DE1469600B - Process for the dyeing of shaped articles based on macroraolecular polyolefins - Google Patents

Description

The invention relates to a method for dyeing shaped structures on the basis of macromolecular ones Polyolefins containing triazole compounds or metal complex compounds thereof.

It is known that macromolecular polyolefins such as polyethylene and polypropylene are difficult to dye. A wide variety of processes have been developed to improve their dyeability. For example It is known to produce polyolefin molding compositions which contain other components which are easier to use Let them be colored, and mix these masses in the melt and then deform them into shaped structures. Attempts have also been made to find special dyes for coloring macromolecular polyolefins to develop.

A method for producing the aforementioned modified polyolefin molding compositions is known, which is characterized in that the macromolecular polyolefin compounds with a Triazole ring incorporated, the mass melts and intimately mixed and formed structures with excellent Produces colorability (cf. Japanese patent application 1 514/1964, French patent 1 328 402, British Patent specification 939 248 and Italian patent specification 657195).

Furthermore, a method is described in Japanese patent application 26 767/1964 in which ; Triazole compounds in the form of a complex with a metal such as zinc, barium, cadmium, aluminum or tin, macromolecular polyolefins are incorporated and the mass is melt-molded will. The moldings obtained are also of improved dyeability.

All of these known processes use anionic dyes, predominantly acidic dyes reacted with the triazole compounds containing basic nitrogen atoms, which are in the macromolecular Polyolefins are included.

The modified polyolefins mentioned can be colored with conventional acidic dyes. However, since many of the acidic dyes _{contain sodium sulfonate groups (—So 3} Na) in their molecule, these compounds are generally very highly hydrophilic and consequently have the disadvantage that their compatibility and affinity for the hydrophobic polyolefin is very poor.

The invention relates to a method for dyeing shaped structures on the basis of macromolecular polyolefins containing a metal chelate compound, which is characterized is that one is the shaped structure containing a known metal complex of a triazole compound contain, dyes with a hydrophobic stain dye.

The advantage over the method of French patent 1 328 402 is that colored polyolefins with better fastness properties are obtained in the process according to the invention. This is shown in the following table, in which the numerical values are determined according to the Japanese industrial test standard are.

Fastness properties of the colored polyolefins to sunbathe
light Dry
pure
supply Wa
ting Friction
firm
speed hue example 4th
3
6th
3 5
3
'. 5
'. 3 ■ 5 ■
3
.. ■ 5 ■
'3 5- · ■■
3
5
■. 3 V Red
Blue to green 1 of the invention
4 of the French
Patent specification
6 of the invention
15 of the French
Patent specification

Also against the Swiss Auslegeschrift 13 985/62, which a process for coloring metal compounds containing polyolefin or polyacetal fibers by treatment with metallizable Dyes, e.g. B. water-insoluble disperse dyes and water-insoluble chelating agents, the method of the invention is fundamentally different. As a result of their content of a triazole compound the products dyed according to the invention have significantly better fastness properties. The dye is bound to the triazole compound in a complex via the metal. The metal salt is on this way at the same time in the form of a higher molecular weight dye-triazole-metal chelate complex in the Substrate stabilized and fixed. The stabilization manifests itself in increased color fastness, in particular Fastness to sublimation and rubbing.

Presumably the metal forms that of the polyolefin molding compound in the form of the metal complex of the triazole compound or the polyolefin molding composition containing the triazole compound by treatment with a Metal salt was incorporated, anchor points for the hydrophobic stain dye, so that the molded article has excellent dye affinity and dyeability.

