US20040231073A1

US20040231073A1 - Method of mass-colouring synthetic materials

Info

Publication number: US20040231073A1
Application number: US10/484,355
Authority: US
Inventors: Peter Aeschlimann; Leonhard Feiler
Original assignee: Individual
Current assignee: BASF Corp
Priority date: 2001-07-26
Filing date: 2002-07-18
Publication date: 2004-11-25
Also published as: WO2003010229A1; EP1409578A1; JP2004536200A

Abstract

The present invention relates to a method of mass-colouring synthetic materials based on terpolymers of acrylonitrile, butadiene and styrene, which comprises using at least one dye of formula (1) wherein R₁is hydrogen, halogen, alkoxy, aryloxy, alkylthio or arylthio, R₂is hydrogen, a carboxylic acid group or a carboxylic acid ester group, R₃is hydrogen, halogen, alkoxy, aryloxy, alkylthio, arylthio, a carboxylic acid group or a carboxylic acid ester group, and W is a radical of formulae (2), (3), (4), (5), (6), wherein R₄, R₈and R₁₁are each independently of the others hydrogen, alkyl, alkoxy, aryloxy, alkylthio or arylthio, R₅, R₇and R₁₀are each independently of the others hydrogen, alkoxy, aryloxy, alkylthio, arylthio, a carboxylic acid group or a carboxylic acid ester group, R₆and R₉are each independently of the other cyano, —CONR₁₂R₁₃or —SO₂R₁₄, wherein R₁₂and R₁₃are each independently of the other hydrogen or C₁-C₄alkyl and R₁₄is C₁-C₄alkyl, and X is —NH—, —O— or —S—, or R₅and R₅′ together form a phenyl or naphthyl radical.

Description

The present invention relates to a method of mass-colouring synthetic materials with dyes based on naphtholactam.

The use of dyes of a wide variety of classes for the mass-colouring of synthetic materials is known. It has been shown, however, that not all synthetic materials can be coloured with satisfactory results with conventional dyes. Such “critical” synthetic materials also include materials based on terpolymers of acrylonitrile, butadiene and styrene which, owing to the very high temperatures that occur during processing and the heterogeneous structure, make specific demands of the dyes used. There is therefore a need for dyes with which such terpolymers (referred to hereinbelow as ABS terpolymers) can be mass-coloured in brilliant colour shades that are light-fast and fast to high temperatures.

It has now been found, surprisingly, that the naphtholactam dyes used in the method according to the invention meet the criteria given above to a considerable degree.

The present invention accordingly relates to a method of mass-colouring synthetic materials based on terpolymers of acrylonitrile, butadiene and styrene (ABS terpolymers), which comprises using at least one dye of formula

wherein

R ₁is hydrogen, halogen, alkoxy, aryloxy, alkylthio or arylthio,

R ₂is hydrogen, a carboxylic acid group or a carboxylic acid ester group,

R ₃is hydrogen, halogen, alkoxy, aryloxy, alkylthio, arylthio, a carboxylic acid group or a carboxylic acid ester group, and

W is a radical of formula

wherein

R ₄, R₈and R₁₁are each independently of the others hydrogen, alkyl, alkoxy, aryloxy, alkylthio or arylthio,

R ₅, R₇and R₁₀are each independently of the others hydrogen, alkoxy, aryloxy, alkylthio, arylthio, a carboxylic acid group or a carboxylic acid ester group,

R ₆and R₉are each independently of the other cyano, —CONR₁₂R₁₃or —SO₂R₁₄, wherein R₁₂and R₁₃are each independently of the other hydrogen or C₁-C₄alkyl and R₁₄is C₁-C₄alkyl, and

X is —NH—, —O— or —S—, or

R ₅and R₅′ together form a phenyl or naphthyl radical.

R ₄, R₈and R₁₁as alkyl are each independently of the others preferably C₁-C₄alkyl, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.

R ₁₂, R₁₃and R₁₄as C₁-C₄alkyl are each independently of the others methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.

R ₁, R₃, R₄, R₅, R₇, R₈, R₁₀and R₁₁as alkoxy are each independently of the others preferably C₁-C₄alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy, it being possible for the carbon chain in alkoxy to be interrupted one or more times by oxygen.

R ₁, R₃, R₄, R₅, R₇, R₈, R₁₀and R₁₁as alkylthio are each independently of the others preferably C₁-C₄alkylthio, for example methylthio, ethylthio, propylthio or butylthio.

R ₁, R₃, R₄, R₅, R₇, R₈, R₁₀and R₁₁as aryloxy are each independently of the others preferably C₆-C₁₂aryloxy, for example phenoxy or naphthyloxy.

R ₁, R₃, R₄, R₅, R₇, R₈, R₁₀and R₁₁as arylthio are each independently of the others preferably C₆-C₁₂arylthio, for example phenylthio or naphthylthio.

The phenyl radicals in phenoxy can be unsubstituted or substituted by methyl, chlorine, C ₁-C₄alkylthio and/or by arylthio.

