CS235034B2 - Method of pigment or dye agents production - Google Patents

Abstract

A process for the preparation of pigmented or dyed compositions by kneading a pigment or a polyamide-soluble dye in a solution of a linear polyamide and by separating the kneading composition, characterised in that the solvent used for the linear polyamide is a solution of an alcohol-soluble inorganic salt in an alcohol. The compositions prepared by this process are suitable for bulk colouring of linear polyamides.

Description

The invention relates to a process for the production of pigment or dye preparations for coloring linear polyamides in a mass.

The polyamide pigment or polyamide dye preparations can be prepared by kneading the pigment or dye which is soluble in the polyamide with a polyamide solution. This kneading process requires a solvent which dissolves the carrier resin and which can again be easily removed from the polymaid or the polyamide composition. The solvent should therefore dissolve the polyamide preferably at temperatures below 100 ° C and preferably should be at least partially soluble in water to allow for decomposition of the mass after kneading and easy removal of the solvent by water at the end of the process, and additionally chemically inert to the individual the components of the kneading mass and the materials used in the respective apparatus. In linear polyamides, however, the choice of suitable solvents is negligible. For the manufacture of polyamide pigment preparations, Swiss patent 308,532 and British patent 944,759 disclose the use of formic acid as a solvent for polyamide. However, formic acid is corrosive, and occupational hygiene, environmental and toxicological problems are associated with its use. Other known solvents, such as β-butyrolactone, require high working temperatures and burden the pigment or dye, or solubilize the polyamide only under elevated pressure, such as methanol, and make the kneading process considerably more difficult or too expensive, such as trifluoroethanol. However, if an organotropic solution of the salt in alcohol is used as a solvent, bypassing the above disadvantages, polyamide pigment formulations can be produced which allow the highest quality requirements to be achieved.

The object of the present invention is a process for the production of pigment or dye preparations by kneading a pigment or a polyamide soluble dye with a solution of a linear polyamide based on ε-caprolactam or hexamethylenediamine and adiipic acid and distributing the mass after kneading by water or alcohol. % of a linear polyamide solvent, using a 5% by weight to saturated solution of calcium chloride, zinc chloride, sodium rhodanide or stannous chloride, in methanol, ethanol, n-butanol or ethylene glycol.

Preferably, calcium chloride, ammonium rhodanide or sodium rhodanide is used.

Ethanol and especially methanol are preferably used in the process according to the invention.

Linear polyamides which can be used in the process according to the invention are, for example, polyamides which can be prepared from ε-caprolactam (polyamide-6), ω-aminoundecanoic acid (polyamide-11), ω-laurinlactam (polyamide-12), hexamethylenediamine and adipic acid (polyamide-6,6) or other aliphatic or aromatic starting materials. Mixed polyamides are also suitable, for example from ε-caprolactam, hexamethylenediamine and adipic acid.

Preferably, polyamide-6 or polyamide-6,6 is used.

The pigments which may be used in the process according to the invention are, for example, inorganic pigments such as carbon black, powdered metals, titanium dioxide, iron oxides, hydrated iron oxides, ultramarine, cadmium sulfides, icadmium sulfoselenides, molybdenum orange or chromium yellow. pigments such as azopigment, azomethine pigment, anthraquin pigment, phthalocyanine pigment, perinone pigment, perylentetracarboxylic acid diimide pigment, dioxazine pigment, iminoisoindolinone pigment or quinacridone pigment.

Metal complexes such as azo dyes, azomethine dyes or pigment-like methine dyes are also suitable.

Of the polyamides soluble in the process according to the invention, disperse dyes, in particular anthraquinone series, for example hydroxy-, amino-, alkylamino-, cyclohexylamino-, arylamino-, hydroxyamino- or phenylmercaptoanthraquinones, as well as metal azo dyes complexes, in particular chromium complexes, are suitable. or cobalt with 1: 2 monoazo dyes.

Mixtures of different pigments or dyes may also be used. When selecting pigments or dyes, care must be taken to meet the high resistance requirements under polyamide processing conditions.

The ratio of the amount of pigment or dye to linear polyamide is suitably chosen so that the proportion of pigment or dye in the finished preparation is 5 to 70% by weight, preferably 10 to 50% by weight.

In addition to the components used according to the invention, other substances remaining in the formulation, such as stabilizers or fillers, may be used. Generally, such an additive is unnecessary.

