CS223068B1 - Method of dyeing thermoplastic materials by pigments under assistance of dispersing agent blends - Google Patents

Description

The invention relates to a method for dyeing plastic materials with organic and inorganic pigments and to fill with fillers using a mixture of additives derived from the group of oil-soluble metal detergent-dispersant additives of the high temperature sulfonates type, alkylphenlates, alkylphenolsulfides and alkylsalicylates. low-ash and medium-temperature, succinimides, bissuccinimides, phosphonates and copolymeric polymethacrylates containing nitrogen-bound molecules and dispersants of the dispersant type of alkoxy-polypropopoxy-polyetoxamers, which achieve a high degree of dispersion of the additive mixture or fillers and their even distribution throughout the 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. The reduction in the melt viscosity of the plastics material further promotes the process of dlspergy.

The plastics are mainly dyeed by yard 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 plastic powder or granulate in mixing units of various types (drum, fluid mixer) and subsequently processed in extruders or spray machines. The plastic may also be colored by adding commercially available or on-site pigment preparations to the processing machine without pre-mixing.

The most important inorganic pigments are TiO ₂ -pigments (especially rutile) and zinc sulphide pigments with up to 100% ZnS content (less effective than TiO ₂ -pigments) for white coloring, iron and chromium oxide pigments (rye, red, brown, black types) and green], particularly stable and virtually 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 Gd- sulphide (selenide, chromate mixed phase pigments of Pb (Cr, S) O ₄ and Pb (Cr, Mo, S) O ₄ .

A filler may also be counted as a pigment 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. For grit and increased technical demands such as. high thermal and migratory stability, wettability and dispersibility, the choice of a large number of organic pigments is considerably narrowed and a suitable pigment must be sought and tested. In order to facilitate this selection, on the basis of the above-mentioned indicators, organic pigments for the plastic sector are generally suited in special assortments, in particular of large pigment manufacturers.

Mixed dispersants according to the invention, consisting of high-temperature, low- and medium-temperature types of known oil-soluble dispersing and detergent-dispersing additives used in lubricating oils (see, e.g., V. Stepin, V. Vesely: Lubricants and Special Oils, SAV 1980) and alkoxy-polypropox-polyetox-amide-type dispersants have the advantage over the use of dispersants of one kind in that they can provide maximum dispersing effect against pigments and fillers over a wide range of processing temperatures, from low to high temperatures and the desired hydrophilic properties of color mixtures and pigment preparations.

The mixed 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. They are suitable, in particular, for high and low pressure polyethylene, polypropylene, polystyrene and styrene blended polymers, polyvinyl chloride and its copolymers, furthermore for phenolic and polyester resins, urea and melamine resins, polymethacrylates, polyamides and others.

High temperature dispersants (effective at high temperatures of about 250-320 ° C or more) according to the invention are oil solutions (concentrates), usually about 30 to 50 washes, preferably in mineral white oil, of alkaline earth metal sulfonates, preferably calcium , neutral and basic, petroleum and synthetic, oil-soluble monosulfoacids having a molecular weight of at least 250, preferably 350 to 490, oil-soluble alkylphenlates and alkylphenol sulfides (sulphated alkylphenols) of alkaline earth metals, preferably calcium and barium, neutral and basic, preferably alkyl C ₈ and greater, alkylsalicylátov calcium, neutral and basic with alkyl C ₁₂ to C _22, preferably C ₁₄ to C _18th

Low temperature and medium temperature disperzan223068 the (effective especially at low temperatures up to about 150 ^Q • C and a mean temperature of about 160- -240 ° C) of the invention are viscous solutions sukcín'midových ingredients, preferably bissukcínimidových, phosphonate and thiophosphonate, especially calcium and barium, intermediate and polymethacrylate containing nitrogen bound in the molecule.

The alkoxy-polypropox-polyetox-amers dispersants (alkoxy-polyethylene oxide-polypropylene oxide copolymers; alkyl-polyethylene-polypropylene-glycols) are of the general formula:

R - (O - CH - CH ₂ ) _X - (O - CH _{2 -} CH ₂ ) _{y -} OH,

I ch ₃ where is

R - alkyl higher fatty alcohol, preferably a C ₄ -C _12, x - from 4 to 40, preferably 4 to 20, y - 2 to 20, preferably 4 to 12.

