DE1619423A1 - Use of disazo dyes for dyeing threads and fibers made from hydrophobic polymers - Google Patents

Description

EASTMAN KODAK COMPANY, 3 ^ 3 State Street, Rochester, New York State, "United States of America

Use of disazo dyes for dyeing threads and fibers made from hydrophobic polymers

The invention relates to the use of disazo dyes of the following formula:

(I)

BN = NR ₁ -HC ₂ H ₄ SO ₂ CH = CH ₂

where mean:

R is an optionally substituted ,, but from vinyl ■ groups of free phenyl radicals

R ^ is an optionally substituted phenyl radical and

R _{2 is} a hydrogen atom, an optionally substituted alkyl radical or an optionally substituted phenyl radical,

for dyeing threads and fibers made of hydrophobic polymers. ■ ■ '1OS02Ö / 192S BAD ORIGINAL

The use of monoazo dyes with a vinyl sulfone group is already known from US Pat. No. 2,784,204. In the known dyes, however, the vinyl sulfone group is always part of the azo component of the dye. Azo dyes of this type are also known from US Pat. No. 2,657,205. With these azo dyes shows the azo component in addition to the vinyl sulfone group a sulfonic acid group.

Those according to the invention differ from the known azo dyes thus used disazo dyes essentially in that they aufitfeisen a vinylsulfonylethyl group, which a constituent of the coupling component of the disazo dye is.

The invention was based on the surprising finding that such dyes are outstandingly suitable for dyeing threads and fibers made from hydrophobic polymers and that dyeings have excellent fastness properties, including excellent lightfastness properties. In particular, the disazo dyes used according to the invention provide considerably more fast colorations than the known azo dyes containing a vinylsulfonyl or vinylsulfonylethyl group.
R.

If / in the given formula (I) has the meaning of a substituted phenyl radical, this can consist, for example

109820/1925

BADORiGiNAL

from an alkylphenyl z..B "an o, m _J prTplylrest; a Alkoxyphenyirest, bZeispielsweise a o, myp ~ Methoxyphenylrestj a Ilalophenylrest, "for example, a ο, ΐη, ρ-Chlorophenylrest; a Mitropttenylrest j, for example, a o, m, p-nitrophenyl radical; a Älkylsulfonylphenylrest _'t for example, a ajmipV-Iethylsuifonyiphenylrest; a AlkylsulfOnamidophenylrest, for example an ο, mjp-Iaethylsulfonamidophenylrest; a di (alkylsuironyl) phenyl radical, for example a 2,5-MCme.tljylsulfonyl) phenyl radical; a DicarboxyIicaeidimidophenylrest, for example a ο, m-succinylluorophenyl, for example a trifylethylphenylphenylphenylphenylphenyl radical; for example an Ojmjp-ÄGet-amidophenylrest j a cyanophenyl radical, for example an o, m, p - cyanophenyl radicalj a carboxamidophenyl radical, for example an Ojmjp-carboxaemidophenyl radicalj a - Benzamidopheny Ire si ;; a thiocyanophenyl radical, for example an o.jmidophenylrest, for example an o.jmidophenylrest hioöyänophenylrest j an ATkylthio phenyl radical, -! for example · - an ο, m, p-MethyIthiophenylrest | a Benzoxyphenylrest, such as a '■ -, Oj.m ^ p-benzoxy' .. j phenyIrest a BenzaminophenyIre st _t be i sp ieIswe is e an o | m, p-Benzaminophenylrest; a Benzylaminophenylresi;, for example a Pjmjp-Benzylaminophenylrest.j a li-r-alkylbenzaminophenylrest, for example an N-Phenylmethylaminophenylrest; a Pörmylphenylrest, for example an o * m, p-Formylphenylrest; a carbalkoxyphenyl radical / for example an Ojmjp-carbethoxyphenyl radical ; a BenzDylpheny-1 radical, such as an o .-, m _> p ~ Ben-zoylpheri.yl, re3t- and the like. ■, - ■ -. .: ■■. ', "■ - - Λ ^: - \"'; /, '.'

