DE1619408A1 - Process for coloring and printing structures made of metal-modified polymers of unsaturated hydrocarbons - Google Patents

Description

PATENT ANWAT-TE - ·

DR. MO!.! '! ; -nORß SäSlJlli 1 R 1 Q £ Π R

UiV L, ING. Cj: -: al.:·:■ ;. Γ.'R. MANITZ

6MONCHENEa ₁ KOLtRT-KOCH-STaI ■

TEi. £ FON 225U0

3. K ο ν,

Durand & Huguenin A.G. » Basel

Process for dyeing and printing structures metal-modified polymers of unsaturated fillets · »

hydrogen

The present invention relates to a method for dyeing and printing structures made from modified polymers of unsaturated, in particular textiles, made from metal-modified polypropylene.

It is bsksnntp that »the Fg

from polymers of unsaturated RdS & ice? a $ eerstdff m is associated with borrowed difficulty to «brewable

209812/1635

Genes are obtained in technology when metal-modified polymers of unsaturated hydrocarbons with Dyes are colored which contain metal-binding groups, but which are free of other water-solubilizing agents Groups are.

The metal-binding groups are capable of the dyes only in external sewing cases, e.g. with a small one The molecular weight of the dye molecule is a satisfactory one To confer water abilities. To level and to produce strong colorations "one is mostly forced * to color metal-modified ones to this day Polymers of unsaturated hydrocarbons known dyes either in an organic Solvent dissolved or finely dispersed in water to be applied. Both procedures are substantial Associated disadvantages. Well the use of organic Solvent special dyeing machines «as well as a solution to regenerate and As a result, operational safety poses major problems. Such procedures have not been found in practice be able to penetrate.

The production of dyes that can be finely dispersed in water has to be done by consuming and costly grinding with the use of dispersants take place. Processing presents particular difficulties

209812/1635 bath

processing into perfectly dispersible powders. But the use of such dyes is also different Unsatisfactory. An addition of dispersants and / or (liver carriers) to the dye bath is essential. When dyeing tightly packed material, For example, spools of thread or wound fabrics, flltratlonsphenoroene can occur. ”Another The disadvantage of the finely disperse dyes is that that the cleaning of the equipment soiled by water-insoluble dye particles is cumbersome.

It has now been found that there are structures made of metal-modified polymers of unsaturated hydrocarbons därbenjund can print if you can the structures with aqueous solutions of organic dyes that contain at least one detachable, water-oil-producing group and at least after this group has been split off, contain at least one metal-binding group and the are free from other water-soluble groups, treated under conditions which lead to the cleavage of the water-solubilizing agents Lead group «The procedure permitted, on the formation of metal-modified polymers more unsaturated Hydrocarbons, especially on textile fibers made of metal-modified varnished polypropylene, with water-soluble ones Dyes without the addition of dispersants and carriers are real, strong and level colorations

209812/1635

1619A08

and produce prints. The procedure thus represents represents a significant technical port step.

Under structures «ind non-textile moldings, such as films and foils, but preferably processing forms suitable for textile purposes, such as staple fibers, Yarns, fabrics »knitted fabrics, etc., to understand»

The metal-modified polymers of unsaturated hydrocarbons are polyolefins, such as polyethylene, polyisobutylene, polymers of sterol and polymers of allyl. VinyJ "and Vi i \ yl idenverbi inventions * inso but sondere polypropylene into consideration tile Yex'bindungc ι polyvalen- ■■ fiv metals such as magnesium, Zinl: _r, copper, vanadium, Elsen, Oh-om, cobalt, before axlem but aluminum and Nir. "el _n homogeneous distribution anthalten" deeignete riecallverbindungen are beiepielf ^ eiae the oxides, salts un ^ complexes of fatty acids, PhenoZatan and Uithiocarbamate ¹ :: Such metal compounds may be the structures of polymers of unsaturated hydrocarbons in any phase of the Herateilungsverfahrens incorporated into the order.

The appropriate method for the erfindungsgemlisse organic dyes with respect to the coloring system the most diverse class '' ■: belong sen, such as the nitroso - nitro azo, forma Ianthen- and Anthrachinonferbstoffen Gpoignet..

2 0 9 812/16 35 BAD original

are also dyes that contain two different types of chromagens, such as Azonitroaofarbatoffe, Duron Mixing different dyes, shades of all kinds can be obtained. The water-soluble dyes but you can also use finely dispersed dyes to « can be used together for hi-fi tones.

