DE2360875A1 - MASS COLORS OF POLYESTERS - Google Patents

Description

The subject of the invention is a Vörfähreii zlifii Färbeii vöii Synthetic linear polyesters in the mass with a ödef several dyes of the formula, .-. ·. ·

Hydrogen or non-ionogical Siibstitüenteii> an integer from Ö Mä ä lifid denotes an integer from i - 4 * where m and together not greater than 4 SincL

Preferred dyes in the context of the formula I are those which the benzothiazolylthio groups and hydroxyl groups in the 6i position wear.

Those compounds in which FL and Rp are hydrogen.

k 15. 401.,

*. 2380175

Purely for the coloring of linear polyesters * especially for the production of transparently colored fibers, - a limited number of dyes has been available up to now * S "or ¹ many of the dyes known for coloring plastics are ^{unsuitable for the coloring of linear 1} polyesters; Because 'these dyes ¹ lose their color shade * their fastness or other desired properties when they are added to the condensation melt or "before spinning due to the high temperatures of 290-30 ° C and the added catalysts, such as phosphoric acid, manganese acetate and antimony trioxide ; Since most organic pigments are also not stable under the conditions encountered in the production or processing of linear polyesters, inorganic pigments have been used for coloring, but these give weak colors and cloudy shades without the clarity and transparency desired for many purposes.

Surprisingly, it was "found riüh that the dye · s" Formula T transparent brilliant ^ * färbstarke and ^very: fast dyeings when dyeing linear polyesters, in OCE Mässä he will hold ¹ ^. ■ "" ■ '■' ■ ' ^: ' · ^: ■ '■ "" · "·

Suitable nonionic substituents Ryuhd Ra are z; B; Halogen atoms such as Flüör ^ chlorine or BroM | straight or branched chain alkyl groups having 1 to 12 carbon atoms such as the methyl, ^ethyl: _f · - '■ propyl ^ i-, tert-i Pröpyl-, butyl ^ i-butyl; ^: -Butyl- "^ - amyl ^, octyl- ^ or 'dodecyl group j', preferably C 1-6 alkyl groups, alkoxy groups, preferably C 1-4 alkoxy groups such as the methoxy | ethoxy-j propoxy or butoxy group , TriflUörmethyl- UNAE. Dif lüör methyl groups Alkylsulfönylgruppen, in particular those having 1 to 4 carbon atoms, optionally substituted on the nitrogen by C, -C r alkyl -or benzyl · 'substituted Sulfbnainidgruppen, Äralkoxygfttpperi ^ preferably benzyloxy, aryloxy groups, in particular. Phenoxy groups, where 'the benzyloxy and phenoxy groups can be further substituted by halogen atoms, C 1 -C 4 -alkyl groups and C 1 -C 4 -alkoxy groups.

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In particular, linear aromatic polyesters such as polyethylene terephthalate or polyester are used as linear polyesters from terephthalic acid and 1, ^ -Bis-ChydroxymethylJ-cycloiiexan, also basic or acidic modified linear aromatic polyesters / as modified with suIfo-isophthalic acid Polyethylene terephthalate. . . ,.-... "" -

To carry out the process, for example, a cohdensation melt can be used from dimethyl terephthalate, ethylene glycol and a manganese acetate-phosphoric acid catalyst with an or put several of the dyes according to the invention, lead the condensation to the end in the usual way and the colored Spin melt into threads or shape it into solid objects. "- ■■ -" "

However, one or more of the dyes mentioned can also be used with the finished, linear polyesters in the usual way mix and then through a spinning or deforming process the Making colored polyester. This is done by the material to be colored in the form of powders, grains or chips with the finely divided dry dye in e.g. a coating drum mixed so that the surface of the material with a The layer of dye is coated, which is then covered with dye coated polyester particles melt and according to known Process · can spin or deform. If necessary, can the covering of the polyester particles with dye can also be carried out in such a way that one with a dispersion of the dye works in a volatile liquid such as water or alcohol and preferably the volatile liquid evaporates before the: melting of the polyester particles coated with dye.

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The compounds according to the invention are among those in the manufacture the linear polyester conditions existing in the condensation melt and surprisingly stable in the spinning process, do not change the viscosity of the polyester melt and do not affect the properties even with deep colors the linear polyesters and the fibers made from them. The linear polyesters colored according to the invention show beautiful clear and transparent colors with very good fastness properties.

