DE2739174B2 - Auxiliary carriers for thermal printing, their manufacture and use - Google Patents

Description

where R is a benzene radical, the l-amino-4- and -5-alkoxyanthraquinones, the l-amino-4-, -5- and -8-benzoylaminoanthraquinones, the l-amino-4- and -S-tchlorbenzoylJ-aminoanthraquinones and the anthraquinone derivatives, the two NH groups in the 1,5 and 1,8 positions and in the 2,4,6 resp. 2,4,7-positions carry hydrogen atoms, as well as possibly other sublimable dyes.

2. Auxiliary carrier according to claim 1, characterized in that that they carry at least two dyes of the type specified in claim 1.

3. Auxiliary carrier according to claim 1 or 2, characterized in that it has one of the in claim 1 indicated red dyes and a yellow azo dye or a dye which has two non-condensed heterocycles of which at least one a chain link-NH- adjacent to one bonded to an oxygen atom Has carbon atom, wear.

4. Auxiliary carrier according to one of claims 1 to 3, characterized in that it also has the yellow dye of the formula

H ₁ CC C-CH-C C-CH,

'Il Il Il

OH O

wear.

5. Auxiliary carrier according to one of claims 1 to 4, characterized in that it is 1,5- or 1,8-diaminoanthraquinone or wear mixtures thereof.

6. Auxiliary carrier according to one of claims 1 to 5, characterized in that, in addition to the dyes, they carry an organic acid which is solid ^{at temperatures below 50 ° C.}

7. A method for producing the auxiliary carrier according to claims I to 6, characterized in that that one of the surfaces of a sheet or a strip of paper with aqueous or organic or printing inks containing a drying oil which contain at least one of the in Claim I contain specified dyes.

8. Use of the subcarriers according to claims I -6 for printing within 30 to 60 seconds at more than 210 ⁰ C pretreated with thermosetting or precondensates nichtwärmehärtbaren cellulose tissue.

When transfer printing, also known as dry printing, the prior to a provisional carrier or auxiliary carrier (hereinafter always referred to as "auxiliary carrier"), in general a strip or a sheet of paper, dyes applied in the heat from the auxiliary carrier to the transferring material to be colored or printed. This very widely used technique for dyeing or Printing of synthetic fibers, in particular vc-n fabrics, tricots and non-woven fabrics made of polyester, can also be applied to natural fibers, especially cellulose fibers, if you use the latter with a Center! pretreated that has an affinity for the has dyes used (cf. e.g. French patents 15 91 909 and 21 93 908). It is also known to pass through fibers pretreated by means of condensates of thermosetting resins Transfer to color and print (see e.g. Swiss patent 5 77 596 and the Japanese Patent applications No. 104 058/74 and 34 706/73, which have been published under numbers 32 887/76 and 118 976/74, the English patent specification 14 45 201 or the French patent applications under the numbers 22 39 553, 22 54 767 and 22 57 730).

The present invention now relates to new supports used in transfer printing can and deliver better results than the known carriers, especially in the case of cellulose fibers which one obtains transfer prints with a better wash fastness.

The auxiliary carriers according to the invention for heat printing in the gas phase are essentially characterized by the dyes they carry. According to the invention, they are characterized in that one of the surfaces of a sheet or strip of paper ^{bears at least one dye which can be vaporized or sublimed below 240 °} C. at atmospheric pressure and is selected from the group of disperse dyes of the general formula

R-N - N-C C CN

HOC

CO

wherein R denotes a benzene radical, the l-amino-4- and -5-alkoxyanthraquinones, the I-amino-4-, -5- and -8-benzoylamidoanthraquinones, the l-amino-4- and -5-chlorobenzoylamidoanthraquinones and the Anthraquinone derivatives which have two NH ₂ groups in the 1,5 or 1,8 positions and hydrogen atoms in the 2,4,6 or 2,4,7 positions, and optionally also other sublimable dyes.

Most of the dyes which characterize the supports according to the invention are known or can be prepared by processes known per se from components which have the above contain specified specific groups or chain links.

In addition to the above-mentioned dyes, the carriers according to the invention can also contain other sublimable dyes Contain dyes, preferably

a) azo dyes of the formula

NH-,

where R is a benzothiazolyl radical which is substituted or unsubstituted, and A is a hydrogen atom, or for an alkyl or alkoxy radical or for an amino group which are unsubstituted or substituted can, stands,

b) Azo dyes containing two Ämino-Gnippen. Those in which the two amino groups have a total of 3, preferably 4, hydrogen atoms, give the best results, especially those that have an NHr group and an NH-COCR3- or NH-CONHrGruppe on a B? Nzolkern, and those who carry two NH2 groups on one Wear a pyridine or benzene ring. Dyes of this type include, for example, the dyes of following formulas

R-N = Nf γ- NH ₂
X-C-HN

Il ο

H ₂ N CN

H ₂ N

H ₇ N

Alkyl-HN

Y = N

JN
RN - N - 4> -NH-alkyl

H ₂ N

In the above formulas, X stands for an alkylresi, preferably for methyl, or for an NH2 group, and R stands for a thiadiazolyl, triazolyl or Benzene radical, preferably a phenyl radical which can carry substituents from the group of Chlorine atoms selected from the nitro, cyano, methyl and trifluoromethyl radicals,

c) dyes which have two non-condensed heterocycles, of which at least one has one -NH chain link which is adjacent to a carbon atom bonded to an oxygen atom is.