The groups which have become known to date come into consideration as cleavable, water-solubilizing groups. the Cleavage of the water-solubilizing groups can occur on the most diverse reaction principles are based, e.g. on a transamidation, decarboxylation or hydrolysis.

Groups which make water soluble are mainly to be understood as meaning strongly dissociating groups. These are mainly the acidic groups of the sulfur _s like the SuIfo-, SuIfato-, SuIfaminogruppen and onium groups, such as sulfonium, Isothiuronium-, quaternary ammonium group. However, less strongly dissociating groups, such as the acidic groups of phosphorus and carbon, as well as non-dissociating groups, such as glucoside and polyethylene oxide groups, are also suitable. Dyes with several, but preferably with only one, removable, water-solubilizing group can be used.

Some such examples are given below Groups listed:

209812/1635

-080, B, -SSOxH, -HHSO ₅ H ₁ -IIHCHgSOxH, -CHOH-SO ₅ H,

-OCOCHOlSO ₅ H, -OCOO ₆ H ₅ (SO ₅ H) ₂ , -OPO ₅ H ₂ , -AHPO ₅ H ₂ ,, -8O ₂ CH ₂ COOH, -OCOCHgl ^ CCHj) ^, CH ₅ ) j, - OCOC ₆ H ₄ H ⁺ (CHx) ₅ , -COCH ₂ S ⁺ (CHj) ₂ , Y also derivatives of sulfopnt / alimide and and groups ₇ as they are formed by addition of biaulfite to certain dyes.

Metal-binding groups include those which can form salsal or complex-like compounds with metal, such as hydroxyl, amino, carboxyl, sulfonamide groups. But are particularly suitable as chelating agents? Groups which, thanks to their particular atomic arrangement, can easily form several annulled or preferably a five- or six-membered ring with metals. Numerous dyes with a wide variety of chelating groups have been proposed to date. Such groups are, for example, the o-hydroxycarboxy, o-dihydroxy-8-hydroxyquinoline, 4-hydroxybecsthiaeol, 4-hydroxybeneoxacolone, 7-HydrozTindasol-, 4-hydroxyacridine, o-hydroxyketone, o-Hydrozyaldehjd-, o -Hydroxjraldozim- «o-Hydroxynitroso-, l-Hydrozyanthraohlnon-, 1-Amlnoanthraquinone-, o-Hydroxyaeo-, 0,0 * -Dihydroxyaio-, ο, ο '-Dihydroxyaaome thin-, o-Hydroxyo'-carboxyaso-, o -Hydroxy-o ⁹ -aminoaso group, also azo-

209812/1835

groups that contain a heterocyclically bonded nitrogen atom in ortho- or peri-division. Suitable auch'solehe groups _s that are performed during the dyeing process in a · metal binding group as © s, for example, when the Schwefelsäureester hydroxyquinoline the case. Both dyes with a single group and with several metal-binding groups are suitable for the process according to the invention.

The arriving for applying dyes shall definitionsgemäSB addition to metallblndenden and cleavable, water-solubilizing groups no further wasserlösliohmachenden groups include, in particular no strongly dissociating groups such as sulfo ~ and onium groups. ₅ In contrast, the dyes without a negative part can contain a small number of weakly dissociating groups. In addition to the previously mentioned groups may contain dyes further customary in organic dyes groups include those which increase the _f Dlffusionsvermögen, such as alkyl groups.

To date, only a few dyes have become known which correspond to the definition given above, but suitable dyes can be produced in large numbers by processes known per se.

The structure made from polymers of unsaturated hydrocarbons is, in terms of dyeing and printing, according to the invention

£ 01812/163 5

BATH

with an aqueous solution of the color defined above Treat fabrics accordingly. The treatment consists of applying the aqueous solution and simultaneously or the subsequent dyeing process.

. In order to obtain optimal dyeing conditions, the material to be dyed can, as usual, be pretreated to remove interfering foreign substances such as oils and metal salts be subjected. This does not exist, for example, in an alkali treatment at pH 8.0 - 9.0 in the presence « ionic detergent and sequestering agent followed by rinsing.

The aqueous solution can be applied by a wide variety of methods, for example by dipping the material, by spraying it on, On drops or brushes on the dye solution, if necessary using stencils. For textile materials, the usual dyeing and Printing process in question, for example, Ausieh-, Klotz- « Pflatsch, whale printing and film printing processes.

