EP0114833A1

EP0114833A1 - Carrier surface for dry thermal printing of cellulose fibers

Info

Publication number: EP0114833A1
Application number: EP83901895A
Authority: EP
Inventors: Wolfgang Mehl
Original assignee: SICPA Holding SA
Current assignee: SICPA Holding SA
Priority date: 1982-07-12
Filing date: 1983-06-30
Publication date: 1984-08-08
Also published as: ATE22418T1; US4682983A; EP0099333A1; JPS59501255A; WO1984000325A1; EP0099333B1; DE3366444D1

Abstract

The transfer sheet is used for dry thermal printing of water swellable celluluse fibers with dyestuffs which are insoluble in water of 60 DEG C. The dyestuffs are difficult to evaporate and cannot be used in a conventional heat transfer printing process. They are transferred at 230 DEG C. and a contact pressure of 104-106 Pa from a base paper provided with a release coating, to cellulose fibers which have been swollen with water and the swollen state of which has been preserved after drying with a polyglycol. I order to increase the penetration of dyestuffs into the textile structure, it is recommended to lower the air pressure in the transfer area down to a pressure ranging from 1 to 5x104 Pa.

Description

Transfer medium for the thermal dry printing of cellulose fibers.

The present invention relates to new transfer printing media, especially those made of paper, for the thermal dry printing of water-swellable cellulose fibers or threads or textiles containing them, optionally in mixtures with synthetic fiber, especially based on polyester, with disperse dyes using polyglycols and / or Polyglycol derivatives.

Conventional transfer printing, the principles of which e.g. in French Patents 1,223,330 and 1,585,119 uses transfer printing supports, generally made of paper, which carry the pattern to be transferred, which consists of several or one dye. In contact with a textile material, the pattern passes from the transfer medium to the textile at 160 to 210 ° C. The dyes customary for transfer printing belong to the class of disperse dyes, which are known to have a low affinity for natural fibers, which is why transfer printing has practically only established itself for synthetic fibers, in particular for fabrics and knitted fabrics made of polyester.

The attempts to make native fibers, especially those made of cellulose, accessible to transfer printing can be roughly divided into three groups: pretreatment with a resin, chemical modification of the fiber and treatment with a solvent for disperse dyes.

The resin pretreatment is known, for example, from Swiss patent 564 637, which teaches that a cotton web is impregnated with an etherified methyl olmelamine. After intermediate drying, the pre-impregnated goods are printed in transfer. The melamine resin is condensed out during the printing process. The main disadvantages of this process lie in the difficulty in ensuring the uniformity of the application of the melamine resin over the textile web, which influences the depth of color, and in controlling the pretreatment in such a way that the condensation takes place properly. For this reason, neither the uniformity of the print nor its authenticity always meet expectations and the process has so far not been able to establish itself correctly.

It is known, for example, from Swiss Patent 560 286 that the cellulose fiber can be given an affinity for disperse dyes by chemical modification, in particular acetylation, benzoylation, cyanoethylation, cyanuration and grafting of styrene. Although the depth of color and the handle of the chemically modified cotton are satisfactory, the process has not been able to establish itself properly, since the method is complex and costly and the washfastness of the prints is unsatisfactory (see, for example, Eisele and Fiebig, Meliand TextiIberichte 61, 956-961 (1980).

It has long been known that cotton fibers and other cellulose substances swell in contact with water, the goods becoming more voluminous and flexible (see, for example, Valko and Limdi in "Textile Research Journal" 32, 331-337 (1962) Open structure of the swollen cellulose materials is easily penetrated by water-soluble, high-boiling compounds. Such compounds are known which maintain the swelling even after the water has been largely removed. Such compounds which maintain the swelling are, for example, polyglycols and polyglycol derivatives, as described in that of the Germans Patent 1 811 796 and German Offenlegungsschrift 2 524 243. Polyglycols and polyglycol derivatives are generally good solvents for disperse dyes, for example if a cotton fabric is impregnated with a 10 to 20 percent aqueous solution of polyethylene glycol 600, dried at 120 ° C. and then thermobedruc at 200 to 210 ° C kt, you get brilliant, color-deep prints. The good dye This is explained by the fact that the hot polyglycol, which is still in the fiber during thermal printing, dissolves the dye vapors and finely distributes the dissolved dye in the fibers.

