DE1942317A1 - Process for the continuous dyeing of synthetic fiber materials - Google Patents

Description

FARBENFABRIKEN BAYER AG

LEVERKUSEN-Beyerwerk August 19, 1969 Patent department

Process for the continuous dyeing of synthetic fiber materials

The invention relates to a process for the continuous dyeing of synthetic fiber materials from organic ones Solvents; the process is characterized in that the fiber materials are impregnated with dye liquors, the anthraquinone dyes of the formula

0 OH

0 OH

contain,

in the

Hai a halogen atom, especially a chlorine or bromine atom,

X is a sulfur atom, an oxygen atom or an NH group,

Y is a simple C-C bond or an oxygen atom,

m is a number from 0-2 and

η is a number from 1 to 3, and

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B for a trifluoromethyl group or in particular for a C. -C - p - ^ - lkyl- * cycloalkyl- or Aralkyl radical, with the proviso that the sum of the total in the "or the substituents B contains at least T carbon atoms and is no more than 12,

and then subjected to a heat treatment.

Mentioned for example for B selenium: as Cj-C.j2-alkyl radicals of the methyl, ethyl, propyl, iso-propyl, η-butyl, iso- _{butyl- s} sec-butyl-, tert-butyl- , .n-pentyl-, iso-amyl-, sec * -pent ^ 1- _? Eeopentyl, n-hexyl, methyl pentyl, dimethyl butyl, n-heptyl, methyl hexyl, dimethyl pentyl, trimethyl butyl, n-oetyl, iso-octyl, methyl heptyl, dimethyl-hexyl, trimethyl-pentyl, tetramethyl-butyl, n-honyl-j iso-nonyl, dimethyl-heptyl, trimethyl-hexyl, decyl, undeeyl and the dodecyl radical; as cycloalkyl radicals the cyclohexyl and the methylcyclohexyl radical and

as aralkyl radicals, in particular the benzyl and the Oc , OL- dimethylbenzyl radical.

According to the invention for dyeing from organic Dyes used in solvents can be obtained by methods known per se, e.g. B. by implementing 1, 4-dihydroxy-2-halogenanthraquinones with. Hydroxy, amino. and thioary! compounds containing a trifluoromethyl group or in particular one or more alkyl or aralkyl or cycloalkyl radicals containing 1-12 carbon atoms wear, in the presence of inorganic or organic bases.

For the process according to the invention come as organic Solvents such solvents into consideration that with

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Water are substantially immiscible and whose boiling points are between 40 and 15O ⁰ C, "for example aromatic hydrocarbons such as toluene or xylene, aliphatic ^ halogenated hydrocarbons, especially chlorinated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane ,. Dichloropropane, pentachloropropane, chlorobutane, dichlorobutane and dichlorohexane and aliphatic fluorine and fluorine chlorine hydrocarbons, such as perfluoro-n-hexane, 1,2,2-trifluorotrichloroethane and trifluoropentachloropropane, aromatic · see chlorine and fluorocarbons, such as chlorobenzene , Fluorobenzene, chlorotoluene and benzotrifluoride.

Tetrachlorethylene, trichlorethylene, 1,1,1-trichloroethane and 1,1,1-trichloropropane. Mixtures of these solvents can also be used.

In the case of those to be colored by the process according to the invention Synthetic fiber materials are in particular fiber materials made of polyesters, e.g. B. polyethylene terephthalate or polyester from 1 ^ -Bis-Chydroxymethyli-cyclohexane and terephthalic acid, from cellulose triacetate, from synthetic polyamides, such as poly - ^ - caprolactam, polyhexamethylene diamine adipate or poly-iJ-aminoundeeanäure, from polyurethanes or made of polyolefins. The fiber materials can be in the form of woven and knitted fabrics.

For dyeing, the dyes to be used according to the invention are dissolved in the organic solvents which are essentially immiscible with water or does it in the form of Solutions in solvents that are infinitely miscible with these solvents, such as alcohols, dimethylformamide, dimethylacetamide, Dimethyl sulfoxide or SuIfolan, to and impregnated with the clear dye solutions obtained, the given

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■■■■■■. ■ ■;. ■■■■■ * '■■. ■■■.; ... ■. ■' "; ·

if there are still soluble non-ionic auxiliaries to improve the levelness of the dyeings, ζ. B, the known surface-active oxethylation and propoxylation products of fatty alcohols, alkylphenols, fatty acid amides and fatty acids, the synthetic fiber materials. The dyes are then fixed on the fiber materials by means of a heat treatment. The heat treatment can result in a short dry heat treatment. 120-230 ⁰ C exist, wherein the dry heat treatment can be preceded, where appropriate, an intermediate drying, or in a treatment of the fiber materials in superheated solvent vapor of 100 - blank 150 ⁰ C. Differential unfixed dye portions be washed by brief treatment with the cold organic solvent. It should be pointed out that mixtures of the dyes to be used according to the invention sometimes give a better color yield than the individual dyes and possibly even better solubility in the organic medium. .

