DE2361121A1 - TRANSFER MATERIALS - Google Patents

Description

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Telex 523903 claim d

IMPERIAL CHEMICAL INDUSTRIES LIMITED,. London, Great Britain. .

"Transmission material"

Priority ; 8th December 1972, UK 56675/72

The invention relates to transmission materials for use in color transfer printing.

In the known method of transfer color printing becomes a. Transmission material made from a. Substrate like e.g. paper, which bears a print pattern that has been made with printing inks which are sublimable Containing dyes, brought into contact with a synthetic textile material, the two then under Touch will be heated .-- Under these conditions will

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the dye is transferred by volatilization or sublimation from the transfer material to the textile material, which is thus dyed in a pattern which is a mirror image of the pattern which is located on the transfer material. Although this method is suitable for use with thin textile materials, the use of thicker textile materials, such as carpets or rugs, can give rise to serious difficulties because only the surface (ie the tips of the tufts or the pile) is colored v / ird and the main part of the goods remains undyed, so that these thicker: 'materials show the well-known error of "grinning". In the case of tufted or needle felt carpets, this difficulty can be eliminated by carrying out the transfer color printing process under reduced pressure, preferably at a pressure of less than 100 mm of mercury, as described, for example, in GB-PS 1 271 327 , since by using the reduced pressure a much better penetration into thick textile materials is obtained. However, it was ^found: that, when the method of the Übertrsgungsfarbdrucks is applied at reduced pressures to very thick goods, such as false fur fabrics or runners with a very-long web of synthetic textile materials, in particular if this a loose or open Flor - The penetration into the pile is very good, so that little or no pile is colored, but the tips of the pile have a "much paler shade of color than the rest of the pile. The surface of such fabrics therefore appears only lightly colored and shows the error known as "frostiness".

It has now been found that this error can be eliminated if a transfer material is used that has been printed with one or more inks,

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each of which contains two or more sublimable dyes that give a similar hue, but each other differ in their volatility. When using such transfer materials in the process of transfer color printing of runners with a very long pile the penetrates more volatile dye, or penetrate the more volatile, dye e to the root of the pile, while the less volatile dye or the less volatile dyes only dye or dye the top of the pile. The pile is therefore from the root to the tips of the pile colored in a substantially uniform shade, thereby avoiding the mistakes known as "grinning" and "frostiness".

Thus, according to the invention, transfer materials are proposed which have a substrate with a or multiple inks have been printed or otherwise colored, each of the inks being two or more Contains sublimable disperse dyes which produce a similar dye but which are different Possess volatility.

The transfer materials according to the invention can be prepared in the usual way by printing a substrate with or several inks can be prepared, each of the inks containing two or more sublimable disperse dyes which give a similar hue, but have different volatility. The printing can be carried out by a conventional printing method such as e.g. Gravure printing, lithographic printing, flexographic printing or screen printing can be carried out on a printing machine as "commonly used for this purpose." is, wherein drying is carried out after each printing ink has been applied. '' ".

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Me for printing on the above transfer materials The printing inks used are of the type commonly used for this purpose. The only difference lies in the use of two dyes · with the properties given above. However, in order to obtain the desired hue, it is often necessary to use mixtures of dyes such as a mixture of a yellow and a blue dye to achieve green colors. Transfer materials printed with inks containing such dye mixtures are also within the scope of the invention. If in fact a mixture of dyes is used, then it is necessary to use mixtures of at least two dyes for each color present in the printing ink, one dye of each color differing in volatility from the other dye or dyes the same color differs. For example, in order to make a green color, it is necessary to have at least two yellow dyes with a similar hue but with different volatility and at least two blue ones Dyes with a similar hue but a different one To use volatility. If such dyes are chosen for mixtures of this type, then it is preferred to use dye pairs that are similar Show differences in volatility to ·; To avoid diffusion effects, which in the printed Textile material could occur and thus could cause color differences due to a separation of the individual dye components. So should for example in the case of a green mixture, the less volatile yellow dye at essentially the same rate as the less volatile blue dye evaporates, what is similar for the more volatile yellow and the more volatile blue Dye applies. In some cases, however, it may not be possible to obtain two single dyes which