The naphthyl radicals in naphthyloxy can be unsubstituted or substituted by methyl, chlorine, C ₁-C₄alkylthio and/or by arylthio.

Halogen is, for example, chlorine or iodine and preferably bromine.

A carboxylic acid group is to be understood as being a —(CH ₂)_n—COOH radical wherein n is a number from 0 to 3. n is preferably 0.

A carboxylic acid ester group is preferably a —(CH ₂)_n—COOC₁-C₆alkyl radical wherein n is a number from 0 to 3. n is preferably 0.

C ₁-C₆Alkyl is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl or hexyl.

R ₁is preferably hydrogen, halogen or C₁-C₄alkylthio.

R ₂is preferably hydrogen, —COOH or —COOC₁-C₆alkyl.

R ₃is preferably hydrogen, —COOH or —COOC₁-C₆alkyl.

R ₄is preferably hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio, C₆-C₁₂aryloxy or C₆-C₁₂arylthio.

R ₅is preferably hydrogen, —COOH, —COOC₁-C₆alkyl, C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio, C₆-C₁₂aryloxy or C₆-C₁₂arylthio.

R ₆is preferably cyano.

R ₉is preferably cyano.

X is preferably —O— and —S—.

For the method according to the invention, preference is given to the dyes of formula

wherein

R ₁₂is hydrogen, a carboxylic acid group or a carboxylic acid ester group,

R ₁₃is hydrogen or C₆-C₁₂arylthio,

R ₁₄is a carboxylic acid group or a carboxylic acid ester group, and

R ₁₅and R₁₆are each independently of the other hydrogen, C₁-C₄alkoxy, C₆-C₁₂aryloxy,

C ₁-C₄alkylthio or C₆-C₁₂arylthio, and of formula

wherein

R ₁₇is hydrogen, a carboxylic acid group or a carboxylic acid ester group,

R ₁₈is hydrogen or halogen,

R ₁₉is hydrogen,

R ₂₀is cyano,

R ₂₁is hydrogen or C₁-C₄alkyl,

R ₂₂is a carboxylic acid group or a carboxylic acid ester group, and

X is —O— or —S—.

For the method according to the invention, special preference is given to the dyes of formulae

The dyes of formula (1) used in accordance with the invention are known, for example, from DE-A-2 736 914, DE-A-2 607 869, DE-A-2 724 566 and DE-A-2 724 567 or can be prepared according to generally known methods.

The dyes of formula (1) used in accordance with the invention are prepared, for example, by condensing a naphtholactam compound of formula

wherein

R ₁, R₂and R₃are as defined for formula (1), in the presence of an acid condensation agent, preferably phosphorus oxychloride, with a methylene-active compound of formula

wherein

R ₆, R₇, R₈and X are as defined for formula (3), and R₉, R₁₀and R₁₁are as defined for formula (4).

The compounds of formulae (50) to (52) are known or can be prepared according to generally known methods.

The present invention relates also to the use of the dyes of formula (1) in the production of coloured plastics or polymeric colour particles, which comprises mixing together a high molecular weight organic material, which consists wholly or predominantly of ABS terpolymers or comprises ABS terpolymers, and a tinctorially effective amount of at least one dye of formula (1).

The colouring of such high molecular weight organic substances with the dye of formula (1) is carried out, for example, by mixing such a dye into those substrates using roll mills, mixing apparatus or grinding apparatus, with the result that the dye is dissolved or finely dispersed in the high molecular weight material. The high molecular weight organic material with the admixed dye is then processed using processes known per se, for example calendering, compression moulding, extrusion, coating, spinning, casting or injection moulding, whereby the coloured material acquires its final form. It is also possible for the admixing of the dye to be carried out immediately prior to the actual processing step, for example by continuously feeding a solid, for example pulverulent, dye and, at the same time, a granulated or pulverulent high molecular weight organic material, and optionally also additional ingredients, e.g. additives, directly into the intake zone of an extruder, where mixing takes place just before processing. In general, however, it is preferable for the dye to be mixed into the high molecular weight organic material beforehand, because more even coloration of the substrates can be obtained.

In order to produce non-rigid mouldings or to reduce their brittleness, it is often desirable to incorporate so-called plasticisers into the high molecular weight compounds prior to shaping. There may be used as plasticisers, for example, esters of phosphoric acid, phthalic acid or sebacic acid. In the method according to the invention the plasticisers may be incorporated into the polymers before or after the incorporation of the colorant. It is also possible, in order to achieve different shades of colour, to add to the high molecular weight organic materials, in addition to the dye of formula (1), also further dyes, pigments or other colorants in any desired amounts, optionally together with further additives, e.g. fillers or siccatives.

Preference is given to the colouring of thermoplastic plastics, especially in the form of fibres or mouldings.

The ABS terpolymer to be coloured comprises repeating monomer units of the formulae

which may be linked to one another randomly, in an alternating manner or in the form of block or graft polymers.

The dyes used in accordance with the invention impart to the mentioned materials tinctorially strong, level red or orange colour shades having very good in-use fastness properties, especially good light fastness and good thermostability.

