DD207382A5 - METHOD FOR PRODUCING PIGMENT OR BZW. FARBSTOFFPRAEPARATEN - Google Patents

Abstract

The invention relates to a process for the preparation of polyamide-soluble dye dyestuffs for the mass staining of linear polyamides. The aim of the invention is to provide an improved process using a suitable solvent for removing the carrier resin. In the process for preparing a prepre-state by kneading a pigment or a polyamido-soluble dye in a solution of a linear polyamide and disassembling the putty, a solution of an alcohol-soluble inorganic salt in an alcohol is used according to the invention as a solvent for the linear polyamide. According to the invention, the alcohol-soluble inorganic salts used are ammonium, alkali metal or alkaline earth halides or rhodanides, preferably calcium chloride, ammonium or sodium rhodanide. The alcohol used is a monofunctional aliphatic alcohol having 1 to 6 C atoms, preferably methanol.

Description

24 6 3 4L · 3] Berlin, May 10, 83

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Process for the preparation of pigment or Farbstoffpräpa rates

Field of application of the invention

The invention relates to a process for the preparation of pigment or dye preparations for the mass coloration of linear polyamides and the preparations prepared by this process.

Characteristic of the known technical solutions

Polyamide pigment or polyamide dye preparations can be prepared by kneading a pigment or a polyamide-soluble dye with a solution of a polyamide. This kneading process requires a solvent which dissolves the carrier resin, and in a simple manner from the polyamide, respectively. Polyamide preparation can be removed again. The solvent should therefore solve polyamide as possible at temperatures below 100 ⁰ C and preferably be at least partially water-soluble, to allow decomposition of the putty and easy removal of the solvent with water at the end of the process, and it must also be chemically inert to the individual components of the Putty and the material of the equipment used. Especially with linear polyamides but the choice of suitable solvents is low. For the preparation of polyamide pigment preparations, CH-PS 308 532 and GB-PS 944 759 describe the use of formic acid as a solvent for the polyamide. Formic acid is now corrosive and creates

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occupational hygiene, ecological and toxicological problems. Other known solvents, such as "f-Butyrolacton _s require high working temperatures and stress the pigment or the dye, or dissolve the polyamide only under elevated pressure, such as methanol, thereby complicating a kneading process considerably, or are very expensive, such as ζ «Β«, trifluoroethanol.

Object of the invention

The aim of the invention is to provide an improved process for the preparation of polyamide-soluble dye preparations, which avoids the disadvantages of known processes.

Explanation of the essence of the invention

The invention has for its object to find a suitable solvent for the preparation of the dye preparations.

According to the invention, an organotropic salt / alcohol solution is used as the solvent. As a result, bypassing the disadvantages mentioned polyamide pigment preparations can be produced, which are able to meet the highest quality requirements.

The invention thus relates to a method for producing a preparation by kneading a pigment or a polyamide-soluble dye in a solution of a linear

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Polyamides and by breaking up the plasticine, characterized! Characterized in that is used as a solvent for the linear polyamide, a solution of an alcohol-soluble inorganic salt in an alcohol.

Suitable alcohol-soluble inorganic salts are those whose solutions are able to dissolve polyamides. In addition, preference is given to those salts which are readily available and technically of interest. For example, the salts used are, in particular, ammonium, alkali or alkaline earth halides or rhodanides, such as calcium chloride, potassium thiocyanides, sodium thiocyanate or ammonium thiocyanate. Of particular interest are calcium chloride, ammonium or sodium thiocyanate, but also salts of selected metals of other groups of the periodic system are suitable, such as, for example, B, FeCl ₃ , ZnCl p or SnCl p,

Suitable alcohols are both mono- and polyfunctional alcohols Suitable monofunctional alcohols are, for example, aliphatic alcohols having 1 to 6 C atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-petanol, tert-amyl alcohol, n-hexanol, cycloaliphatic alcohols having 5 to 7 carbon atoms, such as cyclohexanol and aromatic alcohols, such as benzyl alcohol, as polyfunctional alcohols are preferred glycols, such as ethylene glycol, 1.2 -Propylene glycol or diethylene glycol. It is also possible to use mixtures of the alcohols mentioned.

