CS252352B1 - Method of plastics dyeing - Google Patents

Abstract

The method of coloring plastics by known organic or inorganic pigments and filling with known pinchers for use of these oil-soluble detergent-dispersant detergents additives: metal sulfonates alkaline earth, preferably calcium, neutral and basic, petroleum and synthetic, na molecular weight monosulfoacid base at least 250, preferably 350 to 390, alkali metal alkyl phenol and alkylphenol sulfides soils, preferably calcium and barium, neutral and basic, preferably alkyl Ce and higher metal alkyl alicylates alkaline earths preferably calcium and magnesium, neutral and basic with C12 alkyls to C22, preferably C14 to C18. Said dispersants promote wettability, dispersibility, complete homogeneous dispersion pigments and fillers and allow very quick preparation process gentle, stable) dispersions and reduced pigment consumption a it is suitable for fake and / or stuffing blends, pigment preparations and colorants grain products, powders, foils, moldings and the like high-pressure polyethylene and low pressure, polypropylene, polystyrene and copolymers thereof, polyvinyl chloride a its copolymers, polymethacrylates, polyamides and other.

Description

The invention relates to a process for dyeing plastics with organic or inorganic pigments, filling with fillers and additives using oil-soluble detergent-dispersing additives such as sulfonates, alkylphenols, alkylphenolsulfides and alkylsalicylates of alkaline earth metals, which provide an extremely high degree of full dispersion and pigment dispersions. in plastic.

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 them to be crushed into aggregates 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, namely in the mass during their production or in the mass during the processing of their powder or granulate. The third method, the first coloring of finished plastic products, is rarer. Usually, the pigment or pigment preparation is dry mixed with the powder or granulate of the plastics material in agitators of various types (drum, fluidized-bed mixer, and subsequently processed in extruders or spraying machines. The plastics material can also be colored by adding commercial pigment or prepared on site, into the processing machine without pre-mixing.

The most important inorganic pigments used are TiOz pigments (especially rutile) and zinc sulphide pigments with up to 100% ZnS content (less effective than T; O2 pigments) for white dyeing, iron and chromium oxide pigments (rye, red, brown, black types) and vegetable, particularly stable and practically 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 (selenide), chromate mixed phase pigments of the composition Pb (Cr, S) 04 and Pb (Cr, Mo, S) 04. A filler may also be counted among pigments 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 and increased 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 a suitable pigment has to be searched and tested. To facilitate this selection, according to the aforementioned indicators, generally suitable organic pigments for the plastic sector are summarized in special assortments, in particular of large pigment manufacturers.

The metal dispersants (detergent dispersants) of the present invention promote the wettability and dispersibility of the organic pigments and allow a very rapid process to prepare 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 particularly suitable for high- and low-pressure polyethylene, polypropylene, polystyrene and styrene mixed polymerizates, polyvinyl chloride and its copolymers, as well as 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, of alkaline earth metal sulfotates, preferably calcium, neutral and basic petroleum and synthetic, based on oil-soluble monosulfoacids of at least molecular weight 250, preferably 350 to 490, oil-soluble alkylphenolates and alkylphenolsulfides (sulphated alkoxyphenols) of alkaline earth metals, preferably calcium and barium neutral and basic, preferably alkyls C 6 and higher, alkylsalicylates of alkaline earth metals, preferably calcium and magnesium and magnesium, % of C12 -C22 alkyl groups, preferably C14 -C18 alkyl.

The dispersants of the present invention ensure, on the one hand, the perfect application of the pigment's certain color effects such as color saturation, color tone and its stability, gloss, hiding power, and, on the other hand, improve production economy by significantly reducing pigment consumption by up to one third or more compared to known non-coloring methods the use of dispersants or the use of known dispersants which are less effective.

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

An advantage of the dispersants of the invention is also that, due to their high dispersing effect, no visible grains of pigment are present in the processed compositions, nor remain adhering to the walls of the machine equipment and containers, and allow a sharp, large ^: rapid transition to other products. a new blend of another color, with very confusing production of the intermediate color waste product, without interruption, and the manufacture and purification of the manufacturing equipment.

The dispersants of the present invention can be used to prepare color blends at the place of manufacture of colored plastics, as well as to prepare long-term stable pigment preparations (concentrates which may be conventional commercial products in the form of grandiose, powders, pastes, viscous liquids in which pigments These compositions 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, plasticizers, other auxiliary agents, or mixtures thereof, which are compatible or miscible with the plastic.

