JPH0214185A - Flexible multilayer transfer ribbon and manufacture thereof - Google Patents

Abstract

PURPOSE: To simply, rapidly and uniformly apply even to a paper even by using a manual implement by clearly sharply applying to a place covered with a binder-containing transfer coating by incorporating a tear-off aid in the form of a soluble cellulose derivative in a binder-containing transfer layer. CONSTITUTION: An essential component of a binder-containing transfer coating of the transfer ribbon is a tear-off aid of a cellulose derivative. A clear tear-off is effectively performed under tensile stress condition in the case of applying the transfer coating only to a base material by using such a tear-off aid. Particularly advantageous cellulose derivative includes an organic solvent and/or water soluble cellulose ester. An amount of the aid to be added to the coating is relative to properties of a binder, a pigment and other additive to be added, and about 0.5 to 5 wt.% or particularly about 1.5 to 3.5 wt.% is advantageous.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application: The present invention provides a multilayer flexible film having an auxiliary carrier and a tactile adhesive layer, with a binder-containing transfer layer between the auxiliary carrier and the tactile adhesive layer. For flexible transfer strips or ribbons, the binder-containing transfer layer has stronger adhesion to the auxiliary carrier than the contact adhesive layer.

PRIOR ART: Numerous possibilities are known for using liquid systems containing pigments for coating mistyped displays. In the office, a white pigment dispersion containing a highly volatile organic solvent is applied with a brush to correct typed letters, etc. However, evaporation of highly volatile organic solvents is harmful to the environment. It is necessary to wait for a relatively long time until the evaporation is finished and modification types are possible. Application of the modified dispersion by brush generally does not provide uniform coverage.

A relatively good modification was achieved by DE 1 G 2 6 2 6 891, which describes a multilayer flexible transfer sheet, which comprises an auxiliary carrier coated with an adhesive separation layer, a polyvinyl alcohol bonded transfer layer and a thin adhesive. It consists of a covering. The transfer layer also contains titanium white as a pigment. After removing the auxiliary carrier, the transfer layer serves as a correction cover for mistyped characters. The use of hand transfer rollers as described below in connection with the present invention is not disclosed;
As the test results show, the desired sharp tearing of the modified coating is not thereby achieved.

OBJECT OF THE INVENTION: The object of the invention is to provide a binder-containing transfer coating which can be applied neatly and sharply to the area to be coated, and which can be applied easily, quickly and uniformly to the paper even with the use of manual instruments. Another object of the present invention is to further improve the transfer ribbon.

This problem is achieved according to the invention in that the binder-containing transfer layer contains a tearing aid in the form of a soluble cellulose derivative.

Operation: The auxiliary carrier of the flexible transfer ribbon according to the invention consists of plastic films such as those used in particular in connection with the carrier of type ribbons, such as polyethylene terephthalate, polypropylene, polyethylene, polyvinyl chloride and polycarbonate. Silicone coated paper is also suitable as an auxiliary carrier. The silicone coating reduces adhesion between the binder-containing transfer coating and the auxiliary carrier. Instead of a silicone coating, various antiblocking agents can also be used, such as polytetrafluoroethylene.

Effect: The thickness of the auxiliary carrier is about 10 to 60 μm, especially about 15 to 60 μm.
55 μm, the topcoat has a thickness of about 5 to 40 μm, in particular about 15 to 25 μm, and the contact adhesive coating has a thickness of about 1 to 8 μm, especially about 2 to 5 μm. To optimize the transfer ribbon of the present invention, the ratio of the thickness of the contact adhesive coating to the transfer coating is between about 1:4 and 1:12, particularly between about 8 and 1:1.
It is appropriate to select 0.

The tactile adhesive coating can consist of a commercially available tactile adhesive. These are materials that form elastic and permanent adhesives with high adhesive strength and adhere instantly to various surfaces under limited pressure at room temperature. These are preferably applied in the form of an aqueous solution to the transfer coating already placed on the auxiliary carrier. This is because with this method the binder-containing transfer coating that has already been formed does not dissolve again. Of this type of contact adhesives, those based on acrylates are particularly advantageous. The starting materials are viscous solutions or dispersions based on rubbers, polyacrylates, polyvinyl ethers or polyvinyl in butylene. Polyacrylate materials are preferred. Suitable commercially available products are Ucecryl 913R and Ucecryl PO3Q (UCB, Amm
elicht, Belgium) and plastic dispersion V P 859/6 (Freihof
Commercially available from f company). In particular, the tactile adhesive materials to be applied, which are usually present in an aqueous medium, contain wetting agents or surfactants (sold under the trademark BykW). The solution or dispersion of tactile adhesive for forming the tactile adhesive coating preferably has a concentration of about 1 to 5 g/TrL2, preferably about 2 to 4 g/rr.
A quantity of L2 is applied to the transfer coating.

To form the binder-containing transfer coating, thermoplastic or thermoelastic polymers are used, in particular in the form of solutions or dispersions. Within the scope of the invention, the following substances are advantageously used to achieve the object: a) Polyurethanes with a molecular weight of 15,000 to 50,000, such as Per Stahl-Ohemie.
muthane U4924 or Bayer pe
smolac 2100, b) Molecular weight 20000-30
0000 linear saturated polyesters such as Goodyea
Vital P by Tire & Rubber
E 3 Q 7, c) Styrene-isoprene-styrene copolymer e.g. 0 from Shell-Ohemie
ariflex T R1107, d) Acrylates and methacrylates such as R6h
Pexigum 7 H%e) diphenylcarboxylic acid-modified polyamide from Rhone-Poulenc 5
copy 3 Q or Emery Chemicals
f) Vinyl propionate polymer dispersions such as Propi from BASF.
ofan 6D.

g) Carboxymethyl group-containing water-soluble polymethacrylate such as Rohagit S D 1 from Ri:ihm
5. This list is neither complete nor limiting in terms of selection. It will be readily apparent to those skilled in the art that other binders can be used, particularly as the nature of the binder does not form the subject matter of the invention.

