DE2455616A1 - Substd. aminoanthraquinone dyes for transfer printing - (semi)synthetic materials red-violet shades - Google Patents

Abstract

Transfer printing process, pref. of (semi)synthetic polymers, utilises dyestuffs of formula (I) (where one X is H and the other is -NHR2; R1 and R2 are independently alkyl or cycloalkyl opt. contg. non-ionic substituents). Clear light-fast red-violet shades are obtd. on aromatic polyesters, cellulose triacetate ("S finish") superpolyamides and acrylonitrile polymers, and mixts. of synthetic hydropholic fibres with natural or regenerated fibres.

Description

509 Leverkusen. Bayerv / Erl f K / KV

The invention relates to a method for printing preferably synthetic or semi-synthetic polymeric materials based on the transfer printing principle, which thereby is characterized in that sublimable dyes of the formula

NHR ₁

(D

used, ■ '
wherein

R ₁ and R ₂ independently of one another are alkyl or cycloalkyl radicals which may contain non-ionic substituents,

as well as printing inks or printing pastes for transfer printing, the auxiliary carriers printed or impregnated with such dyes and the substrates which have been colored with such dyes according to the transfer printing principle. Suitable non-ionic substituents are in dyestuff chemistry conventional non-water-solubilizing and the sublimability in the range 120-240 ⁰ C, preferably 140-210 ⁰ C, not significantly affecting residues.

Dyes to be used with preference are those of the formula I in which R _{1 and Rp represent C 1 -C 2} -alkyl, optionally substituted once by hydroxyl, halogen, cyano or C 1-2 -alkoxy, or optionally 1 to 3 times by halogen , Le A 16 138; ' _ 1 .

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or C _1-2 -alkoxy substituted C for ₅ _ ₆ cycloalkyl. Of these dyes, especially those of the formula are

CHNH O

(II)

preferred,

in which

Q ₁ , CU stands for straight-chain C ₁ , -alkyl and Q ₂ , Q ^ for C _1-2 -AlCyI or

in the

Q ₁ and Q ₂ as well as Q and Q ^ together can form the remaining members of a 5- or 6-membered cycloalkyl radical optionally substituted 1-3 times by halogen or methyl, such as cyclopentyl, cyclohexyl, methylcylohexyl, dimethylcyclohexyl, trimethylcyclohexyl, chlorocyclohexyl In the context of this invention, halogen is understood to mean Br and, above all, Cl and F.

A dye to be used with particular preference corresponds to the formula

(III)

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The dyes of the formulas to be used according to the invention I - IJEI can be exchanged by conventional methods des 1,8-dihaloanthraquinone, 1,8-dinitroanthraquinone or anthraquinone-1,8-disulfonic acid and the corresponding Making amines. Such methods are described, for example, in German patents 144 634 and 181 722. By using amine mixtures or by gradually exchanging them for various amines, these can also be eliminated Preparing compounds of formula I in which R ^ and Rp have different meanings.

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The transfer printing process is generally known (see, for example, Color Index, 3rd edition, Vol. 2, page 2480) and is described in detail, for example, in French patents 1,223,330, 1,334,829 and 1,585,119. So-called auxiliary carriers, which are printed with suitable printing inks, are brought into close contact with the substrate to be printed, whereupon the dye is transferred from the carrier to the substrate under the action of heat and, if necessary, pressure.

Flat structures such as paper, Cellophane, cotton fabric, linen fabric, metal foils, etc., are envisaged (see British Patent 1,190,889). Is preferred Paper.

The printing inks can be printed using conventional printing processes (letterpress, flat, gravure or screen / film printing).

The composition of the printing inks depends on the type the substrate, the printing process, the carrier material and other more. Generally they consist of

a) a sublimable dye, in the present case thus dyes of the formula I,

b) a binding agent,

c) a solvent,

d) optionally thickening agents,

e) optionally fillers and

f) optionally dispersants.

Depending on the printing process, chemical and / or physically drying products can be used as binders, as they normally are be used in textile or paper printing.

Products that can be used as thickeners are which bring about a significant increase in viscosity even in low concentrations.

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Non-icnogenic compounds such as Alkyl polyglycol ethers and alkylphenol polyglycol ethers as well as anion-active compounds such as naphthalenesulfonic acid formaldehyde condensates, Lignosulfonates and sulfite waste liquor products. The type of solvent depends very much on the type of printing process away.

Particularly suitable printing processes for the production of printed Paper auxiliary media are gravure printing and rotary film printing. Gravure printing is indicated wherever there is an extremely high screen fineness is required, while rotary film printing is recommended wherever small amounts are printed (i.e. with low Number of editions) and the highest demands on the screen fineness are not made. _.