A particular advantage of dispersants of this type is that the hydrophilic properties of the molecule can be influenced by the chemical structure of the molecule, which allow easy and rapid cleaning of the water of machinery and containers in contact with the color mixtures and pigment preparations. It is known that pure polyethylene glycols HO (C ₂ H ₄ O) _m H include up to a molecular weight of about 600 and higher viscosity liquids besides wax. They dissolve in water perfectly at room temperature. Polypropylene glycols HO (C ₃ H ₆ O) _n H are liquid. Their water solubility decreases with increasing molecular weight. By the mixed polymerization of the two alkylene oxides to form a combination of hydrophilic polyethylene oxide with hydrophobic polypropylene chain chains as well as polyalkoxilization of fatty alcohols, compounds with specific properties such as e.g. with some solubility in water or in organic liquids, with some capillary activity, viscosity, chemical stability, etc.

The mixed dispersants of the present invention are suitable for dyeing with organic and inorganic pigments or pigment preparations and for fillers with plastic fillers such as high and low pressure polyethylene, polypropylene, polystyrene and its copolymers, polyvinyl chloride and its copolymers, phenol, polyester, urea and melamine and urea and melamine. polyamides, polymethacrylates and others.

The blend dispersants of the present invention can be used to prepare concentrated color blends that are immediately processed at the point of manufacture of colored plastics, as well as to produce long-lasting pigment preparations (end-of-wires) which can be conventional commercial products in the form of granules, powders, pastes. viscous liquids in which the pigments are already in dispersed form. These concentrated preparations may contain up to 99.0% by weight, preferably about 30-90% by weight, of the pigment in dispersed form, and comprise, in addition to the pigment, a dispersant and may further comprise a plastic to be colored, wetting agents, other adjuvants or mixtures thereof which are compatible or miscible with the plastic.

The direct use of dispersants at the place of manufacture of colored plastic products such as granules, powders, foils, moldings, castings, etc., is done by mixing the pigment with the dispersant, optionally with the prescribed additives such as thermo-oxidizing stabilizers, glidants, anti-UV -stabilizers, with plasticizers and fillers, and in the form of a liquid mixture or paste, are added to the feed or continuously (by pump), depending on the type of processing machine, in specified proportions to the plastic, through a tube extending to the bottom of the feed hopper melt of plastic placed on a processing machine such as strekolis, extrusion screw and the like.

The advantage of the mixed dispersants according to the invention is their suitability for use in addition to dyeing plastics as well as in the preparation of filled plastics dyed or natural fillers such as e.g. 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, e.g. 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 provide a high degree of dispersion of the fillers, their uniform distribution and easy homogeneous mixing of these mixtures with the plastic. The addition of the dispersant is at most 99.0% by weight, preferably in the range of 20.0 to 90.0% by weight, based on the mixture of dispersant and filler.

The mixed dispersants according to the invention ensure, on the one hand, the perfect color 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 the use of dispersants.

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 pigmentation that only special pigment preparations which are characterized by a particularly high degree of dispersion of the pigments contained can satisfy them.

Another advantage of the dispersants according to the invention is that, due to their dispersing effect, they do not appear in the treated mixtures or remain adhering to the machinery and containers, any visible grains of pigment and allow a sharp, very rapid transition to the products of another mixture. paints, with very little production of the intermediate waste product, without the need to interrupt production and clean the production equipment.

The use of mixed dispersants according to the invention makes it possible to achieve substantial energy savings. The high dispersing effect and the high dispersing speed of these dispersants make it possible to use various concentrated dispersants, pigments and fillers mixtures and possibly other ready-to-use auxiliary agents in the manufacture of colored and filled plastics, thus avoiding the preparation of colored granules, powders and pastes. on energies. It also saves on storage and transport capacities and saves on the storage of raw materials and materials.

The mixed dispersants of the invention also improve the wicked, antistatic and anti-blocking properties of films and other products. They also reduce the energy input required to drive processing machines.

Method of dyeing plastics with known organic and inorganic pigments and filling colored and natural plastics with known fillers, using known processes for producing spirits of concentrated color mixtures, concentrated pigment preparations, filled colored or natural plastics and colored plastic products in the form of granules, powders, foils, moldings, castings and the like. and using mixed dispersants consisting of known oil-soluble low- and high-temperature dispersing and detergent-dispersing additives used as lubricant oil additives and alkoxy-polypropox-polyetox-amers dispersants, characterized in that the dispersants added consist of one or more dispersants. a plurality of additives from each of two or three groups of additives, such as a group of oil-soluble high-temperature metal detergent-dispersing additives consisting of alkaline earth metal sulfonates, preferably calcium, neutral and basic, petroleum and synthetic, based on oil-soluble monosulfoacids of molecular weight at least 250, preferably 350-430, alkylfenolátov alkylfenolsulfidov and alkaline earth metals, preferably calcium and barium, and a neutral base, preferably a alkylrni C ₈ and greater, and, alkyl, hydroxy calcium salicylates, neutral and overbased with C ₁₂ -C ₂₂ alkyls, preferably C ₁₄ -C ₁₈ , a group of low temperature and medium temperature oil-soluble dispersants such as succinimide, preferably bissuccinimide, alkenylphosphonate, thiophosphonate, especially calcium and barium, medium basic, alkenyl methacrylate and alkenyl thiolate phosphate containing nitrogen bonded in the molecule and a group of dispersants of the alkoxy-polypropox-polyetox-amers type of the general formula

