CS212330B2 - Pigment composition in the form of solid particles - Google Patents

Abstract

Pigmented compositions are described which are readily dispersible in oleoresin binder systems. The compositions comprise 25 to 95 % by weight of pigment and from 5 to 75 % by weight of certain water- insoluble, comminutable, thermoplastic polyester resins having a hydroxyl number of at least 50 mg of KOH per gram and having a ring- and-ball softening point of at least 60 DEG C. Particularly preferred polyester resins are the products of the condensation of an aromatic dicarboxylic acid or an anhydride or ester thereof, an aromatic monocarboxylic acid and an aliphatic polyol having at least three hydroxymethyl groups.

Description

The invention relates to readily dispersible solid dyes having broad compatibility with oil-resins binder systems; more specifically, it relates to a particulate non-agglomerating pigment composition that is readily dispersible in industrial-type oil-based binders and which provides color films or coatings with excellent gloss, hardness and durability.

It is known that pigments can be subsequently treated with organic compounds to alter the surface characteristics of the pigments. As such compounds, among others, liquid, non-drying fatty acid-modified alkyd resins (U.S. Pat. No. 2,479,836 to Hoback et al., U.S. Pat. No. 3,728,142 to Rudolf et al.) Are diglycol terephthalates or linear oligomers of terephthalic acid and ethylene glycol. No. 3,607,335 to Belde et al.), Low melting hydroxyl-terminated polylactones (U.S. Patent No. 3,754,956 to Durran et al.), Viscous carboxyesters having an acid number of up to about 140, derived from trimellitic acid and a fatty alcohol, or ester hydroxyl-terminated fatty acids (U.S. Patent No. 4,028,128 to Robertson). Pigments having a post-treatment of more than 10% by weight, based on the pigment of the aforementioned liquid; oils or viscous resins are sticky and clump and require special processing and storage. Furthermore, the resulting pigments are not sufficiently compatible with a variety of commercially available oil-resins carriers, which hinders their widespread commercial use and hence the pigments are used to a limited extent.

The use of liquid pigment dispersions as dyes for paints and inks is also known, and Stansfield in U.S. Patent 3,778,287 discloses dispersions of inorganic pigments, lacquers or tinting in organic liquids containing dissolved polyesters having an acid number of up to 100 derived therefrom. certain hydroxyl-containing saturated or unsaturated aliphatic carboxylic acids. While liquid dyes offer the obvious advantages of being more easily encapsulated in the medium to be dyed than dry pigments, their commercial significance is, however, severely limited due to the problems of processing and storing potentially hazardous liquid chemicals. Thus, from an economic and safety point of view, it is desirable to store the dyes in a dry, stable form that is readily dispersible over a wide range of coating media without compromising the desired properties of the coatings prepared therefrom.

It has now been found that solid particulate pigment compositions that do not have the above disadvantages can be prepared in a stable, non-agglomerating form and that these compositions exhibit excellent dispersing properties in air drying, firing and thermosetting oil-resin binder systems, and obtain so color coatings with excellent gloss, hardness and durability.

The invention thus relates to a pigment composition in the form of solid particles nízkoprášivých granules readily dispersible in olejopryskyřičných binder which is characterized in that it contains by weight from 25 to 95% ^p al.es he is no ^{d h} o ^ ^ gment between 5 and ⁷⁵ % N Spon ^d is not in the water-insoluble friable thermoplastic polyester resin with · a hydroxyl number of from ⁵⁰ to 15 ⁰ m ^g K0H / ^g ram prystyMce and warm-the bo <IU me ^to the ^{nut, and} from ⁶⁰ to 1 ⁰ 0 ^ st ^An OV ^{of e} NEH kroužak-way ball, and also 1 to 15% of a cationic surfactant or mixture of surfactants.

Preferred compositions according to the invention are pigment concentrates containing from 30 to 85% and most preferably from 35 to 75%. % of pigment, from 10 to 70%, and most preferably from 15 to 65% of polyester resin, and from 1 to 15%, and most preferably from 3 to 10%, of a cationic surfactant or surfactant mixture.

