CS258367B1 - Dyeing concentrates or dyeing mixtures - Google Patents

Abstract

The present invention relates to coloring concentrates blends for polymer and polymer dyeing mixtures, in particular from the group comprising polyolefins, polystyrene, terpolymer ABS, polyurethanes, polyvinyl chloride a its copolymers containing as a dye component in the polymer melt ineffective, at all or poorly dispersible dyes. The coloring effect is induced presence of noninogenic and / or anionic surfactants. As a coloring component in particular base-based dyes can be used anthraquinone and pyrazolone, monoazo dyes and di-dyes and naphthylamine-based dyes, N-acetylphenylenediamine and 2-naphthol

Description

The invention relates to dye concentrates or dye compositions for dyeing polymers and polymer mixtures thereof, in particular from the group comprising polyolefins, polystyrene, acrylonitrile-butadiene-styrene terpolymer, polyurethanes, polyvinyl chloride.

Coloring additives for dyeing polymers and polymer blends in the mass are currently applied almost exclusively in the form of coloring concentrates. These are generally prepared by mixing pigments, respectively. dyes with polymeric or oligomeric carriers in the presence of stabilizers, resp. other specific ingredients. In addition to coloring agents in the form of powder, irregular pulp and granules, coloring concentrates of liquid, paste or dough consistency are also produced. In accordance with the requirements of modern plastics technologies, it is clear that preference is given to solid coloring concentrates with a wide range of applicability.

Soluble dyes are used for dyeing plastics in mass only to a very limited extent worldwide. Assuming thermal stability, it is reported that only some types are suitable for coloring amorphous plastics such as polystyrene, polymethyl methacrylate, sometimes also polyamides, acrylonitrile-butadiene-styrene terpolymer, polycarbonates, phenolplastics, cellulose derivatives and casein derivatives. Practically no examples of dye applications in polyolefins, polyvinyl chloride and polyurethanes are known. Since the advantages of applying dyes include the achievement of clear, brilliant shades, a higher color strength than conventional organic pigments, and thus a noticeable economic effect, their low use in polymers so far can be considered a rather significant shortcoming of the prior art.

The dye concentrates or polymer dye compositions and polymer blends of the present invention contribute to overcoming this drawback.

The invention is based on the fact that these dye concentrates or dye mixtures contain inactive, poorly dispersible dyes as a dye component in the polymer melt. The staining effect is caused by the presence of noninogenic and / or anionic surfactants.

In particular, anthraquinone and pyrazolone dyes, monoazo dyes, diazo dyes and naphthylamine dyes, N-acetylphenylenediamine dyes and 2-naphthol dyes can be used as the dyeing component. therefore do not color them.

However, with the aid of surfactants, preferably non-ingenic and / or anionic ones, these dyes can be converted into polymers which are readily dispersible with the ability to color them. Suitable types of noninogenic and / or anionic surfactants are, in particular, oxyethylated nonylphenols, oxyethylated fatty alcohols, ethanolamides of fatty acids, ethylene oxide copolymers with propylene oxide, phosphate dispersants, phosphate esters of oxyethylated products, alkylphenol polyglycol ethers, sulfated, ethoxylated natural fatty acids, of acids with alkylamines and combinations thereof.

The main advantage of the solution according to the invention is that it allows the use of highly efficient dyes, for example Reactive Blue 4/61 205 /, Reactive Yellow 1/18 971 /, Reactive Yelow 3/13 245 /, Disperse Yellow 3/11 855 /, Disperse Yellow 42/10 338 /, Disperse Red 121

Disperse Yellow 60, Disperse Blue 3/61 505 /, Vat Orange 11/70 805 /, Acid Blue 40/62 125 /, Acid Blue 41 for coloring polymers - especially polyolefins, polystyrene, ABS terpolymers, polyurethanes and PVC / pop. mixtures thereof.

The dyes show an easy and fast color development during processing. Their dyeing capacity is used to the maximum - the dye in the polymer is mainly in the form of a molecular solution.

The dyed products exhibit exceptionally good brilliance, purity of shades, and even by using a small amount of soluble dye, saturated shades of the color are obtained.

When pigmented, much higher dosages are required to achieve the same color intensity. The use of dyes also gives the possibility of under-coloring (tinting) of inorganic pigments, especially in ABS copolymers (thus increasing their lightfastness). Intense soluble dyes provide deep / saturated / color shades. The essential advantages of using dyes also include their availability and the possibility of achieving a wide variety of shades, since, as is well known, the domestic range of suitable organic pigments for polymers is greatly limited.