For direct use of dispersions elsewhere in the manufacture of colored plastic products such as granules, powders, foils, moldings, soils, etc., the dispersion of the pigment with dispersantium, optionally with the prescribed additives such as thermo-oxidizing stabilizers, glidants, ainti-UV- stabilizers, with wetting agents and fillers and in the form of a liquid mixture or paste, are added in batches or continuously (by pump), depending on the type of processing machine, in proportion to the plastic, through a tube reaching the bottom of the hopper to dispense granules, powder or melt a plastics material placed on a processing machine such as a shot, extrusion screw or the like.

The use of the dispersants of the invention makes it possible to achieve substantial energy savings. Due to the high dispersing effect and the high dispersing rate of these dispersants, mixtures of dispersants and 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 amtiblocking properties of films and other products. They also reduce the required power input for driving striojov.

A particular advantage of the dispersants according to the invention is their suitability for use in addition to dyeing plastics also in the preparation of filled plastics dyed or with natural fillers such as powder chalk, special fillers for absorbing radiation, flame retardants, pencteor substances 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 the polymers of the plastic. The dispersants ensure a high degree of dergency of the fillers, their even distribution and the easy and homogeneous mixing of these mixtures with the plastic.

Method for dyeing plastics with organic and inorganic pigments and for filling colored, natural plastics with fillers using dispersants of the present invention or mixtures thereof and known processes for producing color mixtures, pigment preparations, filled color or natural plastics and plastic products * from plastics in the form of granules, powders, foils, moldings, castings and the like. characterized in that the addition of dispersants, calculated as 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 on the plastic the substance, dispersant content in color mixtures and pigment preparations is at most 99.0% by weight, preferably: u is in the range of 30.0 to 90.0% by weight, based on the color mixture or pigment preparation, and in filling colored and natural plastic is the addition of d ^; %, preferably from about 30.0 to about 90.0% by weight, based on the dispersant / filler mixture.

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

Example 1

In a conventional mixer, 0.3 kg of white ¹ oil, 0.1 kg of calcium basic alkyl salicylate, with Cu-Cie alkyls and a total alkali (TBN) of 90, which is 50% oil concentrate and 0, is mixed at room temperature. 66 kg TiO2 (Bayer Titan RFKD) until a homogeneous liquid mixture is formed.

The prepared blend is dosed in a weight ratio to a 1:90 granulated extruded polyethylene prior to entering the colorless polymer into the screw, into the bottom of the hopper into which said polyethylene granulate is placed, on a continuous continuous screw machine, where it reaches the extruded molten temperature. to 215 ° C.

To dispense the liquid dispersion, a peristaltic pump, equipped with a turn control, to a continuously operating screw was used.

A length-to-diameter screw of 20: 1 supplied material to the exhaust head from which a 0.3 mm thick white film with a completely uniformly dispersed pigment was obtained, with no visible scratches.

Example 2

A homogeneous liquid mixture consisting of 0.6 kg of white oil, 0.2 kg of calcium-neutral alkylsalicylate with C 14 -C 18 alkyls, 50% of pigments 0.2 kg of Chromphtal Gelb 6 was prepared according to the procedure and conditions as in Example 1. G, 0.05 kg Chromphtal Roth BR and 0.05 kg Chromphtal Grun GF.

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

Example 3

A homogeneous liquid mixture consisting of 0.6 kg of white oil, 0.2 kg of C12-C22 alkyl, 50% and 0.25 kg of Corax soot 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 weight ratio of 1: 95 on a 0.3 mm thick film under normal operating conditions. The foil produced was saturated in black, with completely uniformly distributed pigments, without any visible grains of pigment.

Example 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 RFKD) was prepared according to the procedure and conditions as in Example 1.

The prepared color mixture was treated with ptolyvinyl chloride in a weight ratio of 1:50 on a 0.2 mm thick film under normal manufacturing conditions. The foil produced had a saturated 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% monosulfoacidic calcium petroleum sulfonate with an average molecular weight of 435, low base with TBN 25, 0.3 kg of white oil, 1.0 kg was prepared according to the procedure and conditions of Example 1. T1O2 (Bayer Titan RFKD).

The prepared color mixture was treated with polystyrene in a weight ratio of 1:70 on a 0.2 mm thick film. Made foil had. saturated white in color with a faintly rye tint, with evenly distributed pigments, without visible grains of pigment.

Example 6

A homogeneous liquid mixture consisting of 0.2 kg of calcium alkyl salicylate was prepared by the procedure and under the conditions of Example 1; neutral as in Example 3 to 0.2 kg of magnesium alkyl salicylate basic with TBN 300 mg KOH / g with C14 to C18 alkyls, which is a 50% solution in white oil, 0.6 kg white oil and 1.0 kg T1O2 (Bayer Titan RFKD) ).