The auxiliary carriers according to the invention can be printed by known methods, e.g. B. by ι Offset, helio, flexo or screen printing with a flat Frame or a rotating frame (cf. French patents 12 23 330, 13 34 829, 15 85 119 and 20 76 149). You can click on at least one of their two Surfaces have a layer of a single color or a multi-colored print. The ones to print The printing inks used will differ depending on the carrier and the applied Printing process from each other. In addition to the dye, they generally contain a solvent or Thinner and a binding or thickening agent, which simultaneously regulates the viscosity of the printing ink and maintains the Dye allowed on the auxiliary carrier

In addition, the printing ink can contain various fillers, one or more dispersants, and products (Natural and synthetic resins) contain which the flowability of the printing ink, its adhesion to paper and the like.

As a binding agent is used depending on the

2 "> selected process drying oils (for offset printing) or natural or synthetic products that are often used in printing on fabrics and paper (according to the other methods). One preferably uses "film-forming": products that

κ) cause a noticeable increase in the viscosity of the printing ink even at a low concentration.

Both non-ionic products and anionic compounds can be used as dispersants use.

ji The type of solvent depends on the chosen Procedure from: In general, water is used for screen printing with the rotating frame, organic Solvents in light printing (heliography) and drying oils in offset printing.

In general, one uses a printing ink that from an organic solvent (alcohol, ketone, ester or hydrocarbon, preferably ethanol, Toluene and the like.), A binder (a natural resin or a synthetic resin such as cellulose ethers or

• η cellulose esters, especially ethyl or hydroxypropyl cellulose, Cellulose acetopropionate or acetobutyrate, or such as vinyl resins, especially polyvinyl butyral or polyvinyl acetate and one or more dyes in a very remote state (preferably such a shape that the mean particle size does not exceed 3 microns). It is the case with collotype. As with Offse: Druck, you can use a drying oil that simultaneously plays the role of the solvent and the binder.

When screen printing, on the other hand, aqueous printing inks are preferably used, except for one Dye mixture a binder, fillers, a dispersant and optionally contain a small amount of an organic solvent. As a binder are here the (water-soluble) homopolymers and copolymers of vinyl acetate and vinyl alcohol, of acrylic acid, acrylates and the like. Mention should be made. In addition to carbonates, sulfates and Silicates also derivatives of alkali metals and alkaline earth metals (for example the oxides or salts) into consideration. The auxiliary carriers according to the invention can also be solid at a temperature below 50.degree

organic acid or the amide of such an organic acid, preferably sulfonic acid, contain.

Mii the auxiliary carriers according to the invention can be printed by simple contact in the heat dry any material that has an affinity, a solvent power or a reactivity to the specified dyes, such as. B. flat plastic surface. Films, sheets, fabrics or tricots, and the auxiliary carriers according to the invention are particularly suitable for printing by transferring natural substances, especially cellulose fibers (and their mixtures with synthetic fibers), if they are previously treated with thermosetting or non-thermosetting precondensates, such as. B. those of melamine and / or urea and formaldehyde or glyoxal have been pretreated. These pretreatments are known per se in the textile industry. It is particularly possible to use these auxiliary supports to print ^{cellulose fiber fabrics within 30 to 60 seconds at more than 210 ° C.}

With the auxiliary carriers according to the invention, strong prints with vivid colors are obtained on these materials, which are very fast to washing and to moist treatments if the y, transfer is carried out at temperatures above 190.degree. C., preferably between 215 and 230.degree.

The invention will ert erläu "by the following examples in which, unless otherwise stated, the parts and percentages are by weight and the jo temperatures are in ⁰ C. closer, but are not limited, however it.

example 1

20 parts of 1,8-diaminoanthraquinone are in a sand mill in the presence of 20 parts of hydroxypropyl cellulose and ground 360 particles of water for 24 hours with cooling. Then you remove that Water from the ground product. After spray drying, you get a red powder with a delicate structure.

Yellow powders containing dyes of the formula I are obtained in a similar manner

4 y

wherein X is H, Cl or CN.

The following procedure can be used to produce a printing ink from these powders. Stir 2.5 parts of the like The coloring preparation obtained above, 2.5 parts of ethyl cellulose and 10 parts of isopropanol up to complete dissolution of the resinous product and until complete distribution of the undissolved Dye.

Printing inks are obtained in an analogous manner if bo instead of 10 parts of isopropanol, 10 parts of methyl ethyl ketone or 10 parts of ethanol are used or if the 2.5 parts of ethyl cellulose are replaced by 2 parts of polyvinyl butyral or polyvinyl acetate.