The actual dyeing process consists in subjecting the material with the applied dyeing solution to conditions which cause the water-soluble group to be split off and the resulting dye to diffuse into the material. The split and the diffusion take place with advantage in a single

209812/1635 bad orig.nal

Process stage · They can, however, also be carried out in successive stages. Experience agemäas Strongly dissociated dyes have practically no affinity for hydrophobic materials. Therefore are before especially suitable dyeing conditions that suppress dissociation of the dye. For the procedure suitable metal-binding groups usually have medium to weak acidic character. Furthermore, those formed by the cleavage reaction can also be used Groups and any groups already present in the dye molecule react in a weakly acidic manner. Ss has therefore it has generally proven advantageous to keep the color neutral or in the presence of acidic ones Make connections. In order to split and diffuse the dye in a single process « To be able to carry out stage, those dyes are suitable for dyeing in an acidic medium that are acidic removable, water-solubilizing group. Calibrated conditions have proven to be particularly advantageous, among which the dye, which is sparingly soluble in water, follows Kaeeegabe its creation is absorbed by the polymer.

Inorganic acids, such as sulfuric acid, and, for example, come as acidic compounds organic · acids, such as ants * and acetic acid, as well as acid · sals · such as sodium hydrogen sulfate. Wan

209812/1635 _BÄD

but can also admit neutral connections, which acidic by thermal and / or hydrolytic cleavage are, for example, ammonium salts such as ammonium chloride, ammonium sulfate, and esters with inorganic or organic Acids, * Λ · dimethyl sulfate, ethyl formate, diethyloxalate, Diethyl tartrate.

The dyeing temperature is to be chosen so that on the one hand the cleavage and diffusion takes place at a practically acceptable rate and on the other hand that the temperature is below the melting point of the polymer. The heat transfer can take place by means of convection, contact, radiation or condensation, preferably by heating the dyebath, by steaming or a dry heat treatment. Temperatures between 50 and 140 ^° C., especially between 90 and 130 ^° C., have proven suitable for dyeing polypropylene. The process can be carried out under atmospheric pressure or under excess pressure. The dyeing time is not critical and depends on the dyeing conditions and equipment. The process according to the invention can be carried out both batchwise and continuously on conventional dyeing machines.

The aqueous solution of the definition In addition to the compound that favors the splitting off of the water solubilizing group, dyes can be used against

209812/1635 bad ORIGINAL

■ - 11

if necessary, the usual dyeing and printing auxiliaries can be added. Sole auxiliaries are sB the water solubility increasing Substance® ₉ wi © urea, üJhioharnetoff, diethylene glycol, Taiodiiltiiylenglykol, substances that act as a solvent for the dye produced by the splitting reaction and / od®? Increase the absorption capacity of the polymer by swelling, such as benzyl alcohol, isophorone, o-phenylphenol, chlorobensol, diphenyl ether, aromatic carbonic acid residues, bispergants and emulsifiers, such as lignin sulfonates, additive products and carbonic acid products from higher alcohols and ethoxylic acid sulfide products @n _$ thickener _% such as alginates, inductiongtiei * alkyl cellulose ^ starch derivatives, sequestri @ nidttel, wi @ Aethjlsndiamint®tra · "© ssigs & urejfitrilotrießsigsliir®, Fol ^ hoephater". Tartrat®, weak oxidizing agents like teraeidiang ψ @ & Hsduktlons «ersoheinungen, such as m-HitrobenEol @ ulfonslu? ® _f as well as Snt-building agents, such as n-octyl alcohol, phosphoric acid ester.

The material can then be subjected to the usual Hachb @ handlungs-f-®rfahr @ n be, for example a treatment with non-ionic agents and soda, a rinsing and drying process.

Leave the process according to the invention see on structures made of metal-modified polymers of unsaturated hydrocarbons

209812/1635 bad original

the most well-behaved blow dryers, which are characterized by good fastness properties, such as dry cleaning, rubbing, washing * Light, sublime and exhaust gas fastness.