The triazole compounds, the polyolefin compositions used in accordance with the invention for dyeing are contained are 1,2,4-triazole compounds of the general formula

N-

Il

R-C

-N

Il

C-

■ R '—Z'

in which R and R ', which can be the same or different, are alkylene groups with 2 to 10 carbon atoms, Phenylene, cycloalkylene or naphthylene groups signify, X signifies a hydrogen atom, an unbranched one or branched alkyl group with 1 to 18 carbon

is a phenyl, naphthyl, amino or amino derivative group and if X is present several times in the molecule (nS; 2), these groups can be identical or different, Z and Z ', "which are identical or different, hydrogen atoms, carboxyl - and mean carboxyl derivative groups and η has a value from 1 to 100 ^.:

The metal complexes of the triazole compounds are easy to prepare, e.g. B. by implementing the 1,2,4-triazole compound with inorganic metal salts, such as the hydroxides, halides, sulfates, nitrates or rhodanides, or organic metal salts, such as formates, acetates and laurates, or organic complex compounds of metals, such as copper, magnesium, calcium, strontium, zinc, cadmium, aluminum, tin, lead, titanium, chromium, Manganese, iron, cobalt, nickel and zircon. In this case, the reaction medium or diluent can be used Water or organic solvents such as alcohol, benzene and toluene can be used.

Processes for the preparation of the triazole compounds and their metal complexes are described in US Pat Japanese Patent Application 1,514 / 1964,26,764/1963 and British Patent 939,248.

When treating with a metal salt, inorganic metal salts, such as the hydroxides, halides, Sulfates, nitrates or rhodanides, organic metal salts such as the formates, acetates and laurates, or organic metal complexes of metals such as copper, magnesium, calcium, strontium, barium, Zinc, cadmium, aluminum, tin, lead, titanium, chromium, manganese, iron, cobalt, nickel or zirconium are used. Treatment with metal salts of organic acids, such as the formates, is particularly preferred and acetates. In this process, the metal compounds are preferably in the form of their aqueous Solution or dissolved in an organic solvent used. However, these connections can can also be used as a dispersion in water or in organic solvents.

The hydrophobic mordant dyes which can be used according to the invention contain hydrophobic groups such as Alkyl and / or aralkyl groups, but not water-soluble groups such as sulfonic acid groups. Examples for the dyes are not only azo dyes, such as ο, ο'-dihydroxyazo dyes, o-hydroxy-o-carboxyazo dyes, ο - Hydroxy - ο '- alkoxyazo dyes, ο - Hydroxy - ο' -aminoazo dyes, thiazolyl-ο-hydroxyazo dyes, Anthraquinone dyes, such as alizarin dyes, but also the broad group of hydrophobic mordant dyes that have a salicylic acid, hydroxynaphthoic acid or hydroxyquinoline structure contained in the molecule. Examples of usable dyes are given below.

OH

OH

OH

55

60

C ₄ H ₉

OH

OH

C ₄ H ₉

C ₄ H ₉

OH

OH

Cl

COCH,

V- N == N-CH

OH

CONH - / \

OH

OH

CH

OH

C-N = N

OH

/ S \ = N- . \ ^ C-N \ = COOH = N- OH
I. r -L C ₄ H ₉ >

C ₄ H ₉

OCH,

NO,

OH

N = N

QH ₅

OCH

OH

C ₄ H ₉

N = N

OH

COOH

N = N

N = N

HO COOH

N = N

y ν

N = N

CH,

HO

HO

NH-C ₄ H ₉

NH-C ₄ H ₉

O NH

H ₅ C ₂

H ₅ C ₂

For coloring the shaped objects on the basis of the macromolecular polyolefins, the triazole compounds or contain their metal complexes, it is generally preferred to use the hydrophobic Mordant dye as a dispersion in water using a dispersing agent or solvent to use.

The treatment with the metal salt and the dyeing can not only in a conventional manner at room temperature to 10O ⁰ C or carried about, but also by padding or the thermosol.

You can also use swelling agents and dyeing auxiliaries, such as carriers.

Examples of macromolecular polyolefins are homopolymers and copolymers of olefins, such as ethylene, propylene and 1-butene, and mixtures of these homopolymers and / or copolymers. The polyolefins can contain additives such as UV stabilizers, antioxidants or fillers.
As shaped structures based on macromolecular polyolefins, for. B. films, plates, fibers, threads, yarns, twisted threads, cord, woven, knitted and nonwoven-like products in question. In the case of yarns and woven fabrics, the macromolecular polyolefins can be present together with other natural or synthetic high molecular weight substances.