The pigments useful in the present invention are any solid dyes commonly used in the industry for dyeing paints, inks or plastics. These pigments include colored inorganic and organic base pigments, extender pigments, metal pigments and various finely divided channel and retort blacks, and the like. The pigments may be in the form of dry pieces, wet cakes, pigment slurry in water or a suitable organic solvent or pigment slurry. its synthesis. Where possible, press cakes are preferably used to avoid aggregation that normally occurs during pigment drying. Typical pigments include organic pigments such as diarylide yellow, phthalooyanine blue and green, quinacridone red and violet, dioxazine violet, carbon black and the like, and inorganic pigments such as cadmium red and yellow, lead chromene dyes, including pure lead chromate, as well as also solid solutions containing lead chromate and lead sulphate and / or lead molybdate, yellow and red based, iron oxides, titanium dioxide, etc. ·

As the polyester resin used according to the invention water-insoluble, non-crystalline thermoplastic polymers which are friable at room temperature and having a melting ^{d b} o u softening ^PU with ^{b Z} e em rings -ku ^{to blush} and ^{about 60-100 d} ^ ° preferably 65 to 100 ° C and which contain ^yd roxylov h ^{e f} un ^to protrude with ^the UPI, NY. Hy ^d roxylové ^f un ^CZK with it ^for at ^pi n ^yp r ^y s c ^Kyrie are described as hydroxyl number which indicates the number of milligrams of potassium hydroxide to neutralize the amount of acetic anhydride required to acetylate one gram of resin. ^p ol ^y est ery after ^{ccording to} the invention have ^{hydroxialkyl l} network ^or an SLA ales ^P on ⁵⁰ and above ^h o ^d ou as ^{well as} from ^{75 d 1} 5 ⁰ and are prepared in known manner by the condensation reaction of a dicarboxylic acid, anhydride or ester, and monocarboxylic acids with more than an equivalent amount of an aliphatic polyol containing at least three hours droxymethylov ^{y s y} skupí.n. ^FOLDER formed ^also ar d ^b ^ oxyl tyse Nou may be saturated or unsaturated aliphatic, alicyclic or aromatic acid, anhydride or ester, and preferably phthalic anhydride, o-phthalic acid, terephthalic acid, isophthalic acid or dimethyl terephthalate. The dicarboxylic acid component is usually less than 50 mol% of the total acid components of the peak product. The monocarboxylic acid component may also be aliphatic or aromatic, and is preferably an aromatic acid such as benzoic acid, lower alkyl substituted benzoic acids, and most preferably parasubstituted alkylbenzoic acids, wherein the alkyl group contains 1 to 6 carbon atoms. Particularly preferred is p-tert-butylbenzoic acid. The aliphatic polyols are tri- or higher polyols containing at least three hydroxymethyl groups and are preferably trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol or tripentaerythritol. The condensation reaction is preferably carried out by heating the acid and alcohol to a temperature in excess of about 150 ° C, in the presence of a small amount of an acid catalyst such as an organic sulfonic acid, or a basic catalyst such as a metal oxide. a product with a relatively low acid number, usually less than 15. The acid number of the resin is the number of milligrams of potassium hydroxide required to neutralize 1 gram of resin.