The mechanical treatment according to the present process can be carried out on kneading machines of known construction. In this case, machines operating continuously or discontinuously may be used. Preferably, batch process kneading machines are used in the process according to the invention. The kneading can be carried out at temperatures between temperatures

233034 and the boiling point of the solvent used. Preference is given to operating at temperatures below 100 ° C, in particular at 40 to 100 ° C.

The ratio of the amount of salt soluble in alcohol to alcohol may be between 5% by weight of the salt relative to the alcohol and the saturation point of the alcoholic salt solution, the saturation point depending on the temperature at which the process is carried out. Preferably, the salt that is soluble in alcohol is used in an amount of from 15 to 30% by weight based on the alcoholic solution. In individual cases, care must be taken to ensure that a minimum salt concentration is required to achieve sufficient solubility, which depends on the type of salt and the alcohol used.

The ratio between the amount of alcoholic salt solution and the linear polyamide may vary within wide limits and is dependent in particular on the operating temperature, the kneading machine performance and the nature of the polyamide.

Preferably, the kneading process is carried out in the presence of grinding aids which are insoluble in the alcoholic salt solution and which can be washed out with water. Sodium chloride is particularly used as a grinding aid. The ratio between the amount of the grinding aid and the pigment or dye can vary within wide limits. A small proportion of the grinding aid, for example about 1/5 of the amount of pigment, leads to relatively long processing times. Preferably, at least the same amount of parts by weight of grinding aid or excess thereof is used as parts by weight of pigment or dye. The upper limit of the proportion of the grinding aid depends essentially on the performance of the kneading machine used.

Post-kneading materials in which the polyamide is present in the dissolved state can decompose by precipitating the polyamide from a highly viscous, viscous solution. Water is preferably used as a precipitant. However, precipitation can also be carried out by the addition of an additional alcohol, since the concentration of the inorganic salt in the alcohol can thereby be reduced to such an extent that the alcoholic salt solution is no longer capable of dissolving the polyamide.

It is also possible to decompose the mass after kneading by converting the metal salt into an insoluble product by chemical measures, for example in the case of a solution of zinc chloride in alcohol by the addition of sodium carbonate, thereby forming insoluble zinc carbonate and thereby removing the co-solvent from the mass.

When working with continuous machines, for example using an extruder kneading machine, the extruded mass is removed with a considerable amount of water and mechanically pulverized in suitable wet β

mills are converted into a workable suspension.

The formulations which are formed in the process according to the invention in powder form can be converted into granules by extrusion. It is possible during the extrusion process to reduce the proportion of pigment or dye in the formulation by adding polyamide and to further change the color shade of the formulation by other preparations.

The formulations of the present invention are suitable for coloring linear polyamides in the mass, such as those described above. They are particularly suitable for dyeing fiber-forming polyamides in the mass, in particular polyamide-6 and polyamide-6,6.

The formulations produced by the process of the invention are characterized by good melt dispersibility in the polyamide. In the form of granules, they are abrasion resistant and can be dosed without difficulty and can be pneumatically conveyed.

The polyamides to be dyed can conveniently be mixed with the preparation in the form of powders, cuttings or granules. This is achieved, for example, by dusting the polyamide particles with a finely dispersed composition, optionally containing an adhesive or hot-forming, or mixing the granular composition with the polyamide granulate, or melting the granular composition in an injection extruder and injecting poly into the melt. of the amide to be colored. The ratio between plea ^and formulations by and the polyamide can be varied according to the desired color intensity, within a wide range. In general, it is recommended to use 0.01 to 10, in particular 0.1 to 5 parts by weight of the composition per 100 parts by weight of polyamide.

The polyamide particles mixed with the preparation according to the invention are melted in an extruder by known methods and the melt is processed by casting or pressing into various shaped articles such as plates, foils or, in particular, fibers.

The polyamide articles dyed according to the present invention exhibit uniform and intense coloration with good light fastness. In particular, the fibers also satisfy the requirements for durability in use and physico-technical properties, such as wet and dry cleaning, abrasion stability, extensibility, tensile strength and bond strength.

The following examples serve to illustrate the invention. Parts and percentages are by weight.

