CS221500B1 - Dyeing of plastics - Google Patents

Abstract

Method of coloring plastic materials with known organic or inorganic pigments and filling with known fillers using the following oil-soluble detergent-dispersant additives: alkaline earth metal sulfonates, preferably calcium, neutral and basic, petroleum and synthetic, based on monosulfonic acids with a molecular weight of at least 250, preferably 350 to 390, alkaline earth metal alkyl phenolates and alkyl phenol sulfides, preferably calcium and barium, neutral and basic, preferably with alkyls C5 and larger, calcium alkyl salicylates, neutral and basic with alkyls C12 to C22, preferably C14 to C15. The above-mentioned dispersants promote wettability, dispersibility, complete homogeneous dispersion of pigments and fillers and enable a very rapid preparation of a fine, stable dispersion and a reduction in pigment consumption.

Description

The invention relates to a method for dyeing plastic materials with organic or inorganic pigments and to fill with fillers using oil-soluble detergent-dispersants such as sulfonates, alkylphenlates, alkylphenolsulfides and alkylsalicylates of alkaline earth metals which provide an extremely high degree of dispersion of pigment and filler and their even uniform plasticity substance.

Pigments are organic or inorganic powders practically insoluble in the dyed plastic material. Due to the high thermal stresses during processing, there is a possibility that some organic pigments will at least partially dissolve. Pigments consist of particles whose size increases in order: primary particles (single crystals), aggregates and agglomerates. The color efficiency of pigments increases with particle size. The dispersion of the pigment is, in particular, crushing, removing agglomerates. The dispersant increases the wetting rate of the agglomerates, causes milling to be agglomerates and primary particles, and ensures the stability of the fine dispersion. Reducing the melt viscosity of the plastic further promotes the dispersion process.

The plastics are mainly dyed in two processes, either in the mass of their manufacture or in the mass of their powder or granulate. The third method, the surface coloring of finished plastic products, is rarer. Usually, the pigment or pigment preparation is dry blended with the powder or granulate of the plastics material in agitators of various types (drum, fluid mixer and after-treatment is further processed in extruders or strippers. The plastics material can also be colored by adding commercial pigment preparations or prepared on site, into a processing machine without premixing.

The most important inorganic pigments used are TIO2, pigments (most mercury) and zinc sulphide pigments with varying up to 100% ZnS content (less effective than TiO 2 pigments) for whitewashing, iron and chromium oxide pigments (types of rye, red, brown, black and green ), extremely stable and practically suitable for all plastics suitable mixed phase pigments of different color tones, such as Ni-Sb-Ti, Cr-Sb-Ti pigments, mixed phase pigments of Fe, Cr and Cu oxides, cadmium pigments of CdS or Cd-sulphide composition / selenide, chromate mixed phase pigments of Pb / Cr, S / O4 and Pb / Cr, Mo, S / O4. A pigment may also be counted as a filler if its refractive index in a particular environment is greater than 1.7. Known filler types are powder chalks and various types of calcium carbonates, Ca-Mg-carbonates (dolomites), silicates, barium sulphates and others.

Organic pigments for plastics are characterized by high color intensity, brilliance and purity of color tone. Due to the high technical demands such as high thermal and migration stability, wettability and dispersibility, the choice of a large number of organic pigments is considerably narrowed and the suitable pigment must be sought and tested. In order to facilitate this selection, according to the above-mentioned indicators, organic pigments for the plastics sector are generally suited in special assortments, in particular of large pigment manufacturers.

The dispersants (detergent dispersants) of the present invention promote the wettability and dispersibility of the organic pigments and allow a very rapid process for preparing a fine and stable dispersion.

The dispersants of the present invention are suitable for dyeing with pigments or pigment preparations as well as plastics having high operating temperatures in the range of 200-300 ° C. They are suitable, in particular, for high and low pressure polyethylene, polypropylene, polystyrene and styrene blended polymers, polyvinyl chloride and its copolymers, further for phenolic and polyester resins, urea and melamine resins, polymethacrylates, polyamides and others.

