DE2037123C3 - Bulk colors of plastics - Google Patents

Description

HO Ö NH

wherein X stands for alkyl radicals or alkoxy radicals with 1 to 15 carbon atoms, Y for alkyl radicals or alkoxy radicals with 1 to 15 carbon atoms, for halogen, a hydroxyl group or an optionally acylated amino group, hydrogen, η for the numbers 1, 2 or 3 and m for the numbers 0, 1, 2 or 3 and where the radicals X and / and Y can stand for identical or different substituents, for the mass coloring of plastics.

2. Use of anthraquinone compounds of claim 1, wherein X and Y are identical Are alkyl radicals with 1 to 8 carbon atoms.

3. Use of anthraquinone compounds of claim 2, in which X and Y are tert-butyl radicals and m and π are the number 1.

4. Plastics, stained with Anthrachinonverbin d iingen according to Claim. 1

35

2s

30th

Dyes for coloring plastics in bulk must have a number of properties specific to this purpose, for example heat resistance, weather and lightfastness and good dispersibility or solubility in the plastic. With the development of new plastics, the requirements for the heat resistance of such dyes have increased. This is true T-. As for the coloration of plastics of polycarbonates in which the practice requires a heat resistance of the dyes to 300 ⁰ C.

When coloring polystyrene, polymethacrylates As well as polyamides in the bulk, the dyes also have heat resistance up to at least 250 "C required. In the practice of injection molding, however, this also occurs, for example, in the injection cylinder often temperatures of up to 300 ° C.

Most of the organic dyes attempted to date in this area show only a heat resistance of 180 to 220 ° C.

Dyes that have grown to such increased requirements are generally only from the Range of inorganic pigments known, e.g. B. cobalt pigments, titanium dioxide and some others. With However, these connections can only be identified Achieve tones. Only a few organic dyes stand out for transparent colors the indanthrene dyes, the perinones and the quinacridones are available. These products do not deliver all desired shades.

HP P NH

HO Ö NH

wherein X stands for alkyl or alkoxy radicals with 1 to 15 carbon atoms, Y for alkyl or alkoxy radicals with 1 to 15 carbon atoms, halogen, such as chlorine or bromine, hydroxyl groups, optionally acylated amino groups, hydrogen, η for the numbers 1 to 3, m stands for the numbers 0, I, 2, 3, are suitable for mass coloring plastics such as polycarbonates, polyamides, polymethacrylates, polystyrene and polyolefins.

Bulk dyeing is understood here to mean the addition of dyes, in particular before and after the polymerization.

Those anthraquinone compounds in which the radicals X and Y are identical and m stands for the numbers 1, 2 or 3 are particularly suitable. Alkyl radicals with 1 to 8 carbon atoms are preferred here; Anthraquinone compounds according to the invention in which X and Y are iso-propyl, iso-butyl and tert-butyl radicals are particularly suitable.

Anthraquinone compounds in which X and Y are tert-butyl radicals and m and η are the number 1 are particularly preferred according to the invention.

In addition to high lightfastness and good solubility in the plastics mentioned, they have excellent heat resistance ^{even up to 300 ° C.} Transparent, brilliant blue, yellowish-green colorations are obtained. By adding inorganic pigments that are not soluble in plastics, such as B. titanium dioxide, corresponding opaque colors can be obtained.

From the German Auslegeschrift 1 288 067 it is already known to use such compounds for dyeing polyester fibers by the thermosol process, in which the dyes are only briefly exposed to ^{a heat load of 180 to 210 ° C.} When dyeing polycarbonates, polyamides, polymethacrylates, polystyrene and polyolefins, on the other hand, they have to ^{withstand temperatures of 240 to 300 °} C. for comparatively long periods of time without damaging influences. The high thermal stability and the unusually high lightfastness of these anthraquinone compounds in the plastics mentioned could not be foreseen.

