DE1940532A1 - Sublimation printing form for the transfer of printing ink under the influence of heat - Google Patents

Description

OR. ELISABETH YOUNG. DR. VOLKER VOSSiIfS. BiPL.-PIECE. GERHARD CQLDEWEY

MONKS

8 Munich 23 CLEMENSSTRASSE 30>,

|. PHONE! 34S067 ^ TELEGRAMiM-ABRESSES tNVEMT / MONCMEN

TELEX 5 23 686

ΐ 91G

TQPEAH ΗΗΚ1ΊΚΟ GOMBKST _9s , »Japan

9 «Ap-ria 1969. Japan, Mr * 2739'FZ ¹ SS and 2?

h? tri ££ t> aine- ^ .blijaati

door dl

especially- t

eiae SublitaatlonsdrEiekforaiai ,, with their. help print on vsraehiaäsae- Oberf läolieii ^ argeaommeri, values » where the Brußkiormexi sizable dyes tmd B contain. ".: ...- ■ -" ■ "■

F - * - are ¥ srfahri3a zur Bruakfai'bsiiransferufög · ian.tar i-ti: <i'g on Trerse & iiyJei & cs: ObBrflgciXeiafeekanat ^ where S öruelsfosrmsa asa- "2? R% ßi * fOliois. _N - inebes paper · ,,,

j, 4ie wit ^ immc- Bruekfax ^ beBaefei ^ ikt iait iem, tcr provided siM- with the help of di. © Ber StibMj

_t kiilo «h nw Qm & aXiie Farba ^^ βϊ, βό © iisf 'ax'big-e Biläer ^^ ri &quot; ^^ siii | m ^ Jf ^ Ji: 3 _u ¹ ThI tt © is w * Liss; uösrtragas. wsräesic. They are·. fi | r iis.e MofaE-fiirbsaübos'tr-Hg.iaiiig; therefore "tm ^ ee-Ä ^ s. © ^»: .. because feei

BATH ORIGINAL

Prints from multiple printing forms can be obtained * When the printing ink transfer is carried out under the influence of heat, which have a pattern of yellow , red and blue printing inks printed in layers on the form, the upper layer of blue printing ink is then applied without disturbance by the effect of heat transferase, organic middle layer from the roteii .Dru ^ & f arbe is in the transfer of the upper view from the blue printing color unfettered through the bite, and the transfer of the yellow dye in the bottom layer is "by the two overflowing binary 'telfilae of the blue ' iwä red printing ink, instead of a multicolored, true-to-original impression, either only the blue dye is transferred or a completely differently colored image is obtained from the printing form.

The invention 'is the creation of a sublimation printing form for the multicolor transfer of' printing inks ... 'onto different surfaces by swirling, in the case of which. the shortcomings that occur when applying the well-known SublimaMoas print to multicolor transfer j y &naied; «« will »-.'-. ' ■. '"-." ■ ...-..-. - "--- ■ - .. -; -ä ^>v> / \

The sublimation printing form according to the invention from a with printed binder-containing sublimable Bruckferben Carrier film for the transfer of Bruek colors under the influence of heat is characterized by having several different Distributed in a dry solid resinous medium sublimable bridge colors in SeMcthten überir ^ axuler isaigec * rdnet

. BATH ORIGINAL

contains, the binder either a la binder or printing ink solvent insoluble, at the transfer temperature inert, non-softening or peelable granular inorganic or organic filler and / or a the transfer temperature contains a substance that decomposes with the evolution of gas in such an amount that the printing ferns can become porous when heated.

Due to the becoming porous, each one printed on the printing form In the case of perfume transfer, the gaseous, sublime dyes can also sublimate the lower layers

penetrate and be transferred to the surface to which the dyes are to be transferred. Bas becoming porous Schiohten can be reached in two ways, individually or in combination. One way becomes an ink binder uses an inactive filler in the form of fine grains

which is insoluble in the solvent and the dissolved part of the binder and neither softens nor melts due to the action of heat during transfer. According to the other way a binder is used _for containing a substance, of the vapors or gases on heating forms, whereby the layer is porous, before the dye sublimated. The gases must be inert to the dyes.