With the help of the method according to the invention it is possible to Dyeing from organic solvents on synthetic fiber materials to achieve dyeings that are characterized by high levels of dye Yield, very good structure and excellent 'fastness properties', in particular very good thermal fixation, washing,'. Rubbing and light fastness properties. Another advantage of the dyes to be used according to the invention is their high level Solubility in organic solvents, especially in tetrachlorethylene, trichlorethylene, 1,1,1-trichloroethane and 1,1,1-trichloropropane, which in particular allows the Dyeing can also be carried out without the use of solubilizers.

The parts given in the following examples are Parts by weight. .

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example 1

A fabric made of polyethylene terephthalate fibers is at room temperature impregnated with a clear ruby solution that

10 parts of 1,4-dihydroxy-2- (4-tert-butyl-anilino) -

anthraquinone in
990 parts of tetrachlorethylene

contains. After squeezing to a weight increase of 60 io , the fabric is ^{dried at 80 °} C. for one minute. The dye is then by 45-second heating the fabric at 190 - 220 ⁰ C is fixed. The small amount of non-fixed dye is then washed out by briefly treating for 20 seconds in cold tetrachlorethylene. After drying, a clear ruby-red dyeing is obtained, which is distinguished by its high dye yield, very good structure and excellent fastness properties, in particular very good heat-setting, washing, rubbing and light fastness properties.

In an analogous manner, equivalent clear ruby-red dyeings were also produced on fabrics

a) cellulose triacetate,

b) synthetic polyamides or polyurethanes; and c) polypropylene fibers

obtain; just got the thermal insulation

for a) at 200 - 220 ⁰ C,
for b) at 170 - 200 ⁰ C and
for c) at 120-150 ^° C

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performed.

Equivalent colorations were also obtained when the 990 Divide tetrachlorethylene by an equal amount of one of the following solvent was replaced; Methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, Trichlorethylene, tetrachloroethane, dichloropropane, 1,1,1-trichloropropane, pentachloropropane, chlorobutane, dichlorobutane, Dichlorohexane, perfluoro-n-hexane, 1,2,2-trifluorotrichloroethane and trifluoropentachloropropane.

The dye used was prepared as follows: 16 parts of 1-dihydroxy ^ - ^ - bromo-anthraquinone was dissolved in a mixture of 75 parts of tert-butyl aniline and 100 parts Grlykolmonomethyläther as long as 100 - 110 ⁰ C heated was stopped until the Färbstoffbildung . After cooling, the precipitate was filtered off with suction, washed with some methanol and water, at 35 - 4O ⁰ C dried. 19.2 parts = 99.7% of the theoretical dye were obtained.

Examples

A knitted fabric made of polyhexamethylene diamine adipate threads is impregnated at room temperature with a clear orange solution containing the ";.-.-. ■" ■

TO parts 1,4-dihydroxy-2- (4-iso-octyl-phenoxy) -

anthraquinone and

7 parts of nonylphenol heptaglycol ether in 983 parts tetrachlorethylene -

contains. After squeezing off to a weight increase of 60 fo , the knitted fabric is ^{dried at 80 °} C. for one minute. The dye is then heated for 45 seconds

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of the knitted fabric fixed to 192 ⁰ C. Then, by briefly treating for about 20 seconds in cold tetrachlorethylene, small amounts of unfixed dye components are washed out. After drying, a clear orange coloration is obtained, which is distinguished by its high dye yield, very good structure and excellent fastness properties, in particular very good heat-setting, washing, rubbing and light fastness properties.

An equivalent coloration was also obtained when in place of the 983 parts of tetrachlorethylene the same amount Toluene, xylene, chlorobenzene, dichlorobenzene, fluorobenzene or benzotrifluoride was used.