1 0 9 8 207 1 9 2 5, _eÄÖ

R ₁ can, for example, be a phenylene radical; an alkylphenylene radical, for example an o, m-tolylene radical; an alkoxyphenylene radical, for example an o, m-riethoxyphenylene radical; a halophenylene radical, for example an o, m-chlorophenylene radical; an alkylsulfonylphenylene radical, for example an o, m-methylsulfonylphenylene radical; an alkylsulfonamidophenylene radical, for example an Ojin-methylsulfonamidophenylene radical j a di (alkylsulfonyl) phenylene radical _t for example a 2,5-di (methylsulfonyl) phenylene radical; a dicarboxyl acidimidophenylene radical, for example an o, m-succinimidophenylene radical; an acylamidophenylene radical, for example an o, m-acetamidophenylene radical; a benzamidophenylene radical; a thiocyanophenylene radical, for example in o, m-thiocyanophenylene radical; an alkylthiophenylene radical, for example an o, m-methylthiophenylene radical; a benzoxyphenylene radical, for example an o, m-benzoxyphenylene radicalj a benzaminophenylene radical, for example an o, m-benzaminophenylene radical; a benzylaminophenylene radical, for example an o, m-benzylaminophenylene radical, an N-alkylbenzaminophenylene radical, for example an o, mN-phenylamethylaminophenylene radical; a Carbalkoxyphenylenrest, for example an Ojin-Carbäthoxyphehylenrestj a Benzoylphenylenrest, for example a ο, ΐιι-Benzoylphenylenrest and the like.

If Rp is an alkyl radical, it preferably contains 1 to H carbon atoms. The alkyl radical can be substituted in the most varied of ways and, for example,

109 8 20/1925 bad original

~ ⁵ ~ 1819423

wise consist of a hydroxyalkyl radical, for example a Hydroxyäthylrestj a polyhydroxyalkyl radical, for example a glyceryl radical of the formula! /"-.CH(OH)CH(OH)Ch ₂ OH _- ?; An alkoxyalkyl radical, for example a methoxyethyl radical; a cyanoalkyl radical, for example a cyanoethyl radical; a cyanoalkoxyalkyl radical, for example a β-cyanoethoxyethyl radical; an acyloxyalkyl radical, for example eifieM ⁱ Ä6et- ' ^L "* ^; 'oxyäthylrest; a Carb.alkoxyalkylrest, for example a Carbäthoxyäthylrest; a haloalkyl radical, for example a chloroethyl radical, a hydroxyhalogenoalkyl radical, for example a β-hydiOxy-Y-ehloropropyl radical, an alkylsulfonylalkyl radical, for example a methylsulfonylethyl radical, an alkyl-OCOOCHpCHp radical, for example a radical of the formula CH-OCOOCH ₂ CH ₂ ; a carboxamidoalkyl radical, for example a carboxamidoethyl radical, a benzyl radical or a phenoxyalkyl radical, such as, for example, a β-phenoxyethyl radical; a cyanoalkyl radical, for example a β-cyanoethyl radical; an Alkylsulfonamidöalkylrest, for example a JWethylsulfonamidoäthylrestj an Alkylcarbonamidoalkylrest, for example an Äthylcarbonamidoäthyirest; a Dlcarboxamidoalkylrest, for example a ß-Dioarboxamidoäthylrest and the like.

R ₂ has the meaning of an optionally substituted phenyl radical, this may have the same meaning as R or R _1, that is, for example, an alkylphenyl group, or consist of an alkoxyphenyl.

BATH

0982071925

The substituents of the radicals R, R ₁ and R ₂ are not critical but act primarily as auxochromic groups and control the color of the dye molecule.

The disazo dyes used in the present invention can be by coupling known diazonium salts with a vinylsulfonyl Coupling components containing ethyl group of the following formula ί

(II)

' ^R 2

produce. In the given formula (II), R ₁ and Rp have the meaning already given.

Coupling components of the formula (II) can easily be produced by the following process:

NN + CH ₂ = CHSO ₂ CH = CH ₂

₂ CH = CH ₂

The disazo dyes used in accordance with the invention are suitable for dyeing threads and fibers made from the most varied synthetic polymers and color them in a wide variety of shades, especially red, orange, yellow and purple Shades, whereby they are made up by customary dyeing methods.