An intaglio ink generally contains besides the sublimable one Dye a binding agent commonly used in gravure printing, i.e. physically drying natural or synthetic Hard resins, e.g. cellulose ether, and an organic solvent that does not boil too high, such as ethanol or toluene.

For rotary film printing, on the other hand, aqueous printing inks are preferably used which, in addition to the dye, contain a binder, contain a filler, a thickener and optionally organic solvents and / or dispersants, the binder / filler weight ratio being preferably 1: 6 to 1: 8. Water-soluble binders are mainly used as binders (or solubilized by conventional saponification processes)

natural or synthetic, physically ~~ drying products in question, as they are normally used for the production of flexographic and Screen printing inks can be used. Examples include: shellac and homo- and copolymers based on Vinyl acetate, vinyl alcohol, vinyl chloride, acrylic acid, acrylic ester and / or maleic acid. Carbonates, sulfates, Silicates, oxides and the like of the alkali and alkaline earth metals as well as of aluminum and titanium can be considered. Particularly proven finely divided natural calcium-magnesium carbonates (dolomite).

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Suitable thickeners are swelling clays, vegetable seed meal ether as well as alginates. The solvents used are water-miscible, low-odor, physiologically harmless and proportionate high-boiling solvents such as diacetone alcohol, ethyl glycol, diethylene glycol, glycerol and others are possible. In particular, those made of paper with high absorbency (Cobb value > 80) request. .

Suitable substrates are preferably sheet-like structures, such as nonwovens, felts, furs, foils and, above all, woven fabrics synthetic or semi-synthetic material, especially those made from aromatic polyester, cellulose triacetate (without so-called S-finish), super polyamides and acrylonitrile polymers. Also mixtures of these hydrophobic synthetic fibers with natural or regenerated fibers come into consideration.

The preferred process gives clear violet prints with good fastness properties on these substrates.

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Example 1' . /

A) 75 g of the dye of the formula

50 g of an anionic dispersing agent such as a lignin sulfonate or a condensation product of naphthalenesulfonic acid and formaldehyde, and 100 ml of water are mixed and converted into a finely divided form by grinding for 10 hours in a ball mill. The dispersion obtained in this way and containing approx. 30% raw paint is stable in storage.

B) The aqueous dispersion obtained according to A) can be added as follows a printing paste can be processed. 50-200 g with 400 g of a 10bigen locust bean gum ether thickening and 550-400 ml of water made into a paste.

C) This printing paste is used to print a paper using the gravure printing process. Pressed to this paper during 15-60 seconds at 200 ⁰ C with a fabric made of polyester fibers, we obtain a clear, strong violet color print having good wet fastness properties.

Example 2

Ä) 100 g of a dye dispersion, prepared according to Procedure of Example 1A), with 800 g of water and 100 g of a 5% alginate thickening are intimately mixed.

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A cotton fabric web is soaked with this dye solution on a padder and then dried.

B) The cotton fabric obtained according to A) is suitable for transfer printing, particularly on voluminous materials, such as e.g. Carpets made from polyester fibers.

Example 3

A) 40-50 g of the dye of the formula

NHCH,
3

are made into a paste with 5-10 g of an emulsifier mixture of ethoxylated nonylphenol (4-12 mol of ethylene oxide) in water. 10 g of ethyl cellulose N4 (Hercules Powder) and 30-40 parts of a maleinate resin, which was prepared by condensing rosin with maleic acid, are added. Kneading for about 2 hours at 80 to 100 ⁰ C and then grinding in a usual mills. A fine-grained dye powder is obtained.

B) 200 g of the dye powder obtained according to A) are added with stirring into a mixture

730 g of ethanol
50 g ethylene glycol and
20 g ethyl cellulose N22 (Hercules Powder).

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C) The printing ink thus obtained can be used in gravure printing Printing on papers. From these printed papers one can In the transfer process, textiles made of cellulose triacetate, e.g. knitted fabrics, are printed and given a clear, strong purple color Prints.