The composition further comprises from 1 to 15, preferably from 3 to 10% by weight of a mixture of a water-insoluble, oil-soluble cationic surfactant or a mixture of surfactants that enhance pigment dispersion. Preferred cationic surfactants are substituted tertiary amines such as heterocyclic tertiary amines, for example, alkylimidazolines and oxazolines, polyethoxylated tertiary amines, primary amines such as dehydroabietylamine and N-tallow trimethylenediamine, and quaternary ammonium compounds such as quaternary ammonium compounds, and quaternary ammonium compounds such as quaternary ammonium compounds _Ig-C fatty amines and about 2 to 15 moles of ethylene oxide. One preferred imidazoline is 1- (2-hydroxyethyl) -2-n-heptadecenyl-2-imidazoline. The cationic surfactants are capable of forming water-soluble salts with various acids and are capable of converting aa water-insoluble, oil-soluble forms by reaction with alkaline or anionic surfactants. In the form of acetate salts, they are excellent surfactants with good water solubility. The water-insoluble, oil-soluble forms of these surfactants are, for example, complexes of the above amine surfactants with anionic surfactants, and are also useful when a stoichiometric excess such as at least 10% and preferably 10 to 70 is used. % mole, excess cationic surfactant. Typical anionic surfactants are, for example, sodium oleate, sodium laurate, sodium palmitate, sodium stearate, sodium naphthenate, sulphonated castor oil, sulphonated petroleum, sulphonated tallow oil, sodium salt of butylnaphthalenesulphonate, rosin, and the like. such as Tergitol 4 (sodium 7-ethyl-2-methyl-4-undecanol sulfate), Igepon AC-78 (coconut oil isethionate sodium), Aerosol 22 (sodium tetrasodium N- (1,2-dicarboxyethyl) (N-octadecylsulfosuccinamate), hydrogenated rosin sodium and alkylarylsulfonate sodium.

The choice and amount of surfactants depends, of course, on a number of factors, including HW values of the surfactants or surfactant mixture, and on the surface characteristics of the pigment. Generally, if present, the amount of surfactant is in the range of about 1 to about 15% and preferably about 3 to about 10% by weight of the composition, and the amount is such that the weight ratio of resin to surfactant is about 2: 1. and is preferably in the range of from about 2.5: 1 to about 6: 1.

The composition of the invention can be prepared by any suitable method used to perfectly blend pigmenium with a normally solid resin, such as in a dry ball mill, milling with pebbles in an aqueous medium, mixing at high speeds in the presence of a solvent for the resins and the like, and then removing any aqueous medium or solvent. The composition is preferably prepared by forming an aqueous pigment dispersion, preferably by mixing the pigment in water in the presence of a water-soluble or water-dispersible cationic or anionic surfactant which is convertible into an oil-soluble, water-insoluble form by adding resin to the aqueous dispersion. an aqueous pigment-resin suspension at a temperature above the softening point of the resin, typically at a temperature of about 5 to about 35 ° C above the softening point of the resin, until the pigment is transferred from the aqueous phase to the resin phase to form a substantially pigment free water phase; to the extent that the resin is solid, and the product obtained is isolated.

If granules are to be prepared, and this is the case when fine dispersed pigments are used which tend to be dusted, the temperature of the mixed pigment and resin suspension is adjusted to a range above the freezing point of the resin which provides a sufficiently high viscosity of the resin and controlled coupling of particles and granulation to the desired particle size range, adding cooling water to adjust the temperature to the desired range or interrupting by heating and allowing the suspension to cool to a temperature below the resin softening point; Alternatively, the resin may be added as a solution in an organic solvent and the pigment transferred from the aqueous phase to the resin phase by precipitation of the surfactant or removal of the solvent to form a colored non-aqueous phase as small pigment granules.

Isolation of the product is carried out in a conventional manner. For example, the suspension may be centrifuged or dewatered by pouring with a suitable type of filter apparatus such as filter presses, sieves and the like, and the partially dewatered product may then be washed and dried using dryers and vacuum dryers, etc. Isolation may also be accomplished by conventional spray drying. or drum drying. The product is optionally ground to a powdered form before or after drying.

Pigment compositions in the form of solid particles have excellent high quality and uniformity and are easily dispersible in oil-resin binders and provide films or coatings with excellent color intensity, gloss and transparency with these enamel systems. Ideally suited for use in oil-based binders such as conventional air-drying alkyd enamels, baking alkyd-melamine enamels and eicrylo-melamine heat-curable enamels with which they provide films or coatings with excellent gloss, hardness and durability.

