DE1644399A1 - Process for producing dyes - Google Patents

Description

Dr. Ing. E. BERKENFELD · Dipl.-Ing. H. B ERKEN FELD, patent attorneys, Cologne Attachment file number

for input of i? 6.8.1964 CS / name d. Note Thö Yorkshire DyeWÄTe

& Chemical Company Limited

Black Bull Street,

Leeds 10, Yorkshire / England

Process for making dyes.

The invention relates to new disperse dyes, the production and the dyeing of fiber products, especially synthetic polyester fibers and cellulose triacetate fibers.

Synthetic polyester fibers, of which those under the trademark "Terylene" put on the market polyethylene terephthalate which are known to be dead have the valuable property that they have their internal properties through a heat treatment Structure in the catfish change that by a heat treatment Wrinkles and folds formed on a fabric made of polyester fibers through pockets or use cannot be easily removed, and at the same time the fabric resists the formation of new undesirable wrinkles. Such Fibers are mostly dyed or printed with disperse dyes; these dyes are practically insoluble in water and are applied to the fiber from aqueous bispersions containing the dye in a finely divided state. Many of the currently used disperse dyes volatilize when textiles are heat treated in one

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undesirable dimensions / so that fabrics dyed with them suffer undesirable and uneven changes in color shade, for example when ironing, and adjacent white parts and the apparatus used for ironing can become stained. The same difficulties can arise if, at high temperatures, diapertiionic fibers, color, and buckling of synthetic fibers are fixed by cracks in the dry tissue.

Nitro derivatives of Dipnenylamin weraen used as üispersionsfarbstoffe Zuni Golbfärben synthetisciiei ¹ fibers. The GI Disperse Yellow 'J;. SU the ² i ^ rnino-2 ^l, 4 ^l -aixiitrodi phenyl result uxid deep yellow stains on vernäitnismäßiti Although such simple dyes scnne siüii 11 "build" in, but they have ate technical disadvantage that they sublime at the therapeutic units used for the heat treatment given above.

Monoazo compounds, which are very slightly soluble in lasser, are largely the target of sctiarlaen-red and violet hues used, but many otherwise suitable yellow and orange monoazoverbinuuniieu i-eicen one tiolchea ineffective phototropism that it cannot be brewed 3lnd. Phototropism is a clear one temporary change in color caused by brief exposure to sunlight or other bright! light source and the color is restored more or less quickly if the dyed material is kept in the dark stored Other yellow and orange colored monoazo compounds

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t ORIGINAL BATHROOM

fertilizers that do not have the disadvantage of phototropism are unnecessary at the temperatures that are suitable for the final thermal treatment of thermoplastic fibers. Other yellow uric orange dyes of various chemical structure, the volatility of which is low, are available, but their "build-up" ability is limited so that they do not give deep tints under the usual dyeing and printing conditions. As a result, it has not been possible to date deep golden yellow and lightly colored tints that are sufficiently strong to be achieved on polythene terephthalates and similar polyester fibers. Ä

It has been found that with the dyes of the formula below polyethylene terephthalate and cellulose triacetate under Achievement of orange-brown, gold-yellowcr and yellow-brown or scarlet tint can be obtained, and that these dyes Sublimate to an insignificant extent at the temperatures required for flattening, fixing and the like come to treat textiles infrace; these dyes have the general formula:

NH < V-- Y ¹ (D.

in which Y denotes -N = NA or hydrogen, i ¹ "is hydrogen when Y ¹ -N = NA iatjUnd -Ii-KA when Ϊ ¹ denotes hydrogen, and in which Y denotes a nitro group or the group

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both how

-30 ,,. NR ¹ R ² means in which R ¹ - «* R ^{2 is} hydrogen or alkyl

nd

groups, especially 1 to 4 carbon atoms, have lower Are alkyl groups which cannot be substituted or substituted, for example by a hydroxyl group, or the group SO ₀ AIk, in which Alk is one to 4 carbon atoms alkyl and A is the radical of a phenol or aromatic amine coupling component.

Oils invention relates to the production of new dyes General formula I given above.

The invention also relates to a process for dyeing or printing synthetic thermoplastic fibers of the polyester type or of cellulose triacetate, in which the dye is a disperse dye of the general formula I given above.

The invention also relates to a process for the preparation of the dyes of the general formula I given above, in which an aminontrodiphenylamine of the general formula

NH

NO ₂ Z ²

is diazotized, in which X has the meaning given above,

1 2

ΊΓ is hydrogen or an NHg group, and Z is hydrogen is when Z is NH ₂ , and an NH ₂ group when Z is hydrogen, and the diazo compounds thus formed with

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BATH ORIGINAL

an aromatic hydroxy or aromatic amine coupling component be coupled.

Suitable aromatic hydroxy components are phenolic compounds « e.g. phenol «naphthols, especially ß-naphthol, the Cresols and the phenylphenols. These coupling components result gold-yellow disperse dyes,

Suitable aromatic coupling components are a.B. such, which is the general formula

(in)

to have,

in which R is hydrogen or a low molecular weight alkyl group, especially methyl means, for hydrogen, a low molecular weight alkyl group »especially methyl, a low molecular weight HydroxylalkyIradikal, especially hydroxyethyl, a low molecular weight Cyanalkyl radical, especially cyanoethyl, or a R ^ - radical means in which η is an integer

. ο

is from 1 to 4, especially 2, and R- * is a monovalent hydrocarbon substance radical, especially a low molecular weight alkyl

radical, such as methyl, and R «denotes hydrogen, a low molecular weight hydroxylalkyl radical, especially hydroxyethyl, or a (CH ₂ ) _n -0-g-R5 _{radical of the} ones indicated above

Kind is.