109820/1925 bath

can be colored. The new, disazo dyes have it a particularly good affinity for threads and fibers made of cellulose esters and polyamides. The colorations achieved have excellent fastness properties, in particular excellent lightfastness, s-> Leak fastness, gas fastness and Sublmation fastness properties.

I. Preparation of vinylsulfonylethylaniline couplers

a) Production of 1 \ f-Ethy 1-N-ß-vinylsulfonylethy! aniline of the formula! ;

23.6 g of divinyl sulfone, 2 ^, 2 g of N-ethylaniline and 105 ml of toluene were refluxed for two and a half hours of 0.75 mm distilled over at a temperature of 16? - 183 ° C.

Production of.N-Ethyl-N-ß-vinylsulfonylethy1-m-toluidine of the formula: _ -. '■ ";."■' / ■ -. - _: .'-

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27 g of N-ethyl-m-toluidine, 23.6 g of divinyl sulfone, 5 ml of acetic acid and 100 ml of toluene were mixed together and under Stir at reflux temperature for 12 hours. Afterward The solvent was distilled off under reduced pressure. The desired coupler passed at a pressure of 0.35 mm at a temperature of 157 - 159 ° C above.

c) Production of N-ethyl-N-vinylsulfonylethyl-m-chloroaniline the formula:

C ₀ H ,. SO ₀ CH = CH

²⁴²

According to the method described under b), the coupler from a solution of divinyl sulfone, N-ethyl-m-chloroaniline and toluene.

Preparation of N-ß-hydroxyethyl-N-ß-vinylsulfonylethyl-m anisidine of the formula:

According to the method described under b), the coupler starting from a solution of divinyl sulfone, N-ß-Hydroxyäthyi-m-anisidine and toluene.

1 0 9 8 20/1925 BADORiQiNAL

II. Preparation of the dyes example 1

Preparation of a dye of the formula:

Concentrated to a solution of 1.44 g of sodium nitrite in 10 ml Sulfuric acid was 20 ml of an acid mixture consisting of from 1 part propionic acid and 5 parts acetic acid was added. The solution was then 3 »94 g of p-phenylazoaniline and Another 20 ml of the acid mixture described was added. the The solution was then stirred for 2 hours and then added to a solution of 5.06 g of N-ethyl-N-ß-vinyisulfonylethyl-m-toluidine added in 200 ml of the acid mixture described. The coupling solution was then made by adding solid ammonium acetate neutralized to Congo red paper and left to stand for 2 hours. The reaction mixture was then washed and washed filtered, whereupon the filter residue was dried. Of the Dye colored threads made from commercially available polyamides (nylon), cellulose acetate and polyesters in strong orange shades excellent fastness properties.

example 2

Manufacture of a dye for the mold

1 0 9 8 2 0/19 2 5

BATH ORIGINAL

Ι6Ί94

CH ₃

10 ml of an acid mixture consisting of 1 part propionic acid and 5 parts acetic acid were added to a solution consisting of 0.72 g of sodium nitrite in 5 ml of concentrated sulfuric acid. Then 2.25 g of 4-amino-2 ¹ , "3-dimethylazobenzene were added and then 10 ml of the acid mixture described. The solution was then stirred for 2 hours and then converted to a solution consisting of 2.39 g of N-ethyl M-ß-vinylsulfonylethylaniline, added in 75 ml of the acid mixture described. The coupling solution was neutralized against Congo red paper by adding solid ammonium acetate and left to stand for 2 hours, after which it was washed and filtered. The filter residue was dried. The resulting dye stained threads and Fibers made from polyamides, cellulose acetates and polyesters in strong orange tones.

Example 3 ·.

