CS252353B1 - Method of plastics pigment-dyeing with application of mixed dispergators - Google Patents

Abstract

The method of coloring plastics by known organic and inorganic pigments, filling with known fillers and additivation using mixtures of dispersants from the following 2 or 3 groups: —Olly soluble sulfonates, alkyl salicylates, metal alkyl phenol and alkyl phenol sulfides alkaline earth - oil soluble succinimides, bissuccinimides, phosphonates and polymethacrylates containing nitrogen in the molecule - alkoxy-polypropiox-polyetoixamers defined structure. It ensures maximum dispersing effect against pigmeints, bulking agents and additives at a wide range of processing temperatures a the desirable hydrophilic properties of phare and filled plastics and pigmented commercial preparations.

Description

The present invention relates to a process for dyeing plastics with organic and inorganic pigments, filling fillers and additives using a mixture of dispersing additives derived from the group of oil-soluble metal detergent-dispersing additives of the high-sulfonate type, alkylphenols, alkylphenolsulfides ashless (or low ash), low and medium temperature, succinimide, bissuccinimide, phosphonate and copolymeric polymethacrylate-type copolymers, and alkoxyl-polypropoxy-copolymer-dispersant copolymers-dispersant-type additives, to achieve a high degree pigment or filler and their total uniform dispersion in the plastic.

Pigments are organic or inorganic powders practically insoluble in the dyed plastic material. Due to the high thermal stresses during processing, it is possible that some organic pigments will at least partially pass into solution. Pigments consist of particles whose size increases in order: primary particles (individual crystals, aggregates and agglomerates. The color efficiency of the plments increases with small particle size. In dispersing the pigment it is mainly crushing, removal of agglomerates. to aggregates and primary particles, and ensures the stability of the fine dispersion, reducing the viscosity of the plastic melt further enhances the dispersion process.

The plastics are mainly dyed in two processes, namely in the mass of their production or in the mass of their powder or granulate. The third method, the surface coloring of the 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, fluid mixer and then further processed in extrusion or spraying machines. The plastics material can also be colored by adding commercially available pigment preparations or prepared on site, into the processing machine without pre-mixing.

The most important inorganic pigments used are TiO2-pigments (especially rutile) and zinc sulphide pigments with various up to 100% ZnS content (less effective than T1O2-pigments) for white coloring, iron and chromium oxide pigments (lived, red, brown, member and green types) ], 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 composition

CdS or Cd-sulphide selenide, chnomate mixed phase pigments of Pb (Cr, S) O4 and Pb (Cr, Mo, S) 04. Fillers may also be counted as pigments if their refractive index in a certain environment is greater than 1.7. Known types of fillers are powdered chalk 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 various increased technical demands such as e.g. high thermal and migratory stability, wettability and dispersibility, the choice of a large number of organic pigments narrows considerably and the suitable pigment must be searched and tested. In order to facilitate this selection, according to the aforementioned indicators, generally suitable organic pigments for the plastics sector are summarized in special assortments, in particular of large pigment manufacturers.

The mixed dispersants of the present invention, consisting of the high temperature, low and medium temperature types of the known non-soluble dispersing and detergent dispersing additives used in lubricating oils and of the alktoxypolypropoix-polyetdx-amers dispersants, have the advantage over one type of dispersants maximum dispersing effect against pigments and fillers over a 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 for high-pressure 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 high temperature metal dispersants (effectively even at temperatures of about 250 to 320 ° C and above) of the present invention are oil solutions (concentrates), usually about 30 to 50 percent preferably in mineral white oil, alkaline earth sulfonates, preferably calcium. , neutral and basic, petroleum and synthetic, other bases of oil-soluble monosulphonic acids having a molecular weight of at least 250, preferably 350 to 490, of oil-soluble alkylphenolates and alkylphenol sulphides (sulphated alkylphenol) of alkaline earth metals, preferably calcium and barium, neutral and basic, preferably with alkyls C 6 and higher, alkylsalicylates of alkaline earth metals, preferably calcium and magnesium, neutral and basic with alkyls C 12 to C 22, preferably C 14 to C 18.

Low temperature and medium temperature dispersants (effectively other than low temperatures up to about 150 ° C and medium temperatures around 160-240 ° C), according to the present invention, are viscous solutions of the adducts of succinic mid, preferably bissuccinimide, phosphonate and thiophosphonate, especially calcium and barium, moderately basic and polymethacrylate additives containing nitrogen bound in the molecule.

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

R - (O - CH - Cl 12) _x - (O - CH 2 - CH 2) _{y -} OH CHo where is

R-alkyl of a higher fatty alcohol, preferably C1-C12, x-4 to 40, preferably 4 to 20, y-2 to 20, preferably 4 to 12.