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give the same dye, in which case it is possible is, a single dye with the appropriate hue to be used together with a dye mixture, which differs in terms of volatility from the; The volatility of the single dye differs. So, for example a purple hue to it. could achieve the less volatile dye is a more homogeneous purple Be dye, while the more volatile dye can be a mixture of a red and a blue dye could (the mixture being the same shade as the violet dye), the red and the blue Although the dye is less volatile than the violet dye, it evaporates at essentially the same rate.

As with a particular disperse dye or a mixture 'of disperse dyes / tertiary colors, obtained in the actual trap color tones may change _v depending on the substrate to which they are applied, it is advisable -on selection. to match the color tones of the dyes to be used for the production of the transfer papers according to the invention by transferring the separate dyes (or, depending on the case, mixtures of the individual dyes) onto a thin textile material made of the same fiber type by transfer printing}, which fibers are then im correct textile material to be printed .. In order to continue to select dyes with the corresponding differences in volatility, it is usually necessary. ·; To conduct experiments with the separate dyes (or, as the case may be, mixtures of the separate dyes) using the textile materials and transfer conditions used in commercial production.

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Preferably, the different for the production of the Transfer papers used dyes that were similar Shades result, but have a different degree of volatility, from each other by a t ^ factor of at least 10 seconds, where t ™ is the time required is to achieve 50 # penetration into a pile of carpet using the one of the following methods Conditions running, the degree of penetration is principally related to the volatility of the dye.

It will be a printing paste of the following composition,

pure, diluent-free dye 10 parts isopropanol '110 "

Toluene 880 "

Ethyl cellulose-N22, -50 ""

1000 parts

made in a ball mill, and the ink is

then applied to flexographic printing paper (55 g / m), using a # 4 K-Bsr applicator (R.K. Chemical Co. Ltd.) is used to apply a Thickness of 36 u. The printed paper will then dried at room temperature. Portions of the resulting printed paper are then mixed with pieces of a Carpet brought into contact (the printed surface of the paper is with the pile of the carpet in touch). The carpet has the following description: 1/10 gauge, 4 mm loop pile with each

400 g / m, 3.5 mesh / 25 mm carpet made of a nylon 6,6 yarn (ICI K2O1, 2720 dtex, 136 threads) in a jute back tufted. The composite samples obtained are then placed in a vacuum transfer press, as si.e for example in the German patent application

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P 21 55 Ί ^^ - Ο is described. Then, a transmission at 220 ⁰ C under vacuum of -this:? 10 mm of mercury (which is 50 mm pressure) during different times of between 5 to 120 seconds executed. The degree of penetration of the dye into the carpet pile is then measured, and from these time / penetration numbers the heating time _{required to achieve 50 # pile penetration (tr Q} ) can be measured (that is, the time of Heating, which is necessary for the dye to diffuse into the pile from a paper in contact with the carpet surface to a depth of 2 mm).

For example, a dye can have a tcQ factor of 15 seconds and the second dye that is a similar one Hue like the first results in a t ^ factor of at least * - have at least 25 seconds. If a third dye that gives a similar dye, also apply then it has a t ^ -factor that is at least 10 seconds longer than that of the second dye. Preferably the difference in the t 1 is -Q factors of dyes with a similar hue for at least 15 seconds * - ■

In actual practice, the level of penetration depends of every single dye also to a certain extent on other conditions, such as the concentration of the dye in the printing ink and / or on the paper, the the actual conditions under which the transfer is carried out and the textile material to which the Transfer is in progress. However, it is for the purpose of selecting appropriate combinations of dyes that based on the tt-Q values, these others need to be Factors are ignored and the t, -Q factor among the exact conditions given above is determined. ·

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The disperse dyes used for the preparation of the inventive Transmission materials used can be any of the known classes of disperse Belong dyes, in particular the azo, anthraquinone, nitro and quinphthaIon series, as for example in the Commercially available or described, for example, in the third edition of the Color Index, published in 1971 is. Such dyes are usually the commercially available forms, which contain substantial amounts Contain dispersants and / or other diluents. However, the corresponding pure ones can also be used Colorants that are free from dispersants and / or diluents are used, especially in the case of printing inks that act as liquid media contain organic liquids.