Example la;

99 g of polyethylene terephthalate in the form of pellets are mixed with 1 g of finely divided 1, 4, 5, 8-tetra- (2-benzthiazolyl-thio) -a.nthraquinone in a drum until the polyester particles are evenly coated with dye. The resulting mixture will melted and then spun as usual at 290-295 ° C.

The thread obtained in this way is colored in yellowish red tones. The dye has excellent light, washing and heat setting fastness properties on.

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Example Ib; "

The dye used can be prepared as follows: 15 g of 1, 4, 5, 8-tetrachloro-anthraquinone, 75 g of dimethylformamide, 35 g of 2-Mercaptobenzthiazöl and 30 g of potassium carbonate for about 3 hours at 125 - 130 ⁰ C heated. After cooling, the dyestuff precipitated in beautiful red prisms is suctioned off and washed with methanol and water. After drying, 34 g of 1 * 4, 5, 8-tetra- (2-benzthiazolyl-thio) -anthraquinone = 90% are obtained Theory. '

Uses: one in the production of dyed polyester threads according to Example la instead of the 1, -4, 5/8-tetra- (2-benzthiazolylTthio) anthraquinone mentioned there Corresponding amounts of the dyes listed in the table below are obtained Polyester threads in the specified colors with excellent Fastness to light, washing and thermosetting.

example

dye

hue

1> 4,5,8-tetra- (5-methyl-2-benzthiazolyl -thi ο) -anthraquinone

l, * v5,8-tetra- (6-ethyl-2-benzthiazolyl-thio) -anthraquinone

1,4,5,8-tetra- ( S- tert-butyl-2-benzthiazolyl-thio) -anthraquinone

li4i5,8-tetra- (6-isooctyl-2-benzthiazolyl-thio) anthraquinone

yellowish red yellowish red yellowish red yellowish red

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example

dye

hue

1,4,5,8-tetra- (4-methoxy-2-benzthiazolyl-thio) anthraquinone

Red

l _J 4,5,8-tetra- (5-isopropoxy-2-benzthiazolyl-thio) anthraquinone

Red

. l, 4,5,8-tetra- (5,6-dimethyl-2-benz-

thiazolyl-thio) anthraquinone

1,4,5,8-tetra- (5-chloro-2-benzthiazolyl-thio) -anthraquinone

yellowish red yellowish red

1,4,5,8-tetra- (6-bromo-2-behz'thiazolyl-thio) -anthraquinone

1,4,5,8-tetra- (4-fluoro-2-benzthiazolyl-thio) -anthraquinone

yellowish red yellowish red

12th

14th

16

17th

li ^, 5i8-Tetra- (5-difluoromethyl-2-benzthiazolyl-thio) -anthraquinone

l, 4,5, '8-tetra- (5-trifluomethyl-2 benzthiazolyl-thio) anthraquinone yellowish red yellowish red

2-benzthiazolyl-thio) -anthraciiiritm yellowish red

l, 4,5,8-tetra- (6-methylsulfonyl-2-

benzthiazolyl-thio) -anthraquinone yellowish red

1,4,5,8-tetra- (6-aminosulfonyl-2-benzthiazolyl-thio) -anthraquinone yellowish red

li ^ i5,8-tetra- (6-dimethylaminosulfonyl-2-benzthlazolyl-thio) anthraquinone

yellowish red

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Example l8a:

"OO g of dimethyl terephthalate, 71 g of ethylene glycol ^ 0.0 ~ _j _o 5ΑνΐΒ. ^ Λ = ίχτ) .- acetÄt '-" »i o.rA y Pb -. ^ Pnoi-acid are 4 hours with distilling off the methanol at 197 C stirred. 3 g of 1,4 ", 5 -Tr i- (£ -benzthiazolyl-thio) - -: anthraquinone in 12 g of ethylene glycol are then added and the condensation is carried out in 6 hours at 277 ° C. and 0.3 Torr while distilling off the The usual spinning of the melt gives deep yellow-brown threads, the color of which has excellent fastness to light, washing and heat setting.,

Example l8b;

The dye used can be prepared as follows: 20 g of 4,5-dichloro-1-nitro-anthraquinone and 16 g of potassium carbonate with 38 g 2-Mercapto-behzthiazol in 100 g Dirnethylforma- "mid about 3 hours at 125-130 ⁰ C. After cooling, the product crystallized in red-brown prisms is filtered off with suction, washed with a little methanol and water and, after drying, 40 g of 4,5-tri- (2-benzthiazo.lyl-thio) anthraquinone is obtained Theory.