A benefit of dispersants of this type is that the hydrophilic properties of the molecule can be affected by the chemical structure of the molecule, making it easy and quick to clean the water of machinery and containers coming into contact with color mixtures and pigment preparations. It is known that pure polyethylene glycols HO (C2H4O) _m is H and the molecular weight of about 600 and higher fluid viscosity of the wax. They dissolve in water perfectly at room temperature. Polypropylene glycols HO- (CHNoO) _n H are liquid. Their water solubility decreases with increasing molecular weight. By the mixed polymerization of both alkylene oxides to form combinations of hydrophilic polyethylene oxide with hydrophobic chains of polypropylene oxide, as well as polyalkoxylation 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 blend dispersants of the present invention are suitable for dyeing with organic and inorganic pigments or pigment preparations and for filling with fillers of plastics such as high and low pressure polyethylene, polypropylene, polystyrene and its copolymers, polyvinyl chloride and its copolymers, phenol, polyester, urea, melamine 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 long-term stable pigment preparations (concentrates) which can be conventional market 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, a plasticizer, other auxiliaries 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 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 bottom of the hopper melt of plastic placed on a processing machine such as a shot, 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 also in the preparation of filled or dyed filled plastics with fillers such as e.g. powder chalk, especially radiation absorbers, 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 processed in the form of a liquid mixture or paste with the 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. 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 of the present invention provide both a perfect non-coloristic effect of the pigment, such as color saturation, color tone and its stability, gloss, hiding power, and, secondly, improve production economics, significantly reducing pigment consumption by up to one third or more compared to known without 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 pigment disintegration that only special pigment preparations which are characterized by a particularly high degree of dispersion of the pigments can satisfy them.

An advantage of the dispersants of the present invention is also that, due to their dispersing effect, they do not appear in the processed compositions or remain on the walls of the machinery and containers, any visible grains of pigment and allow a sharp and very rapid transition to products from a new blend of a different color, with very little production of the intermediate color waste product, without the need to interrupt the production and cleaning of the production equipment.

The use of the mixed dispersants of 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 variously concentrated on-site mixtures of dispersants, pigments and fillers and possibly other on-site auxiliaries in the manufacture of colored and filled plastics, thereby eliminating the pre-preparation of colored granules, powders and pastes. brings energy savings. It also sows with storage and transport capacities and saves on the storage of raw materials and materials.

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

Method for dyeing plastics with known organic and inorganic pigments and for 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 dispersants and detergent-dispersants of low, medium and high temperature, used as additives to lubricating oils and dispersants of the alkoxy-polypropox-polyetox-amers type, characterized in that the dispersants added consist of one or a plurality of additives from each of the two or three additive groups, such as a group of oil-soluble high-temperature metal detergent-dispersants, consisting of alkaline earth metal sulfonates, preferably calcium, neutral and basic, petroleum and synthetic, based on oil-soluble monosulfoacids 250, preferably 350 to 490, alkylphenolates and alkylphenolsulfides of alkaline earth metals, preferably calcium and barium, neutral and basic, preferably with alkyls of Ca and more and alkylsalicylates of alkaline earth metals, preferably foamy and magnesium, neutral and basic with C12 to C22 alkyls, preferably C14 a, C18, a group of low temperature and medium temperature oil-soluble dispersants such as succinimide, preferably bissuccinimide, alkenylphosphonate, thiophosphonate, alkali biphenylphosphonate, especially calcium biphenyl and phosphorate polymethacrylate additives containing nitrogen bonded in the molecule and a group of dispersing additives of the alkoxy-polypropox-polyetox-amers type of the general formula R- (O-CH-CH 2) _X - (O-CH 2 -CH 2) _y -OH

CH5 where is

R-alkyl of a higher fatty alcohol, preferably C4-C12, x-4 to 40, preferably 4 to 20, y-2 to 20, preferably 4 to 12, the addition of mixed dispersants to the plastics is at least 0.01% by weight preferably from 0.2 to 3.0% by weight, based on the plastic, of the dispersant content in the color mixtures and pigment preparations is at most 99.0% by weight, preferably in the range from 30 to 30% by weight, 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% by weight. calculated on the basis of the dispersant / filler mixture. The weight ratio of the dispersants of the high temperature, low and medium temperature and alkoxy-polypropox-polyetox-amers can be varied according to the process conditions, such as the maximum processing temperatures and the desired hydrophilic properties of the compositions to be treated, generally in the range of 1: 1: 0.5 to 3: 1. : 4.

By way of illustration, the following non-limiting examples are provided.

Example 1

In a conventional mixer, 900 g of white oil, 100 g of basic calcium alkylsalicylal and 100 g of basic magnesium alkylsalicylate, both of which are C14-C18 alkyls, which are 50% oil concentrates, 100 g of bissuccinimide additive S5A, are mixed at room temperature. g T102 (Bayer Titan 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 into which the polyethylene granulate is placed, placed on a continuous screw auger, 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.