Example 1

In a laboratory kneader, knead 70 parts of finely dispersed β-phthalocyanine, 105 parts of fiber-reinforced polyamide-6 (coarse powder with particle size <1 mm) and 126 parts of calcium chloride solution 235034 in methanol containing 23 ·% calcium chloride , for 3 hours at 40 to 45 ° C. 150 parts of methanol are added dropwise over 10 minutes, the kneaded mass is decomposed and a fine dispersed slurry is formed within 15 minutes. This slurry is taken up with about 2000 parts of water and after passing through a gear colloid mill, the suspension is filtered and washed with water to remove salt and solvent. The residue on the filter was dried in a vacuum oven at 100 ° C for 24 hours. A blue powder formulation is obtained which contains 40% pigment and 60% polyamide-6.

If calcium chloride solution is used instead; in methanol 150 parts of a 25% solution of calcium chloride in n-butanol, then a good preparation is also obtained.

Example 2 parts of crude copper / phthalocyanine, 40 parts of polyamide-6 suitable for fiber production (powder with particle size <500 µm), 200 parts of ground sodium chloride and 70 parts of calcium chloride in methanol containing 23% calcium chloride knead in a kneader equipped with a reflux condenser for 6 hours at reflux (about 60 ° C). After adding 50 parts of water, the kneaded mass is decomposed and ground to a fine granulate within a short time (5 to 10 minutes), which is taken up with about 1000 parts of water, the suspension obtained is filtered, and the residue is washed with water . the product was dried in a vacuum oven at 100 ° C for. 24 hours. a blue powder preparation containing 50% pigment and 50 o / ₀ polyamide 6.

Example 3

The procedure is as in Example 1, but instead of 70 parts of copper phthalocyanine, 70 parts of carbon black (Printex 35 Degussa) and 140 parts are used instead of 126 parts of 23% calcium chloride solution in methanol, then a black powder is obtained, which contains 40% carbon black and 60% polyamide-6.

Example 4

The laboratory mixer was charged with 32 parts of crude indanthrene crystalline modification a, 48 parts of fiber-grade polyamide-6 (particle size <1 mm), 192 parts of ground sodium chloride, 25 parts of anhydrous calcium chloride and 75 parts of methanol. The mixture is kneaded for 4 hours at reflux, decomposed and the kneaded mass is decomposed by adding 40 parts of water, the very fine granulate is suspended in about 1000 parts of water, filtered, washed with water to remove salt and solvent and dried. hours at temperature

100 ° C under vacuum. A dark blue formulation is obtained which contains 40% indanthrene and% polyamide-6.

Example 5

150 parts of a solution consisting of 25% NaSCN and 75% ethanol (technical, containing 5% water), 65 parts of polyamide-6 suitable for fiber production (grain size 0.5 mm) and 43 parts of finely dispersed β-phthalocyanine The copper was kneaded for 4 hours at 80-85 ° C. When 50 parts of 60 ° C water are added dropwise, the kneaded mass is decomposed, further kneaded with cooling for 20 minutes to form a fine moist powder. This powder is processed analogously to Example 1 into a powdered blue formulation containing 40% pigment and 60% polyamide-6.

Example 6

63.6 parts ethanol (technical, containing 5 ·% water), 27.3 parts NHiSCN, 40.8 parts polyamide-6 suitable for fiber production (0.5 g particle size), 27.2 parts chlorinated copper phthalocyanine (CI) Pigment Grun 7) and 163.2 parts of ground sodium chloride (60 g particle size) were kneaded for 6 hours at 80-85 [deg.] C. By adding 50 parts of water, the kneaded mass was decomposed and then kneaded further for 15 minutes with cooling. A fine granulate is formed which is processed analogously to Example 1. A powdery green preparation is obtained consisting of 40% pigment and 60% ipolyamide-6.

Example 7 parts of anhydrous methanol, 36 parts of zinc chloride, 30 parts of polyamide-6 suitable for fiber production (0.5 g particle size), 20 parts of red pigment (CI Pigment Rot 149) and 160 parts of ground sodium chloride (particle size 60 g) It was kneaded at 60 DEG-65 DEG C. for 5 hours while adding 50 parts of water while cooling, forming a finely dispersed slurry within a few minutes, eluting with 3000 parts of water from the kneading machine. The residue on the filter was dried in a vacuum oven at 100 ° C for 48 hours to give a red powder formulation consisting of 40% pigment and 60% polyamide-6.

Example 8

10 parts of crude copper-phthalocyanine, 15 parts of polyamide-6 suitable for fiber production (0.5 g particle size), 60 parts of ground sodium chloride, 25 parts of lime chloride are placed in a laboratory kneader235034

And 75 parts of ethylene glycol. The mixture is kneaded at 80-85 ° C for 6 hours, then the kneaded mass is decomposed by adding 50 parts of water while cooling, and the mixture is worked up analogously to Example 1 into a powdered blue preparation. This consists of 40% pigment and 60% polyamide-6.