The substrate for the transfer material according to the invention is preferably paper, but other substrates such as aluminum foils can be used if desired. The substrate can be porous or non-porous.

The printing inks required for the production of the transfer materials according to the invention can be used in a conventional manner be prepared, for example by the fact that the mixture of dyes, a binder or a resin, a liquid medium and possibly additional components, such as dispersants, grinds in a ball mill. '

Water can be used as the liquid medium, but it is preferred to use an organic liquid or a mixture of organic liquids, such as hydrocarbons, for example toluene, xylene and aliphatic petroleum fractions, which ^{boil in the range from 80 to 200 0} C, Alcohols such as isopropanol, ketones such as methyl ethyl ketone, and esters such as methyl acetate *

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The binder used in the printing inks or the one in the Resin used in printing inks can be any known binder or any known resin such as those used in manufacture used by printing inks. The selection of the binder and the resin that is used depends on the liquid Medium and physical properties of the resulting printing ink. Such binders or resins are for example in the first edition of the Printing Ink Manual, which was published in 1961, and in Ink Technology for Printers and Students by E.A. Apps, which came out in 1963. in the In the case of printing inks based on organic liquids as media, binders are particularly suitable Cellulose ethers that are soluble in such liquids, such as ethyl cellulose and hydroxypropyl cellulose. .

The transmission materials according to the invention are suitable especially for dyeing thick synthetic textile materials, especially carpet = and runners, with one long pile or artificial fur fabrics, the Transmission, for example, in an intermittent Transfer press operating under an applied vacuum works, is executed, for example, in the. DT-PA.en P 21 55 144-.0 and P 23 IJ 006.5 is described. When the transfer printing is carried out, the printing surface of the transfer material is with the Surface of the synthetic textile material that is dyed should be in contact. .

Examples of synthetic textile materials are cellulose acetate - Textile materials, such as those made from secondary Cellulose acetate and cellulose triacetate, polyacrylonitrile textile materials, Polyurethane textile materials, aromatic Polyester textile materials, such as those made of polyethylene terephthalate, and textile materials made from synthetic poly-

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such as those made from nylon-6, nylon-6,6 and Quiana. (registered trademark). If appropriate, mixtures of such materials can also be used be used.

If the erfindungsgeinässen transmission materials for the transfer color printing process is used on thick synthetic fabrics, particularly in Carpets or rugs with a long pile or artificial felt fabrics, then the conditions for penetration are good obtain. In addition, there is little change in hue through the entire depth of the tints.

The invention is illustrated in more detail by the following examples, in which the parts and percentages are expressed by weight are.

Three inks were prepared using the components listed below in a ball mill for 24 hours were ground:

Printing color A Parts 25th Il 25th Il 50 ti 100 Il 800 Parts 1000

i-Amino - ^ - hydroxyanthraquinone, (t | -Q = 15 see)

1, ^ - Diamino ^ -methoxyanthraquinone (t ™ * 60 see)

Ethyl Cellulose-N22 (Hercules Powder Co.)

Isopropanol

toluene

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^ 11. - ■ '

Printing color B - ^ - -. "" · .- ■.