However, these prints have very poor fastness to washing with the disperse dyes that are common in transfer printing, so that this process has not yet become established.

The problem of fastness to washing could be solved by using disperse or vat dyes which are absolutely insoluble in water even at elevated temperatures, for example 60 ° C.

To test this property, saturated solutions or dyes are expediently prepared in boiling 0.1 molar sodium carbonate solution and the optical absorption capacity is measured using a commercial spectrometer. Only those disperse or vat dyes are considered whose absorption capacity is not greater than 0.3. Such dyes are known from German patent specification 1 811 796 and from German patent application 25 24 243. They are mainly molecules with a molecular weight greater than 350 and high sublimation fastness, which are difficult to volatilize.

Even in the temperature range of 225 to 235 ° C, which is unusually high for sublimation transfer printing, the evaporation rate of these dyes is generally so slow that transfer printing is not possible.

The use of vacuum calenders known from my Swiss patent application 2316-79, which allow the mean free path of the molecules of the dye vapors to be increased at an air pressure reduced to 0.5 to 1 x 10 ⁴ Pa, has proven to be unsuccessful in practice because the rate of evaporation remains very low, the

Dyes are transferred from the transfer medium to the substrate in low yield and the prints lack the color depth. The penetration of the textile fabric remains inadequate, with poor rub fastness obviously caused by the build-up of large dye aggregates on the surface of the textile material. These shortcomings of the known technology are remedied by the new transfer printing medium of the present invention.

The transfer printing media according to the invention are characterized in that they carry a release layer on a flexible, heat-resistant base, for example a paper web, on which a mixture of a binder with one or more dyes is applied in the form of a uniformly colored layer or pattern. The motif can be printed using any printing method, e.g. Gravure, screen printing, offset can be applied. The motif consisting of binders and dyes, which has the form of either a colored layer or a pattern containing one or more shades, is transferred in its entirety to the textile substrate by applying pressure and temperature. The release layer makes it easier to transfer the motif from the transfer printing medium to the textile web by reducing the strength of the motif's adhesion to the base. Release layers are well known to the person skilled in the art; they consist, for example, of a silicone resin layer or of a layer of another resin with low adhesive properties. The printing of surfaces with a release layer with aqueous printing inks is problematic because of the poor wettability, which is why inks with a non-aqueous solvent are advantageously used.

The binder consists of one or more high molecular weight organic substances, at least one of which is a film former. The high molecular weight organic substances are characterized in that their softening or. Melting point is between a minimum of 50 and a maximum of 150 ° C, preferably a maximum of 100 ° C. The high molecular weight organic substances are examples of the class of resins and waxes. Examples include natural waxes, maleinate resins, phenolic resins, urea resins, resins from unsaturated hydrocarbons, epoxy resins, polyamide resins, polyglycols with a molecular weight of at least 1000, polyolefin waxes, natural waxes, Fischer-Tropsch waxes, amide waxes, fatty acid esters, fatty alcohols. Maleinate resins and resins based on it are preferred

Rosin used, for example the esters of polyvalent

Alcohols such as glycerol and pentaerythritol esters.

The dyes are characterized in that they belong to the

Disperse and vat dyes belong and that they are insoluble in water at 60 ° C. They are examples of the following types of dyes:

Anthraquinone dyes, azo dyes, indigo dyes and thioindigo dyes. Dyes from the following series have proven to be particularly advantageous:

halogenated, preferably chlorinated or brominated diphenylaminoanthraquinones;

Alkylimides of 1,4-diaminoanthraquinone-2,3-dicarboxylic acid, the alkyl group of which carries one or two phenyl radicals;

1-benzoylaminoanthraquinones which have a phenyl-NH radical in the 4-, 5- or 3-position;

Phenyl amide of 1-phenylazo-2-hydroxy-3-naphthoic acid, preferably those which are free from nitrogen-containing substituents; and

Phenyl- or naphthylamides of -phenylazo-acetyl acetic or of -phenylazo-benzoylacetic acids, in particular those which are free of nitrogen-containing substituents.