The dye used had been prepared as follows: 140 parts of 4-iso-octylphenol and 15 parts of potassium carbonate were heated ^{to 150 ° C. while the water of reaction was distilled off.} After introduction of 32 parts of 1,4-Dίhydroxy-2-bromo-anthraquinone, the reaction mixture was heated to 170 ⁰ C until completion of the dye formation. The reaction mixture was then diluted with methanol and the dye crystallized in prisms was filtered off with suction and washed neutral with hot water. After drying at 4O ⁰ C 41.5 parts = 93 $ of theory were obtained dye.

Example 3

A fabric made of polypropylene fibers is impregnated at room temperature with a clear orange solution which

10 parts of the dye mentioned in Example 2 and

7 parts of nonylphenol heptaglycol ether in 983 parts of tetrachlorethylene

contains. After squeezing on a weight gain of Le A 12 456 - 7 -

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The fabric is ίο 60 for one minute at 8O ⁰ C-getrocknet. is then fixed by the dye for 30 seconds heating the fabric to HO ⁰ C. Brief treatment in cold solvent can wash out unfixed dye components. It. a clear orange coloration is obtained, which is distinguished by a high dye yield, very good structure and excellent fastness properties, in particular very good heat-setting, washing, rubbing and light fastness properties.

Example 4

A fabric made from poly-1,4-cyclohexanedimethylene terephthalate is used impregnated with a clear ruby red solution at room temperature, the

10 parts of 1,4-dihydroxy-2- (4-cyclohexyl-anilino) -

anthraquinone and

7 parts of nonylphenol heptaglycol ether in 983 parts of tetrachlorethylene

contains. After the squeezing off to a weight increase of 60 io the fabric is dried for one minute at 8O ⁰ C. The dye is then fixed by 45-second heating the fabric to 190 -22O ⁰ G. Then the small amount of non-fixed dye is washed out by briefly treating for 20 seconds in cold tetrachlorethylene. After drying, a clear ruby-red dyeing is obtained, which is distinguished by its high dye yield, very good structure and excellent fastness properties, in particular very good heat-setting, washing, rubbing and light fastness properties.

The dye used was as described in Example 1 were produced, only instead of 75 parts were tert -butylaniline 75 parts of M-cyclohexylaniline used.

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Example 5

A fabric made of cellulose triacetate fibers is impregnated at room temperature with a Maren orange-red solution which

10. parts 1,4-dihydroxy-2- (4-iso-octyl-phenyl-thio) -

anth.rach.inon in
990 parts of tetrachlorethylene

contains. After squeezing to a weight increase of 60 io , the fabric is ^{dried at 80 °} C. for one minute. Subsequently, the dye is fixed through one-minute heating the fabric to 215 ⁰ G. A clear orange-red dyeing is obtained, which is distinguished by a high dye yield, very good structure and excellent fastness properties, in particular very good heat-setting, washing, rubbing and light fastness properties.

The dye used was prepared as follows: 16 parts of 1 ^ -dihydroxy-S-bromo-anthraquinone, 14.5 parts of 4-iso-octyl-i-mercapto-benzene, 7 parts of potassium carbonate and 75 parts of glycol monomethyl ether were provided to 110 ⁰ C heated until dye formation was complete. After cooling, the precipitate was filtered off with suction, washed with a little methanol and with warm water and dried at 40 ⁰ C. 21.1 parts = 92% of the theoretical dye were obtained.

Example 6

A fabric made of anionically modified polyethylene terephthalate fibers (Dacron 64 ^) is used at room temperature with a clear orange solution impregnated that

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ία

10 parts of r, 4-dihydroxy-2- (3,5-diisopropyl-phen6xy) -

anthraquinone and ι

7 parts of nonylphenol heptaglycol ether in ^r

983 parts of tetrachlorethylene

contains. After the squeezing off to a weight increase of 60 fo the fabric is dried for one minute at 8O ⁰ C. The dye is then by 45-second heating the fabric at 190 - fixed 22Q ⁰ C. Then the small amount of non-fixed dye is washed out by briefly rinsing with cold tetrachlorethylene. After drying, a clear orange dyeing is obtained which is distinguished by its high dye yield, very good structure and excellent fastness properties, in particular very good heat-setting, washing, rubbing and light fastness properties.

The dye used had been prepared as described in Example 2, only instead of 140 parts 4-iso-octylphenol the equivalent amount of 3 »5-diisopropylphenol used.

Example 7

A fabric made of anionically modified polyamide fibers (nylon T 844 ^) is impregnated at room temperature with a clear orange-red solution which

10 parts of T, 4-dihydroxy-2 ° (2,5 ™ diisopropyl-phenyl-

thio) anthraquinone and

7 parts of nonylphenol heptaglycol ether in 983 parts of tetrachlorethylene '

contains. Daa tissue is fo after squeezing off to a weight increase of 60 a miaowed at 8O ⁰ C and dried

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Dye. - by heating the fabric to 192 C for one minute fixed. A clear orange-red color is obtained, which is characterized by a high dye yield, very good structure and excellent Fastness properties, in particular very good heat-setting properties, wash, rub and light fastness properties.