Monofunctional aliphatic alcohols having 1 to 6 C atoms, in particular those having 1 to 4 C atoms, preferably ethanol and especially methanol, are preferably used in the process according to the invention.

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Linear polyamides used in the process of this invention: may be, for example, those made of 'l-caprolactam (nylon 6), from MZ-aminoundecanoic acid (nylon 11), from UKLaurinlactam (polyamide-12) _i from hexamethylenediamine and adipic acid (Polyamide-6,6) or from other aliphatic or aromatic starting materials can be produced. Also suitable are mixed polyamides, for example from J-caprolactam, hexamethylenediamine and adipic acid.

Preference is given to polyamide-6 or polyamide-6,6.

Pigments which can be used in the process according to the invention are, for example, inorganic compounds such as carbon black, metal powders, titanium dioxide, iron oxides, iron oxyhydrates, ultramarine, cadmium sulphides, cadmium sulphoselenides, molybdate orange or chromium yellow, but in particular organic pigments, such as e.g. Azo, azomethine, anthraquinone, phthalocyanine, perinone, perylenetetracarboxylic acid diimide ". Dioxazine-iminoisoindolinone or quinacridone pigments. Also metal complexes, for example of azo, azomethine or methine dyes with pigment character are suitable:

As polyamide-soluble dyes are in the inventive process preferably disperse dyes, especially those of the Anthrachinonreihe, for example, hydroxy, amino, Älkylamino-, Cyclohexylamino-, arylamino, hydroxyamino or Phenylmercaptoanthrachinone, and metal complexes of azo dyes, especially 1: 2 chromium or Cobalt complexes of monoazo dyes ^

It is also possible to use mixtures of different pigments or dyes. When choosing the pigments or dyes, it must be ensured that they meet the high requirements for the resistance to the processing conditions of the polyamides.

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The ratio between pigment or dye and linear polyamide is suitably chosen so that the pigment or dye content in the finished preparation 5 to 70, preferably 10 to 50 wt .-% is. ,

Apart from the components to be used according to the invention, further substances remaining in the preparation can be used, such as stabilizers or fillers. In general, however, such additives are superfluous.

The mechanical treatment according to the present process can be carried out on kneading apparatuses of known construction. You can use continuous or discontinuous machines. Preferably, in the process according to the invention discontinuous kneading apparatuses are used. The kneading can be carried out at temperatures between room temperature and boiling temperature of the solvent used. Preferably, one works at temperatures below 100 ⁰ C, in particular at 40 to 10O ⁰ C.

The ratio between the alcohol-soluble salt and the alcohol may be between 5% by weight of salt, based on the alcohol and the saturation point of the salt / alcohol solution, the saturation point being dependent on the process temperature. Preference is given to using the alcohol-soluble salt in an amount of 15 to 30 wt .-% based on the alcohol solution. In individual cases, it must be noted that to achieve a sufficient dissolving power dependent on the type of salt and the alcohol used minimum salt concentration is required.

The quantitative ratio between the salt / alcohol solution and the linear polyamide can be varied within wide limits and depends in particular on the working temperature, the kneading apparatus and the nature of the polyamide.

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Preferably, the kneading process is carried out in the presence of grinding aids that are insoluble in the salt / alcohol solution and can be washed out with water. As Mahlhilfs.mittel is particularly suitable sodium chloride. The amount ratio between grinding aid and pigment or dye can be varied within wide limits. A small proportion of grinding aids, for example about one fifth of the amount of pigment, leads to relatively long processing times. It is advantageous to use at least equal to parts by weight of grinding aid or a multiple thereof such as Pigmentbzw. Dye parts by weight. The upper limit of the Mahlhilfsmittelanteils depends largely on the performance of the kneading machine used.