In all of these dyes, the phenyl and benzoyl radicals can contain simple substituents, such as, for example, methyl, ethyl, chlorine, bromine, methoxy, trifluoromethyl radicals, even butyl or isoamyl radicals, but preferably they do not contain any nitrogen-containing substituents. Other characteristic examples are:

1-Amino-2-methoxy-4-toluene-sulfonylaminoanthraquinone 1,4- and 1,5-dibutyrylaminoanthraquinone as well as the corresponding derivatives of methoxybenzoic acid and trifluoromethylbenzoic acid, benzoylamino-isothiazolanthrone, diphenylamides of 1-phenylazo-2-hydroxy -3-naphthoic acid which has one or more substituents on one or on the other or on both phenyl radicals, which are selected from the group of halogen atoms, especially fluorine, chlorine and bromine atoms, methyl, ethyl, Isopropyl, methoxy, ethoxy, trifluoromethyl and acetyl residues, 1-benzoylamino-4-anilinoanthraquinone, 1-phenylbenzoylamino-an-trachinone, 1-phenylazobenzoylaminoanthraquinone, 1-phenyl benzoylamino-4-methoxyanthraquinone -iso propyl- or- isoamylanilino) anthraquinone, the monoazo dyes that are obtained by coupling the naphthanilide

Acetyl or benzoylacetic acid with diazotized nitraniline or nitrotoluidine, the product of coupling barbituric acid with diazotized nitroanisidine, those obtained by coupling the diazo compound of nitrophenylaniline with the naphthanilide of acetyl acetic acid or benzoylacetic acid, the condensation products obtained by cyclizing the dioxazines of chloranil (tetrachloro-p-neighboringo) with naphthylamine, aminopyrene, aniline and its derivatives such as p-chloroaniline, toluidine, anisidine, cresidine, p-isopropylaniline, m-trifluoromethylaniline and p-dimethylaminoanil in.

In order to select the dyes, they have to produce a printing ink. These printing inks can be of the offest type, aqueous printing inks or solvent printing inks, and the techniques for producing printing inks are known.

For example, the dye is used in 100% pure form as a dry press cake in a ball mill, e.g. of the "Dynomill" type (Bachofen, Basel) ground in industrial ethyl alcohol, which is a binder known from the technique of conventional sublimation transfer printing, for example ethyl cellulose N-7 (Dow

Chemicals) contains. The preferred concentrations are 5-102 binders and a maximum of 10% dye. The grinding process is carried out until 90% of the dye particles have a diameter of less than three micrometers and none of them larger than five micrometers. With the printing inks produced in this way, a paper carrier is printed in gravure, as is known from conventional transfer printing. These transfer printing carriers are then used to carry out transfer printing tests on a swollen cotton fabric.

The swelling of the cotton fabric was carried out according to the instructions known from German patent 1811 796.

The patent teaches that the state of swelling of the cotton caused by treatment with water by a polyglycol e.g. Polyethylene glycol with a molecular weight between 300 and 1100 can be maintained after drying, the concentration of the glycol being, for example, 10 to 20% of the cotton weight.

To select the dye, the plain print carrier is pressed against the swollen cotton fabric for 30 seconds with a contact pressure of 5 x 10 ⁴ Pa at a temperature of 235 ° C, while the sandwich is held at an air pressure reduced to 10 ⁴ Pa.

Those dyes are selected that at least 60% of the transfer printing medium transferred to the textile substrate under these transfer printing conditions. Typical examples of colored dyes in this way are: the yellow dyes: C.I. Disperse Yellow 213

C.I. Disperse Yellow 214 C.I. Disperse Yellow 136,

The red dyes CI Disperse Red 346 CI Disperse Red 271 CI Disperse Red 220 The blue dyes:

C.I. Disperse Blue 192

C.I. Disperse Blue 238

C.I. Disperse Blue 327

C.I. Disperse Blue 328

and C.I. Disperse Orange 125, C.I. Disperse Green 7, C.I. Disperse Violet 64, C.I. Disperse Violet 89 and C.I. Disperse Brown 21

To produce the novel transfer printing medium with these dyes, a printing ink is produced which contains, for example, 10% dye, 10% binder and 80% solvent. This printing ink is used to print a motif containing one or more dyes on a base paper provided with a release layer.