R - (O - CH - CH ₂ ) _x - (O - CH _{2 -} CH ₂ ) _{y -} OH,

I ch ₃ where is

R - alkyl group as above-fatty alcohol, preferably a C ₄ to C _12, x - from 4 to 40, preferably 4 to 20, y - 2 to 20, preferably 4 to 12, the addition of the mixed dispersants to · plastic materials is at least 0, 01% by weight, preferably in the range of 0.2 to 3.0% by weight, calculated on the plastic, the content of dispersant in the color mixtures and pigment preparations is at most 99.0% by weight, preferably in the range of 30%, 0 to 90.0% by weight, based on the color composition or pigment preparation, and when filling colored and natural plastics, the dispersant addition is at most 99.0% by weight, preferably in the range of 20.0 to 90.0% % by weight, based on the dispersant / filler mixture. The weight ratio of the dispersants of high temperature, low and medium temperature and alkoxy-polypropox-polyetox-amers can vary according to the production conditions as the minimum processing temperatures and the desired hydrophilic properties of the compositions to be treated, generally between 1: 1: 0.5 and 3: 1: 4.

In order to illustrate the invention, the following non-limiting examples are provided.

Example 1

In a conventional mixer, 900 g of white oil, 200 g of calcium basic alkyl salicylate with C ₁₄ -C ₁₈ alkyl, which is a 50% oil concentrate, 100 g of bissuccinimide additive S5A and 2000 g of TiO ₂ (Bayer Titan) are mixed at room temperature. RFKD) until a homogeneous liquid mixture is formed.

The mixture is dosed in a weight ratio to a 1: 95 granulated high pressure polyethylene before the colorless polymer enters the screw, into the bottom of the hopper to which the polyethylene granulate is placed, placed on a continuous screw auger, where the molten mixture temperature reaches 215 ° C. .

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

A length-to-diameter snake of 20:

1, the material was supplied to the blow head from which a 0.3 mm thick, white film, with a completely uniformly dispersed pigmentor, without any visible grain of pigment, was obtained.

β

Example 2

A homogeneous liquid mixture consisting of 950 g of a white oil, 250 g of a 32% low-base monosulphonic acid monosulphuric acid, average molecular weight 460, 100 grams of bissuccinimide additive S5A, 130 grams 2- ethylhexyl-polypropox-polyetox-amer, whose mole of polypropox contained on average 16 molecules of propylene oxide and mole of polyetox on average 4 molecules of ethylene oxide, 350 g of Chromphtal Gelb 6 G pigment, 100 g of Chromphtal Roth BR pigment and 100 g of Chromphtal Grun GF pigment.

The prepared homogeneous, concentrated dyed mixture was treated with granular high pressure polyethylene at a weight ratio of 1: 100 on a 0.3 mm thick film on the apparatus and under the conditions of Example 1. The produced film was khaki color, with a completely uniformly dispersed pigment, without any visible pigment grains. The color mixture was easily removed with water from the used containers and manufacturing equipment.

Example 3

A homogeneous liquid mixture consisting of 100 g of nitrogen-containing polymethacrylate additive Plexol 956, 200 g of bissuccinimide additive S5A, 400 g of 2-ethylhexyl-polypropox-polyetox-amer, whose mole of polypropox containing an average of 20 moles was prepared according to the procedure and conditions as in Example 1. propylene oxide with a mole of polyetox on average 6 molecules of ethylene oxide, 850 g of white oil and 2100 g of TiO ₂ (Bayer Titan RFKD).

The prepared color mixture was treated with polypropylene in a mass ratio of 1: 55, on a 0.2 mm thick film, following the procedure of Example 1. The produced film had a saturated white color, with perfectly uniformly distributed pigment, without visible pigment grains. The color mixture was easily rinsed with water from used containers and production equipment.