The kneading materials in which the polyamide is present dissolved can be decomposed by precipitating the polyamide from the viscous, viscous solution. The precipitant used is preferably water. The precipitation can also be done by adding more alcohol, as this, the concentration of the inorganic salt in the alcohol can be reduced so far that the salt / alcohol solution is no longer able to solve the polyamide.

It is also possible to disassemble the kneading compounds by converting the metal salt into an insoluble product by chemical means, e.g. with a ZnCl "/ alcohol solution by addition of Na_C0, whereby the insoluble ZnCO is formed and the plasticine thus the solvent is removed.

When working with continuous machines, e.g. with a kneading extruder, the extrudate is advantageously taken up in a large amount of water and converted by mechanical comminution in suitable wet mills in a workable suspension.

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Preparations which are obtained in powder form according to the process according to the invention can be converted into granules by extrusion. It is possible during the extrusion process to reduce the pigment or 'dye content in the preparation by adding polyamide, and also to change the color shade of the preparation with differently colored preparations.

The preparations prepared by the method according to the invention are suitable for the mass coloration of linear polyamides as described above. They are particularly suitable for the mass coloration of fiber-forming polyamides, especially of polyamide-6 and polyamide-6,6.

The preparations produced by the process according to the invention are distinguished by a good dispersibility in the polyamide melt. In granular form they are resistant to abrasion and easily metered and pneumatically conveyed.

The polyamides to be dyed can be usefully mixed with the preparation in the form of powders, chips or granules. This is achieved for example by powdering the polyamide particles with the finely divided preparation with or without adhesive or by hot coating or by mixing the Präpärategranulates with the polyamide granules or by melting the preparation granules in an injection extruder and injection into the polyamide melt to be dyed. The ratio of preparation to polyamide can, depending on the desired color intensity, within wide limits

vary. In general, the use of 0.01 to 10, in particular 0.1 to 5 parts by weight is recommended. Preparation for 100 parts by weight of polyamide.

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The mixed with the preparation polyamide particles are melted by known methods in the extruder and molded or pressed into various forms, such as plates, films or in particular fibers.

The polyamide articles dyed with the preparations according to the invention exhibit a uniform and intense coloration of good light fastness. In particular, the fibers also fulfill the requirements of service and physical-technical properties, such as wet and dry fastnesses, rub fastness, extensibility, tear and tear properties splitting strength "

Working Example

The following examples illustrate the invention. The parts mean parts by weight and the percentages by weight.

, , · Example 1:

In a laboratory kneader, 70 parts of finely divided ß-copper phthalocyanine, 105 parts of fiber-grade polyamide-6 (coarse grain 1 mm) and 126 T CaCl ₂ / methanol solution containing 23 % CaCl ₂ , for 3 hours at 40 to 45 ⁰ C kneaded. Within 10 minutes, 150 parts of methanol are added dropwise, whereby the clay breaks down and forms a finely divided pulp within 15 minutes. This is taken up in about 2,000 parts of water and the suspension is filtered after one pass through a toothed colloid mill and washed free of salt and solvent with water.

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The filter cake is dried in a vacuum oven for 24 hours at 100 ⁰ C. A blue powdery preparation containing 40% pigment and 60 % polyamide-6 is obtained.

If one takes instead of the CaClg / methanol solution 150 T 25% CaGlp / n-butanol solution, we also get a good preparation.

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Example 2: 40 parts of crude β-copper phthalocyanine, 40 parts of fiber-amide-6 of fiber grade (500 grit powder), 200 parts of ground sodium chloride and 70 parts of CaCl / methanol solution containing 23% CaCl are combined in a ( "-6O C ⁰⁾ are kneaded reflux condenser provided kneader for 6 hours at reflux temperature. the kneaded material is decomposed and in a short time by adding 50 parts of water (5-10 minutes) ground to a fine granulate. This is in approximately 1000Teilen water The product is dried in a vacuum oven at 100 ^° C. for 24 hours to give a blue, pulverulent preparation containing 50% of pigment and 50% of poly-1-ol. amid-6.