With the new transfer carriers according to the invention, the transfer printing on dry, swollen cotton is then carried out at 235 ° C. with a contact pressure of at least 10 ⁴ Pa, in 30-60 seconds.

Brilliant prints are achieved, which are characterized by high wash fastness and sometimes high light fastness.

The handle is remarkably good and after the first wash the rub fastness is very good.

The new transfer printing media are characterized by the possibility of being able to use dyes that cannot be transferred at all in conventional sublimation transfer printing due to their high sublimation fastness and in sublimation transfer printing with reduced air pressure, despite the high mechanical effort, only with moderate yields. This makes it possible to take advantage of the adaptability of the transfer print on natural fibers while maintaining the textile mechanical properties and respecting the required fastness properties, in particular the fastness to washing. Example 1

A screen printing ink is made by dissolving

40 parts of the phthalate resin "ERKAREX 1560" (R.Kraemer GmbH.) And 5 parts of Polywachs 6000 in 90 parts of ethyl alcohol. To

150 parts of this solution become 50 parts of a 20% alcoholic

C.I. Disperse Red 346 added.

In a conventional flat stencil screen printing machine, a release paper is printed with it, which is coated by coating a 60 g / m ^{2 base} paper with polyvinyl alcohol type "Polyviol

W 25/140 "(Wacker-Chemie) was manufactured.

To prepare the transfer printing, a cotton fabric with a solution of 10% polypropylene glycol 425 in water is squeezed to 100% weight gain with a padder and dried in a tenter at 120 ° C. for one minute. For transfer printing, the paper is held against the pretreated cotton fabric for 45 seconds using a thermal printing press from Kannegiesser (Vlotho) with a contact pressure of 5 × 10 ⁴ Pa at 235 ° C. (temperature of the heating plate of the press).

The result is a brilliant red print with good fastness to washing, light and sweat. The rub fastness is acceptable. After rinsing the fabric in cold water, they become good and after washing at 60 ° C they are very good (grade 4-5 dry and wet). Be pi el 2

To produce an offset ink, a varnish is produced on a three-roll mill by mixing 42 parts of lacquered linseed oil, 20 parts of mineral oil and 38 parts of a "Alberto! KP 351" phenolic resin (Hoechst AG)

The printing ink is made on a three-roll mill from 20 parts of the dye C.I. Disperse Blue 327, 85 parts of varnish, 5 parts of Aerosil R 972 (Degussa AG) and 2 parts of co-siccative.

A release paper is produced by coating a 60 g / m ^{2 base} paper with a solution of 67 parts of ethyl alcohol, 3 parts of toluene, 25 parts of the "Eurelon 2300" polyamide resin (Schering AG) and 5 parts of the "Cibamin M-100 melamine resin "(Ciba-Geigy AG).

This release paper is printed on a conventional offset machine from "Heidelberg Offset". To prepare the transfer printing, a fabric made of 50% cotton and 50% polyester is squeezed off by treating it with a 10% aqueous solution of polypropylene glycol 425 with a pad to 80% weight gain and dried on a tenter at 120 ° C. for one minute.

Then the offset-release transfer paper is printed on the mixed fabric for 45 seconds with a contact pressure of 5 × 10 ⁴ Pa at 230 ° C.

A brilliant blue print is created. The feel of the fabric and the fastness properties are acceptable after the transfer printing, after rinsing with cold water they become very good. Example 3

The part of a cotton fabric that is to be printed is pretreated by spraying with a 2% aqueous solution of polyethylene englykol 600. The mixture is then dried at 190 ° C. for 30 seconds. For printing, a transfer support produced according to Example 2 is placed on the pretreated part of the cotton fabric for 45 seconds at 230 ° C., a contact pressure of 5 × 10 ⁴ Pa and an air pressure of 2 × 10 ⁴ Pa.