These printing inks are used to print using (, -, For the motifs dyed by several pressure rollers, see a narrow or wide strip of paper by placing for example, a printing ink formulation is used.

which contains 10 parts of dye, which is finely divided in a varnish of 9 parts of ethyl cellulose, dissolved in 81 parts of ethyl alcohol. In this way, a printing ink is obtained which is evenly distributed with the printing roller on the paper in an amount of about 10 g per m ^2. After drying, an auxiliary carrier with the dyes is obtained, which can be used as follows: A cotton fabric (weighing 200 g / m ² ) which is mixed with a mixture of equal parts hexamethylolmelamine is placed on the printed surface of the paper and polyethylene glycol has been impregnated in an amount about 0.25 times its weight. The whole is heated for 35 seconds in a press heated to 225 ° C. After the paper has been separated from the fabric, one of the surfaces of the cotton fabric is given a beautiful print that is resistant to washing, even when cooking.

Bc-is pie '2

As in Example 1, make a transfer paper here, but this time using a printing ink made as follows: Man grinds 10 parts of the yellow dye of the formula I (where X is H) and 8 parts of 1-amino-4-phenylaminoanthraquinone with 4.5 parts of ethyl cellulose, 30 parts of sodium chloride and 8 parts of diacetone alcohol, while 4 hours in a suitable device. The ground is granulated by adding 1 part of water Mass, then 75 parts of water are added for wet grinding. The obtained is separated by filtration Suspension off, the product washes with water to remove the solvent and salts from it and the filter cakes obtained are dried in a vacuum oven. In this way a powder is obtained from where a printing ink is made by mixing 12 parts of this powder in a varnish of 7 parts of ethyl cellulose Stirring in 100 parts of ethyl alcohol.

The printing ink produced in this way is used to print a green motif on a sheet of paper, which is then dried. The transfer print carrier obtained in this way allows a green motif to be printed by contact at 218 ° C not only on a tricot made of polyester (polyethylene terephthalate), but also on cotton that has been impregnated with hexametboxymethylmelamine and polyethylene glycol, as well as on mixtures of cotton and polyester (50:50), impregnated in an amount of about 80% by weight by padding with an aqueous solution containing 150 parts of partially methylated methylolmelamine in 750 parts of water and 100 parts of polyethylene glycol and 2 tests of magnesium chloride and then dried i 'iid.

Example 3

A red printing ink is obtained by placing in 100 parts of a varnish of cellulose acetopropionate or Ethyl celluloses in ethyl alcohol (the viscosity of which in the Ford cup is 40 seconds) 5 parts 1,5-diaminoanthradiinone dispersed. If you do the same with 8 parts of the dye of the formula

CN

H ₃ C

HO

or the dye of the formula

H, (((CII C C <II,

■ i ':'

Nf (N

N OH O N

Il

Il

and 4 parts of 1,4-diaminoanthraquinone or 4 parts of amino-4-phenvlaminoanthraquinone is obtained one green printing ink while one with 9 parts 4- (p-Mitrophenyla / .o) -3-methyl-5-pyrazolone a yellow Printing ink received. With these three printing inks and three pressure /> relieve you can print a yellow, red and green Motif iiiif a coated paper strip underneath Use of the customary collotype printing process.The paper obtained in this way allows printing of ULrtciJOii ciuS tJiiiifnwwrit: uuci ruiycMCl / munitwoiiL '.

which have been impregnated with thermosetting aminoplasts by dry transfer at 220 C in very u ash-resistant colors.

Example 4

A varnish is produced by cleaning 1 part of e-melted phenolic resin and 1 part at 260 C. Mixing linseed oil, one loud to 190 ° C cool, I part mineral oil to and IaUt cool.

Part I 1.5-diaminoanthraquinone is added to 10 parts of this varnish by mixing this mixture in a cylinder mill to disperse the dye in the varnish, which is 0.5 parts Cobalt naphthenate adds.

The printing ink produced in this way is used to print a red motif using the offset printing process Sheet of paper. The print obtained forms neither a deposit nor dirt. The transfer print carrier thus produced allows a red motif to be printed by operating as indicated above.

Equally advantageous results are obtained if a printing ink is produced as stated above, but starting from a varnish which has been produced from 1 part of phenolic resin, 2 parts of linseed oil and 1.2 parts of alkali resin modified with linseed oil , 0, which has been modified with L.einoi parts of mineral oil I ¹ J parts of linseed oil and 0.i 5 parts of alkyd resin. or by replacing the 0.5 part of cobalt naphthenate with 0.5 part of cobalt oetoate or manganese octoate or with 0.4 part of cobalt linoleate or with 0.05 part of commercially available stabilized aluminum chelate. Very satisfactory results are also obtained if 7% of a wax-polyethylene paste, which softens at about 105 ° C., or 15% aluminum hydrate is added to the printing ink.

Claims (1)

Patent claims: 1. Auxiliary carrier for thermal printing in the gas phase, characterized in that one of the surfaces of a sheet or strip of paper ^{carries at least one dye which can be vaporized or sublimed below 240 0} C at atmospheric pressure and is selected from the group consisting of the disperse dye ρ of the general formula