Preparation of a dye of the formula:

// W ^ ^C 2 ^H i » ^S0 2 ^CHsCH 2 -N = N- (Z ^X \ -N

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A diaiizoniuin solution prepared as described in Example 1 was added to a solution consisting of 5.46 g of N ^ ethyl-M-vinylsulfonylethyl-m-chloroaniline and 150 ml of the acid mixture described. * The coupling solution was then added by adding ammonium acetate neutralized against Congo red paper and left to stand for 2 hours "The coupling solution was then washed"; filtered off and the filter residue * dried. The dye obtained dyed "threads and _: fibers made of polyamides / cellulose acetates and polyesters in deep orange shades on V '-"_'_'--

Example 4 ;; '";". ■ _: V-:

Preparation of a: dye of the formula:;

O
CH ₃ CNH

-N-N - ^ .- ΛΥ-Ν-Ν - ^. "- ■ -; M-N

.. OCH

C ₀ Hj ₁ SO ₀ CH = CH ₀ 2 4 2 2

3.14 g of S'-acetamido-il-am ^^

dlazotiert according to the method described in Example 2. pie diazonium solution was then a solution of 2.53 S N - * - Ethyl-N-ß-vinylsulfonylethyl-m-toluidine in 100 ml ^ of the acid mixture described was added. The solution obtained. was compared to Congo red paper by adding ammonium acetate neutralized and left to stand for 2 hours. The coupling solution was then washed and filtered, whereupon the "filter trickle." would be dried

^; 109820/1915 ^

IbI94 23

The dye obtained dyed threads and fibers made of polyamides and polyesters in deep red shades with excellent fastness properties at.

Example 5,

Preparation of a dye of the formula:

-N = N - // YS-N = N-,

C ₂ H ₁₁ SO ₂ CH =

4.62 g of 4-AmInO-S-ChIOrOaZObBnZOl were prepared according to the method described in Example 1 diazotized process described. The diazonium solution obtained then became a solution of / 5.06 g of N-ethyl-N-ßvinylsulfonylethyl-m-toluidine added in 200 ml of the acid mixture described from acetic acid and propionic acid. the Solution was then neutralized to Congo red paper by adding ammonium acetate and allowed to stand for 2 hours. The coupling solution was then washed and filtered, whereupon the filter residue was dried.

The dye obtained dyed threads and fibers made of polyamides in strong red shades with excellent fastness properties on »

ORIGINAL 10 9820/1925

Example 6

Manufacture of a dye for the mold

2.25 g of ^ -Ämino- ^ ¹ , 3-dimethylazobenzene were diazotized according to the method described in Example 2, whereupon the resulting solution to a solution of 2.86 g of N-ß-hydroxyethyl-N-ß-vinylsulfonylethyl-m -anisidine in 50 ml of the acid mixture consisting of propionic acid and acetic acid was added. The solution was then neutralized against Congo red paper by adding ammonium acetate and allowed to stand for 2 hours. The coupling solution was then washed and filtered, after which the filter residue was dried.

The dye obtained dyed threads and fibers made of cellulose acetate en and polyamides in strong red tones.

Examples 7-26

Manufacture of dyes of the formula:

_{= N} / ^ \ _{N = N} .R y

^R 2

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" ¹⁴ ~ 'IbI 9423

Further disazo dyes of the formula indicated were prepared by the processes described in Examples 1-6. To prepare the dyes, diazonium salts were used with vinylsulfonylethylaniline couplers of the formula (II) given. coupled «The following table shows the more precise composition of the dyes produced.

109820/1925

example

, ',: ΝΓ, ■■

Azobenzene components

Substituents; am ·.,: Sübs tit ueji ten am.; ■, ■, Ring A ',.'. ■ / ■ ...:, ". ■■;. ■.. Ring · 3 '^1;y.;" .

Vinylsulfonylethylaniline Coupler '

■■ &,

Shade, on ^: P Q.ly aiTii df äden; '

■ 25

26th

2-CH _3. ■, ■ ',';,
3> Acetamido ,, '■■
S'-hydroxyethyl

10
- ■ '.11 Vv- ^CH 3, ■■: ■■■
4-CH " ¹ V ,; 12 ' V ^ 'V,'; ¹ ^, / -. ":. 4-CH ₃ ;. ■■ ·: ■; ■ ■ ■ / ■ "■■■ v ' ^: ä' | * ,: : ■■, ': .. "'''" V '/ " ^: ''^:'' ■■■■ 'S ^a6 4N- (C ₂ H ₄ OH) ■■ '■' '-J 18 , 4-COCH, 4-OCH-
< oil 20 ., ^; '21' :, none. , ''. ' ■ 2: 2 ,,; ;, none ';. . ■■■■ EtJ- ^: / V .23 · V :. ■■■ '■; none ■■. 1
O
to ■ / ·: ■ ZK ■■■■ '. ■', Vnone, ".. '. ^: , Q ¹ ,

none

none

2-oiiloro,; ■ none '· ^; 'none'. ·

none

3 " ^CH 3 .. ',

^:; "■ '■. 3' ¹ .. 2,5-di- (

, none-

none

none

none '

none

none

IU-toylene phenylene.

len .- ', _ra-3 -phenyl QCH: ^{iii-tolylene,::} m-ci-'Phenylen phenylene m-Tolyien ■ ■■.

