DE1769601A1 - Process for coloring synthetic organic materials - Google Patents

Description

New full agreement for the printing of the disclosure step Registration documents

File number: P 17® 601.4-43 ι

U. Sign: 21328-BR / bu l

CIBA AKTIENGESELLSCHAFT, BASEL (SWITZERLAND)

Case 6206 / E
Germany

Process for coloring synthetic organic materials.

The well-known dyeing and printing processes of organic synthetic materials such as knitted fabrics, nonwovens and blended fabrics made of polyesters, polyamides or polyacrylonitrile are all cumbersome, requiring either the manufacture of special auxiliary carriers or post-treatment. Direct printing with pigments does not pose any significant difficulties per se, but production does brilliant prints that have the desired depth of color,

"New documents (Art. /1.1 λ;. ·« Μ sentence 3 of the Anderunoeo ··. Ν. 4. a. 109827/1671

BATH

is a still unsolved problem: according to the gravure printing technique, very deeply engraved rollers can be used; however, the thickness of the printed areas increases very sharply and there is a lot of resin with the pigment in the printed areas deposited so that the handle and other properties of the fabric to be printed are adversely affected can.

The present new method overcomes these difficulties. The method also has the advantage a very simple implementation that requires neither the production of auxiliary carriers nor aqueous aftertreatments.

The method according to the invention is characterized in that synthetic materials such as knitted fabrics, woven fabrics or mixed fabrics, but in particular carpets and non-woven moldings such as films and especially nonwovens (hon woven "backing) made of polyesters, both from cellulose esters and from linear polyesters such as polyethylene terephthalate, printed from polyamides, polyacrylonitrile, or mixtures thereof with natural fibers such as mixtures of polyester with cotton or wool directly with a solution or dispersion of an at about l4O to 230 ⁰ C, preferably I8O-22O C, subliming dye and the printed area heated to the sublimation temperature.

Suitable substrates are, in particular, structures that are at least in part produced without a thread linkage,

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1 V B y 6

such as foils and fleeces, as well as those e.g. by electrostatic Application and subsequent gluing of short fibers made flock carpets.

For the purposes of the invention, sublimable dyes are those dyes which are produced according to the "Method of Determination the fastness to dry fixing and pleating of dyeings and prints (dry heat) "of the Swiss Association for Standards, Standard SNV 95 8 33/1961, which is sufficient in terms of color Bleeding (staining) result. With the standard SNV 95833/1961 takes a sample of the colored material in close contact with an uncolored material for which the dye is after has a good affinity for conventional staining methods,

2 under a pressure of 4o g + 10 g per cm at certain Test temperatures heated for 30 seconds. The present invention According to the definition, however, it also includes dyes which, after a heating time of less than 30 seconds. and until for 2 minutes and / or both with lower and higher contact pressure or without contact pressure the uncolored Have bled (stained) the textile material sufficiently. It does not matter whether the dye is in the physical Sense sublimates or penetrates into the textile material in a state other than gaseous if it is only from a substrate transfers to the other. A test similar to that in the SNV 95833/1961 standard is used in the American Association of Textile Chemists and Colorists AATCC II7-1966T described.

10 9 8 2 7/1671 ORiGiNAL INSPECTED

Γ / 69601 ..

Advantageously, such dyes which sublimate in a time interval of 15 to J50 seconds, but not more than 120 seconds at lQO to 210 ⁰ C are used.

The term “dyes” also includes the optical brighteners which are required according to the invention Have sublimability.

From the dyes and optical brighteners used according to the invention, preference is given to choosing those which do not contain an ionogenic group.

While the use of dyes that are as fast as possible to migration is sought for conventional printing inks, those dyes are preferably used in the printing inks according to the invention which are at the sublimation temperature have a low sublimation fastness. At temperatures below 120 C, however, the migration fastness should be so great be that with the printing inks according to the invention at room temperature stable and storable prints can be produced.

Suitable dyes are generally the so-called disperse dyes, i.e. dyes that are insoluble in water, which dye polyester and / or cellulose ester fibers from aqueous dispersion, as well as polyamide or given

(Poiyy

ifYa are able to dye crylonitrile fibers, whereby one im In the case of the dyeing of polyester and cellulose acetate fibers, it is usually assumed that the dyes in the fiber

loosen material.