According to a preferred embodiment of the invention, the top layer of the sublimation printing form contains larger ones Quantities of the filler and / or of the substance that decomposes with evolution of gas and / or it becomes - a dye in the lower Layer used whose sublimation ability is greater than

009817/1273

ν ■ BAD ORIGINAL

that of the dyes in the upper layers.

In general, multi-color prints retain their color tint by a combination in compliance with gradations dor three primary colors yellow, red. and blue, which are printed in this order, although not necessarily limited to this order. The printing ink layers from the yellow, red and blue printing dyes are each printed on using printing plates for offset printing, gravure printing, embossing printing or screen printing, produced by conventional photographic processes.

Multicolor layers from the three printing inks are also in accordance with the invention usually printed on the sublimation printing form in the usual manner. The following detailed explanation the invention relates to such three-color printing forms. Eb can also use more colors in the same way Sublimation printing forms applied and by the action of heat be transmitted.

During the production of the multicolor printing forms according to the invention, the printing inks are printed in three layers in the order yellow, red and blue on a carrier material, for example paper. The printing ink of each layer consists of a dye and a binder containing the filler or gas evolving agent for making porosity. In particular, it is preferred to carry out the Zümisehung of the filler or the binder for gasentwikkelnden.Stoffs so that the "off fill quantity or the amount of substance in the gasentwiokelnden ■» uppermost layer is highest and / or lowest for the

BATH ORIGINAL

Layers a dye is selected »which sublies more easily than the dye of the printing inks printed on later. For example, a yellow printing ink is first printed on a film, such as paper, which consists of a sublimable yellow dye and a binder with A% by weight of a filler or gas-generating substance that makes the binder porous when heated red printing ink is printed over the yellow printing ink, which consists of a sublimable red dye and a binder with B weight percent of the same filler or gas-evolving substance. Finally, a blue printing ink composed of a sublimable blue dye and a binder which contains C% by weight of the same filler or gas-developing substance is printed over the red printing ink layer. The concentrations of fillers or gas-evolving substances are chosen so that A4B <C. A multicolor sublimation paper printing form according to an embodiment of the invention is obtained.

Another embodiment of a multi-color sublimation paper printing form is made by printing a yellow ink on it Paper made from a highly sublimable yellow dye and a binder containing the filler or gas-evolving substance, overprint the yellow layer with a red printing ink from a massively sublimable red dye and the same binder and finally overprinting this layer with a blue ink made a slow sublimable blue dye and the same binder

BATH ORIGINAL

Suitable dyes for printing inks that can be used according to the invention are, for example, basic shriphenylmethane dyes * disperse dyes, * mordant dyes, azo-anthraquinone-triphenylmethane dyes and oxidation dyes. The chemical constitution The coloring is particularly limited as long as it is are sublimable dyes.

Useful binders include other carboxymethylcellulose, alginic acid and its derivatives, and polymers which contain one or more of the following: vinyl alcohol "W vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid and maleic acid.

Inert fillers which are used in the sublimation printing forms according to the invention are simple inorganic compounds and compounds which contain one or more silicon ·? * Barium, calcium, potassium, magnesium, zinc, iron, aluminum, tin _r Contain lead, cadmium, sulfur and / or carbon atoms, such as sulfates, especially barium and calcium sulfate _F carbonates, such as calcium and magnesium carbonate, * silicates such as aluminum and magnesium silicate, sulfides such as zinc sulfide, oxides such as aluminum -and silicon oxides, and or-

.. * - "--- '. - " ■■ "■■■ ^: ■ ■'""■■■■■■'■■■'". v -; 'Tvi -.-' ■■

Ganistic substances such as synthetic resins, of which "hard" and resins are preferred, natural resins such as renewable rubber, and natural substances such as charcoal powder and cellulose powder. The grain size of the filler must be selected according to the desired purity of the print color imprint. Grain sizes below 5 microns in diameter are usually preferred.