A screw with a length to diameter ratio of 20: 1 supplied material to the blow mold

232353 of the head, from which a foil of 0.3 millimeter depth, of a deep white color, was obtained, with a completely uniformly distributed pigment, without any visible grains of pigment. Example 2 · '·· .....

A homogeneous liquid mixture consisting of 950 g of white oil, 250 g of 32% low-base monosulphonic acid mono-sulfonic acid, average molecular weight 460, 100 g of bissuccinimide additive S5A, 130 g 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 Chromphtaf Gelb 6 G pigment, 100 g of Chrompbtal Roth BR pigment and 100 g of Chormphtal Griin GF pigment.

The prepared homogeneous, concentrated color mixture was treated with granulated high-pressure polyethylene at a weight ratio of 1100 on a 0.3 mm thick film on the apparatus and under the conditions of Example 1. The produced film was khaki color, with completely uniformly dispersed pigment, without any visible beads pigment. The color mixture was easily removed with water from used containers and production equipment.

Example 3

A homogeneous liquid mixture consisting of 100 g of nitrogen containing Plexol 956 polymethacrylate additive, 200 g of bissuccinimide additive S5A, 400 g of 2-ethylhexyl-polypropox-polyetox-amer, whose mole of polypropoxide contained an average of 20 moles propylene oxide with a mole of polyetox on average 6 molecules of ethylene oxide, 850 g of white oil and 2100 g of TiO2 (Bayer Titan RFKD).

The prepared color mixture was treated with polypropylene in wt. 1: 55 ratio, 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

A homogeneous liquid mixture was prepared according to the procedure and conditions as in Example 1, consisting of 500 g of 50% calcium alkylphenolate basic with C16 alkyls, 550 g of 2-ethylhexyl-polypropox-polyetox-amine as in Example 2, 2000 g of white oil. , 2,450 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 thick film on a device as in Example 1. The film manufacturer had a saturated white color, with a slight hint of rye, completely uniformly dispersed pigment, without visible pigment grains. The color mixture was easily removed with water from used containers and production equipment.

Example 5

The prepared color mixture as in Example 2 was treated with polyvinyl chloride in a ratio of 1: 55 by weight to a 0.3 mm thick sheet under conventional manufacturing conditions. The foil produced had a khaki color, with a completely uniformly distributed pigment, without visible grains of pigment.

Example 6 kg of the prepared color mixture as in Example 3 was added to 45 kg of methyl methacrylate prepolymer with stirring. After all the color mixture was added, stirring was continued for 12 minutes. The mixture was then 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 3 mm depth.

In the dispersant-free 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 polystyrenes at a ratio of 1:80 on a 0.3 mm thick film. The product had a white color, with a completely uniformly distributed pigment, without its visible grains.

Example 8

The prepared color mixture as in Example 4 was treated with granulated colorless polyamide in wt. 1: 45 ratio on 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.

SUBJECT

Claims (4)

SUBJECT 1. Method of dyeing plastics with pigments using mixed dispersants such as dyeing low-pressure and high-pressure polyethylene, polypropylene, polystyrene and its copolymers, polyvinyl chloride, polyamide, polymethacrylate and other plastics with organic or inorganic pigments, filling with known fillers and additives, and additives processes for producing color blends, pigment preparations, filled color and natural plastic materials in the form of granules, films, powders, moldings, castings and the like. characterized in that 0.01 to 99.0 wt. 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 sulfonates, preferably calcium, neutral and basic, petroleum and synthetic, based on oil-soluble monosulfoacids of at least molecular weight 250, preferably 350 to 490, alkylphenolates and alkylphenolsulfides of alkaline earth metals, preferably calcium and barium, neutral and basic, preferably with alkyls C 6 and higher and alkylsalicylates of alkaline earth metals, preferably calcium and magnesium, neutral and basic with C 12 alkyl to C22, preferably C14 to C18, a group of oil-soluble dispersants of low and medium temperature as succinimides, preferably bissuccinimides, alkenylphosphonates, thiovynAleze phosphonates, in particular calcium and barium, medium-basic, alkenylthiophosphates and polymethacrylates containing in the moiety a nitrogen-bound nitrogen and a group of dispersants of the alkoxy-polypropox-polyetox-amers type of the generalized formula R- (O-CH-CH2- _x - (O-CHa-CH3-OH) CH3 where is R-alkyl of a higher fatty alcohol, preferably C4-C12, x-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. _The 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 pigment preparation. 4. 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 from 20.0 to 90.0% by weight, based on the mixture, when filling colored and natural plastics. dispersant and filler.