The invention is illustrated by the following examples in which all parts and percentages are by weight unless otherwise indicated.

Example 1

The vessel, equipped with stirrer and heating, is filled with a pressed cake of pale chrome yellow pigment containing 224 parts (based on dry matter) pigment yellow 34 (Cl # 77 603) and sufficient water to obtain a 1,660 part batch. . After stirring is started, the mixture is heated to 55 ° C and 9.6 parts of coconut oil isethionate sodium salt (0.023 equivalents of anionic surfactant) and sufficient 5% aqueous sodium carbonate solution are added to the suspension to adjust the pH of the suspension to 7,0 ,. and 72.0 parts of powdered aromatic polyester resin. Stirring is then continued for a further 5 minutes while maintaining the temperature of the suspension at 55 ° C. The polyester resin has a softening temperature (ring-ball method) of about 82 ° C, an acid number of 14 and a hydroxyl number of about 110, and can be prepared by the condensation reaction of 0.9 mol of o-phthalic anhydride and 2.3 mol of p-tert-butylbenzoic acid. 1.7 mol of trimethylolethane. 48.0 parts of an aqueous solution containing 12.0 parts of dehydroabietylamine (0.038 equivalents of cationic surfactant) and 2.4 parts of glacial acetic acid are added, the pH of the suspension is adjusted to 6.5, and the suspension is heated to 90 ° C. maintained at 90-95 ° C during two hours of stirring. Water was then added at 25 ° C to obtain a volume of 3500 parts of the suspension, which was stirred for an additional two hours. The batch is then poured over 40 mesh sieves and the dewatered material is dried in an oven at 70 ° C. The product consists of 235 parts (73.8% yield) of a non-stick granulated pigment containing about 70.5% lead chromene, 22.7% polyester resin, and 6.8% surfactant based on the total weight of the composition. The granules consist of non-dusting, essentially spherical, free-flowing particles, the major part of which has a diameter of between 1 and 2 mm.

The dispersion characteristics of the pigment composition of the invention are determined in an alkyd ameail in air-drying manner as follows. A yellow enamel paste is prepared by mixing 170.2 parts of the granules of this example and 47.2 parts of commercial soybean and linseed oil, an alkyd alkyd resin (Aroplaz 1445-M50) and 32.8 parts of mineral varnish polishers for a period of time. 15 minutes using a small Cowles dispersion propeller at 5,000 rpm, then adding 306 parts of 20-30 mesh and then stirring for 15 minutes using a sand mill. After removal of the sand, the paste in the Hegman apparatus yields values greater than 7. From the paste thus prepared, an enamel is prepared by mixing 68.6 parts of this paste with 54.9 parts of Aroplaz resin, 25.3 parts of mineral paint polishers, 1.0 0.2 parts of cobalt desiccant until a uniform viscosity of 20 to 25 s is obtained using a Zahn dish # 4. EmmH is then sprayed onto standard test plates (7.5 x 22.8 cm) to obtain coatings. 0.7 µm thickness and the plates were dried at room temperature for 48 hours. The resulting boards are smooth, glossy, with a bright yellow coating. When these boards are exposed Cleve ^y ^ nd vlhkootí controlled chamber for ²⁴ hours s ⁶⁶ ° C after which time significantly alter the smooth glossy surface plates. When tested in a weather meter, after 100 hours the color of the panel is somewhat darker than the color of the panel that has not been exposed but the changes that have occurred suggest that the properties of the coatings are fully satisfactory.

In this example, also the value of the yellow paste in the curing process of the alkyd-melamine is prepared by milling three times the mixture containing the paste.