The process according to the invention makes it possible to create colors of high uniformity on metal-modified polymers of unsaturated carbons, which were often difficult or impossible to achieve with the previously known processes, especially with densely packed or large-area material. Another advantage of the process according to the invention is that, if desired, additional amounts of dye can be added to the dyebath during the dyeing process without causing uneven dyeing (cf. AauDyeat. Rep. 1965 , p. 56 * 1 ·) ·

The following examples are intended to illustrate the various embodiments of the method according to the invention, without the invention in any way one way to restrict. In the examples, unless otherwise stated, parts are parts by weight. Parts by weight have the same relationship to parts by volume as kilograms to liters. The temperatures are given in degrees Celsius.

Example 1 I rope of the Bisulflt-Addltlonsverblndung des

20SS12 / 1635 bad original

1-Hitroso-2-naphtols (dye according to the Color Index, 2nd edition, Mr. 10 005) is violated in 4000 parts of water. After addition of dilute acetic acid to sum reached a pH of about 3.5 is heated with 100 parts of material to be dyed from niekelhaltigem polypropylene in yarn form at 90 ¹ C. Hach 1 hour 1st staining terminated. The yarn is rinsed cold and hot, then boiled with a solution containing 1 % of a non-ionic detergent and 1 % soda, soaped, then rinsed and dried. A strong, uniform brown coloration with very good fastness properties is obtained.

Polypropylene containing daajnickel can also be used in the form of a carpet with equal success.

Example 2

1 part of the Ifatriumealea of the 1-Hydroxyanthraquinonyl- (2) -8sulphurfel8äureeeters are in 4000 parts Dissolved in water. After adding dilute sulfuric acid, it is heated until a pH value of about 1.5 has been reached 100 parts of a knitted fabric made of non-containing polypropylene are added to 90 T. After 1 hour, the dyeing is finished. The knitted fabric is finished as usual. A uniform, violet dyeing with good fastness properties is obtained.

BATH ORIGINAL

209812/1635

If 5 parts of the sulfur or phosphoric acid ester are used in place of the above-mentioned dyes of the dyestuff from diasotized p-toluldin and 8-Hydroxyquinoline, this gives nan a yellow-orange color.

When using the aso dye off

diasoped 2-aminophenylsulfuric acid ester and 2-hydroxy-3-naphthoic acid-o-toluidin, bsw. l-phenyl-3-methyl-5-pyrasolone, one obtains the brown-violet _t bsw. golden yellow color.

Example 3

3 parts of the dye "Graines de Ferse ^K (CI Natural Yellow 13)" present as glucoside and 120 parts of bensyl alcohol are dissolved in 4000 parts of water Dividing a knitted fabric made of nickel-containing polypropylene to 90 ° C. After 1 hour, the dyeing is finished. The knitted fabric is finished as usual. Nan receives a uniform · yellow dyeing with good fastness properties ·

Example .4 3 parts of the bisulfite addition compound des

209812/1635 bad original

Cöruleins (dye gea & ss CL No. Ί · 5 510) are gelSat in 4000! Dents of water. Ks.cfc Add 8 layers of Hatriutfhexametaphosphat and 2 files of the condensation pro ectes clay Naphthalene-2-sulfonic acid® with formaldehyde (as Katrluasalc) one adjusts the coloring solution with vinegar to a pH-value of about 3.5 «Then the solution becomes old 100 parts "heated to 90 ⁰ C in" ε tissue ATAS polypropylene. After 1 hour, the dl® staining is over. It is finished as usual »Han is given an olive green color with good washing and drying properties.

In 800 pounds of water, 0 * 1 pods of the dye derivative obtainable by the action of sulphonic acid on the ffonosso dye from 1 mol of dlaaotlertem ^ -Ni.tro-2-eiminothieiol and 1 hole 2.7% .BÜi7droäs ^ afhtalin la rridin @s ₉ wel@l£.habens in ferns of free acid true-

209812/1635 -

BAD ORlGiNAL

soheialioh corresponds to the above formula, below Adding Toa dilute sulfuric acid at pH ▼ on 2.0 ge 15et. Nan goes on with 20 parts of a yarn made of staple-containing polypropylene in the form of crosses * - coil in, heated in a Druok vessel inside an hour to 130 ° and colors an hour at this Temperature. As indicated in Example 1, the dyeing is soaped and rinsed. A deep blue, uniform dyeing with very good lightfastness is obtained.