009817/1273

The inert filler is preferably used in an amount of 50 to 150 parts by weight per 100 parts by weight of binder are used. If the binder sw contains large amounts of filler »will the adhesive strength of the printing ink surfaces is too weak, while if the amount of filler is too small, the porous areas are too far apart and the subliming dye comes from the lower ones Shifts no longer find a passage *

Transfer of the color reports from the multi-color sublimation printing form to the receiving surface onto which the dye is transferred is to be promoted by the fact that the filler content the binder of each printing color is different, where the amount of filler in the upper layer is greater than that in the lower layer is. For example, the amount of filler increases in the order of yellow, red and blue when printing the Sublimation printing! "Orm is done with multi-colored layers in the order yellow, red and blue.

The filler makes the ink layer porous so that it is can be penetrated by the subliming dye. the Porosity of the base of the transfer paper on The most distant layer must be larger than that of the others Be careful so that dye can sublimate from the lower layers. The amount of filler in each layer will be therefore adjusted so that it is greatest in the layer facing away from the carrier material.

All of the example of a paper printing format explained for sublimation printing according to the invention is applied to the image area on the Receiver flech applied and heated under pressure, e.g. with

'' "". ' 0 Ö ÖS 17/127 3 - ■

■. 'BAD ORIGINAL

an electric iron whose heat has been set to a certain temperature. The dyes printed in each layer sublime and the sublimate penetrates the overlying porous layers and is deposited evenly on the receiving surface with condensation. In this way, the same color image is transferred, which carries the paper printing form _o One can transfer to make some ten Me.l, although the transferred image is gradually doing worse.

When used in place of a filler, a gas-evolving material and printed on the Siiblimationsäruckfonn ink layer is made porous by heating, for example, the following compounds can be used as gas-evolving materials: azo compounds such as azodicarbonamide, azobisisobutyronitrile, azocyclohexylnitrile, diazoaminobenzene and barium azodicarboxylate, sulfonyl hydrazides such as benzenesulfonyl hydrazide _f Benzenesulfonylhydrazine, toluenesulfonylhydrazide and diphenylsulfon-313'-disulfonylhydrazide _f nitroso compounds such as N, N-dinitroso-pentamethylenetetramine and HjN-dimethyl-NjN'-dinitrosoterephthalic acid, or inorganic compounds such as ammonic bicarbonate and sodium bicarbonate, sodium bicarbonate. - ■ "- ■; ■ ·

If such a gas-generating substance is used to compensate for the heat transfer of each dye in the layers when printing the pattern in the order yellow _P red and blue and the amount of substance in the binder of the printing ink was A, B or C GeWc- £, the following applies: - That A <B <C, where A _r B and C »preferably 2 to 30 is'v. ~ ^ _f related to the resin content of the

009817/1273 -

BATH ORIGINAL

Binder.

The Suftliiaationsdruekforra, which is composed in this manner, ν; ν · .α with the Bi ^ dflache to one receiver * laugh brought raid heated under pressure to -Beispiel'mit an electric iron with the temperature set. Here the gas is evolving. ' Foaming agent is released and the printing inks in question are made porous. At the same time, the dyes sublime and migrate through the porous printing ink layers onto the recipient surface. In this case is the amount of gas ··. Developing substances in the upper layer are greater than those in the lower layers, whereby the porosity of the upper layer is greater than that of the lower layers and the transfer rate of the sublimed dye in the upper layer is about the same as that in the lower layer Layers will. It's wrong! practically the same color scheme ... and the symmetry of the print form. Transferring the egg-filling surface. If dyes are used in every BruükfarbenaahiGht of the Sufolimationuruokform dyes in the different sublimation properties, - ■ so ■ can the dye viahl as successQn ₈ that the dye "the lower, !! Layers sahnsllsx * sublisiiert as the dye in the obsrea Sehioiit _tf wodiir-ch further a Änglöiohuiig the Farbstoffübertragi.mg arfolgt,

Me invention-wix'd explained in more detail by the following examples.