Suitable bis-arylamino-quinizarin dyes are among other things:

5,8-bis (p-n-butyl-anilino) -quinizarin, 5,8-bis- {p-isobutyl-anilino) -quinizarin, 5,8-bis- {p-tert-butyl-anilino) -quinizarin, 5,8-bis- {n-pentyl-anilino) -cninizarin, 5,8-bis- <isopentyl-anilino) -quinizarin, 5,8-bis (n-propyl-anilino) -quinizarin, 5,8-bis- <isopropyl-anilino) -quinizarin, ί |> υ33Ι1 ^ 1Η

chinizarin, 5,8-bis- {p-dodecyl-anilino) -quinizarin,

SHp-Brom-anilinoJ-S-ip-butPxy-anlUno) -htoi

, {pyH | rin, S ^ -BuKo-roetboxy-anilinoJ-chroizarin, 5,8-BMm-metboxy-aniliiiQ) -chimzarin, 5,8-BJ »- {p'roethoxy-anilino) -chwuzarin, S.e-BisHo-ätboxy-anilinoli-clunizarm, 5,8-B | s- <n> -ätboxy-8nHwo) -cbiiii2arin, S.S-Bis-ip-ethoxy-anilinoIl-cbinizarin, 5-AnQino-8- {p-n-butyl-anilino) - <Äinizarm, 5-anilmo-8- (p-isobutyl-aiiilino) -chinizariq, 5-anflino-8- (p-tert-butyl-anilmo) -quinizarin, 5- <i> -Methoxy-anilino) -8- <p-n-butyl-anilmo> chinizarin,

5- (o-methoxy-annino) -8- (p-isobutyl-anUino) -quinizarin,

5- (o-methoxy-anilino) -8- (p-tert-butyl-anilino) -quinizarin,

5- {m-Methoxy-aniUno) -8- {p-n-butyl-anilino) -quinizarin,

chinizarin,

5- {m-methoxy-anilino) -8- {p-tert, butyl-anilino) -quinizarin,

5- {p-methoxy-an 11 i η o) -8 (p-ti-butyl-anilino) -quinizarin,

5- {p-Methoxy-ani! Ino) -8- <p-isobutyl-anilino) -quinizarin,

5- {p-methoxy-anilino) -8- (p-tert.butyl-anilino) -quinizarin,

5- {o-ethoxy-anilino) -8- (p-n-propyl-anilino) -quinizarin,

5- <o-ethoxy-anilino) -8 - ("- isopropyl-anilino) -quinizarin,

yJ ^ chinizarin,

5- {m-ethoxy-anilino) -3- (p-isopropyl-anilino) -quinizarin,

5- (p-ethoxy-anilino) -ii- (p-n-propyl-anilino} -

quinizarine, 5- {p-ethoxy-anilino) -8- (p-isopropyl-anilino) -

quinizarine, 5- {o-methyl-anilino) -8- (p-n-octyl-anilino) -

quinizarine, 5- (o-MethyI-anilino) -8- (p-isooctyl-anilino) -

quinizarine, 5- (m-methyl-anilino) -8- (p-n-octyl-anilino) -

quinizarine, 5- (m-methyl-anilino) -8- (p-isooctyl-anilino} -

quinizarine, 5- (p-Methy! -anilino) -8- (p-isooctyl-anilino) -

quinizarine, 5- (p-methyl-anilino) -8- (p-n-octyl-anilino) -

quinizarin, 5- (m-chloro-anilino) -8- (m-butoxy-anilino) -

quinizarine, 5- (m-chloro-anilino) -8- (p-butoxy-anilino) -

quinizarine, 5- {p-chloro.anilino) -8- (p-butoxy-ani! ino> -

quinizarin, 5- (p-chloro-anilino) -8- (m-butoxy-anilino> ·

quinizarine, 5- {nvBroin-anilino) -8- (m-butoxy-anilino) -

quinizarin, 5- {m-Brotn-anilino) -8- (p-butoxy-antlino) -

quinizarin, 5- <p-broin-anilino) -8- (m-butoxy-anilinoV chinizarin,

chtoiaarm, ....