The dye used had been prepared as described in Example 5, only instead of 14.5 parts 4-iso-ethyl-i-mercapto-benzene'12.7 parts of 2,5-diisopropyl-1-mercapto-benzene used.

Example 8

A fabric made of polyethylene terephthalate fibers is at room temperature impregnated with a clear ruby solution that

5 parts of 1,4-dihydroxy-2- (4-tert-butyl-anilino) -

anthraquinone and
5 parts of 1,4-dihydroxy-2- (4-cyclohexyl-anilino) -

anthraquinone in
990 parts of 1,1,1-trichloroethane

contains. After the squeezing off to a weight increase of 60 io of the dye by 45-second treating the fabric with superheated 1,1,1-trichloroethane vapor is fixed by 14O ⁰ C. The small amount of non-fixed dye is then washed out by briefly rinsing in cold 1,1,1-trichloroethane. After drying, a ruby-red dyeing is obtained, which is distinguished by its high dye yield, very good structure and excellent fastness properties.

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Example 9

A fabric made from poly-1,4-cyclohexanedimethylene terephthalate is used impregnated at room temperature with a clear orange solution which

10 parts 1,4-dihydroxy-2- (2-cyclohexylphenoxy) -

anthraquinone in
990 parts of tetrachlorethylene

contains. After ¹ the squeezing off to a weight increase of 60 io the dye is fixed through 35-second treating the fabric with superheated steam of 150 Tetrachlorethylene ⁰ C. Then, by briefly rinsing in cold tetrachlorethylene, the small amount of non-fixed dye is washed out. After drying, a clear orange coloration is obtained, which is distinguished by its high dye yield, very good structure and excellent fastness properties.

Strong dyeing on fabrics made of polyester, triacetate, polyamide, polyurethane and polyolefin fibers with excellent Fastness properties were also obtained if, instead of the dyes given in Examples 1-9, the same dyes Amount of one of the dyes indicated in the following table was used. The shades obtained are in the given in the last column:

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Example dye

hue

10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25

1,4-dihydroxy-2- (2-methyl-4-cyclohexyl ruby anilino) anthraquinone

1,4-dihydroxy-2- (4-dodecyl-anilino) - - ruby

anthraquinone

1,4-dihydroxy-2- (3,5-bis-trifluoromethyl ruby anilino) anthraquinone

1 _t 4-dihydroxy-2- (3-trifluoromethyl ruby anilino) anthraquinone

1,4-dihydroxy-2- (2-chloro-5-trifluoruby) methyl anilino) anthraquinone

1,4-dihydroxy-2- (3-methyl-anilino) ruby

anthraquinone

1 _f 4-dihydroxy-2- (4-iso-butyl-anilino) ruby

anthraquinone

1,4-dihydroxy-2- (3,4-dimethyl-anilino) ruby

anthraquinone

1,4-dihydroxy-2- (3,5-dimethyl-anilino) ruby

anthraquinone

1,4-dihydroxy-2- (3,4-diisopropoxy red

anilino) anthraquinone

1,4-dihydroxy-2- (4-iso-amyloxy-anilino) - red

anthraquinone

1,4-dihydroxy-2- (2-iso-propyl-anilino) ruby

anthraquinone

1 _t 4-dihydroxy-2- (2,6-diethyl-4-niethyl- ruby anilino) -anthraquinone

1,4-dihydroxy-2- (3-iso-amyloxy-anilino) - red

anthraquinone

1 _t 4-dihydroxy-2- / T- (2-phenyl-propyl- (2)) -

phenoxj [7-anthraquinone orange

1 _f 4-dihydroxy-2- (4- "benzyl-phenoxy) - orange

anthraquinone

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Example color off _ hue

26 1 _f 4-Mhydroxy-2-C4-tert-butyl-phenoxy) - orange anthraehinone.