The result is a brilliant blue print with very good penetration.

Example 4:

A stock thickening for a gravure ink is produced by dissolving 12.5 parts of a glycerol resin ester type "Ha lwepa l - G" (Chemical Works Hü tteπes -A l be rtus) in a mixture of 40 parts of ethyl alcohol and 40 parts of methyl - Ethyl ketone. This thickening of the trunk is divided into three parts.

The first part of this solution is mixed with 92.5 parts of stock thickening 7.5 parts of the dye C.I. using a "Dynomill" ball mill (Bachofen AG). Ground Disperse Red 346. The grinding process. is carried out until 90% of the dye particles are smaller than 3 micrometers and the largest particles are smaller than 5 micrometers.

In the second part of the solution 8% of the dye C.I. Oisperse Yellow 213 and in the third part of the stock thickening 9.5% of the dye C.I. Disperse 31 and 327 dispersed.

This gives three gravure inks in shades of red, yellow and blue.

The base release paper described in Example 1 is then printed with three cylinders using a conventional gravure printing machine. Intermediate drying is required after each cylinder.

The cylinders are engraved in such a way that the superimposition of the three prints according to the trichomy principle provides an image of a motif.

To prepare the transfer, a fabric made of mercerized cotton is padded with a ten percent aqueous solution of a polyglycol-boric acid ester, which is commercially available under the name "Glyecin -CO" (BASF), and a Minute dried in the stenter at 120ºC. The Helio Reliability Transfer paper is printed on the goods prepared in this way for 40 seconds at 230 ° C. with a contact pressure of 10 ⁵ Pa.

The result is a brilliant multicolored print with good light and wet fastness properties.

Claims

1. Transfer printing media, which consist of an inert, flexible release layer provided with a release layer, preferably made of paper in the form of a sheet, a tape or a strip, on at least one of their surfaces on the release layer in the form of a uniformly colored layer or a sample carry a mixture of a binder with one or more disperse or vat dyes, characterized in that the binder consists of one or more high molecular organic matter, at least one of which has a softening point between 50 and 150 ° C and that the dyes are insoluble in water of 60 ° C are, in particular, that they have an optical absorption capacity of not greater than 0.3 in the form of a boiling saturated solution in ol molar aqueous sodium carbonate solution and that they are transferred by a paper subcarrier customary in sublimation transfer printing to a maximum of 40% if the latter is used with a m at a pressure of 5 x 10 ³ Pa at 200 ° C and atmospheric pressure for 30 seconds against a cotton fabric that has been swollen by water and the swelling state of which after drying is preserved by a polyglycol or a polyglycol derivative, while the dyes transfer more than 60% be when the

Auxiliary carrier is held against the same cotton fabric for 30 seconds at 230 ° C with a contact pressure of 5 x 10 ⁴ Pa and an air pressure of 10 ⁴ Pa.

2. Transfer medium according to claim 1, characterized in that the binder contains at least one resin of the following classes: natural resins, maleate resins, phenolic resins, urea resins, resins made from unsaturated hydrocarbons, epoxy resins, polyamide resins, rosin-modified resins.

3. Transfer medium according to claim 1, characterized in that the binder contains at least one wax of the following classes:

Polyglycols with a molecular weight of at least 1000, polyolefin waxes, natural waxes, Fischer-Tropsch waxes, amide waxes, fatty acid esters, fatty alcohols.

4. transfer printing medium according to one or more of claims 1 b i s 3 characterized in that they carry one or more azo, anthrachi non-, indigo or thioi ndigo dye with a molecular weight between 350 and 600.