5- (m-AcetyIainJno-aniHno) -8- (n'bwtyl-ttiunno) -

chinizatin,
5- (roΆcetyl8mίno-an ^ Hno) -8-ί ^ 8obwtyl anll ^ ⁿ o ^

cbinizarin,

py

chinizarin,
5- {ro-Acetylainwo-anilino) -8- {tert.butyl-anilmo) -

chinizarin,
5- (p-Acetylamino-aniljno) -8- {isobu * yl-antHno) -

chinizarin,
5- {p-Acetylamino-anilino) -8- (tert-butyl-anilino) -

chinizarin,
5- (2,4,6-triniethyl-anilino) -8- {p-terLbutyl-

anüino} -cbinizarin,

5-anilino-8- {2,6-dimethyl-anilüio) -quinizarin,
5,8-bis- {2,6-diethyl-4-methyl-anilino> -quinizarin,
dhliliVhiiri

The dyes mentioned are used in finely divided form, in general no dispersants are used. The pigments either fall during manufacture

in finely divided form or are converted into such a form by known, suitable processes, such as by grinding in dry or moist form, optionally together with organic ones Solvents, or by kneading or

grinding the crude product in the presence of solid grinding aids such as sodium sulfate, sodium chloride or other sets that can be washed out after the grinding process. Received by other methods the pigments in finely divided form by first dissolving the crude product in sulfuric acid and precipitates again or treated with organic solvents.

The pigments are dry mixed or ground with the plastic granulate and this mixture

7. B. plasticized on mixing rollers or in screws and homogenized. The dyes can also be added to the molten mass and this through Stir homogeneously. The material pre-colored in this way is then used as usual, for. B. by spinning further processed into bristles, threads, etc. or into molded parts by extrusion or injection molding.

It is also possible to use the monomeric dyes

Add starting materials for the plastics and then in the presence of polymerization catalysts to polymerize. On the one hand, this requires the dyes in the monomeric components to dissolve or to mix with them intimately, on the other hand the dyes must withstand the action of the polymerization catalysts.

The known thermoplastic polymerization products from methacrylic acid esters, whose alcoholic radical is preferably derived from low molecular weight alcohols, like methanol or ethanol. They are made from monomeric methacrylic acid esters by known processes obtained in the presence of catalysts such as benzoyl peroxide. Particular technical importance have suspension or bead polymerization, emulsion and block polymerization.

High molecular weight thermoplastic polycarbonates suitable according to the invention can, for example are represented by the reaction of aromatic dihydroxy compounds, such as hydroquinone or resor-

a, particularly suitable are DHmonobydroxyarylhalkanes, which themselves or mixed with aliphatic or cycloaliphatic dihydroxy compounds with aliphatic or cycloaliphatic diesters of carbonic acid or with phosgene, or through Reaction of bis-cblor carbonic acid esters more aromatic Dibydroxy compounds with aromatic, aliphatic or cycloaliphatic dibydroxy compounds, z. B. by the method according to British patents 772 627, 808 485 and 808 487 (cf. also Ang. Chem. 68 [1956] 633 to 640).

Polycarbonates particularly suitable according to the invention are prepared from the following di (monohydroxyaryl) alkanes:

4,4'-dihydroxy-diphenyl-methaa,
4,4'-dihydroxy-diphenyl-dimethyl-methane,
4,4'-DJhydroxy-diphenyte-l, l-cyclobexane,
4,4'-dihydroxy-33 '- <limethyl-diphenyl-

1,1-cyclohexane,
2,2'-dihydroxy-4,4'-di-tert-butyl-diphenyl-

dimethyl methane,

4,4'-dihydroxy-diphenyl-3,4-n-hexane,
2,2- {4,4'-dihydroxydiphenyl) -b! Itane,
2,2- {4,4'-dihydroxy-diphenyl) -pen tan,
3,3- {4,4'-dihydroxydiphenyl) pentane,
2,2- (4,4'-dihydroxy-phenyl) -3-methyl-butane,
2,2- (4,4'-dihydroxydiphenyl) hexane,
2,2- {4 ₎ 4'-dihydroxydiphenyl) heptane,
4,4- (4,4'-dihydroxy-diphenyl) -heptane and
2,2- (4,4'-dihydroxydiphenyl) tridecane,
2,2- (4,4'-dihydroxydiphenyl) -4-methyl-prntane.