The dispersants of the invention are oil solutions (concentrates), usually about 30 to 50%, preferably in mineral white oil, alkaline earth metal sulfonates, preferably calcium, neutral and basic petroleum and synthetic, based on oil-soluble monosulfoacids and molecular weight of at least 250, preferably 350 to 490, oil-soluble alkylphenlates and alkylphenolsulphides (sulphated alkylphenol alkaline earth metals, preferably calcium and barium neutral and basic, preferably with C8 and higher alkyls, calcium, neutral and basic alkylsalicylates of C12 to C22, preferably C14 to C18.

The dispersants of the present invention ensure, on the one hand, the perfect colorist effect of the pigment such as color saturation, color tone and its stability, gloss, hiding power and, on the other hand, improve production economies by significantly reducing pigment consumption by up to one third or more compared to known non-coloring methods dispersants, or using known dispersants that are less effective.

The properties of the dispersants according to the invention are particularly valuable, especially in the film sector, which places such high demands on the fineness of pigment disintegration that only special pigment preparations which are characterized by a particularly high degree of dispersion of the pigments contained can satisfy them.

It is also an advantage of the dispersants of the invention that, due to their high dispersing effect, no visible grains of pigment are present or adhere to the walls of the machinery and containers due to their high dispersing effect, and allow a sharp, large-edged transition to products from the new mixture. other color with very little production of intermediate waste product, without the need to interrupt production and clean the production equipment.

The dispersants according to the invention can be used for the preparation of color mixtures at the place of manufacture of colored plastics, as well as for the preparation of long-term stable pigment preparations (concentrates which can be common market products in the form of granules, powders, pastes, viscous liquids These preparations may contain up to 99.0% by weight, preferably about 30-90% by weight, of pigment in dispersed form, and consist in addition to the pigment of a dispersant and may further comprise a plastic to be dyed, wetting agents , other auxiliaries or mixtures thereof which are compatible or miscible with the plastic.

When dispersants are used directly at the place of manufacture of colored plastic products such as granules, powders, foils, moldings, castings, etc., the pigment is mixed with the dispersant, optionally with the prescribed additives, such as thermo-oxidizing stabilizers. glidants, anti-UV stabilizers, with plasticizers and in the form of a liquid mixture or paste, are added by hatching or continuously (by pump), depending on the type of processing machine, in a specified proportion to the plastic, through a tube extending to the feed hopper a granulate, a powder or a melt of a plastics material placed on a processing machine such as a strekolis, an extrusion screw and the like.

The use of the dispersants according to the invention makes it possible to achieve substantial energy savings. Due to the high dispersing effect and the high dispersion rate of these dispersants, mixtures of dispersants or other auxiliaries prepared on site can be used in the manufacture of colored plastics, thereby avoiding the preparation of colored granules, powders, pastes, which brings energy savings. It also saves on storage and transport capacities and saves on the storage of raw materials and materials.

The dispersants of the invention improve the sliding, antistatic and anti-blocking properties of films and other articles. They also reduce the power input required to drive processing machines.

A particular advantage of the dispersants of the present invention is their suitability for use in addition to coloring plastics as well as in the preparation of filled plastics dyed or natural fillers such as powder chalk, special radiation absorbing fillers, flame retardants, foaming agents and the like. The procedure is similar to that used for dyeing plastics with pigments, i.e.. j. the fillers are mixed with the dispersant and treated in the form of a liquid mixture or paste with a polymer of the plastic. The dispersants ensure a high degree of dispersion of the fillers, their even distribution and the easy and homogeneous mixing of these mixtures with the plastic.

Process for dyeing plastics with organic and inorganic pigments and for filling colored, natural plastics with fillers using the dispersants of the present invention or a mixture thereof and known processes for producing color mixtures, pigment preparations, filled colored or natural plastics and colored plastic products in the form of granules, powders, films, moldings, castings and the like. characterized in that the addition of dispersants, calculated in the form of 50% solutions in oil, to the plastics is at least 0.01% by weight, preferably in the range of 0.2 to 2.5% by weight, calculated per plastic, the dispersant content of the color blends and pigment preparations is not more than 99.0% by weight, preferably in the range of 30.0 to 90.0% by weight, calculated on the color mixture, or the pigment and / or pigment, and when filling colored and natural plastic materials, the dispersant addition is at most 99.0% by weight, preferably in the range of 30.0 to 90.0% by weight, based on the mixture of dispersant and filler.

To illustrate the invention in an illustrative manner, non-limiting examples are provided.

