DE2046480A1 - Temporary thrust bearings - Google Patents

Description

"Provisional pressure medium"

The invention relates to temporary print media.

Certain materials cannot because of their shape or their lack of dimensional stability can be printed directly. In such cases, a transfer printing process is used. For example To print on polyvinyl chloride bottles or foils, a temporary carrier is used first, on which you can easily find the desired pattern or motif

Case TTT-5 / E - WMy

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can apply and then transfer this motif from the temporary carrier to the final carrier.

It is known for this purpose to use an aluminum foil as a temporary carrier, which has a coating made of ethyl cellulose, to which you can transfer the Imprinted pattern. Through the ethyl cellulose is prevents the PiIm to be transferred from sticking too tightly to the printing surface.

The present invention relates to temporary carriers that are used temporarily to move towards a final object bear transferring pressure

Temporary supports of this type are described, for example, in French patent specification 1,479,558 of the applicant. These supports based on aluminum exhibit u "a _e the drawbacks that the strength of the very thin aluminum foil is insufficient, and that when DIE

that this disadvantage tries to remedy / you either increase the thickness of the films or put them on a paper tape sticks on, their cost price is too high. Furthermore, the thermal conductivity of aluminum is so high that that in certain cases, as a result of too rapid cooling in the die in which they are made, bad prints are produced. From these and from cost

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Establishment has long been the case with the aforementioned provisional Carriers tried to replace the aluminum foil carrying the pattern with a paper foil, »

The new carrier according to the present invention solve the aforementioned problem and have compared to the hitherto known carriers have considerable advantages. These new carriers are characterized in that they consist of a Foil consist, a strip or a tape of paper or regenerated cellulose, preferably a little or non-porous paper, such as an art paper or a heavy satin paper, the carries a thin and flawless layer of a mixture of nitrocellulose and an aminoplast on which the The motif or pattern to be transferred is printed which consists of a pigmented layer of a polymer or copolymer consists of vinyl chloride.

Examples of those for making the new temporary supports according to the present invention in the first place The line of papers to be considered are heavily calendered kraft papers and art print papers of the type Beghin paper, as well as other papers of this type.

For the manufacture of the provisional beam it will be done first on a surface of the paper with the help of pressure «y-

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alleviate or in some other suitable way (rotary or helicopter printing, offset, etc.) a thin and fenler-free Layer of a mixture of nitrocellulose and a curable aminoplast applied · One can apply to a or several times apply 1 to 10 g of the mixture / m paper. One preferably uses one for this purpose Varnish, an emulsion or a solution of the mixture in a volatile organic solvent · After the Drying and eventual recovery of the solvent used remains uniform on the paper Layer the aminoplast and the nitrocellulose back, which in individual cases contain a very small amount of plasticizer may contain, which is optionally used to ensure the homogeneity and flexibility of the resulting To ensure shift

The best results have been obtained with mixtures containing 4 to 6 ropes of nitrocellulose / 10 parts of the mixture, the best consisting of the aminoplast used

A condensation product of formaldehyde and melamine or preferably urea is used as the curable aminoplast used. Urea formaldehyde resins soluble in alcohol give the best results. The coating according to the present Invention can also be used with a 50- to

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6The above solution of a condensation product of urea with formaldehyde in butanol can be obtained, into which the desired amount of nitrocellulose is mixed · Instead of butanol, ethyl alcohol or methyl ethyl ketone can also be used for the preparation of the solutions _e

The production of the aminoplasts to be used is "known {see, for example, British patent specification 483 399 or Vol. 3 _f p. 482, Ullmanns Enzyklopadie der Technischen Chemie. Ullmanns Enzyklopadie der Technischen Chemie" Contains a proportion of alkyd resins to soften the coating

The mixture to be used according to the invention can easily be added simply by adding a nitrocellulose solution to a Solution of the chosen aminoplast are produced. A nitrated cellulose with about 11 ^ nitrogen, i.e. dinitrocellulost or gun cotton be used. Then you can optionally the Gfemisoh obtained, for example with acetone or dilute with methyl ethyl ketone to the desired To maintain viscosity · You can also use a small amount of plasticizer, for example $ 0.3-0.8 Add octyl adipate to prevent the layer from becoming brittle. The solution of the mixture of amino

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plast and nitrocellulose can be applied to the paper or to the Regenerated cellulose film, which forms the basis of the temporary support, on any suitable Way, preferably by means of heliogravure.