The following Examples serve to illustrate the invention. Unless otherwise indicated, the parts are parts by weight and the percentages are percentages by weight. The temperatures are given in degrees Celsius. The relationship between parts by weight and parts by volume is the same as that between grams and cubic centimetres.

EXAMPLE 1

1200.00 g of an acrylamide-butadiene-styrene terpolymer (ABS) (Terluran 877M from BASF) are mixed homogeneously with [0067]
2.4 g of the dye of formula [0068]
in a “roller rack” mixing apparatus for 15 minutes at 60 revolutions per minute. The homogeneous mixture is extruded in an extruder (twin screw 25 mm from Collin, D-85560 Ebersberg) with 6 heating zones at a maximum temperature of 200° C., cooled with water, granulated in a granulator (Scheer, Stuttgart) and then dried in a granule drier (Turb Etuve TE 25 from MAPAG AG, CH-3001 Bern) for 4 hours at 60° C. [0069]
The resulting yellowish-red-coloured ABS granules are stable to high temperatures and have good allround fastness properties, especially very good light fastness and high-temperature light fastness properties. [0070]

EXAMPLE 2

By following the procedure of Example 1 but using, instead of 2.4 g of the dye of formula (9), the same amount of one of the dyes of formulae (10) to (28), there are likewise obtained coloured ABS granules which are stable to high temperatures and have good allround fastness properties, especially very good light fastness and high-temperature light fastness properties. [0071]

EXAMPLE 3

1200.00 g of an acrylamide-butadiene-styrene terpolymer (ABS) (Terluran 877M from BASF) are mixed homogeneously with [0072]
2.4 g of the dye of formula [0073]
and [0074]
12.0 g of TiO[0075] ₂(Kronos 2220)
in a “roller rack” mixing apparatus for 15 minutes at 60 revolutions per minute. The homogenous mixture is extruded in an extruder (twin screw 25 mm from Collin, D-85560 Ebersberg) with 6 heating zones at a maximum temperature of 200° C., cooled with water, granulated in a granulator (Scheer, Stuttgart) and then dried in a granule drier (Turb Etuve TE 25 from MAPAG AG, CH-3001 Bern) for 4 hours at 60° C. The resulting orange- to yellowish-red-coloured ABS granules are stable to high temperatures and have good allround fastness properties, especially very good light fastness and high-temperature light fastness properties. [0076]

EXAMPLE 4

By following the procedure of Example 3 but using, instead of 2.4 g of the dye of formula (28), the same amount of one of the dyes of formulae (9) to (27), there are likewise obtained coloured ABS granules which are stable to high temperatures and have good allround fastness properties, especially very good light fastness and high-temperature light fastness properties. [0077]

Claims

1. A method of mass-colouring synthetic materials based on terpolymers of acrylonitrile, butadiene and styrene, which comprises using at least one dye of formula

wherein

R₁is hydrogen, halogen, alkoxy, aryloxy, alkylthio or arylthio,

R₂is hydrogen, a carboxylic acid group or a carboxylic acid ester group,

R₃is hydrogen, halogen, alkoxy, aryloxy, alkylthio, arylthio, a carboxylic acid group or a carboxylic acid ester group, and

W is a radical of formula

wherein

R₄, R₈and R₁₁are each independently of the others hydrogen, alkyl, alkoxy, aryloxy, alkylthio or arylthio,

R₅, R₇and R₁₀are each independently of the others hydrogen, alkoxy, aryloxy, alkylthio, arylthio, a carboxylic acid group or a carboxylic acid ester group,

R₆and R₉are each independently of the other cyano, —CONR₁₂R₁₃or —SO₂R₁₄, wherein R₁₂and R₁₃are each independently of the other hydrogen or C₁-C₄alkyl and R₁₄is C₁-C₄alkyl, and

X is —NH—, —O— or —S—, or

R₅and R₅′ together form a phenyl or naphthyl radical.

2. A method according to claim 1, wherein R₄, R₈and R₁₁as alkyl are C₁-C₄alkyl.

3. A method according to claim 1, wherein R₁, R₃, R₄, R₅, R₇, R₈, R₁₀and R₁₁as alkoxy are C₁-C₄alkoxy.

4. A method according to claim 1, wherein R₁, R₃, R₄, R₅, R₇, R₈, R₁₀and R₁₁as alkylthio are C₁-C₄alkylthio.

5. A method according to claim 1, wherein R₁, R₃, R₄, R₅, R₇, R₈, R₁₀and R₁₁as aryloxy are C₆-C₁₂aryloxy.

6. A method according to claim 1, wherein R₁, R₃, R₄, R₅, R₇, R₈, R₁₀and R₁₁as arylthio are C₆-C₁₂arylthio.

7. The use of a dye of formula (1) according to claim 1 in the mass-colouring of synthetic materials based on terpolymers of acrylonitrile, butadiene and styrene.

8. A synthetic material based on a terpolymer of acrylonitrile, butadiene and styrene coloured according to claim 1 with a dye of formula (1) according to claim 1.