Example 1

In a conventional mixer, 0.3 kg of white oil, 0.1 kg of basic calcium aralkyl salicylate, with C 14 -C 18 alkyls and a total alkali (TBN) 90 of 50% oil concentrate and 0.66 are mixed at room temperature. kg T1O2 (Bayer Titan RFKD) until a homogeneous liquid mixture is formed.

The prepared mixture is dosed in a weight ratio to the granulated high pressure polyethylene 1:90 before the colorless polymer enters the screw, into the bottom of the hopper into which said polyethylene granulate is placed on the continuous screw machine where the extruded molten mixture temperature reaches 215 C.

A peristaltic pump equipped with speed control was used to dispense the liquid dispersion into a continuously operating screw.

With a length to diameter ratio of 20: 1, material was fed to the blow head from which a 0.3 mm thick white film with a completely uniformly dispersed pigment was obtained, without any visible grains.

Example 2

A homogeneous liquid mixture consisting of 0.6 kg of white oil, 0.2 kg of calcium-neutral alkylsalicylate with Cu-C18 alkyls, 50% of pigments, 0.2 kg of Chromphtal Gelb 6 G, was prepared according to the procedure and conditions as in the example, 0.05 kg Chrcmphtal Roth BR and 0.05 kg Chromphtal Griin GF.

The prepared homogeneous color mixture was treated with granulated high pressure polyethylene at a weight ratio of 1:95 on a 0.3 mm thick film on the apparatus and under the conditions of Example 1. The produced film was khaki in color, with completely uniformly dispersed pigment, without any visible beads.

Example 3

A homogeneous liquid mixture consisting of 0.6 kg of white oil, 0.2 kg of neutral calcium alkyl salicylate with C 18 -C 22 alkyl, 50% and 0.25 kg of Corax carbon black was prepared by the procedure and under the conditions of Example 1.

The prepared color mixture was treated with granulated low pressure polyethylene in a weight ratio of 1:95 on a 0.3 mm thick film under normal operating conditions. The foil produced was saturated in black, with a completely uniformly distributed pigment, without any visible grains of pigment.

Example 1 4

A homogeneous liquid mixture consisting of 1.0 kg of basic calcium alkyl salicylate, with C12-C22 alkyls and with TBN 110 and 1.5 kg of TiO2 (Bayer Titan RFKDj) was prepared according to the procedure and conditions as in Example 1.

The prepared color mixture was treated with polyvinyl chloride in a weight ratio of 1:50 on a 0.2 mm thick film, under normal manufacturing conditions. The foil produced was a deep white color, with a completely uniformly distributed pigment, without any visible grains of pigment.

Example 5

A homogeneous liquid mixture consisting of 0.3 kg of 30% calcium monosulfoacid petroleum sulfonate with an average molecular weight of 435, low base with TBN 25, 0.3 kg of white oil, 1.0 was prepared according to the procedure and conditions of Example 1. kg T1O2 Bayer Titan RFKDj.

The prepared color mixture was treated with polystyrene in a weight ratio of 1:70 on a 0.2 mm thick film. The foil produced had a saturated white color with a faintly brown tinge, with a completely uniformly distributed pigment, without visible grains of pigment.

Example 6

A homogeneous liquid mixture consisting of 0.4 kg of neutral calcium alkyl salicylate as in Example 3, 0.6 kg of white oil and 1.0 kg of T102 (Bayer Titan RFKDj) was prepared according to the procedure and conditions as in Example 1.

The prepared color mixture was treated with polypropylene, in a weight ratio of 1:50, to a 0.2 mm thick film. The foil produced was a saturated white color, with a completely uniformly distributed pigment, without visible grains.

Example 7

A homogeneous liquid mixture was prepared according to the procedure and conditions as in Example 1, consisting of 1.0 kg of basic alkyl phenolate, with C 18 alkyls and with TBN 220, 45%, 2.0 kg of white oil, 2.5 kg of zinc white and 0.1 kg Cyasorb 531 (UV stabilizer).

The prepared color mixture was treated with granular colorless polyamide in a weight ratio of 1:45 on a 0.3 mm thick film. The foil produced was saturated white in color, with a slight tinge of rye, with a completely uniformly distributed pigment, without visible grains.