009834/1516 BAD ORIGINAL. ₅ _

The invention is described in more detail in the examples:

Example I.

If> parts of 4-AmInO-S ¹ , 4'-dinitrodiphenylamiii, 200 parts of water and 82.1 parts of aqueous hydrochloric acid (35 %) were stirred together at 0 to 5 ° C in a suitable, glass-lined container .

A solution of 4 parts of sodium nitrate in 60 parts of water was then slowly added over about 2 hours. The reaction mixture was stirred for 12 hours and the temperature was allowed to rise to 1;> ^O C during (reading time; then i) 00 parts of water were added and the yellow diazo solution was freed from insoluble impurities by filtration. The filtered solution was then slowly stirred, with rapid stirring, of a solution of 10 parts of orthophonylphenol and cooled to 0 ° C. by adding ice. 30 parts of sodium hydroxide in 1QQ parts of water are added. The azo dye thus formed separated out as an orange-colored precipitate which was filtered off, washed and ground with a formaldehyde / cresol sulfonic acid condensation product which is sold under the trademark "Dyapol PT".

The dye can be used on polyester fibers, it gives golden-yellow colors, namely from a boiling water bath containing, for example, dichlorobenzene as a carrier, or in pressurized vessels at X2 ^k j up to 14 ° C or by padding an aqueous dispersion the fabric, which is dried and then heated to 200 ° C for 30 to 60 seconds.

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BATH ORIGINAL Example II

Hs was prepared from I ^ parts of 4-amino-2 ^f -iiitrodiphenylamin-4 acid ^t -sulfonli-butylamiu, 'jh parts of concentrated hydrogen chloride and li? O parts of water a diazo solution by stirring at 0 ° C and then JQ parts of an aqueous 10 Sodium nitrite solution added. After stirring for 12 hours, ISO parts of cold water were added and the diazo solution was filtered and allowed to run into a solution cooled to 0 ° C. which contained ¹ J parts of para-cresol, 22 parts of sodium hydroxide in 100 parts of water.

The monoazo dye which separates out dyes polyester and cellulose acetate fibers golden-yellow.

Example III

Ib parts of 4-AmInO-S ¹ , 4 * -dinitrodiphenylamine were diazotized as in Example I and the filtered diazo solution was rather quickly a solution of 8.6 parts of N-ethyl-N-hydroxyethyl-m-toluidine in a cooled to 0 ° C 600 parts of water "is added containing 12 parts of concentrated hydrochloric acid (Jb%) *, as were then 5 parts sodium acetate were added and the mixture stirred ..well, anda aqueous, ice-cooled Natriumhydroxydlosunü slowly added, the pH at t> urn to bring up to the 6th

The monoazo dye which separates out dyes polyester fibers orange-brown

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BAD ÖfiiöiNAL

Example IV

* Are, 4'-dinitrodiphenyl amine · PY parts ^ -amino-S'jV-dinitrodiphenylarain when used in Example I instead of 4-amino-2 'is obtained, a similar golden-yellow dye.

Claims

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Claims (4)

Claims 1 »Process for the preparation of dyes of the general formula NH- / VY ¹ U) Y ² in which Y -N = * N-A or hydrogen means, 1 Y is hydrogen when Y is -N = N-A and -N «N-A when Y is hydrogen, A is the residue of a phenolic or aromatic amine coupling component, or ■ η ο X is a nitro group the group -SO ₂ NR R in which 1 2 R and R are hydrogen or substituted or not substituted alkyl groups, especially those having 1 to 4 carbon atoms, or the group SOpAIk, at most in the alk one aa 4 carbon atoms having Is an alkyl group, characterized in that an aminonitrodiphenylamine of the general formula Z ¹ (II) 009834/1516 diazotized, in which X has the meaning given above, Z is hydrogen or an NH ₀ group, 2 1 Z is hydrogen when Z is an NHg group, and one NHg group means, if Z. <Is hydrogen, and the thus formed diazo compound with an aromatic one Hydroxy or aromatic amine coupling component couples. 2. Method according to claim 1, characterized in that the aromatic hydroxy component is a phenolic compound, j5 · Method according to Claim 2, characterized in that the aromatic hydroxy compound is phenol, a naphthol, especially β-naphthol, a cresol or a phenylphenol. 4. The method according to claim 1, characterized in that the aromatic arairi coupling component the * 'ormel; has, in which R is hydrogen or a low molecular weight alkyl group, especially a methyl group, R- 'hydrogen, a low molecular weight alkyl group, especially an ethyl group, a low molecular weight hydroxylalkyl group, especially a hydroxyethyl group, a low molecular weight
Cyanalkyl group, especially a cyanoethyl group, or a ) -o-C-R - ^ - group means in which η is an integer of 0 0 0 9 8 3 4/1516 BATH ORIGINAL 1 to H, especially 2, and For a monovalent hydrocarbon group, especially a low molecular weight alkyl group and R hydrogen, a low molecular weight hydroxyalkyl group, especially a hydroxyethyl group, or the above means defined - (CH ₂ ) _n -0-CR ^ group. - 11 - 009834/1516 BATH