Kornpposce by type. With this

62.8 parts gram! according to this example and 40.0 parts of a commercial non-oxidizing short alkyd resin oil (Koj (R) Resyl 99-5) using three passes through the mL. From paste prepared. as above, emmU was prepared by mixing 67.0 parts of the paste with 29.5 parts of alkyd resin, 27.7 parts of a commercially curable melamine-formaldehyde type resin (Koppers Melamine resin 61-8.55% solids), and 24.9 parts of xylene and the xylene is adjusted to viscosity of 20 seconds Ford cup # 4. Emil then sprayed on test des ^{Tyr alkyl} and O-VYPA tO, tHE ³⁰ min ¹² s 1 ° C. ^S desk originated HLA mmají ^{d y} ky, ^{il l} es ^{ý clearly} yellow surface hardness TESE Siarda by number 48. After exposure in the Cleveland chamber controlled vlhkootí ²⁴ hours s 66 ° C ^and with no к GIIF molding ^and a change in H ADK him ^{l é l} esklého board surface. When the boards are tested in a weather meter, after 100 hours the board exposed to the weather is somewhat darker than the unexposed board and the coating properties are fully satisfactory. Control boards were also prepared in the same manner except that 46 parts of yellow pigment 34 and emmU formed using 56.1 parts of paste, 46.5 parts of alkyd resin, 29.1 parts of melamine resin and 17.4 parts of xylene were used. has the same solids content. The control boards were carried out in the same way and it was found that the boards were smooth and shiny and that the Siard hardness was 20 and that the surface and color characteristics did not change in the moisture and weather tests.

according to Example 1, except that the compressed red mopigment cake containing 224 parts (based on dry matter) is pressed Pigment red 104

The Lybdenum procedure (Cl # 77 605) is used instead of a bright chrome yellow pigment and 60.0 parts of polyester resin are used and the final pH is adjusted to 6.0. The product of this example (91.6%) is obtained in the form of a free-flowing grandiose content of 73.3% orange pigment, 19.7% polyester resin. and 7.0% surfactant mixture. If the granules are dispersed in an air-drying alkyd amide and the plates prepared as in Example 1 are of a wall value, smooth, glossy, red-tinted orange surfaces are obtained which do not significantly change in the moisture test and are only slightly darker in size. 200 hours in a weather meter.

The pigment composition of the present invention is also suitable for use in a heat-curable acrylaminimino-type. The evaluation is carried out as follows. The orange paste is prepared by milling with three rolls and three mill passes to give a mixture of contents. 61.4 parts of granules according to this example and 22.5 parts of a commercial acrylic resin solution (A? 1? 1? 1? Iride AT-56, 50% solids). The above paste is prepared by mixing 55.9 parts of the above paste with 37.2 parts of an acrylic resin solution, 24.8 parts of a commercial melamine-formaldehyde type resin (Uformit Ш-74, 60% solids). 3.6 parts of butanol and 19.6 parts of xylene and the addition of xylene adjusts the viscosity so that it reaches 20 seconds in the Cord S dish. ^P and ^K st to ^said testing ^d and ^{d lis lis} for ^HRI VaJ ^s 30 m ^and the nut at 121 ° C. Control plates are prepared in the same manner, except that the paste is prepared using 45 parts of Pigment Red. 104 and enamel prepared using 45 parts of paste, 57.6 parts of acrylic resin solution, 26.0 parts of melamine formaldehyde resin, 3.6 parts of aromatic petroleum solvent, 3.6 parts of butanol and. 10 parts xylene will provide an email with the same solids content. Visual comparison of test plates (prepared from the enamel containing pigment composition of this example) and control plates show that the test plates are darker colored and less glossy than the control plates. Sward hardness values are 44 for the test plates and values were found for the control plates. 28.