Claims (1)

221500 1, a homogeneous liquid mixture was prepared consisting of 0.6 kg of white oil, 0.2 kg of calcium alkylsalicylate with C 1-4, C 16, 50%, pigment 0.2 kg Chromphtal Gelb 6 G, 0.05 kg Chrcm- phtal Roth BR and 0.05 kg Chromphtal GrünGF. The prepared homogeneous color mixture was treated with granulated high pressure polyethylene in a weight ratio of 1: 95 to 0.3 mm thick foil on the apparatus and condition as in Example 1. The produced khaki color foliamala, with a completely uniformly dispersed pigment, without any visible grains. Example 3 A homogeneous liquid mixture consisting of 0.6 kg of white oil, 0.2 kg of calcium alkyl salicylate neutral, Cis-C22 alkyl, 50% and 0.25 kg of Corax carbon black was prepared by the procedure and under the conditions of Example 1. . The prepared color mixture was treated with granular low pressure polyethylene in a 1:95 weight ratio on a 0.3 mm thick foil under conventional working conditions. The filaments produced had blackufarcate, with the pigment evenly dispersed, without any visible particles of pigment. EXAMPLE 4 A homogeneous liquid mixture consisting of 1.0 kg of lime alkyl salicylate, with C12-C22 alkyls and TBN110 and 1.5 kg of TiO2 (Bayer Titan) was prepared by the procedure and under the conditions of Example 1. RFKD). The prepared color mixture was treated with co-vinyl chloride in a weight ratio of 1: 50 on a 0.2 mm thick foil, under normal manufacturing conditions. The malasyt foliage produced is white in color, with a uniformly distributed pigment, without any visible pigment beads. EXAMPLE 5 A homogeneous liquid mixture consisting of 0.3 kg of a 30% by weight monosulfonic calcium petroleum sulfonate having an average molecular weight of 435, a low base with a TBN of 25, 0.3 kg was prepared by the procedure and as in Example 1. white oil, 1.0 kg T1O2 (Bayer Titan RFKDj. The prepared color mixture was treated with cystyrene in a weight ratio of 1: 70 to 0.2 mm thick foil). Example 6 A homogeneous liquid mixture consisting of 0.4 kg of calcium alkyl salicylate neutral as in Example 3, 0.6 kg of white oil was prepared by the procedure and under the conditions of Example 1. and 1.0 kg of T1O2 (Bayer TitanRFKD) The prepared color mixture was treated with propylene, in a ratio of 1: 50 by weight, 0.2 mm in thickness on a foil foil. EXAMPLE 7 A homogeneous liquid mixture consisting of 1.0 kg of basic calcium alkylphenolate, with alkyls of Cis and with TBN of 220.45% by weight, was prepared by the procedure and under the conditions of Example 1. , 0 kg of white oil, 2.5 kg of zinc white and 0.1 kg of Cyasorb 531 (UV stabilizer). The prepared color mixture was treated with a granulated colorless polyamide in a 1:45 weight ratio on a 0.3 mm follicle. The film produced had a white color, with a slight tinge of rye, with a completely uniformly dispersed pigment, free of viscous beads. OBJECTS OF THE METHOD OF COLORING, PLASTIC MATERIALS OF AICOPYLETHYLENE low pressure and high pressure, polypropylene, polystyrene and its co-polymers; preparations and color plastics including filled plastic dyes of color and natural form in the form of granulates, powders, foils, moldings, casting. characterized in that at least one of the dispersants is used, such as oil-dispersible alkaline earth metal sulfonates, preferably calcium, neutral and basic, petroleum and synthetic, based on oil-soluble monosulfoacids having a molecular weight of at least 250, s preferably 350 to 490, alkaline earth metal oil-soluble alkylphenates and alkylphenol sulfides, preferably calcium and barium, neutral and basic, preferably with Ca and larger alkyls, calcium, neutral and basic alkyl alkyls with alkyls C12 to C22, preferably C14 to C 18, with the addition of dispersants, calculated in the form of 50% oily solutions, up to 221500 10 of the final dyestuffs at least 0.01% by weight, preferably between 0.2 and 2.0% % by weight, based on the plastic compound, of color mixtures and pigment preparations is not more than 99.0% by weight, preferably 30.0 to 90.0% by weight, calculated on the color composition or pigmentary product. The composition of the filled colored and natural plastic materials is at most 99.0% by weight, with the advantage of 30.0 to 90.0% by weight, calculated on the mixture of dispersant and filler.