Then a \ suitable manner (rotary printing, gravure printing, photogravure, Offeet etc.) is printed to be transmitted motif or pattern on the resulting layer.

To counter the pattern after the transfer, for example To protect against abrasion, you can also apply a protective varnish to the nitrocellulose and aminoplast coating Print on acrylic resins (acrylonitrile or methacrylates) or a varnish that has the same properties . like the colors of the subject to be transferred. One of those Protective varnish can consist of an emulsified synthetic resin.

Wae the on the intermediate layer to form the to be transferred When it comes to the colors to be applied to the motif, these must contain dyes that are present in the final support do not migrate, which have good resistance to the action of light and which in the case of overlay of colors are transparent so that the obtained

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Staining after transfer not under the influence the opacity of one or the other of the constituents can be changed.

In contrast, if one wishes to transfer onto a transparent, final support, one can use the transferred Make patterns transparent by the last layer on top of those worn by the final support Pattern applies a white color "

Pur the case that the final carrier comprised of a polymer or copolymer of vinyl chloride, are the used to make layer to be transferred colors in detail of a pigment, a vinyl resin such as _# a polymer or copolymer of vinyl chloride, for example, the copolymer of 85 # vinyl chloride and 15 # vinyl acetate or 835 * vinyl chloride and 17 # vinyl acetate, as well as a solvent or a mixture of organic solvents.

The pigments used are preferably pigment preparations based on dyes, which in general of organic nature and of high molecular weight as well as finely dispersed and embedded in the vinyl resins · The Pigments themselves can be azo pigments, which by coupling or by means of condensation from anthraquinone, perinone

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Perylene, Chinaerldon, Thioindigo, Dioxazine or even Phthalocyanine dyes or other analogous organic pigments will cool down.

In cases where transparency is not an issue, you can mineral pigments may also be useful. Pas applies to the color white, for which a pigment based on titanium oxide is preferably used, or for metallized colors, which generally contain a more or less fine aluminum powder as a pigment. In the for the manufacture The pigment preparations used in the paints are pigments from a polymer or copolymer of vinyl chloride embedded, preferably in vinyl chloride acetate, an copolymer of 85 # vinyl chloride and $ 15 Vinyl acetate.

Suitable pigment preparations are described in French patent 1,079,477, and Bind in particular eolehe that contain, for example, one or more of the dyes of the following formula:

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A-NH-CO-CH-N = N-

ΗΝ ·

'V

JO 3Η,

H-

HB

! Η,

CH-! 5

CO -NH-

yellow

blue

CH,

Cl-

OH

CO-N

ORIGINAL INSPECTED

Ν «HO

NH-CO-

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Red

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which are embedded in Rhodopas AX, a copolymer made of vinyl chloride and vinyl acetate.

Various organic solvents can be used to produce the paints: aromatic and non-aromatic hydrocarbons, ketones, esters and alcohols. Preferably used solvents or solvent mixtures ν whose boiling point is below 125 ⁰ C. The pigment preparation is diluted to between 5 and 20% with 5 to 15% vinyl chloride acetate in 90 to 65% solvent and the color thus obtained is applied to the intermediate coat to produce the desired motifs and patterns. The application is carried out with the help of conventional methods, ie by printing with color printing rollers

After drying, a paper carrying on a 'of its faces a polychromic film of Yinylharz that is it easily separable separated from the paper carrier and for this reason by an underlying layer of a mixture of nitrocellulose and a curable aminoplast, preferably a condensation product of urea and formaldehyde. The thickness of the transferable film can vary; good results are already obtained with films of 0.05 mm, but thicker films, for example films from

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ORIGINAL INSPECTED

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0.8 to 1.2 mm, can also be easily removed.