Colorants can be applied directly - to achieve transparent coloring or as indicated in combination with inorganic, organic pigments, such as carbon black, to tint them, and to achieve bright, especially pastel shades. Dyes can also be used for the preparation of dye concentrates according to the current world trend. The dye content of the concentrate is 2 to 3 times lower than that of the corresponding organic pigments.

The following practical examples serve to illustrate the invention in greater detail.

He did

On a fluidic mixer, it was maintained for 5 min. homogenized 19 wt. parts of high-pressure polyethylene powder having a melt index of 219 wt. parts of granulated polyethylene having a melt index of 200, 27 wt. parts of titanium white of the rutile type, 2.57 wt. % of a non-ionic leveling agent based on oxyethylated nonylphenol /. of oxyethylated fatty alcohol], 2.26 wt. % of lauric acid diethanolamide and 0.87 wt. % of soybean oil fatty acids. Then 11.3 wt. % of soluble monoazo dye / pyrazolone derivative - C.I. (Color Index) Reactive Yellow 1 (18,971) and the mixture was stirred for an additional 10 min.

At the end of stirring, 18 wt. parts of quicklime (calcium oxide). The resulting mixture was then extruded and granulated on a continuous kneader under the following operating mode; screw and cylinder temperature 130 ° C, extrusion head temperature 140 ° C, screw speed 60 min ´ ´ !; the extruded belt was air cooled. The granular dye concentrate thus prepared can be used to dye polyolefins in the injection molding and extrusion processes, and to include foil materials after melt filtration has been included.

The dosage of the concentrate is 1 to 2 wt. parts per 100 wt. parts of the dyed polymer.

Example 2

The mixture of 24.1 wt. % by weight of branched polyethylene of melt index 2 in the form of powder, 24 wt. parts of branched polyethylene with a melt index of 70, 0.5 wt. a portion of soybean oil fatty acids (as a titanium white dispersant),

2.46 wt. % of lauric acid diethanolamide, 2.46 wt. part of oxyethylated nonylphenol,

6.9 wt. % of calcium oxide, 29.6 wt. rutile type titanium dioxide and 9.9 wt. % of soluble dye C.I. Reactive Yellow 3 (13 245), which is a monoazo dye derived from naphthylamine. The use of the concentrate obtained is similar to Example 1.

Example 3

On a fluidic mixer, it was maintained for 5 min. premixed 43 wt. parts of branched polyethylene powder having a melt index of 2; 43 wt. % of branched polyethylene with a melt index of 200 and 4 wt. parts of a nonionic dispersant based on copolymers of ethylene oxide with propylene oxide (containing 40% ethylene oxide). Then 10 wt. parts of the acid dye C.I.

Acid Blue 40 (62,125), an anthraquinone derivative, and stirring was continued for another 10 min.

Other conditions for the preparation of the concentrate were identical to those of Example 1.

The obtained dye concentrate can be used to dye polyolefins in the mass at dosages of up to 2 wt. parts. Preferably, in this case, combinations of said dye with inorganic pigments such as titanium dioxide and iron oxide can be used.

Example 4

On a fluidic mixer, it was kept for 15 min. premixed mixture 20 wt. parts of the dispersion dye C.I. Disperse Red 121, an anthraquinone derivative, with 79 wt. parts of standard polystyrene with a melt index of 20 and 1 wt. % of Duvikol PPV, which is a combination of sulfated and ethoxylated natural fats and a condensation product of fatty acids with alkylamines.

Said mixture was then extruded into a continuous kneader BUSS conditions: screw temperature of 150 ° C cylinder temperature of 190 ° C, temperature of extruder head 210 ° C Screw speed 50 rpm · ^-!. The extruded belt was cooled on water-cooled rollers and granulated on a belt granulator. The concentrate obtained can be used to dye polystyrene, tough polystyrene and ABS terpolymer in a mass at a dosage of 1 to 2 wt. parts of dye concentrate per 100 wt. parts of the dyed polymer. No dye migration to the surface of the products was noted in the dyed articles.

Example 5

On a fluidized bed mixer it was kept for 10 min. premixed 84.5 wt. parts by weight of vinyl acetate-vinyl acetate copolymers having a vinyl acetate content of 17 wt. parts, 15 wt. parts of the dipser dye CI Disperse Yellow 3 (11 855), which is a monoazo dye derived from N-acetylphenylenediamine and 0.5 wt. % of the phosphate ester of the oxyethylated product (e.g. Slovafos 1 /. The obtained mixture was extruded on a KO kneader under the conditions: roller temperature 170 ° C, screw temperature 140 ° C, extrusion head temperature 160 ° C, speed 35 min. ¹ . The extruded belt was cooled with air and ground on a knife mill to irregular grit. The obtained dye concentrate is useful for dyeing polyvinyl chloride and its copolymers, as well as polyvinyl chloride-polyurethane systems and the like, at a dosage of 1 to 2 wt. parts per 100 wt. parts of the dyed polymer.