The examples explain the process according to the invention. Parts and percentages relate to the weight, unless otherwise stated.

example 1

9 parts of poly (3,5-octamethylene-1,2,4-triazole), prepared by the condensation of dihydrazide sebacate and hydrazine hydrate, and 11 parts of zinc acetate are refluxed with 100 parts of benzene for 10 hours cooked. When the reaction has ended, the benzene is distilled off and the product is isolated and purified. The obtained zinc complex becomes polypropylene powder having an average molecular weight of 150,000

incorporated in an amount of 5% and the mixture melt-spun into a filament of lüden. The thread obtained was dyed with the following dye

OH

N = N

C ₄ Hn

C ₂ H ₅ dispersed in an aqueous solution which

a nonionic wetting agent in an amount of 2 g / l contained that for the most part

C ₁₇ H ₃₅ O (C ₂ H ₄ O) ₂₀ H ■

duration. The dye concentration was 3% based on the weight of the thread, the bath temperature was 95 to 100 ^° C., and the dyeing time was 90 minutes. The thread was then soaped, rinsed with water and then dried. A clear, deep red colored thread was obtained. The resistance of the product to dry cleaning, washing and rubbing was 5 according to the Japanese industrial test standard (JIS).

B e i s ρ i e 1 2

14 parts of poly (3,5-tetramethylene-4-amino-l, 2,4-triazole), produced by the condensation of dihydrazidipate and hydrazine hydrate, and 25 parts of nickel acetate were refluxed with 150 parts of xylene for 10 hours. After implementation was completed the xylene is distilled off, the product is isolated and purified. The obtained nickel complex became polypropylene powder of the average molecular weight 150,000 incorporated in an amount of 5%. The Mixture was melt spun into 10 denier filament. The thread obtained was with following dye

HO O NH- (H) C ₆ H ₁₃

HO

O NH- (H) C ₆ H ₁₃

colored in an aqueous dispersion containing a nonionic wetting agent of the formula

C ₁₇ H ₃₅ O (C ₂ H ₄ O) ₂₀ H

contained in an amount of 2 g / l. The dye concentration was 3%) based on the yarn weight, the liquor ratio 1: 50, the bath temperature from 95 to 100 ⁰ C, dyeing time 90 minutes. After soaping, rinsing with water and drying, a dark blue-colored product with excellent fastness to sunlight was obtained.

. ·, .. B e i s ρ i e 1 3

15 parts of the polymeric mixed condensate of 3,5-phenylene-l, 2,4-triazole and 3,5-phenylene-4-amino-1,2,4-triazole, produced by condensation of dihydrazide terephthalate and hydrazine hydrate, as well 8 parts of chromium acetate are in 150 parts of a mixture of water and ethanol for 20 hours refluxed. The chromium complex produced is polypropylene powder with an average molecular weight of 150,000 in an amount of 5% incorporated. The mass was melt spun into a filament of 10 denier and the one obtained Thread with the following dye

CH

N = N

OH

OH

colored in an aqueous dispersion containing a nonionic wetting agent of the formula

C ₁₇ H ₃₅ O (C ₂ H ₄ O) ₂₀ H

contained in an amount of 2 g / l. The dye concentration was> 3% based on the weight of the thread, the liquor ratio 1:50, the bath temperature 95 to 100 ° C, the dyeing time 90 minutes. After soaking, rinsing with water and drying A yellow-colored product with excellent fastness properties was obtained.

Example 4

20 parts of 3,5-diundecyl-4-amino-l, 2,4-triazole and 13 parts of nickel acetate were mixed with 100 parts of benzene Boiled under reflux for 10 hours. The obtained nickel complex became polyethylene powder of average molecular weight 100,000 incorporated in an amount of 4%. The mass became a thread of 10 the melt-spun and the resulting thread with the following dye

OH

OH

colored in the form of an aqueous dispersion containing the nonionic wetting agent mentioned in Example 1 in an amount of 2 g / l. The dye concentration was 3%> based on the weight of the thread, the liquor ratio 1:50, the bath temperature 80 ° C, the dyeing time 90 minutes. After soaking, rinsing with water and drying, a Obtained deep red colored product. Resistance to sunlight, dry cleaning, washing and According to the Japanese industrial test standard, rubbing had a value of 5 or better.