5. Transfer carrier according to one or more of claims 1 to 4, characterized in that it contains at least one dye of the formula

D a residue of a diazo component of the aniline, aminoazobenzene, aminophthalimide, aminonaphthalimide, anthrachi or benzanthrone series,

RC ₁ - to C ₄ alkyl or phenyl optionally substituted by chlorine, bromine, methyl, methoxy or ethoxy and

R ¹ - optionally substituted by chlorine, bromine, methyl, ethyl, methoxy, ethoxy, benzyloxy, phenoxy, chlorophenoxy, optionally N-substituted carbamoyl or sulfamoyl, optionally N-substituted phthalimidyl, C ₁ - to C ₈ -alkoxycarbonyl, cyano or phenylsulfonyl Phenyl mean. Transfer printing support according to one or more of claims 1 to 4, characterized in that they contain at least one dye which contains a phenyloxyacetoamino, phenyl-OCO-O, phenyl-O-CO-NH or benzoylamino group, each bound to a monoanthraquinone nucleus , whose phenyl or benzoyl radical can carry one or more substituents which are selected from the group consisting of methyl, ethyl, methoxy, ethoxy, tri fluoromethyl radicals and fluorine, chlorine or bromine atoms.

Transfer medium according to one or more of claims 1 to 4, characterized in that they contain at least one or more dyes from the group

(a) Halogenated dianilinoanthraquinones

(b) N-alkylimides of 1,4-D i on inoanthraquinone-2,3-dicarboxylic acid, the alkyl group of which carries one or two benzene residues,

(c) Arylides of 1-phenylazo-2-hydroxy-3-naphthoic acid

(d) naphthylamides of α-phenylazo-acetylacetic acids and phenylamides of α-phenylazobenzoylacetic acids,

(e) 1-Benzoylamino-anthraquinones which carry a phenyl-NH radical in the 4-, 5- or 8-position, the phenyl and benzoyl radicals of which are methyl, ethyl, methoxy, ethoxy or trifluoromethyl substituents or can carry a fluorine, chlorine, or a bromine atom.

Transfer printing medium according to one or more of claims 1 to 4, characterized in that one of the dyes is 1-beπzoylamino -4 or -5- anilino-anthraquinone, in which at least one of the benzoyl and anilino residues carries one or more of the following substituents: fluorine, Low molecular weight chlorine, alkyl or alkoxy, trifluoromethyl or bromine.

9. Transfer printing medium according to one or more of the claims 1 to 4, characterized in that it contains at least one dye from the group

C.I. Disperse Yellow 214

C.I. Disperse Yellow 213

C.I. Disperse Red 346

C.I. Disperse Blue 327

C.I. Disperse Blue 328

C.I. Disperse Brown 21

C. I. Disperse Violet 89 included.

10. Transfer carrier according to one or more of the claims

1 to 9, characterized in that the dyes from an auxiliary medium of sublimation transfer printing made of paper in the temperature range 220 to 240 ° C with analog sublimation curves at a contact pressure of 5 x 10 ⁴ Pa, an air pressure of 1 x 10 ⁴ Pa and a contact time from 45 sec. to a cotton fabric which was swollen by water and whose swelling state after water removal was preserved by 10% polyethylene glycol 600.

11. Use of a transfer medium according to one or more of claims 1 to 10 for dyeing or dry thermal printing of textile material made of cellulose fibers or mixtures of cellulose and synthetic fibers, characterized in that the cellulose fiber part is swollen with water, that the swelling state after drying a polyglycol or a polyglycol derivative is maintained and that the printed surface of the transfer carrier is brought into contact with the material to be inked locally or in its entirety for 45 seconds at 200 to 240 ° C with a contact pressure of 10 ⁴ to 10 ° Pa , so that after the contact has ended, the layer or pattern of binder and dye remains on the textile material.

12. Use of a transfer medium according to claim 11, characterized in that the transfer pressure at 200 to 240 ° C, a contact pressure of 10 ⁴ to 10 ⁶ Pa and an air pressure of

10 ⁴ to 5 x 10 ⁴ Pa takes place.

13. Use of a transfer printing medium according to claim 11 or 12, characterized in that after the dry pressure the swelling stabilizer and the binder are removed from the fiber, preferably by rinsing with water or a solvent.

14. Use of a transfer printing substrate for local or full-surface pretreatment of textile material made of cellulose fibers or mixtures of cellulose and synthetic fibers according to one or more of claims 11 to 13, characterized in that the textile material before the dry printing locally or over the entire surface with an aqueous solution of less than 5 % Polyglycol or polyglycol derivative is sprayed and then dried.