The high molecular weight polycarbonates made from 4,4'-di- (monohydroxyaryl) -alkanes correspond to the formula

ίο

3 °

35

Il o — c — ο

where X is for the groups

1'

—C— or

where R ₁ and R _{2 represent} hydrogen atoms or monovalent hydrocarbon radicals with up to 10 carbon atoms, monovalent cycloaliphatic radicals, monovalent aralkyl radicals, phenyl and furyl radicals, Z the remaining members required to form the cycloaliphatic ring, R 'hydrogen, monovalent, straight-chain or branched aliphatic hydrocarbon radicals with up to 5 carbon atoms or monovalent cycloaliphatic or aromatic carbon radicals and η is an integer> 20, preferably> 50.

To prepare such polycarbonates, the processes of British patents 808 448, 808 489 and 808 4ΓΌ can be used.

Further high molecular weight polycarbonates suitable according to the invention can be obtained by Reaction of dihydroxy-diaryl sulfones or mixtures of dibydroxy-diaryl-sulfones with others bifunctional dihydroxy compounds according to the method of British Patent 808486 or from dihydroxy-diaryl-ethers or dihydroxy-diarylthio-ethers or from mixtures of these components with other dihydroxy components according to British U.S. Patent 809,735. Such polycarbonates are obtainable, for example, using the following Dihydroxy compounds:

4,4'-dihydroxy-diphenyl-sulfone,

^ '- Dibydroxy-diphenyl-sulfone,

3,3'-dihydroxy-dipbenyl-sulfoo,

4,4'-dihydroxy-2 ^ '- dimethyl-djphenyl-sulfone,

4,4'-dihydroxy-3,3'-dimethyl-diphenyl-sulfone,

2 ^ '- dihydroxy-4,4'-dimethyl-diphenyl-sulfone,

2,2'-dihydroxy-l, r-dinaphthyl sulfone,

4,4'-dihydroxy-dipheayl ether,

4,4'-dihydroxy-2,2'-dimethyl diphenyl ether.

4,4'-dihydroxy-3,3'-dimethyl-diphenyl-ether and

their homologues,
4,4'-dihydroxy-diphenyl sulfide,
4,4'-Dihydroxy-3,3'-dimethyl-diphenyl-suIfid and their homologues.

The most common polyamides are those known commercially under the names polyamide 6, Polyamide 6,6 and polyamide 12 products in question.

The anthraquinone dyes corresponding to formula 1 are used for coloring the plastics mentioned in amounts of 0.005 to 1%, preferably 0.05 to 0.5%, based on the amount of plastic c. used.

Titanium dioxide can be used in an amount of 0.1 to 2%.

The plastics colored by the process according to the invention are distinguished by clear, brilliant colors Shades with excellent lightfastness, migration resistance and weather resistance.

In the following examples, unless they mean nothing otherwise noted, the parts are parts by weight.

example 1

a) 0.1 part of a dye, consisting of 5,8-bis [p- (tert-butyl) -anilino] -quinizarin, is mixed with 100 parts of polycarbonate - from l, l- (4 ₍ 4'-dihydroxy- diphenyl) cyclohexane - with a K value of about 50, mixed dry and homogenized in a 2-screw extruder at 280 ° C. A transparent yellowish green coloration with very good lightfastness is obtained in the injection molding process to be worked into molded parts.

b) The procedure is as described above, but below Addition of 1% titanium dioxide results in a subdued color in a beautiful shade of green.