109827/1671

ORIGINAL INSPECTED

17696Q1

These are, for example, dyes of the
following chemical classes: anthraquinone dyes such as hydroxy and / or aminoanthraquinones, azo dyes / quinophthalone dyes, azomethine dyes, stilbene dyes, nitrodiarylamines, etc.

Particularly suitable dyes are the monoazo, nitro, anthraquinone and quinophthalone dyes such as
the dyes of the following formulas:

O NH,

0 NH,

OH,

0 NH,

0 NH,

0 NH,

0 NHCH,

0 NHCH, ti

0 NHCH,

NO

CJ NH

C ₀ H-OH
^{2 4}

-N = N- <> —N ^/

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NH,

CH ₂ CHpOH

OH

NH-CO-CH ₂ -CH ₂ CH ₃

N-S

CO

NH,

CO

NO ₂ NH-A

The optical brighteners are mainly mono- and bisazole and benzoxazole derivatives such as the brighteners of the formulas

H (J CH

Il Il C! c Q _c

R = H, iso-propyl, methyl, tert. Butyl

109827/1671

O O \ /

C-CH = CH-C

where R has the same meaning as above, as well as brightener the Coumarin group, such as the brighteners of the formula

RpN '
wherein R is a methyl or ethyl group.

However, there are also optical brighteners of stilbene, benzothiophene-S-dioxide, pyrazoline, coumarin or des Benzimidazole type in question, which are necessary according to the invention Have sublimation properties and what affinity "have for the structures to be printed. These dyes and optical brighteners can be used in

^ organic or g)
Form-aqueous-organic dispersion or preferably as

nVo

SolutionsOrganic or aqueous-organic solvent-diluents can be used according to the usual printing techniques, preferably graphic printing techniques.

When using dispersions, the

r -

Printing ink dispersing dyes mainly have a particle size of ^ 10μ, preferably ^ 2μ. In addition to water, there are practically all organic solvents that occur at atmospheric pressure at temperatures below 220 ^° C.

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preferably boiling below 150 C, and the ones to be used Dyes and binders have sufficient solubility or emulsifiability (dispersibility). As examples of useful organic solvents the following may be mentioned: aliphatic and aromatic hydrocarbons, for example n-heptane or benzene, xylene or toluene, halogenated hydrocarbons such as methylene chloride, trichlorethylene or chlorobenzene, nitrated aliphatic hydrocarbons such as nitropropanes, aliphatic amides such as dimethylformamide or mixtures thereof, also glycols such as ethylene glycol or polyethylene glycols, their mono- or dialkyl ethers, Ethylene glycol monoethyl ether or diethyl ether, diethyl carbonate, Dimethyl carbonate or esters, such as ethyl acetate, propyl acetate, butyl acetate, ß-ethoxyethyl acetate, aliphatic or cycloaliphatic ketones, for example methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, mesityl oxide or diacetone alcohol. A mixture of an aliphatic ketone, for example methyl ethyl ketone, also proves to be expedient. and an aromatic hydrocarbon, especially toluene. The use is particularly advantageous of alcohols such as methanol, ethanol and preferably n-propanol, iso-propanol, n-butanol, tert. Butanol, sec-butanol or benzyl alcohol; In addition, mixtures of several solvents, which at least one solvent from a of the classes mentioned. It is advantageous to use practically anhydrous printing inks.

109827/1671 originally inspected

" ₉ .. 17 & 9601

In addition to the dye or brightener and solvent (diluent) contain those to be used according to the invention Printing inks (inks) preferably also at least ■ one binder that acts as a thickener of the printing batch and as an at least temporary binder of the dye

acts on the material to be printed. As such a binder

synthetic, semi-synthetic and natural are suitable Resins, both polymerization and polycondensation and polyaddition products. In principle, everyone can Resins and binders commonly used in the paint and printing ink industry, such as those used in paint raw materials tables by Karsten (4th edition Hannover 19 ^ 7) and in the work on synthetic lacquer resins by Wagner and Sarx (4th edition Munich 1959) are described. Preferred catfish used physically drying resins, i.e. * resins that do not chemically react (or crosslink) in air or with themselves, but which leave a dry film after the solvent has been removed »It is advantageous to use - of Resins that are soluble in the solvents used.