.m-IOlylen; '. m-tolylene

, m-tolylene,.

m-iölylenV o-Tolyien

C ₂ H ₄ Cl

-C ₂ H ₄ OCOCH ₃ , ■

-C ^ ₁ OCH _n ,,,; ,,

₂ H ₄

.C ₂ H ^ sO ₂ CH ₃ ■■■■ ',.

CO-CH,

CO-CH,

-C ₂ H ₄ OCONH ^ / V;

hydrogen

/ Orange V

Violet Violet Orange Red "Orange Orange, Violet Red ■■ '■■,, ^:

Red; , ·

Yellow ■ '■; Red . , Red-orange, orange Orange orange,

Orange ^:

; orange

yellow

III «dyeing process

The new disazo dyes used according to the invention leave on threads and fibers as well as textiles made from linear polyesters, cellulose esters, acrylonitrile polymers, Coloring polyamides and the like by methods such as those used, for example in U.S. Patents 2,880,050; 2,757,064; 2,782,187 and 2,043,827 are described.

For example, a polyester fabric can be used in the following manner
be dyed with the disazo dyes used according to the invention:

0,1.g one of the dyes used in the invention is dissolved in a Färbetopf by heating in 5 cm ^J Athylenglykolmonomethyläther. Then enough of a 2% strength sodium N-methyl-N-oleyl taurate solution and a 0.5% sodium lignosulfonate solution are added to the solution until a

fine emulsion is obtained. Then there is slowly so much water

• 5

added until a total volume of 200 cm ^{J is} reached. Then 3 cm ^ of an emulsion consisting of chlorinated benzenes (Dacronyx) are added as a carrier. In the
The resulting liquor is then added to 10 g of a fabric made from polyester threads (Kodel). First, the tissue is 10 minutes
long in the fleet moved without the application of heat and after ~ 10 minutes at 8O ⁰ C. Subsequently, the dyebath on-
Boiling temperature, whereupon it was dyed for 1 hour while boiling «The fabric was then washed with warm water _

109820/1925

BAD ORiGJNAL ■

rinsed with an O, 2 $ aqueous soap solution and a 0.2- ^ igen soda solution treated. Then the Fabric rinsed again with water and dried.

Since the disazo dyes used according to the invention are water-insoluble They can be colored from aqueous dispersions in the manner of so-called disperse dyes. The dyes However, they can also be used for the manufacture of spider-woven fabrics Threads and fibers are dispersed by making the spinning roots be incorporated.

The disazo dyes used according to the invention are particularly suitable for dyeing threads and fibers made of polymeric linear polyesters of the so-called terephthalate type, such as in U.S. Patents 2,465,319; 2,945,010; 2,957,745 and 2,989,363. Such threads, Fibers and yarns are under the trade names Kodel, Dacron and Terylene in trade. The dyes used according to the invention are of particular importance for coloring such linear aromatic polyesters that have melting points of at least 200 ° C. . .

The new dyes are also of particular importance for dyeing threads and fibers made of polyamides, for example those from ε-caprolactan as well as adipic acid and hexamethylenediamine, which are known under the trade drawings Perlon and nylon are available in stores.

- 109 820/19 2 5

Claims (1)

Claim / use of disazo dyes of the following formula: WOr ¹ In mean: - R is an optionally substituted but vinylsulfonyl group free phenyl radical; R _{1 is} an optionally substituted phenylene radical and R _{2 is} a hydrogen atom, an optionally substituted alkyl radical or an optionally substituted phenyl radical, for dyeing threads and fibers made of hydrophobic polymers. SAD ORiGiJSJAl