If a non-transparent bridge is desired, the the last inking roller should be provided with an opaque color, for example with a color that contains IO36 titanium oxide holds that in 10% Bhodopas AX and 6 $ Vinylit VMCH or TTHH, IO36 toluene and 64 $ methyl ethyl ketone embedded is·

-The colors can be made in the following way, for example will:

With constant charging, 12 parts of a dispersion are added from 50 ^ of a dye of the following formula

OCH ₃ COCH ₃ COCK ₃ HCO

H ₅ CO Cl

in 505t of a copolymer made from $ 85 vinyl chloride and 155t vinyl acetate ,, (the mean particle size of the dye being less than 0.5 / U) with 5 parts of the copolymer of vinyl chloride and vinyl acetate (vinyl chloride acetate), 5 parts of a resin that ' by condensation of cyclohexanone with formaldehyde

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OBiGlNAL INSPECTED

and is sold by the Bayer paint factories under the trade name "Kunstharz ÄFS ^M ", 1.0 parts, toluene and 68 parts methyl ethyl ketone mixed.

A red color is obtained if one proceeds in the same way, but using a mixture of 8 parts of dispersion with hO% of a dye of the formula

H_C Cl 'oil CH

in 60; » of said Copoylmerlsats and 2 parts of dispersion with ^ 5% of a dye of the formula

in $ 55 of the same copolymer works, the two Dispersions have an average particle size of the dispersed pigment of less than 0.5 μm.

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ORIGINAL INSPECTED

With the temporary I carriers of the present invention you can lend all objects made of vinyl resins, in particular Flacons of the most vexsenieäeen shapes, solirs, ought or Strip aas vinyl chloride or an oil polymer Printing on vinyl chloride and vinyl acetate; the foils or strips to be printed can also be fabrics or guns be those with polymers or polymers of vinyl chloride or even coated with foils made of an aluminum coated with such a polymer. You wish not just objects made of polymers! Vinyl chloride, but rather items made of polystyrene, it is sufficient to the strippable layer according to the present invention with a layer of acrylic resins overlay. This can be done, for example, with the aid of a solution of the acrylic resin in a mixture of organic solvents such as methyl ethyl ketone and methyl isobutyl ketone take place.

Carriers according to the present invention which are of particular interest are those which are made up of a thin film Carry aluminum, which adheres to the removable film, i.e. to the pigmented layer; this thin aluminum foil wears on her back, that is, on the side that is not in contact with the pigmented layer, a coating of either a polymer or co-polymer Clay vinyl chloride or made of vinyl resins, preferably made of

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-H-

Methy! Polymethacrylate or even from polyamides. This Coating allows the aluminum foil to be transferred together with the pigmented and removable layer on various objects, for example on objects from polymers or copolymers of vinyl chloride (if the coating itself is made from a polymer or copolymer vinyl chloride), on items made of polystyrene (if the cover is made of an acrylic resin) and even on items made of polyolefins such as items made of polyethylene (if the cover that the Aluminum foil covered, made of polyamides).

Instead of using the above-mentioned temporary supports for printing objects, they can also be used as a basis on which certain materials such as imitation leather, more or less thin polymer layers covered with fabrics or irregular fiber arrangements of the kind of tangled fleece are applied . One can likewise a provisional carrier according coating the vorliegendeil invention with a relatively thick layer of a PIastisols based on Vinylehloridpolymeren and separated after gelation, the paper of the formed polymer film} This pulls the part of the provisional support with it, which from the paper through the layer of Nitrocellulose and aminoplast was separate. Man

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lasts more or less in this way and in a single operation, i.e. directly during production thickness. Films made of polymers or copolymers of vinyl chloride, all the desired motifs, patterns and prints wear"