He attaches

Following the procedure of Example 5, a mixture of 84.6 wt. parts in Example 5 of said copolymer, 0.4 parts of alkylphenol polyglycol ether, e.g. Slovafol 909 / a 15 wt. parts of C.I. Disperse Red 121 (anthraquinone derivative). The use of the obtained concentrate is similar to that of Example 5.

Example 7

On a conventional mixer type (fluid, boom, drum) for 15 min. premixed 99.7 wt. parts of granulated high-pressure polyethylene of melt index 7 with 0.2 wt. % dye / anthraquinone derivative / C.I. Reactive Blue 4/61 205 / and 0.045 wt. % of a non-ionic leveling agent, based on oxyethylated nonylphenol /. of oxyethylated fatty alcohol / 0.045 wt. % of lauric acid diethanolamide. The resulting mixture can be directly processed by extrusion or injection molding.

Example 8

On a fluidized bed mixer it was kept for 10 min. premixed mixture: 84 wt. parts of vinyl chloride-vinyl acetate copolymers / containing vinyl acetate 17 wt. parts /, 15 wt. parts of C.I.

Disperse Yellow 3 (11 855), which is a derivative of N-acetylphenylenediamine, further 0.2 wt. parts of a non-ionic leveling agent based on oxyethylated nonylphenol / resp. of oxyethylated fatty alcohol / 0.2 wt. % of lauric acid diethanolamide and 0.6 wt. The powder mixture may be used in a dosage of 1 to 2 wt. parts (for direct dyeing of polyvinyl chloride / especially unplasticized) and its copolymers, as well as polyvinyl chloride-polyurethane systems and the like5

Example 9

On a fluidized bed mixer, 15 wt. pre-mixed 40 wt. parts of soot (IASE type), wt. parts of C.X. Disperse Blue 3 (61,505), an anthraquinone derivative, and 4.4 wt. parts of a non-ionic dispersant based on copolymers of ethylene oxide with propylene oxide, 8.43 wt. parts of high-pressure polyethylene powder having a melt index of 2 and 16.87 wt. The mixture was further processed by extrusion on a KO kneader or a twin-screw extruder with melt filtration and subsequent granulation. Said coloring concentrate can be dosed at 1 wt. parts per 100 wt. Polystyrene, polyolefins and ABS terpolymer can be colored in the polymer parts.

Claims (4)

object of the invention Dye concentrates or dye mixtures for polymers and polymer mixtures, characterized in that they contain, in combination, a dye which, in itself, is ineffective, non-dispersible or poorly dispersible and non-ionic and / or anionic surfactant, respectively. a surfactant mixture, at a dosage of 0.1 to 1000 parts by weight per 100 parts by weight of colorant. 2. The dyeing concentrate or dye composition of claim 1, wherein the dye or dye mixture is selected from the group consisting of anthraquinone and pyrazolone dyes, monoazo dyes, diazo dyes and naphthylamine, N-acetylphenylenediamine and 2-naphthol dyes, and a surfactant or mixture. The surfactants are preferably selected from the group consisting of oxyethylated nonylphenol or fatty alcohol surfactants, fatty acid diethyl amides, ethylene oxide copolymers, phosphite compounds, phosphate esters of oxyethylated products, alkylphenol polyglycol ethers, suflated and ethoxylated natural fats, fatty acid condensation products with higher alkylolamines. 2. Dye concentrates or dye mixtures according to Claims 1 and 2, characterized in that they preferably contain dyes having one or more functional groups of the SO2N2 type attached to the aromatic core. Fourth color concentrate or a dye composition for polyurethanes and polyvinyl chlorides, and copolymers according to claims 1 and 2, characterized in that it preferably contains a dye with at least one of the functional groups of the type - N0 ₂ and / or CH.jCO.NH-, bonded to an aromatic core. 5. The dye concentrates or dye mixtures according to claim 1 or claim 1 or any of claims 2 to 4, characterized in that they contain, in combination with a dye, an organic and / or inorganic pigment or a colorant. a mixture of pigments, including carbon black, wherein the weight ratio of dye / dye-pigment / pigments ranges from 1: 100 to 100: 1.