Example 4

75 g of the dye of the formula given in Example 1 are made together with 50 g of a condensation product Naphthalenesulfonic acid and formaldehyde and 100 g of water in finely dispersed in a ball mill. The dyestuff dispersion thus obtained is stirred into a thickening that results from

21 parts of water

7 parts of diacetone alcohol

(R)
41.3 parts Microdol ^ 'extra (natural calcium-magnesium

Carbonate)

0.2 parts of sodium hexametaphosphate 0.5 parts of naphthalenesulfonic acid / formaldehyde condensation

product

8 parts Bentone ^ EW 3% ± g (source clay)

12 parts of acrylate binder DA (50% solution of the ammonium salt of a polyacrylate in 33% aqueous ethyl alcohol. The polyacrylate is a copolymer the end

60 ethyl acrylate 25 ethyl methacrylate 15 acrylic acid) '

This printing paste is printed with screen printing stencils or with round stencils on an intermediate carrier, preferably paper with a weight per square meter of about 60-80 g / cm and a Cobbg ₀ value of about 80. A smooth print is obtained.

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With the thus prepared paper to k * textiles from polyester, polyamide, polyacrylonitrile, and cellulose triacetate nn print in the mold by bringing the fabric to the paper during 15-60 seconds in contact and heated to temperatures of 190-200 ⁰ C. Brilliant, violet prints are obtained on the fibers mentioned.

Example 5

With a printing paste as described in Example 3, a print is made from paper, fleece material or a cotton nettle. If one compressed this pressure with carpet material made of polyester fibers for 30 seconds at 200 ⁰ C, to obtain a brilliant violet pressure.

Example 6

A printed paper is used as described in Example 4, and pressed this with blankets made of polyacrylonitrile material. You work in one Chamber under reduced pressure between 70 and 200 mm Hg column. A print is obtained in which the violet dye is deep has penetrated into the voluminous material.

Example 7

Papers produced according to Example 3 are used and foils made from polyester or polyamide are printed with them or polyacrylonitrile. Transparent violet prints are obtained.

Example 8 . ·

If instead of the films described in Example 7 with plastic-coated fabrics or nonwovens, the result is strong purple prints that tend to run a little over time. '

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Example 9 * *

Papers produced according to Example 4 are used were used to print objects made from foam. The foams can on Be made from polyester, polyether or polystyrene. Again, a strong purple color is obtained Pressure.

Example 10

29.8 parts of 1,8-dinitro-anthraquinone in 120 parts of nitrobenzene with stirring to 170 - 180 ⁰ C heated. With the distillation bridge in place, a sufficient amount of 35% strength aqueous methylamine solution is then slowly added dropwise so that excess methylamine is always present in the reaction mixture, while the water is distilled off evenly. After about 20 hours at 170-180 ⁰ C is allowed to cool, filtered with suction, washed with methanol, dilute hydrochloric acid and water and dried at 6O ⁰ C. 21.4 parts of 1,8-bis-methylamino-anthraquinone are obtained.

Example 11

In example 10, the 35% strength aqueous methylamine solution is replaced by a 70% aqueous isopropylamine solution, so 18.8 parts of 1,8-bis-isopropylamino-anthraquinone are obtained with the same reaction time and work-up.

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Claims (8)

Patent claims% * « 1. Method of printing on, preferably synthetic or semi-synthetic polymeric materials based on the transfer printing principle, which is characterized by that one dyes of the formula NHR ₁ used,
wherein
R ₁ and R ₂ independently of one another are alkyl or cyclo alkyl radicals which may contain non-ionic substituents mean. 2. The method according to claim 1, characterized in that dyes of the formula given are used in which R _{1 and Rp for C 1} g -alkyl or optionally 1, optionally substituted once by hydroxy, halogen, cyano or C _{1 2 -alkoxy} C 1 -C 6 -cycloalkyl radicals which are substituted up to 3 times by halogen, C 1 -C -alkyl or C _{1-2 -AIkOXy.} 3. The method according to claim 1, characterized in that one dyes of the formula used, in which Q ₁ and Q ₂ stand for straight-chain C ₁ , -alkyl and Q ^ and Q ₄ for C _1-2 -AIkYl or in the Q ₁ and Q ₂ as well as Q, and Q ^ together the remaining links Le A 16 138 - 12 - 609822/0855 once if necessary 1-3 times durol '. Halogen or methyl substituted 5- or 6-membered cycloalkyl radical. 4. The method according to claim 1, characterized in that the dye of the formula NHCH ^ -CH ₃ used. 5. Auxiliary carrier for transfer printing, characterized in that it is printed or with dyes of claims 1-4 are impregnated. 6. Printing inks and printing pastes for transfer printing, characterized in that these dyes of the claims 1-4 included. 7. Synthetic or semi-synthetic polymeric materials, characterized in that they are mixed with dyes of the claims 1-4 have been colored according to the transfer printing principle. 8. polyester fiber materials, characterized in that these with dyes of claims 1-4 according to the transfer printing principle have been colored. Le A 16 138 - 13 - 6 09822/0855