An important advantage of dyeing and printing with the temporary supports according to the present invention is that even manufacturers who are not equipped with printing machines can produce prints by transferring them to all suitable objects. Another advantage is the possibility of obtaining transparencies, films, ribbons or strips that are very thin and that show prints with a very high degree of accuracy. Furthermore, the solvents are avoided by the Troekenübertragung by simple heating, which many in the classic printing methods source difficulties such as _e the attack of the thin films by the residual solvent uncomfortable odors, damage to the properties of the produced film, block, and so on. Furthermore, by using the new provisional carrier according to the present invention, it is not only possible to carry out front-to-back prints in one or two work steps, but also to successively transfer different patterns without loss of material if one

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ORIGINAL INSPECTED

the PYC produces a paper reel that is made from the various patterns to be reproduced "exists, which are rolled up one after the other and one behind the other together are added.

The new carriers according to the present invention make the storage of finished and therefore expensive products superfluous and replace this with a storage of printed paper, thereby reducing the value the inventory is achieved. Furthermore, waste of finished material is avoided, as would be the case during the printing process occur on the printing press. Finally, the quality of the prints obtained is better and as a result the dimensional stability of the carrier base (paper), the sharpness and quality of the color values are excellent.

The carriers according to the present invention can also apply well to unsupported films, coated fabrics, and even molded articles.

The invention is described below with the aid of non-limiting examples in which, unless expressly stated otherwise, the parts and percentages relate to ^{weight and the temperatures relate to 0 ° C.}

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example 1

One covers a surface of a foil made of Kraft paper with the help of a varnish of the following composition:

Urea-formaldehyde resin from

of the type Plastopal AT (BASF) 21 parts

Collodion nitrocelluloae 49 ^M.

Methyl ethyl ketone 30 ⁿ

in a way that after volatilization of the solvent and drying at 90 ° per m 5 g of dry product remain.

Colored motifs are printed on the surface covered in this way with the help of various inking rollers, whereby Colors of the following composition can be used: $ 12 Pigment preparation, e.g. Mikrolithe K, 6 # Oopolymerisat from vinyl chloride and vinyl acetate, 10 # toluene and 72 $ Methyl ethyl ketone.

After drying, provisional supports are obtained according to of the present invention, the underlying layer of urea-formaldehyde-nitrocellulose allows one easy separation of the film to be transferred from its paper base.

If the temporary beam is made in this way, so the transfer by application to the final

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204B48Ö

valid carrier, the application being secured by tearing off the temporary and the final carrier at the same time. No measurement is therefore required to obtain a multicolor print at this stage of manufacture. The transfer is carried out by applying heat, pressure, or both at the same time. When using heat, it should be pointed out that one should stay in the vicinity of a temperature range of no more than 120 to 150 ⁰ C, namely between the cylinders, if the transfer takes place by rolling, between the plates or between the matrices and molds, when the transfer takes place on one or on a series of specific objects. It must therefore be noted that it is the effective temperature of the material to be printed on. It is clear that at an increased speed, the temperature of the calender can be higher, provided that the temperature absorbed by the carrier does not exceed the limits given above. The heat application stage is followed by a cooling stage at ordinary temperature, which can immediately be followed by the easy removal of the temporary support.

With or without a protective varnish, you can also produce a full color flat print, especially with

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metallized paribs, whereby a coloring of the final! support in the mass can be avoided »

Such a transfer method allows printing of final supports, their strength or lack thereof Solidity a passing "of a classic printing press would make difficult.