Example 3: If, as in Example 1, but instead of 70 parts of copper phthalocyanine 70 parts of carbon black pigment (Printex 35, Degussa) and 140 parts, instead of 126 parts of 23% CaCl./Methanollösung, we obtain a black preparation, containing 40% soot black and 60% polyamide-6.

EXAMPLE 4 A laboratory kneader is charged with 32 parts of crude indanthrone of α-crystal modification, 48 parts of fiber grade polyamide-6 (grain size Xl mm), 192 parts of ground sodium chloride, 25 parts of anhydrous CaCl and 75 parts of methanol.

The mixture is kneaded for 4 hours at reflux temperature, disassembled and granulated the dough by addition of 40 parts of water, the very fine granules suspended in about 1000 parts of water, filtered, washed with water salt and solvent-free and dried for 48 hours at 100 ⁰ C in vacuo , This gives a dark blue preparation containing 40% indanthrone and 60% polyamide-6.

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Example 5; 150 parts of a solution of 25% NaSCN and 75% ethanol (techn., Containing 5% water), 65 parts of nylon-6 of fiber grade (granularity £ 0, 5 mm) and 43 parts of finely divided ß-copper phthalocyanine are for 4 hours at 80 Kneaded to 85 ° C. By dropwise addition of 50 parts of water from 60 ° C, the clay is disassembled, kneaded with cooling for 20 minutes, so that a fine moist powder is formed. This is worked up analogously to Example 1 to give a pulverulent blue preparation containing 40% of pigment and 60% of polyamide-6.

Example 6: 63.6 parts of ethanol (technical grade, containing 5% water), 27.3 parts of NH.SCN, 40.8 parts of fiber grade nylon-6 (grain size <0.5 mm), j27.2 parts of chlorinated copper phthalocyanine CI Pigment Green 7 and 163.2 parts of ground NaCl (grain size <60 μm) are kneaded for 6 hours at 80 to 85 ° C. By adding 50 parts of water, the clay is disassembled and kneaded with cooling for 15 minutes. The result is a fine granules, which is worked up analogously to Example 1. This gives a powdery green preparation consisting of 40% pigment and 60% polyamide-6.

Example 7; .84 parts of anhydrous methanol, 36 parts of ZnCl, 30 parts of fiber-grade nylon-6 (grain size: 0.5 mm), 20 parts of CI. Pigment Red 149 and 160 parts ground NaCl (grain size "c60jum") are kneaded at 60 to 65 ° C for 5 hours. With simultaneous cooling, 50 parts of water are added. Within a few minutes, a finely divided porridge is formed, which is rinsed with 3000 parts of water from the kneader. The resulting suspension is filtered, washed with water until salt and solvent. The filter cake is dried in a vacuum oven at 100 ° C for 48 hours. This gives a red powdered preparation consisting of 40% pigment and 60% polyamide-6.

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Example 8; 10 parts of crude β-copper phthalocyanine, 15 parts of fiber-grade polyamide-6 (grain size 0.5 mm), 60 parts of ground NaCl, 25 parts of CaCl 2 are loaded into a laboratory kneader. and 75 parts of ethylene glycol. The mixture is kneaded for 6 hours at 80 to 85 ° C, decomposes the dough by addition of 50 parts of water with simultaneous cooling, and works analogously to Example 1 to a powdered blue preparation. It consists of 40% pigment and 60% polyamide-6,

Example 9; 60 parts of the preparation from Example 2 and 90 parts of fiber-grade polyamide-6 (grain size mm) are mixed for 20 minutes on a Turbula mixer, the mixture extruded on a 1-shaft laboratory extruder to a wire (extruder temperatures 190 to 240 ° C) and this cut into cylindrical granules of 2 to 3 mm in length and 3 mm in diameter. This gives a preparation in granular form, containing 20% pigment and 80% polyamide-6.