Used in the manufacture of dyed polyester threads according to Example 18a instead of the 1,4,5-tri- (2-benzthiazolyl-thio) anthraquinones mentioned there corresponding amounts of the dyes listed in the following table, one obtains poly- ' Ester threads in yellow-brown shades with excellent light, washing and thermosetting fastness.

Example dye "hue

19 l, 4,5-tri- (7-methyl-2-benzthia-

zolyl-thio) -anthraquinone yellow-brown

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example

dye

23B0875

hue

20th

1,4,5-tri- (6-methoxy-2-benzthiazolyl-thio) -anthraquinone

1,4,5-tri- (6-dimethylamino-sul-

fonyl-2-benzthiazolyl-thio) -anthra

chinone

1,4,5-tri- (6-ethylsulfonyl-2-benzthiazolyl-thio) -anthraquinone

1,4,5-tri- (5,6-dichloro-2-benzthiazolyl-thio) anthraquinone

Example 24a;

yellow-brown

yellow-brown yellow-brown yellow-brown

One blended 99 g of the polyester from terephthalic acid and l _J 4-bis (hydroxymethyl) -cyclohexane in the form of chips with a finely divided part ■ 1,5-di- (2-benzthiazolyl-thio) anthraquinone until uniform occupancy of the polyester . The mixture obtained is melted and, by conventional spinning at 290-295 ° C., a clear yellow-colored thread is obtained, the color of which has excellent fastness to light, washing and heat setting. =

Example 24b;

The dye used can "be prepared as follows: 15 g of 1,5-dichloro-anthraquinone and 9 g of potassium carbonate with 22 g of 2-mercapto-benzthiazole in 60 g of dimethylformamide for about 3 hours at 125 - 130 ⁰ C heated after cooling. The product, which has crystallized out in yellow prisms, is filtered off with suction, washed with a little methanol and water and, after drying, 26.8 g of 5-dir. (2-benzthiazolyl-thio) -anthraquinone = 92% of theory

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Used in the manufacture of dyed polyester threads according to Example 24a instead of the 1,5-di- (2-benzthiazolyl mentioned there) -thio) -anthraquinones corresponding amounts of the dyes listed in the table below, polyester threads are obtained in the specified, color shades with excellent Fastness to light, washing and thermosetting.

Example "Dye. Hue

25 1,5-di- (5-butoxy-2-benzthiazolyl-. thio) anthraquinone. yellow

26 l, 5-di (5,6-dichloro-2-benzthia- -zolyl-thio) -anthraquinone · yellow

27 l, 8-di- (2-benzthiazolyl-thio) -

anthraquinone ■ reddish yellow

28 1,8-di- (6-ethoxy-2-benzthiazolylthio) anthraquinone reddish yellow

29 1,8-Di- (6-phenoxy-2-benzthiazolyl-thio) -anthraquinone reddish yellow

JiO l- (5-BenzylOxy-2-benzthiazolyl-

thio) anthraquinone yellow

31 l- (6- (2-phenylethyloxy) -2-benzthiazolyl-thio) -anthraquinone yellow

32 l- (6- (4-chlorobenzyloxy) -2-benzthiazolyl-thio) -anthraquinone yellow

33 l-O ^ -C ^

thiazolyl-thio) -anthraquinone yellow

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Example dye hue

34 1- (6- (4-Methoxybenzyloxy) ~ 2-benzthiazolyl-thio) -anthraquinone · yellow.