Suitable resins are, for example, the following! Rosin and its derivatives, hydrogenated rosin, dioder polymerized rosin, as calcium or zinc salt, -with monohydric or polyhydric alcohols esterified rosin; with resin formers such as acrylic acid and butanediol or maleic acid

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and pentaerythritol modified rosin; the soluble rosin modified phenolic resins and resins on Baals of acrylic compounds, maleinate resins, oil-free alkyd resins, styrenated alkyd resins, vinyltoluene-modified alkyd resins, Alkyd resins with synthetic fatty acids, linseed oil alkyd resins, ricine alkyd resins, castor oil alkyd resins, soybean oil alkyd resins resins, coconut oil alkyd resins, tall oil and fish oil alkyd resins, acrylated alkyd resins, as well as oils and oil varnishes. Further Terpene resins, polyvinyl resins such as polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetals, polyvinyl alcohol, Polyvinylether, mixed and graft polymers with different Vinyl monomers, polyacrylic acid resins, acrylic resins,

Polystyrenes, polyisobutylenes, polyesters based on phthalic acid, adipic acid, sebacic acid, etc., naphtha linformaldehyde resins, furan resins, ketone resins, aldehyde resins, polyurethanes (especially urethane resins that only harden at elevated temperatures Precursors), epoxy resins (especially resin-hardener mixtures that only harden at elevated temperatures) and their Precondensates. Precursors of unsaturated polyester resins,

Dallyl phthalate prepolymers, polyolefins such as polyethylene linden unc ""

or polypropylene wax / Cuinaronindenharze, carbamide and sulfonamide resins, polyamide and polyester resins, silicone resins, rubber and its derivatives, such as cyclo and chlorinated rubber, but especially cellulose derivatives such as cellulose esters (nitrocellulose, cellulose acetate and the like.), and especially cellulose ethers, such as methyl cellulose , Hydro ^ tyethylcellulose, ⁴

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- li -

Hydroxypropyl cellulose, cyanoethyl cellulose, ethyl cellulose, and benzyl cellulose. The corresponding derivatives can also be used other polysaccharides can be used.

Those with the resins, dyes, solvents or printing varnishes mentioned by per se customary methods produced printing inks (solutions, dispersions, emulsions) are applied directly to the material to be printed according to the most varied Printing techniques, e.g. emulsion printing, flat printing (e.g. offset), according to Letterpress printing (e.g. letterpress, flexographic printing), according to gravure printing (e.g. Rouleaux printing, rotogravure printing, intaglio printing), through printing processes (e.g. screen printing, film printing) or using electrostatic printing processes.

To improve the usability of the printing inks may optional components such as plasticizers, swelling agents, high-boiling solvent such as tetralin or decalin, ionogenic ode "r nonionic surface-active compounds such as the condensation product of beta-naphthalenesulfonic acid with formaldehyde, partially desulfonier- tes lignin sulfonate, or the condensation product of 1 mole of octylphenol with 8 to 10 moles of ethylene oxide can be added.

The 'quantitative composition of the printing inks

'' with regard to the resin mixture and the solvent mixture is determined by two requirements :

If solvents are used, the

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be present in such amounts that the resin remains dissolved and / or dispersed and, on the other hand, the amount of solvent must be within such limits . that the viscosity of the printing ink has the value required to carry out the printing process. In gravure printing, for example, good results are generally obtained with a quantity ratio of resin: solvent which is between 1: 1 and 1:50, preferably between 10 and 1:20.

It is advantageous to print in such a way that there is little binding agent on the printed material, preferably at most

2 2

about 10 g / m 2 and suitably below 5 g / m 2 remains.

The printed goods are subjected to a heat treatment after any drying and regeneration of the solvents used e.g. subjected to steaming or preferably dry heat treatment. The printed goods can e.g. be heated by means of infrared rays or in a drying cabinet. It is advantageous to have closed heating, i.e. e.g. in an ironing press or with a heating plate, or by letting it pass between heated cylinders or Rolling, by heating in a bath of molten metals, in special heating cabinets, etc. It is recommended to warm to the sublimation temperature of the dyes and / or brighteners used or a little above. Advantageous becomes a few seconds, i.e. 10 to 120 seconds, to 180 to

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ORIGINAL INSPECTED

25O ⁰ C, preferably about 15 to 50 seconds to 200 to

230 ⁰ C heated.