Example5

Poly- (3,5-octamethylene-1,2,4-triazole), produced by condensation of dihydrazide sebacate with hydrazine hydrate, became 150,000 average molecular weight polypropylene powder in an amount incorporated by 5%. The mass was melt spun into a filament of 10 denier and with the following dye

OH

N = N

C ₄ H ₉

C ₄ H ₉

C ₄ H ₉

colored in an aqueous dispersion which contained the nonionic wetting agent mentioned in Example 1 in an amount of 2 g / l. The dye concentration was 3% based on the weight of the thread, the liquor ratio 1:50, the bath temperature 95 to 100 ^° C., the dyeing time 90 minutes. The colored product was then boiled in a 3% aqueous zinc acetate solution at a liquor ratio of 1:30 for 60 minutes. After soaping, rinsing with water and drying, a clear deep red colored product was obtained.

009 533/268

Example 6

Polytetramethylene aminotriazole, produced by condensation of dihydrazide adipate with hydrazine hydrate, became polypropylene powder of average molecular weight 150,000 in an amount incorporated by 5%. The mass was melt spun into a 10 denier filament. The received The thread was in a 3% aqueous nickel acetate solution Boiled at a liquor ratio of 1:30 for 120 minutes, then thoroughly with water rinsed and dried. The treated thread was then treated with the following dye

HO

HO

(n) QH ₁₃

O NH- (n) QH ₁₃

colored in an aqueous dispersion which contained the nonionic wetting agent mentioned in Example 1 in an amount of 2 g / l. The dye concentration was 3% based on the weight of the thread, the liquor ratio 1:50, the bath temperature 95 to 100 ^° C., the dyeing time 90 minutes. After soaping, rinsing with water and drying, a blue-colored product was obtained whose resistance to dry cleaning, washing or rubbing corresponded to a value of 5 or better of the Japanese industrial test standard.

colored in an aqueous dispersion which contained the nonionic wetting agent mentioned in Example 1 in an amount of 2 g / l. The dye concentration was 3% based on the weight of the thread, the liquor ratio 1:50, the bath temperature 95 to 100 ^° C., the dyeing time 90 minutes. A yellow-colored product with excellent fastness properties was obtained.

'Example 8

3,5-Diundecyl-4-amino-1,2,4-triazole became polyethylene powder of average molecular weight 100,000 incorporated in an amount of 5%. The mass was melt spun into a 10 denier filament and the thread obtained in an alcoholic dispersion of 3% aluminum acetate, which contained the nonionic wetting agent mentioned in Example 1 in an amount of 2 g / l for 60 minutes cooked at a liquor ratio of 1:30. The thread treated with the metal salt was then with following dye

OH

Example 7

35

The polymer co-condensate of 3,5-phenylene-1,2,4-triazole and 3,5-phenylene-4-amino-1,2,4-triazole, produced by the condensation of dihydrazide terephthalate with hydrazine hydrate, became polypropylene powder with an average molecular weight of 200,000 in incorporated in an amount of 4%. The mass was melt-spun to a single thread of 10 denier, and the thread obtained was boiled in a 3% strength aqueous chromium acetate solution at a liquor ratio of 1:30 and a bath temperature of 95 to 100 ^° C. for 120 minutes. The thread thus treated was coated with the following dye

colored in an aqueous dispersion containing the nonionic wetting agent mentioned in Example 1 in a Amount of 2 g / 1 contained. The dye concentration was 3% based on the weight of the thread, the liquor ratio 1:50, the bath temperature 80 ° C, the dyeing time 90 minutes. After soaping, rinsing with water and drying a deep blue colored product was obtained. The resistance to Sunlight, dry cleaning, washing and rubbing corresponded to the value 5 of the Japanese industrial test standard.

CH

OH

Claims (1)

Claim: Process for dyeing shaped structures based on macromolecular polyolefins, which contain a metal chelate compound, characterized in that the shaped structures that contain a known metal complex of a triazole compound, stains with a hydrophobic stain dye.