35 1- (6- (4-Methoxyphenoxy) -2-benzthiazolyl-thio) -anthraquinone yellow

36 1- (6- (3,4-Dichlorophenoxy) -2-benzthiazolyl-thio) -anthraquinone yellow

31 1- (5,6-dichloro-2-benzthiazolyl-

thio) anthraquinone yellow

Example 38a:

One mixes 99 S Polyätnyier \ i: erephfcha-. _a t in the form of pellets with 1 g of finely divided 1,3,5,7-tetra- (2-benzi,:. iazolyl-thio; - "anthraquinone in a drum until the polyester particles are evenly coated with dye The mixture is melted and spun as usual at 290-295 ° C. The thread obtained in this way has a reddish-tinged yellow color.

Example 38b:

The dye used can be prepared as follows: 15 g 1,3,5 / 7-tetrachloro-anthraquinone and 30 g potassium carbonate are heated with 35 g of 2-mercapto-benzothiazole in 80 g of dimethylformamide at 125 ° -130 ° C. for 5 hours. After cooling down, ^ sucks the product crystallized in yellow-brown prisms, washed with a little methanol and water and, after drying, obtained 35 g 1,3,5,7-tetra- (2-benzthiazolyl-thio) -antraquinone = 93 $ der Theory.

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Example 39:

If one proceeds as indicated and used in Example 38a instead of the dye mentioned there, corresponding amounts l, 4,6-Tri- (2-benzthiazolyl-thio) -anthraquinOn, is obtained an orange color, which is characterized by very good light, Excellent washing and thermosetting fastness properties.

Example 40a:.

One blended 99 g of polyethylene terephthalate in a drum with 1 gl, 5-dihydroxy-4, ö-di- (2-benzthiazolyl-thio) -anthrachirion and 3 g of water until there is a uniform mixture, and drying the mixture at 100 ⁰ C The mixture is then melted and spun in the usual way at 290-295 ° C., threads dyed with a deep blue tinge of violet, the color of which has excellent light, washing and heat-setting fastnesses.

Example 40b; - '

The dye used can be made as follows: 20 g of 1,5-dihydroxy-4,8-dinitro-anthraquinone and 11 g of potassium carbonate are bis with 26 g of 2-mercaptobenzothiazole in 80 parts of dimethylformamide. to stop dye formation Heated to 125 - 135 ° C. After cooling, you suck the purple one Product crystallized out from prisms, washed with methanol and water and, after drying, obtained 31 g of r, 5-dihydroxy-4,8-di- (2-benzthiazolyl-thio) -anthraquinone = $ 89.5 of theory.

Example 4l:

Proceed as indicated in Example 40a and use instead of the dye mentioned there corresponding amounts of 1,8-dihydroxy-4,5- (2-benzthiazol-thio) -anthraquinone, this gives a deep purple color, which is characterized by very good light, Washing and thermosetting rights are distinguished. . Le A 15 401 - 11 - -

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te

Example 42; ^

99 g of polyethylene terephthalate in the form of grains are mixed with 1 g of 1,4-dihydroxy-2- (2-benzthiazolyl-thio) anthraquinone and 5 g glycol monomethyl ether until a uniform hybrid yields and then dries in vacuo at 120 C. After melting the mixture and conventional spinning at 290-295 C. scarlet-colored threads are obtained, the coloring of which has very good fastness to light, washing and heat setting. Scarlet fever Dyed polyester threads are also obtained if, instead of the abovementioned 1,4-dihydroxy-2- (2-benzthiazolylthio) anthraquinone, one obtains corresponding amounts of 1,4-dihydroxy-2- ν (5-methyl-, 6-methoxy-, 4-chloro- or 7-bromo-2-benzthiazolylthio) anthraquinone used.

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Claims (4)

Claims - & ■ 1. Process for dyeing synthetic linear polyesters in the mass, characterized in that one or several dyes of the formula _ wherein
R ^ and m
η Hydrogen or a non-ionic Substi tuenten,:; : an integer from Q to 2 and mean an integer from \ to 4, where m and η together are not greater than 4, begins'. _: ; 2. The method according to claim 1, characterized in that one such dyes of claim 1 are used, which carry the benzothiazolyl thio and hydroxyl groups in the oC positions. 3. The method according to claim 1, characterized in that dyes of claim 1 are used in which R ,, and R _{2 are} hydrogen. 4. Synthetic linear polyester, dyed according to the mass Claim 1. ... ". ■ - ■" :. Le A 15 401 - 13 - SO 98 247 090