The prepared color mixture was treated with polypropylene, in a weight ratio of 1 to 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 consisting of 1.0 kg of calcium alkyl phenolate; basic, with C16 alkyl and TBN 220, 45%, 2.0 kg white oil, 2.5 kg 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 µl and a foil of 0.3 mm thickness. The foil produced was saturated white in color, with a slight tinge of rye, with a completely uniformly distributed pigment, without visible grains.

Claims (7)

252352 Example 2 In a procedure and as in Example 1, a homogeneous liquid mixture was prepared consisting of 0.6 kg of white oil, 0.2 kg of calcium alkylsalicylate neutral with C14-C18 alkyl, 50% of pigments 0.2 kgChromphtal Gelb 6 G , 0.05 kg ChromphtalRoth BR and 0.05 kg Chromphtal Griin GF. 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 the condition as in Example 1. The foil produced had a khaki color, with a completely uniformly dispersed pigmeint, without any visible grains. Example 3 Using a procedure and as in Example 1, a homogeneous liquid mixture was prepared consisting of 0.6 kg of white oil, 0.2 kg of C12-C22, 50% and 0.25 kg of Corax carbon black. The prepared color mixture was treated with a granulated low pressure polyethylene in a 1: 95 weight ratio on a 0.3 mm thick foil under the usual operating conditions. The filaments produced were black-black stained, with uniformly distributed pigmentation, without any visible pigment pigment. Example 4 Using a procedure and as in Example 1, a homogeneous liquid mixture was prepared consisting of 1.0 kg of calcium lime alkyl salicylate, with C12-C22 alkyls and TBN110 and 1.5 kg T1O2 (Bayer Titan RFKD). The prepared color mixture was treated with 1: 50 wt% polyvinyl chloride on a 0.2 mm thick foil under the usual conditions. The produced white foliamala, with a uniformly dispersed pigment, without any visible grains of pigment. Example 5 By way of example and under conditions 1, a homogeneous liquid mixture consisting of 0.3 kg of 30% by weight calcium sulphate oil * based on monosulfoacid of average molecular weight 435, low base with TBN 25, 0.3 kg of white 0-lye was prepared. , 1.0 kg of T1O2 (Bayer Titan RFKD). The prepared color mixture was treated with cystyrene in a weight ratio of 1: 70 to 0.2 mm thick foil. Made foliage ma-la. white color with a faint rye, with a completely uniformly distributed pigment, without visible pigment grains. Example 6 Using a procedure and as in Example 1, a homogeneous liquid mixture was prepared consisting of 0.2 kg of calcium neutral alkyl salicylate as in Example 3 and a 0.2 kg of magnesium alkyl salicylate with TBN of 300 mg KOH / g with alkyls. C14 to C18, which is a 50% solution in white oil, 0.6 kg of white oil and 1.0 kg of T1O2 (BayerTitan RFKD). The prepared color mixture was treated with propylene, in a mass of 50 mm, on a 0.2 mm thick foil. The leaves were white in color, with the pigment evenly distributed, without visible grains. Example 7 In a procedure and under the conditions of Example 1, a homogeneous liquid mixture was prepared consisting of 1.0 kg of basic calcium phthalate, with alkyls of C18 and TBN220, 45%, 2.0 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 weight ratio of 1: 45 µm and 0.3 mm thick foil. The produced foliage was white in color, with a slight tinge of rye, with a completely uniformly dispersed pigment, and an invisible grain. SUBSTITUTE Dyeing of plastics such as low pressure polyethylene and high pressure, polypropylene, polystyrene and its polymers, polyvinyl chloride, polyamide, and other organic or inorganic polymers, filling with known fillers and the addition of metal oil-soluble dispersants and known sequential fabrication processes. Pigmented OUTDOOR preparations and colored plastics including filled plastics color and natural, in the form of granulates, powders, foils, moldings, castings and the like. characterized in that at least one dispersant is used, such as the oil-soluble alkaline earth metal sulfonates, preferably calcium, neutral and basic, petroleum and synthetic, based on oil-soluble monosulphosulfonates of a molecular weight of at least 250, preferably from 350 to 490, oil-soluble alkylfemolates and alkylphenol sulfides of metal-alkaline soils, preferably calcium-alkaline, neutral and basic, preferably by alkyl-Ce and larger, alkyl-alkali-earth alkylsalicylates, preferably calcium-magnesium, neutral and basic with alkyl-C12 to C22, preferably C14 to C18, with the addition of dispersants, calculated as 50% oily solutions, to at least 0.01 pounds per colorless plastic. %, preferably in the range of from 0.2 to 2.5% by weight, based on the plastics material, of the dyestuffs and pigment preparations is at most 99.0% by weight, preferably 30.0 to 90.0% by weight. , calculated on the color mixture or pigment preparation and into the full-color and natural plastics, at least 99.0% by weight, preferably 30.0 to 90.0%. mass, calculated on the mixture of dispersant and filler.