Example 2

On a printing press one covers a surface of heavily calendered paper using the following Lacquers:

Paint No. 1

Condensation product of urea and formaldehyde (type Plastopal AT from BASF) 21 parts

20th ti 2 it 10 η 47 «

Nitrocellulose with 11.4% nitrogen

Octyl adipate

Isopropyl alcohol methyl ethyl ketone

Paint No. 2

Vinyl chloroacetate obtained from 85 # Vinyl chloride and 15 # vinyl acetate (molecular weight about 9,000) 15 parts

Methyl ethyl ketone 85 ^M

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ORIGINAL INSPECTED 1Q9822 / 1117

The two lacquers are applied using the Helio process j the first with a grid of 120 lines (viscosity of the use of the paint 30 see with a Ford cup 4 mm), the second with a grid of 150 lines (viscosity of the use of the paint 20 see with a Ford cup 4 mm), which means a dry separation on m of about 4 to 6 g for the first and 0.8 to 1.5 g for the second corresponds.

It is dried and colored motifs are applied to the surface covered in this way with the help of various inking rollers applied using colors of the following composition:

12 $ pigment preparation, e.g. Microlithe K, 6% of the copolymer of vinyl chloride and vinyl acetate
Toluene, and
Methyl ethyl ketone

After drying, a temporary support according to the present invention is obtained. That way The support obtained is applied with a layer of about 1 mm plastisol of the following composition:

60 parts of vinyl chloride polymer, for example Geon 121 from Goodrich,

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37 parts dioctylplrfchala-fc,

3 parts of epoxidized soybean oil containing of epoxy oxygen from 6 to 6.5 and a viscosity of 500 to 600 cP (e.g. Advaplast 39)

2 parts stabilizer (e.g. 1.5 parts Advastab B-26

and 0.5 part of Advastab OH 300, complex stabilizers from BjBtrium and cadmium salts)

10 parts of barium sulfate and
5 parts of titanium oxide,

The whole is then brought into a heating cabinet and the plastisol is allowed to gel ^{for 5 minutes at 170 ° C.,}

After gelation, before or after cooling, the paper foil, which is the base of the temporary support, can be used formed, easily detach, and a film made of polyvinyl chloride is obtained in this way, to which firmly adheres the pressure originally worn by the provisional carrier is located.

Instead of methyl ethyl ketone and toluene, the same can be used in the present example isopropyl alcohol or another mixture of suitable solvents are used,.

Of course, the formulation of the plastisol

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can also be changed both quantitatively and qualitatively, without this being essentially different Result would be achieved.

Instead of polyvinyl chloride, for example, copolymers of vinyl chloride can also be used successfully use "for example those that generally contain a small amount of vinyl acetate or vinylidene chloride contain.

Pigment preparations used in the preceding examples Can be used are:

The dispersion made from 50 $ copper phthalocyanine in 50 $ vinyl acetate chloride, i.e. an copolymer from $ 85 vinyl chloride and $ 15 vinyl acetate (a dispersion, whose pigment particles have an average size of less than 0.5 / U) j

the dispersion of $ 40 titanium dioxide in $ 60 vinyl acetate chloride and

the $ 45 tetrachlorothioindigo dispersion in $ 55 of the same copolymer (with all of these dispersions having an average particle size of the dispersed pigment of less than 0.5 / U).

The manufacture of the temporary carrier can be either

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on a separate machine or at the same time as printing. The choice of one or the other The procedure simply depends on the number of colors a "b with which the machine is equipped. You can click on this way on a six-color machine with the help of two of the lacquers described above and four pigment preparations make a temporary carrier that has a four-color detachable print, according to the application of the two lacquers to the paper, one the underlying layer and the other a protective layer forms and can be produced on the machine on which the actual printing takes place, as two available heads are available o

Example 3

You work in the same way as in Example 2 the modification that after the drying of the colored A very thin aluminum foil (0.01 mm) is applied to the carrier obtained in this way which has a coating of a copolymer of vinyl chloride and vinyl acetate on one of its surfaces wearing. Then cover the other surface of the aluminum foil with one of the following solutions (corresponding to the intended use of the temporary carrier) and dries:

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Solution a
Methyl polymethacrylate

Mixture of ethyl and isobutyls thyIketon

30 ropes

70 "