It will be an iMafdrucicpapier "isittsls Tx & f printing plates with three r" following. Siis.amms5Ji £ tetsu »g in the order

alau ba <lruck: ·; .....- '- "-.-"

00981771273

.-'- "BADORtGiNAL

a) Ge3.be printing ink
WhatBarlöaliches Acrylic Resin Water *

Silicon dioxide (medium particles gröasQ 1 - 2)

Diacelliton Eehtgelb G (Mi beübiehi K, K », Japan)

8th Parts by weight 92 η 5 Il 15th Il 8th. Parts by weight 92 I)

b) Red printing ink
Water, like acrylic resin, water
Silicon dioxide

Xayalon Eeh / trubin B {fliiion layaku K.K., Japan)

g) Blue print color
Water soluble acrylic resin water "

Silicon dioxide.

Sumikalon Blue FB (Sumitomo Kagaku, KtK. _R Japan)

A multicolored sublimation printing form made of paper is obtained. The paper is brought into close contact with a clean white polyester fabric and heated to 180 ° C. for 30 seconds. A polyester fabric is obtained with the same multicolored pattern as shown in the printing form.

15 "

B CiSwichtsteiXe 92 "α n

A rotogravure paper is printed with three printing inks of the following to & amamBetzvBig in the order yellow, red and blue, which contain azodicarbonamide of a particle below 0.0.4 rm, which under Geeentv / icklung

0098 17/1273

BAD ORiGlHAL

190 to 200 C decomposed.

a) Yellow printing ink. Water-soluble acrylic resin. Water

Azodiearbonamide (foaming agent)

Diacelliton Eohtgelb G (Mitsubishi Easel K.K., Japan)

b) Red printing ink. Water-soluble acrylic resin. Water

Azodiearbonamide (foaming agent)

Kayalon Echtrubin B (Nihon Kayaim K.K., Japan)

c) Blue printing ink. Water-soluble acrylic resin water

Azodiearbonamide (foaming agent)

Sumikalon Blue FB (Sumitomo Kagaku K.E., Japan)

7 parts by weight

93 ■ .- "■ 0.7 (lOjC)

7 parts by weight 93 ° 1.05 «

15 "

7 parts by weight 93 "1.4 ^M.

15 .- ■■■ ". ■

A multicolored sublimation printing form is obtained which on a clean, white polyester fabric and 60 Seconds to 195 ° C is heated. It will be on the polyester fabric the same multicolored pattern as on the printing plate.

A sublimation printing form made of paper according to Example 2 is used using the following printing inks:

009817/127 3

a) Yellow printing ink Water-soluble acrylic resin water

Dinitrooopentamethylene tetramine (Foaming agent)

Diacelliton real yellow G (Mitsubishi Kaeei K.K., Japan)

b) red printing ink
Water soluble acrylic resin water

Dinitrosopentamethylenetetramine (Foaming agent)

Kayalon Echtrubin B (Kihan Kayaku K.K., Japan)

c) Blue printing ink Water-soluble acrylic resin water

DinitroBopentamethylenetetramine (Foaming agent)

Sumikalon Blue FB (Sumitomo Kagaku K.K., Japan)

8th Parts by weight 92 η 1, 6 υ 10 ti 8th Weight parts 92 It 1, 6 " 12, 5 " 8th Gewiohtsteile 92 Il

1.6

15th

A polyester fabric is dyed according to example 2 and that get same result.