No aqueous post-treatment is necessary after heating. The dyeings obtained in this way are washable and, depending on the quality of the print carrier used, also dry-cleaning-proof. According to the present simplified Direct printing process gives you depth of color and, depending on the selected colorants and brighteners, also brilliant prints, as they have not done so far with graphic printing methods, with textile printing methods not without laborious and expensive ones Washing and rinsing processes were producible.

In the examples below, the parts mean, unless otherwise stated, parts by weight, the Percentages by weight and temperatures are given in degrees Celsius.

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'Γ / 69601

Formulas

example 1

5 parts of a mixture of the blue dyes of the

0 NH-CK

and

NHCH.

NHCH

10 parts of ethyl cellulose (Ethocel E 7, Dow Chem.) And 85 parts Ethanol are rubbed in a ball mill for 24 hours; the printing ink thus obtained is used for printing Polyester fleece or a polyester film, so that the printed area has about 0.4 to 0.6 g of dye per square meter. After removing the ethanol by drying, the printed goods are heated to approx. 200 ° for 30 seconds with the iron heated. A deep blue print pattern is obtained.

109827/1671

ORlGiNAL INSPECTED Example 2.

5 parts of the red dye l-amino-4-hydroxyanthraquinone,

15 parts of nitrocellulose A 250 (containing 18 # dibutyl phthalate), 10 parts of glycol monoethyl ether,
30 parts of methyl ethyl ketone and
40 parts of ethanol

are with a toothed disc agitator with a peripheral speed stirred at about 12 m / sec for 15 minutes and the printing ink thus obtained on a polyester fleece and also on a polyester film printed. Drying in a stream of warm air at 50-60 ° and subsequent fixation of the dye dry heating to approx. 200 ° for 30 seconds (iron) result in a deep red print pattern.

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V / 69601 - 16 -

Example ^.

5 parts of the blue dye 1,4-di (methylamine) anthraquinone
35 parts of an acrylic resin solution (30% solids content) in

Ethanol / water (Acryscope 85-1; Johnson Chemical Division) 20 parts of ethanol and
40 parts of water

are mixed analogously to Example 2 and on the one hand on polyester fabric on the other hand, printed on a polyester film. Fixation of the dye by dry heating to approx. 200 ° for JO seconds (iron).

109827/1671 originally inspected

• ■ - 17 -

example

5 parts of the blue dye mixture used in Example 1, 15 parts of Desmophen 800 (BAYER), 32.5 parts of methyl-ethyl-ketone and 32.5 parts of toluene

are ground in a ball mill for 24 hours. Immediately before printing

a) polyester fleece or

b) Polyester film will be this printing ink

15 parts of Desmodur IL (BAYER) were added. Fixation of the dye by dry heating to approx. 200 ° for 30 seconds (Iron).

10 9827/1671

ι Example 5 «

10 parts of the dye preparation, consisting of equal parts of the yellow dye of the formula

and hydroxypropyl cellulose (Klucel E, HERCULES) are for 30 minutes with a standard two-blade stirrer in 90 Parts of isopropanol are stirred in. The printing ink thus obtained which has a uniform fine distribution of the dye, is printed on polyester fleece and the dye fixed by dry heating in a drying cabinet at 195 ° for 45 seconds. Instead of heating in the drying cabinet becomes an iron (approx. 210 °, 25 seo) with equal success

used.

ORIGiNAL INSPECTED

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Example 6.

5 parts of the dye preparation, consisting in equal parts of the red dye of the formula

0 NH ₂ OC ₂ H ₄ OH

O OH

and ethyl cellulose (Ethocel E ¹ J, Dow Chem.) are stirred into a solution of 6.5 parts of ethyl cellulose (Ethocel E 7, Dow Chem.) in 88.5 parts of isopropanol using a standard two-blade stirrer for 30 minutes. The printing ink thus obtained, which has a uniform fine distribution of the dye, is printed on polyester fleece and the dye is fixed by dry heating for a short time under an infrared heater. Instead of heating under the * infrared heater, an iron (approx. 200 °, 30 seconds) is used with the same success.