25 parts 1,4-Oi- (methylamino) anthraquinone (tcQ = -15 see)

25 "partially methylated 1, S-hydroxy-4,5- '.

diaminoanthraquinone Ct ₁ -Q = 45 see)

50 "ethyl cellulose-N22

100 "isopropanol

800 "toluene" .- ■■■

1000 parts

Printing ink C

25 parts of 2-hydroxy-5-methyl-4 ^l -acetylaminoazobenzene (tcQ = 60 see)

25 "■■" N-Ethylindole-J ^ '- isoindolindigo Ct ₅₀ = .30 see)

50 "■ ethyl cellulose-N22

100 "isopropanol.

800 "Toluene .-- '.'

1000 pieces ''_,"'

example 1

A mixture of 80 parts of printing ink and 20 parts of printing ink B is applied to paper by gravure printing, whereby a smooth roller is used. The paper is then dried.

A piece of the transfer paper thus obtained is brought into contact with a piece of nylon carpet (with a pile of nylon 6,6 fibers tufted into a burlap backing), the printed surface of the paper with the pile of the runner in Contact comes, whereupon the transfer pressure is carried out in an intermittent vacuum press of the type described in GB-PA P 21 55 144.0. In this case, a vacuum of 710 nm mercury is applied at 240 ⁰ G for 45 seconds. The nylon runner is overall in a purple shade with

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an excellent penetration into the pile. There is with little or no change in the depth of the shade of the pile.

Example 2

The printing ink B 'is applied by a gravure printing process Paper applied using a smooth roller. The paper is then dried.

The resulting paper is then used to carry out transfer printing onto a nylon traveler using the press described in Example 1 and the conditions described in Example Λ. The nylon runner is dyed a blue shade everywhere, with excellent penetration into the pile. There is little or no change in the depth of the shade of the pile. '-

Example 3

Paper is made in a similar way with printing ink A or printing ink C or a mixture of equal parts of printing ink A and 0 or a mixture of equal parts printing inks B and C are printed. The papers obtained are then used for transfer printing of a nylon runner, the press described in Example 1 and the press described in Example 1 being used Conditions are used. The nylon runners are colored in red, yellow, orange and green shades', excellent penetration into the pile prevails. There will be little or no differences in the Preserve the color depth of the pile

Example 4- '.I

A printing ink that consists of a mixture of the following components:

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25th Parts 9 Il 16 Il 50 Il 100 Il 800 Il ii000 Parts

- 13 -. "■ -.

1- (p-Toluidino) -4-hydroxyanthraquinone (^ ₅₀ = 30 sec),

i-Amino-4-hydroxyanthraquinone (t ™ = -15 sec)

1 ^ -Di-CmethylaminoO-anthraquinone (tc _Q = '15 see)

Ethyl cellulose-N22

Isopropanol

toluene

is made by, a gravure print using a smooth Roll applied to paper, and then the printed one Paper dried.

A piece of the obtained transfer paper is attached to a Nylon runner (the printed surface of the paper lies with it with the pile of the traveler) "and then the transfer pressure is made using the press and using the conditions set out in Example 1 described are carried out. The nylon runner comes in a bluish purple hue with a good one Penetration into the pile and colored with little or no difference in shade depth within the pile. -;

Example 5 . -

A printing ink made from a mixture of the following components consists: .

10 parts A-Nitro - ^ '- aminoazobenzol Ct ₅₀ ■ 15 see) 15 "4-Nitro - ^' - anilinoazobenzol (^ c ₀ - ^ 5 see)

5 "1-Phenylazo-4- (p-hydroxyphenylazo) -naphthalene

(t ^ ₀ = 65 see).

50 "ethyl cellulose-N22

120 "mesitylene ■.

800 "xylene

1000 parts

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is durcti. Engraving print applied to Pepier, and that printed paper is then dried.

A piece of the transfer paper obtained is attached to a. Is brought Polyestern8delfilz into contact, having a velor surface, and the transfer is then carried out in the press and, under the conditions described in Example 1, except that a temperature of 21O ° C (instead of 24O ⁰ C) . The needle felt is dyed in an orange shade.