Example 3

Vessel fitted with stirrer and heating device was charged with 1,600 parts' (v) a slurry containing 85.5 parts (dry mass) Copper-phthalocyanine Pigment Green 7 (CI 74 2 ⁶ °), and in then ^d ^ ·. · For m-ic ^h th ^e suspension for ^HRI weighing at ⁵⁵ ° C. ^p and ^{k when 0} ^ 3 gives ^d clay aqueous solution containing 30% of commercial anionic surfactant Alkanol WXN (alkylarylsulfonate sodium salt), pH was adjusted to 6.0 by adding dilute acetic acid, and stirred ^and n ^s is ^p okračuje. 30 m ⁱ nu ^{i tp} of ⁵⁵ ° C. ^p and ^{k p} s ^d and ¹¹⁴ l ^of polyester ^says LINES ^{p y} r ⁱ ce ^{of ex} after ^dL e and ^d at ^1, and the suspension mtehá 5 m ⁱ nu ^t Arr. 55 ° C, then BC postepně ^ID RECOGNITION ^{part 80.8} is obtained ^with copper solution containing 10.1 parts of commercial cationic surfactant Duomeen T an N-tallow trirnethylendiamin and 7.3 parts of 100% acetic acid and the pH was dilute ^d No ^h $ a flowable ^'H u if ^or carbonate solution in a ^p rav ^{d 7,} No. ^{1. p} Ense then from ^ahří 9 V ^{and 0} ° ^C and the reaction-mixture is ^E m ^I C ^{HA 2 d} him ins 90 to 95 ° ^F ^ nate was ^added the same as ^d AAO ^b Jem. rav u ^p to ^s' 3500 parts. Pouring the suspension onto 40 mesh screens and drying the resulting granules yielded the product of this example, which consisted of 154 parts (70% yield) of free-flowing, non-dusting granules containing 38.7% pigment, 51.7% polyester resin and 9%, 7% surfactant based on product weight.

The dispersion characteristics of the pigment composition of this example are determined in a vinyl varnish as follows. A green paste is prepared by mixing 21.4 parts of the granules of this example with 75 parts of a paint solution consisting of a 35% vinyl chloride acetate copolymer (86: 14 weight ratio), 32.5% xylene and 32.5% methyl ethyl ketone for a period of time. 30 minutes using a small Cowles dispersion vane at 5000 rpm, then 33.5 parts of a mixture of xylene solvents and methyl ethyl ketone (50:50) are added gradually over 30 minutes. A lacquer is prepared from the above paste by mixing 43 parts of the paste with 70.1 parts of the solvent mixture and 2.6 parts of dioctyl phthalate for 30 minutes. The lacquer gives a Hegman meter of 7.5 and after microscopic evaluation it has been found that the dispersion quality is excellent and that substantially all pigment particles are below 2 micron in size. If the varnish is applied to the HLI-Kem oteŽený ^{p p} and r ^pi vrsteu tloušíty at ^1, 5 / ш ^p oskytuje film had good color and excellent clarity and transparency.

Control lacquer was prepared as above, except that 8.3 parts of the commercial ^pig ment Green 7 and 13.1 Tone @ ^says! U ^p o ^ly ester ^{of ex} after ^dL e and ^d at ¹ mtete 21.4 parts granules according to this example. The control lacquer gives a value of 6 in the Hegman meter and, after microscopic examination, has a very large number of particles of 10-25 microns. The lacquer on aluminum shows a color intensity of approximately the same as the test lacquer, but is less. clear and less transparent.

Claims (5)

1. A pigment composition in the form of solid particles nízkopráSivých granules readily dispersible in olejopryskyřičných vehicle systems, characterized in that it contains 25 to 95% of at least one hmoonostnic ^h P ^ig ment, ^5-75% hmotanotních ales ^ n one water-insoluble friable ^ ORAL termoopastické polyester resin with a hydroxyl number of 50 to 150 mg KOPV / gram ^p ryskyřice and temperature bo ^d u měknnt d ^60, and ^{a 100} ° C determined from ^ manner ring knuičk ^ and further 1-15% tomSnostních ka ^ optician ^ ého surfactant of an active agent or mixture of a surface. active agents. 2. The pigment collision according to item 1, a ganic pigment. 3. The pigment composition of item 2 containing lead chromate. characterized in that it contains an pigment as an pigment, characterized in that it contains a pigment as pigment 4. The pigment composition of claim 1 wherein the pigment is an organic pigment. 5. The pigment composition according to item 4, based on copper phthalocyanine. characterized in that it contains pigment as pigment