109827/1671

Example 7.
A printing ink consisting of 5 parts of the yellow

Dye of the "formula

CH CONH

dissolved in 5 parts of ethyl cellulose (Ethocel E 7, Dow Chem.) and 90 parts of methyl-ethyl-ketone, is on polyester fleece or printed on polyester film. When the print * dries, the yellow dye dissolved in the printing ink crystallizes in a very fine form and is then fixed by dry heating.

10 9 8 2 7/1671

- 21 examples 8 to 10.

An ink consisting of $ 10 of the below in Column 1 indicated dye, 25 $ of an acrylic resin solution (consisting of $ 60 water, $ 10 ethanol and $ 30 acrylic resin; Density 0.996, p "value 7.3 and viscosity 21000 eps;" available under the trade name "Acryscope 85-I" from Johnson & Son Inc.) $ 35 of a 2 $ aqueous solution of methylcellulose and $ 30 Ethylene glycol, is gravure printing (engraving depth 110 μ) printed on nylon 6 carpeting at a printing speed of 15 m / minute. The carpet is at 60 ° in one Circulating air drying cabinet dried for 5 minutes and then to sublimation temperature heated. The print obtained had the color indicated in column 2.

example

1-amino-4-hydroxy-anthraquinone

1,4-bis (methylamino) anthraquinone

CH,

N0

-N = N-C C C-CH.

HO-C N

Red Blue

yellow

^G 6 ^H 5

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Claims (16)

Claims. 1. Process for single or multi-colored printing and dyeing of knitted fabrics, fabrics, foils, fleeces (non-woven Carriers) and molded articles made of synthetic hydrophobic materials, as well as mixtures of these materials with one another or with natural fibers, characterized in that these materials are mixed directly with a solution or dispersion φ sion of a dye subliming at 140 to 250 ° and / or optical brightener printed and the printed areas preferably heated to sublimation temperature. 2. The method according to claim 1, characterized in that foils, fleeces and carpets are printed. j5. Process according to claims 1 and 2, characterized in that that a graphic printing ink and a graphic printing method are used. fe 4. The method according to claims 1 to 3 »characterized in that that an at least partially organic printing ink is used. 5. Process according to Claims 1 to 4, characterized in that the printing ink consists only of dyes and solvents and solids. 6. The method according to claim * 5, characterized in that that the amount of solids is so low that it is unnecessary to wash out the printed goods. 10 9 8 2 7/1671 _{Λβ1ΛΙΝΑ} , inspected > 17 6 9 β Ο Ί 7. Process according to claims 5 to 6, characterized in that that the residue left on the substrate is so small that it affects the textile properties not changed. ^: 8. The method according to claims 5 to 7, characterized in that the dye-solids ratio is chosen so that after the solvent has evaporated from the printing ink, the dye is partially precipitated from the remaining solid. 9. Process according to Claims 5 to 8, characterized in that that you can get practically anhydrous printing inks fine]) used in which the binder inValiphatic or cycloaliphatic ketone, ester or alcohol, optionally mixed with an aromatic hydrocarbon is. • 10. The method according to claims 4 to 9 *, characterized in that that one uses practically anhydrous printing inks, in which a resin component is present, which when heated hardens and / or is hardenable by treatment with hardening agents, or contains a hardening agent. 11. The method according to any one of the preceding claims, characterized in that printing inks are used in which contains a cellulose derivative as a binder, preferably a cellulose ether, in particular ethyl cellulose, or a hydroxyalkyl cellulose, advantageously hydroxypropyl cellulose • 109827/1671 12. The method according to claim 4, characterized in that that printing inks are used that contain synthetic resin polymers as binders « 13. The method according to claim 12, characterized in that that carpets are printed with acrylic resins and aqueous-organic liquor. 14. The printed according to one of claims 1 to 13 synthetic materials. 15 · Films, nonwovens and moldings made of polyester, polyamide or polyacrylonitrile according to claim 14. 16. Knitted fabrics, woven fabrics and mixed fabrics according to claim 14. 109827/1671