Example 4

Following the procedure and conditions as in Example 1, a homogeneous liquid mixture consisting of 500 g of a 50% basic calcium alkylphenolate with alkyl C _18, 550 g of 2-etylhexyI-polypropoxy-AMER-po'.yeíox that in Example 2, 2000 g of white oil, 2450 g of zinc white, and 100 g of Cyasorb 531 (UV stabilizer).

The prepared color mixture was treated with granular high pressure polyethylene in wt. 1: 25 ratio on a 0.2 mm millimeter film on a device as in Example 1. The film produced was a saturated white color, with a slight tint of rye, completely uniformly dispersed pigment, without visible pigment grains. The color mixture was easily removed with the guide from the containers used and from the manufacturing equipment.

Example 5

The prepared color mixture as in the example was treated with polyvinyl chloride in a weight ratio of 1: 55 to a foil of 0.3 millimeters depth under usual manufacturing conditions. The foil produced had a khaki color, with a completely uniformly distributed pigment, without visible grains of pigment.

Example kg The prepared color mixture as in Example 3 was added with stirring to 45 kg of methyl methacrylate prepolymer. After addition of all the color mixture, stirring was continued for 12 minutes. The mixture was then not allowed to stand for 25 minutes while removing air bubbles. The mixture thus prepared was filled into glass molds in which, according to the usual manufacturing process, it was allowed to be co-polymerized to solid sheets of depth mm.

In a dispersant-free manufacturing process, the preparation of the color mixture takes about 24 hours or more and the pigment is not as completely dispersed as in the dispersant process.

Example 7

The color composition prepared as in Example 1 was treated with polystyrene at a ratio of 1:80 to a film of 0.3 mm thickness. The product had a whitish-white color, with a completely uniformly distributed pigment, without its visible grains.

Example 8

The prepared color mixture as in the example was treated with granulated colorless polyamide in wt. ratio of 1:45 to 0.2 mm thick film. The foil produced was saturated white in color, with a slight hint of rye, completely uniformly distributed pigment, without visible grains.

Claims (4)

SUBJECT 1. A process for dyeing plastics with pigments using mixed dispersants such as dyeing low and high pressure polyethylene, polypropylene, polystyrene and its copolymers, polyvinyl chloride, polyamide, polymethacrylate and other plastics with organic or inorganic pigments, and filling known known fillers with mixtures of known dispersants. the preparation of colored precipitates, pigment preparations filled with colored and natural plastic materials in the form of granules, films, powders, moldings, castings, etc., characterized in that 0.01 to 99.0% by weight of the compositions are used. dispersant mixtures consisting of one or more dispersants of each of two or three dispersant groups such as a group of high temperature oil-soluble metal dispersants such as alkaline earth metal sulphonates, preferably calcium, neutral and basic, petroleum and synthetic, based on oil-soluble monosulphonic acids of at least molecular weight 250, preferably 350-490, alkylfenoláty and alkylíenolsulfidy alkaline earth metals, preferably calcium and barium, neutral, and basic, preferably with alkyl C ₈ and greater, and alkylsalicyláty calcium neutral and basic with alkyl C ₁₂ to C 22, preferably C ₁₄ to _C18 , a group of oil-soluble dispersants of low and medium temperature as succinimides, preferably bissuccinimides, alkenyl phosphonates, thiophosphonates, in particular calcium and Barium medium-basic, alkenylthiophosphates and polymethacrylates containing nitrogen-bound molecule and a group of dispersants of the alkoxy-polypropox-polyetox-amers type of the general formula R - (O - CH - CH ₂ ) _x - (O - CH _{2 -} CH ₂ ) _{y -} OH, CH ₃ where is R - alkyl higher fatty alcohol, preferably a C ₄ to C _12, x - from 4 to 40, preferably 4 to 20, y - 2 to 20, preferably 4 to 12. 2. Method according to claim 1, characterized in that the addition of the dispersant mixture to the plastic is at least 0.01% by weight, preferably in the range of 0.2 to 3.0% by weight, calculated on the plastic. 3. Method according to claim 1, characterized in that the content of the mixture of dispersants in concentrated color mixtures and pigment preparations is at most 99.0% by weight, preferably in the range from 30.0 to 90.0% by weight, calculated on the concentrated color mixture. or a pigment preparation. '4. The method according to claim 1, characterized in that the addition of the dispersant mixture is at most 99.0% by weight, preferably in the range of 20.0 to 90.0% by weight, based on the dispersant / filler mixture, when filling colored and natural plastic materials.