Example 10:

a) 50 parts of preparation according to Example 4 and 50 parts of nylon-6 of fiber quality (grain size <-0.5 mm) are mixed for 20 minutes on a Turbulamischer. The mixture is extruded to a wire on a 1-shaft laboratory extruder (extruder temperatures 210 to 230 ° C). The wire is cut into cylindrical granules of 2 to 3 mm in length and 3 mm in diameter. This gives a dark blue preparation in granular form, containing 20% pigment and 80% polyamide-6.

b) to e) If instead of the preparation according to Example 4

50 parts of preparation according to Example 5 ,: 6, 7 or 8, the procedure is otherwise as described, we obtain a blue, or a green or red preparation in granular form, containing 20% pigment and 80% polyamide-6.

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Example 11:

a) 98 parts of polyamide from & caprolactam (polyamide-6) in the form of chips are dry-powdered with 2 parts of the blue preparation obtained according to Example 1. The chips are spun at 290 to 295 ° C in an extruder. The resulting thread has a uniform blue color and contains the pigment in a very good distribution.

b) If, instead of the blue preparation according to Example 1, 2 parts of the black preparation obtained according to Example 3 are used, and the procedure is otherwise analogous to Example 11a, a uniformly black-colored thread containing the pigment in good dispersion is obtained. , \

Example 12:

a) 96 parts of polyamide-6 in the form of chips are mixed with 4 parts of the granules obtained in Example 9 and spun at 290 ° C to 295 ° C in the extruder. The resulting yarn has a uniform blue color and contains the pigment in excellent fine distribution.

b) to f) If, instead of the dark blue preparation according to Example 9, 4 parts of preparation according to Example 10a, 10b, 10c, 10d or 10e are used, as described, the result is uniformly dark blue or blue, green or red-colored threads which contain the respective pigment in excellent fine distribution.

Example 13 If the procedure is analogous to Example 11 and instead of the preparations according to Example 1 or 3 used 2 parts of the preparation according to Example 4, we also obtain a uniformly colored thread in which the pigment is in excellent fine distribution.

Claims (10)

AP C 09 B / 246 323323 1 .12. 6 "69612 invention claim 1. A process for the preparation of a preparation by kneading a pigment or a polyamide-soluble dye in a solution of a linear polyamide and by breaking the plasticine ^ characterized characterized »that is used as a solvent for the linear polyamide, a solution of an alcohol-soluble inorganic salt in a • '. Alcohol used. '.' ^ V .:; ί; ^"1:;..> · Ν '· /''^ - -;' .: ^ί'ν;: - ·;. '' ^ Ϊ́ ^·; '' ]] '' - ^{^: -:: -:,:;:.:} ' ". 2. The method according to item 1, characterized in that one uses as alcohol-soluble inorganic salt ammonium, alkali or Erdalkalihalogenide or -rhodanide. 3. The method according to item Iv, characterized in that is used as the alcohol-soluble inorganic salt calcium chloride, ammonium or Natriumrhodanid. 4. The method according to item 1, characterized in that the alcohol used is a monofunctional aliphatic alcohol having 1 to 6 carbon atoms. 5. The method according to item 1, characterized in that one uses methanol as the alcohol. 6. The method according to item 1, characterized in that one uses the alcohol-soluble inorganic salt in an amount of 15 to 30 wt .-%, based on the alcohol solution. 7. The method according to item 1, characterized in that one AP C 09 B / 246 323
61 696 12 23 1 - 13 - used as a linear polyamide is a polyamide of c-caprolactam or a polyamide of hexamethylenediamine and adipic acid, 8. Use of the preparations prepared according to item 1 characterized in that they are used for the mass coloration of linear polyamides 9 * Use of the preparations prepared according to item 1, characterized in that they are used for the mass coloration of fiber-forming polyamides. « 10. Use of the preparations prepared according to item 1, characterized in that they are used for the mass coloration of polyamide from ε-caprolactam.