A printing paper is printed with the following partial printing inks: a) Yellow printing ink

Water-soluble acrylic resin 12 parts by weight

Water 98 "

Silicon dioxide. 10 "p-Ainlnoacel-anili.d 10 η

0098 17/1 273

BATH ORIGINAL

12th Parts by weight 93 η 10 M. 10 12th Gauge parts 93 -H-" 10 Il 10 Il

b) Red printing ink. Water-soluble acrylic resin water

Silicon dioxide
2-chloro-4-nitroaniliiri

c) Blue ink. Water-soluble acrylic resin. Water
Silicon dioxide

1.4 "Diza © thy laminoanthraehinone

The printing inks are put into the ink container in the order mentioned filled in a rotogravure printing machine. A multicolored paper is produced in the form of a sublimation print. the Measurement of the sublimation rate of the dye shows that p-amiftoacetanilide is the fastest, 2 ~ chloro-4-nitroaniline moderately fast and 1,4-dimethylaminoanthraquinone the slowest sublimated. When the sublimation printing form has a receiver sheet is pressed and heated, the same color pattern is obtained as on the printing form,

Example

According to Example 4, a sublimation printing form is printed with the following printing inks:. a) Yellow printing ink

Polyvinyl alcohol 20 parts by weight

Water . 150 ■ .-, ⁰ ^

- Soft clay. ■■. · 15 '. ■. ■ = / ■ * ■, ■ · ■ .., - ···? ■■ - ..

Diaöelliton -Eohtgelb G (Mitsubishi ■. Kasei K>& ·, Japaa) .. ^: ■■ - 10. " ^M

* ^V "' Ö 0 98 17/127 3

BATH ORIGINAL

b) Red printing ink »

Polyvinyl alcohol 20 parts by weight

Water 150 "»

Soft tone 15 ^m

Cibaoet Brilliantrosa 4 BN (Ciba AG, Switzerland) 12 ^M

. c) Blue ink

Polyvinyl alcohol 20 parts by weight

Water 150 »

Soggy 15 ^M

Gibacat brilliant blue 3 tbsp (Ciba A.G., Sweat) 15 "

Of the dyes mentioned, Diaoelliton Real Yellow G sublimates the fastest, Cibaoet Brilliant Pink 4 BK massive and Cibacet Brilliant Blue 3 BL the slowest. Sas with the inks in the order named printed transfer paper is placed on a receiver material and heated for 60 seconds 18O ⁰ C under pressure. Ss will be the same multicolored pattern as on the

Preserved printing form. ,

; . . - - .- .; ■. ■. ■■■. V-: .- ■ The image obtained on the surface of the receiver material, which is obtained with the aid of the sublimation printing forms according to the invention has a superior color scheme compared to with known sublimation printing forms. Exactly the same color patterns become clearer and through heat transfer generated clean form, as they are on the printing form.

The receiving material can be ordinary paper, a plastic, -Fiber material or a metal. Except for multi-color printing

Ό09817 / 1273 -

single-color prints can be produced with the printing forms according to the invention. <

- patent claims -

0 098 1 7/1 27 3

Claims (4)

Claims 1.1 Sublimation Printing form made of a sublimable brackish ink containing all of the ink, printed carrier film for you. Dnökfarben transferimg under the influence of heat, thereby k β η η se is worthwhile, Sees it contains several different sublimable printing inks distributed in a dry solid resinous binder in layers arranged one on top of the other »whereby the binder. contains either a granular inorganic or organic filler which is insoluble in the binder or printing ink solvent, is inert at the transfer temperature, does not soften or melts and / or a substance which decomposes at the transfer temperature under d & sentklung in such an amount that the printing ink layers become porous when heated. 2. Sublimationsdruekform according to claim! k s η ζ η h eic et that the Bruckfarbena hloht®n @ d @ r carrier film of each of a rising amount of the inert fillers and / or disintegrating of the material in the binder. 3. Sublimation printing forme according to claims 1 to 2 _1, characterized in that the bruok dye layers contain 50 to 150 parts by weight of inert filler per 100 parts by weight of binder. 4. Sublimation printing form according to claim 1 to 2, characterized ge k e η n_z e 1 without t that the BriAok color oohte 2 to 30 percent by weight of the decomposing substance, based on the binder. 009817/1273 5 * Sublimatioaßäruokforiß table claims 1 to 4 _f daduroii leke & SBii eh. η ® t, that the Sruokfarbeneehie ^ th from the Urägerfoli "aua dyes with waste &sublimation" - contain. Q09817 / 127