Example 2

100 parts of polymethyl methacrylate and 0.1 part of 5,8-bis (p-i-pentyl-anilino) -quinizarin become dry mixed and homogenized in a 2-spindle extruder. That from the mouthpiece of the extruder emerging material is granulated and can then be compressed into shapes in the usual way. Man receives a transparent green colored plastic.

Example 3

0.1 part of 5-p-anisidino-K- [p- (tcrt.butyl) -anilino] -quinizarin is converted into 100 parts of molten polycarbonate at 300 "C from 2,2- (4,4-dihydroxydiphenyl | - propane and phosgene from the K-Wcrt about 50 entered and homogeneously distributed with constant stirring.

A green coloration of good lightfastness is obtained. The colored polycarbonate is available as a strand or ribbon discharged from the mixing bowl and processed into granules. The granules can according to the usual Methods of processing thermoplastic masses, such. B. in the extruder process, to threads, bristles. Foils, plates, pipes or other profiles are processed.

Example 4

a) To 100 parts of polystyrene in the form of granules, 0.05 parts of 5,8-bis (butoxy-anilino) -chinizarin are added and homogenized in a heating roll at 160 ⁰ C. The mixture, which is in the form of a fur, is broken up and the corresponding granules are further processed into plastic parts by injection molding, with transparent green-colored plastics of good lightfastness being obtained.

b) 0.5 part of titanium dioxide is also added. this gives a nice, muted color.

Example 5

0.1 part of 5-p-toluidino-8 - [p - (1,1,3,3-tetramethyl-butyl) -anilino] -quinizarin is dry-mixed with 100 parts of polystyrene and dried in a 2-spindle extruder at 170 ⁰ C homogenized. The material emerging from the mouthpiece of the extruder is granulated and can then be compressed into shapes in the usual way. A transparent green colored plastic of good lightfastness is obtained.

Example 6

0.05 part of 5 - mesidino - 8 - (p - ethyl - anilino) quinizarine are dissolved in 100 parts of monomeric methyl methacrylate. After adding 0.5 parts Hcn / oylpcroxid becomes the mass at 70 to 80 ° C polymerized, in transparent blue-green block polymer is received.

B c i s ρ i c I 7

0.01 part 5- (p · dodecyl-anilino) -8-m-phcnctidinoquinizarin is added to KX) parts of poly (methyl methacrylate) and the mixture is homogenized on a Mcizwalzc. The film obtained is broken, the granules obtained are colored transparent green.

Example 8

100 parts polyamide-6-Sthnitzcl. received by Polymerization of »-Caprolactam, be 0.1 part Rolled 5,8-bis - [(p-tert-butyl) -anilino] -quinizarin in a ball mill for 20 hours. The so obtained powdered schnitzel are at 260 ° C in one The extruder melted, the resulting melt through a single-hole nozzle with a diameter of 0.5 mm pressed and the emerging thread pulled off at a speed of about 25 m / minute. the The thread can be stretched four times in hot water. A transparent, brilliant green color is obtained Thread of excellent lightfastness.

SUz.t instead of 0.1 part 1 part of the same dye one, so wildly obtained a deep green, less transparent coloration.

The downtime in the extruder can be

.10 the color shade can take up to 30 minutes.

Example 9

100 parts of commercially available polyamide granules are mixed with 0.05 parts of 5.8-bis- {isobutyl-ani1ino) -quinizarin intimately mixed, then injected into strips or wires in the extruder and finally granulated. If no uniform color results after a single extrusion, the process can be carried out be repeated. The transparent green-colored granules obtained in this way can be used in the usual way Molded parts are injected.

If you want to obtain a subdued color, add 0.5 part of titanium dioxide to the polyamide granules.

409647/2

Claims (1)

Patent claims: 1. Use of anthraquinone compounds of the formula HO O NH It has now been established that anthropomorphic compounds of the a4lga "form a formula I.