A similar result is obtained when using this transfer paper is used to dye an acrylic cut pile carpet, the transfer pressure being at at a temperature of 1-5 ° C.

Example 6 · '_

The printing ink described in Example 5 is printed onto paper on a rotary screen printing machine showing a pattern. The printed paper is then dried in a hot air stream at a temperature below 150 ^0C.

A piece of the obtained transfer paper is attached to a Shaggy pile carpet tile made of nylon-6,6 brought into contact, and the transfer is then carried out using the press and the conditions described in Example 1 executed. The carpet tile is printed in a bright orange and white pattern. It becomes an excellent penetration in those parts of the pile in those parts of the tile that have been printed orange.

Example 7

A mixture of

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20th share 20th π 5 Il 5 Il

15 -

Λ -Amino-4-hydroxyanthraquinone 1,4-diamino-2-methoxyanthraquinone 1,4-di (methylamino) anthraquinone

partially methylated 1,8 ~ dihydroxy-4,5-diaminoanthraquinone '".

25 "'of a 50 ^ igen solution of a condensate of tolylene diisocyanate / 1,6-hexanediol / hydroxy ester of 12-hydroxystearic acid and a hexadecanol / octadecanol mixture in an aliphatic petroleum distillate', the condensate according to Example 1 of BE-PS 795 74- 8 has been produced, 125 parts of aliphatic petroleum fraction in a boiling range, from 100 to 120 ° C _}

is ground in a ball mill to a flowable Prepare dispersion in which the dye particles are smaller than 3 u / and-the main part is greater than 1 u "

The dispersion obtained then becomes an iron 50 solution Parts of ethyl cellulose-N22 in a mixture of 100 parts Isopropanol and 850 parts of toluene were added. *.

The printing ink obtained is printed on paper by gravure printing is applied using a smooth roller. The paper is then dried. '

The obtained Pepier is used for transfer printing on a Nylon runner used, with the press and conditions of Example 1 can be used »The runner is colored in a purple shade. It finds an excellent

O'Cl PT * \ C € * T Tl

penetration into the pile, with only a slight / hue, there is a difference in the pile.

Claims: 409 824/1 03A

Claims (10)

PATENT CLAIMS: · ■ ■ ' 1. Transfer materials, consisting of a substrate, which has been printed or otherwise 'colored with one or more printing inks, characterized in that a' each color contains two or more sublimable disperse dyes which give similar hues but which differ in terms of color of volatility. 2. · transfer materials according to claim 1 - _r characterized in that each dye which provides a similar color tone, consisting of a mixture of dyes, which volatilize at substantially the same speed. 3. Transfer materials according to claim 1, characterized in that that at least one of the dyes consists of a single dye which has the corresponding hue results, and that the remaining dye or dyes consist of a mixture of dyes, which give the same hue as the single dye, the dyes present in the mixture im have essentially the same volatility, which is either greater or lesser than the volatility of the only one Dye of the same shade. 4 ·. Transfer materials according to one of Claims 1 to 3, characterized in that the dyes which produce similar hues differ from one another by a te _Q factor of at least 10 seconds. 5 · Transfer materials according to one of claims 1 to 4-, characterized in that the difference between the tj-Q factors is at least 15 seconds. 409824/103 4 6. Transfer materials according to one of claims 1 to 5, characterized in that the substrate is made of paper consists. - 7. A method for producing the transfer materials according to claim 1, characterized in that a substrate printed with one or more inks, of which each contains two or more sublimable disperse dyes which produce similar hues but which are different Having volatility, drying being carried out after the application of each ink. 8. Using the transfer materials after a of claims 1 to 5, for printing synthetic textile material! en. . ;, .- ■ ". 9. 'Use according to claim 8, characterized in that that the process is carried out under reduced pressure. 10. Use according to claim 8 or 9, characterized in that that the synthetic textile material consists of a Carpet, a runner or a fur textile fabric, which has a pile or tuff made of synthetic textile material having. " 4 0 9 8 2 4/1034