Example 6

C ₂ HjO

-CO-,

400 parts of water are 0.1 part of the 3-Stslf above-Boylohlorid by action of the Monoaso dye from 1 Hol diasotlertem S-ethoxy-S-aminobonB-tMasol and 1 Hol 2-Baphtol available in Fyridln Dye of the tates, which in the form of the free acid probably corresponds to the above formula, neutral solved. You start with 10 parts of a knitted fabric

209 812/1635 bad original

nickel-containing »polypropylene, heated slowly to 90 ° and colored for one hour at this temperature. The dye is soaped and rinsed as usual. There is obtained a uniform, dark greenish-blue color, which is characterized by a ine excellent fastness to light, washing, rubbing and solvent fastness.

Example 7

OSO _x B

GOOH

20 parts of the monoazo dye, which corresponds in form to the free acid of the above formula _s are indicated with 30 parts of 2 ₉ 2 ⁰ ~ dihydroxyethyl sulfide. The mixture is then dissolved in 300 parts of water at 80 ° and stirred into 300 parts of a ready-to-use Alginatverdiokung containing 6% alginate. After adding 50 parts of diethyl tartrate, the mixture is diluted to 1000 parts with water. A fabric made of nickel-containing polypropylene is printed with this paste produced in this way, dried at 80 ° and steamed 50 Hinutei ^. Man

209812 / 163S _{8AD O} rk, _N al

gets a bright yellow print with good Authenticity characteristics.

The dye used in this example is obtained by coupling 1 hol diazotized Aniline Bit 1 Hol 4-Carboxy ~ 3-hydroxypteoylsulfuric acid ester.

Example β

OSO ₃ H

20 parts of the Honoazofarbstoffes, the above standing in the form of the free acid corresponds to the formula _s and 50 parts of urea are dissolved in 400 parts of water. This solution is mixed with 200 parts of a ready-to-use alginate thickener ₍ containing 6 % alginate, mixed with 5 parts of ammonium chloride and diluted to 1000 parts with water. A fabric made of nickel-containing polypropylene is padded with this preparation, dried at 80 ° and for 50 minutes attenuated. One receives

209812/1635 ^ßAD ofhginal

an equal ₉ strong orange color old very good integrity properties.

The dye used in this example is obtained by coupling 1 mol of diasotated 2-aminophenylsulfuric acid with 1 pint of SH ^ droxychlnoline.

öemäBS those given in Examples 1-8 Procedure let see with the dyes of the following Table on niekelBodifsiertea felypropylene fibers also want to produce colorations.

example

Dye

hue

OSO ₅ H

H-GE

CO

OSO, H

Brown

brown violet

209812 / 163S

BATH ORIGINAL

Se i at? IeI

- 20 -

Color toff

OSCUH

OH

OSO _x H

OC ₂ H ₅

CH,

hue

Gray

rotbrara.

yellow-orange

> H

^ y ^ V-OCO

SO3H

Orange red

209812/1635 BAD ORIGINAL

example Dye hue

OH

orange

-8th

_oreü g _e

COOH

golden yellow

209812/1635

example Dye hue

<y

Il

- H

HH

SO ₃ H

OCO

orange

Red

green

red triolet

209812/1635

example

eibjtcli

hue

(XJ-.

green

OCO

MGOOH ₃ olive ©

yellow-brown

OSOjH

violet

209812 / 1S35

example

F ar b at off

hue

OSOjH

blue

OSO ₅ H

he QSo ₅ H

C-N-NH COCH,

violet

209812/1635

Claims (2)

Claims 1) Process su® dyeing and printing of forms from metal-modified p®ljm @ ren of unsaturated hydrocarbons * thereby g @ k®s && ®lehnet, össs the structures with aqueous solutions of organic dye, which at least one cleavageb & r®, ^ asserldslichmachende group and sum mi @ d @ itäm ®B®h @ r follows @ r splitting off of this group at least @ im @ m @ tellMM @ & do group and which are free of mtltimn
Groups are to lead under i§di & guag @ E b @ lmaS @ lt _@ Si © tung of waeserlösliobnscheades groups. 2) Method according to claim I ₉ dadur @ li, knowing that one f @ s © rmmt © ^ ial mm polypropylene with aqueous IS @ ung @ n ^ ron o ^ g @ nis @ k @ m dyes that at least @ in® aau @ r rsp ^ lfbaren, ^ aaserlös llehmaehende Grupp® unfold, b @ if © mp @ ratisren of 90 130 ΐ and in the presence of must be treated. Burand St Huguenln representative BATH ORIGINAL 209812/1635