Solution b

Mixture of 20 parts of Versamid 950 and 20 parts of Versamid 930, polyamide resins obtained by condensation of diamines with linoleic acid, trichlorethylene
Isopropanol

20 parts

49 "

21 "

Solution Ό

Vinyl chloride acetate, obtained from 85% vinyl chloride and 15% vinyl acetate (Molecular weight approx. 9000)

Methyl polymethacrylate methyl ethyl ketone

toluene

15 parts

5 "70 ^M 10"

In this way, three types of temporary supports are obtained which can be used to transfer multicolor prints onto different supports. Those obtained with the aid of solution A allow transfer to polystyrene objects made with the aid of solution B

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obtained are suitable for polyethylene, while for the transfers to polymers and copolymers of yinyl chloride the! supports must be used that were obtained with the help of solution C

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Claims (1)

Patent claims: Temporary support made of paper or regenerated cellulose, characterized in that it is on one of its Surfaces a removable film made of pigmented vinyl resins, which preferably has a polychrome pattern or motif carries, and has an underlying layer of a mixture of nitrocellulose and an aminoplast. 2β film according to claim 1, characterized in that they have a coating of a mixture of nitrocellulose and a urea-formaldehyde resin on one of their surfaces having, with a film based on polyvinyl chloride or a copolymer of vinyl chloride and vinyl acetate is covered and has multicolored motifs 3. Film according to claim 2, characterized in that the underlying layer also contains an alkyd resin. 4. Film according to one of claims 1 to 3, characterized ο
characterized in that they per m 2 to 7 g of a mixture also nitrocellulose and a urea-formaldehyde resin wearing. 5. Film according to one of claims 1 to 4, daduroh characterized in that they have a coating for transferring a 109822/1117 nes multicolored rlotivs, the thickness of which is 0.05 to 1.0 min cheats. 6. Film according to one of claims 1 to 5 _S, characterized in that it carries a film to be transferred, which is made of polyvinyl chloride or a copolymer !! consists of vinyl chloride and vinyl acetate and contains 10 to 50% very finely divided pigment. 7. Paper film according to one of claims 1 to 6, characterized characterized in that it carries a mixture of 4 to 6 parts liitrocellulose / 10 parts mixture, the The remainder is a condensation product of urea and formaldehyde. δ. Paper foil according to one of Claims 1 to _9, characterized in that it carries a thin layer of ethyl polymethacrylate or a very thin aluminum foil on the film which is detachable from the carrier base, which in turn is on the surface which is not in contact with the detachable film , carries a thin layer of polyamide, methyl polymethacrylate or polyvinyl. 9. Printing process for dry transfer of all p-e - 28 - 109822/1117 desired motifs on a final support, characterized in that a temporary support according to one of claims 1 to 8 and a final carrier, optionally already during the manufacture of the the latter, superimposed that one allows heat, pressure or both to act on the support, that one optionally cools and that the temporary carrier is detached from the final carrier. 10. The method according to claim 9, characterized in that that the coating to be transferred is made of pigmented polyvinyl chloride or a pigmented copolymer Consists of vinyl chloride and vinyl acetate. 11. The method according to any one of claims 9 to 10, characterized in that the provisional carrier a Paper foil is covering one of its faces a) a transparent or opaque print based on finely divided organic pigments in polyvinyl chloride or a copolymer of vinyl chloride and vinyl acetate are embedded, and b) carries an underlying layer of a mixture of 4 to 6 parts of microcellulose / 10 parts of mixture, the remainder being a condensation product of urea and formaldehyde. - 29 - 109822/1117 - 29 - 12. The method according to any one of claims 9 to 11, characterized characterized in that a thin aluminum foil adheres to the coating to be transferred. 13. The method according to claim 12, characterized in that that the aluminum foil on the surface that does not adhere to the coating to be transferred, a layer Polyamide, acrylic or vinyl resin. 14. Carrier, characterized in that it is after a Process of claims 9 to 12 are printed. 109822/11 17