adding 5 g of an anionic aromatic sulfonate surfactant, the resulting mixture was stirred at 60 ° C for one hour and allowed to cool to 30 ° C. The resulting suspension was filtered and washed with water. The wet cake of the filter press was dried in the oven at 60 ° C overnight to obtain 32 g of a magenta pigment having good dispersibility in PVC, as shown in Table 3. TABLE 3 Dispersibility in PVC for the 2,9-dimethylquinacridone pigment of Example 4 Test sample Dispersibility Example 4 3 Standard A 1-2 Example 5 Crude cake was resuspended from the filter press of 2,9-dimethylquinacridone (67.5 g, corresponding to , 0 g of 100% strength pigment) in 140.0 g of water and 1.0 g of t-Amine B. The suspension was heated at 140-145 ° C for two hours in a laboratory Parr reactor. The mixture was allowed to cool to room temperature and the pH was adjusted to 3.2. An emulsion of 1.2 g of an anionic sulfosuccinate surfactant and 16.2 g of petroleum distillate in water was added and the mixture was stirred at 50 ° C for three hours. The resulting suspension was filtered and washed with water. The wet cake of the filter press was dried in the oven at 60 ° C overnight to obtain 19.5 of a magenta pigment having good dispersibility in PVC, as shown in Table 4. TABLE 4 Dispersibility in PVC for the 2,9-dimethylquinacridone pigment of Example 5 Test sample Dispersibility Example 5 3-4 Standard A 1-2 Example 6 A sample was resuspended (150.0 g, corresponding to 50.0 g of 100% strength pigment) ) of a solid solution cake from the filter press containing 75% 2,9-dimethylquinacridone and 25% quinacridone, which had been finished but not surface treated, at 650, 0 g of water and 5.0 g of t-Amine A. The suspension was heated at 60 ° C for one hour and allowed to cool to 50 ° C. After adjusting the pH to 3.4, the suspension was heated at 60 ° C for one hour. The resulting suspension was filtered and washed with water. The wet cake was dried from the filter press in the oven at 60 ° C overnight to obtain 54.0 g of a magenta pigment having good dispersibility in PVC, as shown in Table 5. TABLE 5 Dispersibility in PVC for the solid solution pigment of Example 6 Test sample Dispersibility Example 6 2-3 Standard B 1-2 Example 7 A sample was resuspended (150.0 g, corresponding to 50.0 g of 100% strength pigment) of a solid solution cake from the filter press containing 75% 2, 9-dimethylquinacridone and 25% quinacridone, which had been finished but not surface treated, in 650.0 g of water and 5.0 g of t-Amine A. The suspension was heated at 60 ° C for one hour and allowed to cool to 50 ° C. After adjusting the pH to 3.4, the suspension was heated at 60 ° C for one hour. An emulsion of 2.5 g of an anionic sulfosuccinate surfactant and 30.0 g of petroleum distillate in water was added and the mixture was stirred at 50 ° C for three hours. The resulting suspension was filtered and washed with water. The wet cake was dried from the filter press in the oven at 60 ° C overnight to obtain 52.1 g of a magenta pigment having good dispersibility in PVC, as shown in Table 6.