27 1,4-Dihy <iroxy-2-iionyl-piieiioxy-orange anthraehinone

28 1 ^ -Dihydroxy ^ -Ca-Isopropyl ^ -methyl- orange phenoxy) anthraquinone

29 .1 _l 4-dihydroxy-2-C2-iaopropyl-4-methyl orange

phenoxy) anthraquinone

30 1,4-Mhydroxy-2-C2-bromo-4-iso-oetyl-orange phe noxy) -ant hraeh.in.on

31 1, ^ - Dihydroxy-ii-Caje-iiferom- ^ ieo-octyl-orange phenoxy) -anthraehinone

32.1 ^ -Dlhydroxy ^ -C ^ -eyelahexyl-phenoxy) - orange anthraehinone

33 1 ^ -dihydroxy ^ -CZiss-diethyl-phenoxy) - orange anthraehinone

34 1,4-DihydΓoxy-2- <iodeeyl-ph.enoxy-orange anthraehinone

35 1,4-Mhydroxy-2- (3-XBOPrOPyI-S- orange tert-butyl-phenoxy) -anthraehinone

36 '1,4-dihydroxy-2- (2,4 _> 5-triethyl-orange

phenoxyI-anthraehinone

37 1,4-I) ihydroxy-2-C2-chloro-4-iso-hexyl-orange phenoxy) anthraquinone

38 1,4-Dihydroxy-2- {2 _f 3,5-trimethyl-orange phenoxy) -anthraehinone

39 1,4-hydroxy-2-C4-chloro-3,5-dimethyl-orange phenoxy) anthraquinone

40 1,4-dihydroxy-2- (3-iaethyl-phenoxy) - orange anthraehinone

41 1,4-Dihydroxy-2-C2-isolJutyl-phenoxy) - orange anthraehinone

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Example dye Far Ij ton

42 1,4-dihydroxy-2- (4-tert-butyl-phenyl-orange-red thio) anthraquinone

43 1 _f 4-Mhydroxy-2- (2-ynethyl-phenyl-thio) - orange-red anthraquinone

44 1,4-Dihydroxy-2- (4-methyl-phenyl-thio) - orange-red anthraquinone

45 1,4-dihydroxy-2- (2,6-dibromo-4-iso-octyl-orange-red phenyl-thio) anthraquinone

46 1 _> 4-Dikydroxy-2- (2-chloro-4-iso-oetyl-orange-red phenyl-thio) -anthraquinone

47 1,4-dihydroxy-2- (2,6-dimethyl-4-tert-orange-red buty1-phenyl-thi ο) -anthraquinone

48 1,4-dihydroxy-2- (2,4-diisopropyl-phenyl-orange-red thio) anthraquinone

49 1 ^ -Dihydroxy ^ -Ciso-dodecyl-phenyi- orange-red thio) anthraquinone

50 1 _f 4-dihydroxy-2- (4-benzyl-phenyl-thio) - orange-red anthraquinone

51 1,4-Dihydroxy-2- (2-benzyl-phenyl-thio) - orange-red anthraquinone

52 1 _f 4-dihydroxy-2- (3-isopropyl-phenyl-orange-red thio) -anthraquinone

53 1,4-dihydroxy-2- (2-isopropoxyphenoxy) - orange
anthraquinone

54 1 _f 4 ~ dihydroxy-2- (2-methoxy-4-n-propyl-orange
phenoxy) anthraquinone

55 1,4-I) ihydroxy-2- (2 _t 4-di-selc.-butyl-orange
phenoxy) anthraquinone ■

56 1,4-I) i-hydroxy-2- (2-methyl-4-tert-butyl-orange
phenoxy) anthraquinone

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Example Farias toff, hue

5 * 7- ,. i _f 4- "Dilqrdro ^ -2- (2 _f 4-tert-butyl-orange"-'- ■■■ phenoxy) -anthraquinone

58 - "" "■" ■ 1> 4-Mfaydroxy-2- (2,3-dimethyl-5-tert-orange butyL-phenoxy) anthraquinone

VC

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Claims (2)

Claims 10 J Process for the continuous dyeing of synthetic fiber materials from organic solvents, characterized in that the fiber materials are impregnated with dye liquors, the anthraquinone dyes of the formula (Hal) _m contain, in the Shark a chlorine or bromine atom, X is a sulfur atom, an oxygen atom or a NH grouping, T is a simple G-C bond or an oxygen atom, m is a number from-0 -2 tmd η is a number from 1-3 , and B represents a irifluormethylgruppe or a C ^ -C ^ g-alkyl, cycloalkyl or aralkyl radical _V, with the proviso that the sum total in which the substituent or carbon contained B atoms is of at least 1 and at most 12, and then subjected to a heat treatment. 2) synthetic fibers, dyed according to claim 1. La A 12 456 * 17 - ORKaINAL INSPECTED