Example 9

60 parts of the composition of Example 2 and 90 parts of polyamide-6 suitable for fiber production (1 mm grain size) are mixed within 20 minutes - using a turbulent stirrer, extruded on a single screw laboratory wire extruder (extrusion temperature 190 to 240 °) C) and cut into cylindrical granules of 2 to 3 mm in length and 3 mm in diameter. A granulate preparation is obtained which contains 20% pigment and 80% polyamide-6.

Example 10

a) 50 parts of the preparation of Example 4 and 50 parts of polyamide-6 suitable for fiber production (0.5 mm grain size) are mixed for 20 minutes using a turbulent mixer. The wire is extruded from the mixture on a single screw laboratory extruder (extrusion temperature 210 to 230 ° C). The wire obtained is cut into cylindrical granules of 2 to 3 mm in length and 3 mm in diameter. A dark blue granular preparation is obtained which contains 20% pigment and 80% polyamide-6.

(b) to (e) If 50 parts of the preparation of Example 5, 6, 7 or 8 are used instead of the preparation of Example 4 and otherwise proceed as described above, a blue, optionally green or red preparation is obtained in the form of a granulate containing 20% pigment and 80% polyamide-6.

Example 11

(a) 98 parts of ε-caprolactam (polyamide-6) polyamide in the form of cuttings are dry-dusted with 2 parts of the blue preparation obtained according to Example 1. These cuttings are spun at a temperature of 290 to 295 ° C in an extruder. The fibers obtained are uniformly blue in color and contain a very finely dispersed pigment.

b) If, instead of the blue preparation of Example 1, 2 parts of the black preparation obtained by the procedure of Example 3 were used and otherwise proceeded analogously to Example 11a), a black uniformly dyed fiber is obtained which contains a pigment which is well finely dispersed.

Example 12

a) 96 parts of polyamide-6 in the form of cuttings are mixed with 4 parts of the granulate obtained according to Example 9, and this mixture is spun in an extruder at a temperature of 290 to 295 ° C. The fiber obtained is uniformly colored in blue and contains a pigment which is dispersed in fine form in an excellent manner.

b) to f) If 4 parts of the preparation according to Example 10a), 10b), 10c), 10d) or Юе) are used instead of the deep blue preparation according to Example 9, and the other procedure is analogous to that described above, then uniformly dark a blue, optionally blue, green or red colored fiber, the fibers comprising the respective pigment dispersed in a fine manner.

Example 13

If analogous to Example 11 is used and 2 parts of the preparation of Example 4 are used instead of the preparations of Example 1 or 3, then a uniformly dyed fiber is also obtained in which the pigment is present finely dispersed.

Example 14

10 parts of crude (M) talocyanine, 15 parts of polyamide-6 (fiber quality, 0.5 mm particle size), 60 parts of ground sodium chloride and 65 parts of 50% solution are placed in a laboratory kneader equipped with a reflux condenser. The mixture is kneaded at 60 ° C for 6 hours, then the kneaded mass is decomposed by the addition of 50 parts of methanol under cooling, and the mixture is worked up analogously to Example 2 to give a powdery blue preparation. This preparation consists of 40% pigment and 60% polyamide-6.

Example 15

The procedure is as in Example 4, but instead of polyamide-6, polyamide-6,6 (particle size 0.5 mm) is used, and instead of 100 parts, 160 parts of a 25% solution of calcium chloride in methanol are used. In this way a dark blue formulation is obtained which contains 40% indanthrene and 60% polyamide-6,6.

Claims (3)

SUBJECT OF THE INVENTION Process for the production of pigment or dye preparations by kneading a pigment or a polyamide soluble dye with a solution of a linear polyamide based on ε-caprolactam or hexamethylenediamine and adipic acid and by decomposing the mass after kneading by the addition of water or alcohol, using a 5% to saturated solution of calcium chloride, zinc chloride, ammonium rhodanide, sodium rhodanide or stannous chloride in methanol, ethanol, n-butanol or ethylene glycol. 2. A process according to claim 1, wherein a solution of the salt in methanol is used. 3. The process according to claim 1, wherein a 15 to 30% by weight solution of the inorganic salt in the alcohol is used.