TABLE 6 Dispersibility in PVC for the solid solution pigment of Example 7 Test sample Dispersibility Example 7 3-4 Pattern B 1-2 Example 8 Crude cake was resuspended from the filter press of 2,9-dichloroquinacridone (200.0 g , corresponding to 66.7 g of 100% strength pigment) in 470.0 g of water and 12.0 g of t-Amine A. The suspension was heated at 140-145 ° C for two hours in a Parr reactor. from laboratory. The mixture was allowed to cool to room temperature and the pH was adjusted to 3.2. The suspension was stirred at 60 ° C for 60 minutes, after which the resulting suspension was filtered and washed with water. The wet cake was dried from the filter press in the oven at 60 ° C overnight to obtain 69.2 g of a magenta pigment having good dispersibility in PVC, as shown in Table 7 (which further shows the data for a comparative pigment prepared therefrom, without using t-Amin A), TABLE 7 PVC Dispersibilities for the 2,9-dimethylquinacridone pigment of Example 8 Test sample Dispersibility Example 8 3-4 Comparative 1-2 Example 9 resuspended crude cake from the press of the 2,9-dichloroquinacridone filter (50.0 g, corresponding to 16 g of 100% strength pigment) in 150.0 g of water and 3.2 g of t-Amine A. The suspension was heated at 140-145 ° C for two hours in a laboratory reactor. The mixture was allowed to cool to room temperature and the pH was adjusted to 3.2. An emulsion of 1.3 g of an anionic sulfosuccinate surfactant and 18 g of petroleum distillate in water was added and the mixture was stirred at room temperature for three hours. The resulting suspension was filtered and washed with water. The wet cake was dried from the filter press in the oven at 60 ° C overnight to obtain 16.6 g of a magenta pigment having good dispersibility in PVC, as shown in Table 8. TABLE 8 Dispersibility in PVC for the 2,9-dichloroquinacridone pigment of Example 9 Test sample Dispersibility Example 9 4-5 Pattern C 3-4 Pattern D 3-4 Example 10 Crude cake was resuspended from the quinacridone filter press (150.0 g , corresponding to 50.0 g of 100% strength pigment) in 255.0 g of water and 9.0 g of t-Amine A. The suspension was heated at 140-145 ° C for two hours in a Parr reactor. from laboratory. The mixture was allowed to cool to room temperature and the pH was adjusted to 3.3. The suspension was stirred at 60 ° C for 60 minutes, after which the resulting suspension was filtered and washed with water. The wet cake of the filter press was dried in the oven at 60 ° C overnight to obtain 52.9 g of a violet pigment having good dispersibility in PVC, as shown in Table 9, The pigment also exhibited better storage stability in a water-based latex paint system (as indicated by an essentially constant viscosity after stirring for two weeks at approximately 50 ° C). TABLE 9 PVC Dispersibility for the Quinacridone Pigment of Example 10 Test Sample Dispersibility Example 10 3-4 Pattern E 2-3 Example 11 Crude cake was resuspended from the quinacridone filter press (50.0 g, corresponding to 18, 3 g of 100% strength pigment) in 145.0 g of water and 3.0 g of t-Amine A. The suspension was heated at 140-145 ° C for two hours in a laboratory Parr reactor. The mixture was allowed to cool to room temperature and the pH was adjusted to 3.2 with phosphoric acid. An emulsion of 0.65 of an anionic sulfosuccinate surfactant and 9 g of petroleum distillate in water was added and the mixture was stirred at room temperature for three hours. The resulting suspension was filtered and washed with water. The wet cake was dried from the filter press in the oven at 60 ° C overnight to obtain 19.5 g of a violet pigment having good dispersibility in PVC, as shown in Table 10, TABLE 10 Dispersibility in PVC for the quinacridone pigment of Example 11 Test sample Dispersibility Example 11 4-5 Standard E 2-3 Example 12 Crude cake was resuspended from the filter press 2, 9-dimethylquinacridone (160.0 g, corresponding to 40.0 g of 100% strength pigment) in 310.0 g of water and 4.0 g of t-Amine B. The suspension was heated to 140-145. ° C for two hours in a laboratory Parr reactor. The mixture was allowed to cool to room temperature and the resulting suspension was filtered and washed with water. The wet cake of the filter press was dried in the oven at 60 ° C overnight to obtain 44.0 g of a magenta pigment. The water-based and solvent-based paints prepared as described above showed no improvement compared to the water-based and solvent-based paints prepared using Pattern A. Example 13 Crude cake was resuspended from the filter press. , 9-dimethylquinacridone (160.0 g, corresponding to 40.0 g of 100% strength pigment) in 310.0 g of water and 4.0 g of t-Amine B, The suspension was heated to 140-145. ° C for two hours in a laboratory Parr reactor. The mixture was allowed to cool to room temperature and the pH was adjusted to 3.4 with phosphoric acid. An emulsion of 1.75 g of an anionic sulfosuccinate surfactant and 23.0 g of petroleum distillate in water was added and the mixture was stirred at 45 ° C for three hours. The resulting suspension was filtered and washed with water. The wet cake was dried from the filter press in the oven at 60 ° C overnight to obtain 46.0 g of a magenta pigment. Water-based and solvent-based paints prepared as described above exhibited a more chromatic dye and a higher metallic luster as compared to the water-based and solvent-based paints prepared using Pattern A and the pigment of Example 12. Example 14 Crude cake was resuspended from the copper phthalocyanine filter press (Pigment Blue 15: 1 containing 13.5% chlorine) (266.0 g, corresponding to 40.0 g of 100% strength pigment ) in 375.0 g of water. The pH was adjusted to 4.4, after which, 4.0 g of neodecanoic acid and 3.0 g of t-Amine C were added sequentially with stirring. The suspension was heated at 130-135 ° C for one hour. Hour in a laboratory Parr reactor. The mixture was allowed to cool to room temperature, after which the resulting suspension was filtered and washed with water. The wet cake of the filter press was dried in the oven at 60 ° C overnight to obtain 45.0 g of a blue pigment.

Claims (10)

1. CLAIMS 1. A process for the preparation of a pigment composition, consisting of (a) treating an organic pigment with (1) about 0.1 to about 100% by weight, relative to the organic pigment, of an alkyl -primary-primary amine having the formula R2
2. R-C-NH2 i 'wherein R1 is a C5-C30 aliphatic (cyclo) group and R2 and R3 are independently C? -Cg alkyl, (2) 0 to about 100% by weight, based on the organic pigment of a surfactant and (3) about 5 to about 15 parts by weight per part by weight of the organic pigment of a liquid in which the organic pigment is substantially insoluble, thereby forming a suspension of the surface treated pigment composition in the liquid, and (b) collecting the pigment composition, 2. A process according to Claim 1, wherein the organic pigment is treated with 2 to 20% by weight, relative to the organic pigment, of the alkyl-tertiary-amine primary.
3. 3. A process according to Claim 1, wherein the primary alkyl tertiary amine is a compound having the formula R ' where R1 is a C5-C22 aliphatic group and R2 and R3 are methyl.
4. 4. A process according to claim 1, wherein from 6 to 12 parts by weight per part by weight of the liquid organic pigment (a) (3) are employed.
5. 5. A process according to Claim 1, wherein the liquid (a) (3), in which the organic pigment is substantially insoluble, is water, an organic liquid miscible with water or a mixture thereof.
6. 6. A process according to Claim 1, wherein the pigment composition is collected by filtration.
7. 7. A pigment composition prepared according to the method of Claim 1.
8. 8. A pigmented macromolecular material containing, as a pigment, a pigment composition prepared according to Claim 1.
9. 9. A pigmented coating containing, as a pigment, a composition of pigment prepared according to Claim 1.
10. 10. A pigmented printing ink containing, as a pigment, a pigment composition prepared according to Claim 1.