In order to achieve optimal embodiments of the invention, the nature of the plasticizer used must be taken into account when selecting the particular binder forming the transfer coating. When applying the transfer coating to the surface to be modified or coated, the plasticizer generally does not penetrate the thin contact adhesive coating, does not come into contact with the points to be modified or the colorant placed there, and does not cause the colorant to It must be used that will not undesirably dissolve and cause discoloration of the transfer coating. Standard plasticizers such as silicones, castor oil and mineral oil have proven suitable. Other plasticizers which are advantageously used in other fields, such as phthalates and oleic alcohols, are unsuitable. To prevent the adverse effects of plasticizers in marginal cases, it is possible to add so-called "lukes" to the binder-containing transfer coating. Since lakes precipitate or render the migrating colorants insoluble,
The colorant does not migrate to the applied transfer coating and recolor it. Suitable lakes are tannins and tannin derivatives. Lakes of the type generally known in the ink and ink ink art can be used. The rake is particularly important in binder-containing transfer coatings.
% by weight, in particular from 1.5 to 6.5% by weight. Approximately 2
~2.5% by weight is particularly advantageous.

During the preparation of the transfer strip according to the invention, the binder selected for forming the transfer coating is in particular in the form of a solution or used as a dispersion if a polymer dispersion is present. The choice of solvent depends on the nature of the binder used. Alcohols such as ethanol, impropatol and butanol; ketones such as acetone and methyl ethyl ketone; esters such as methyl and ethyl acetate; aromatic hydrocarbons such as toluene; boiling range 70
It is advantageous to use low- or medium-boiling organic solvents from the group of aliphatic hydrocarbons, such as benzine at ~140° C., alone or in mixtures, and water, alone or in mixtures with low-boiling water-soluble organic solvents. . The binder concentration in the solution or dispersion is not critical to the invention. As a rough guide, this concentration ranges from about 6 to 15% by weight, particularly from about 4 to 10% by weight. To form the transfer coating, the solution or dispersion is applied to the auxiliary carrier in an amount of preferably 15 to 25 g/m@2, particularly preferably 18 to 22 g/rrL@2.

Within the scope of the present invention, the term "colorant" has a broad meaning and is a collective noun for all color-giving substances, including dyes and pigments, the pigments also having the properties of fillers. Unlike pigments, it refers to colorants that are soluble in water, organic solvents, or binders.Coloration appears directly, but can also be developed through fluorescence.

Fluorescence is applied, for example, in the case of fluorescent colorants. When the transfer ribbon of the present invention is used to modify typed text, image displays, etc., the binder-containing transfer coating readily includes a white pigment such as titanium white, precipitated calcium carbide, alumina or Colloid V silicic acid. When coloring the transfer coating,
The colorants used are chromium chloride, ocher, iron oxide red, cobalt blue, ultramarine blue, inorganic pigments such as Berlin blue or alkali blue, organic pigments such as 7 talocyanines, azo dyes, anthraquinone r1 metal complex pigments, and carbon black and iron oxides. It is black. An example of a fluorescent dye is Dayglo's B.
laze Orange T 5 Q, C1ba Ge
igy's Maxilon Brilliant F'may
in 10 GFF Bayer A,G.

Pyranin from BASF and Ba5onyl-R from BASF
ot 54 Q.

Control of the optimum coating performance of the transfer ribbons of the invention, especially of the binder-containing transfer coatings, takes place via the pigment content. The optimum pigment content will vary depending on various factors such as the binder selected, the actual pigment and any additives added.

No particular critical value or range can be given.

As a rough guide for the binder/pigment ratio, it is approximately 1:1 to 1:1.
A weight ratio of 2, in particular 1=3 to 1:8, more preferably about 1=4 to 1, is indicated.

A major component of the binder-containing transfer coating of the transfer ribbon according to the invention is a tear aid. Only by the use of such tear aids can a clean tear be achieved under tensile stress conditions when applying a transfer coating to a substrate. It has surprisingly been found that a relatively limited group of compounds, namely soluble cellulose derivatives, have the desired properties as tearing aids within the scope of the present invention. Particularly preferred cellulose derivatives are organic solvents and/or water (C soluble cellulose ethers such as methyl, ethyl, hydroxyethyl, ethylhydroxyethyl and carboxymethyl cellulose; cellulose esters f, :, t, t, cellulose acetate, acetobutyl esters and propionates.However, a number of soluble cellulose derivatives are suitable and will give the desired effect.The basic cellulose structure in the soluble cellulose derivatives is important, especially by introducing groups such as ethyl groups. A derivative is obtained which is soluble in the chosen solvent.

The amount of tear aid added to the transfer coating is not critical and will depend on the nature of the binder, pigment and other additives added. About 0.5-5% by weight, especially about 1.5-3.5% by weight
Amounts of are advantageous. A range of about 2-2.5% by weight is even more advantageous. These values relate to dry matter. The amount ratio of tear aid and binder can also be used as a basis for the composition of the transfer coating. As a rough guide, the ratio of tearing aid to binder is about 1:2 to 1:20, especially about 1:4 to
1:10 is shown.

Additional additives can be added to the transfer coating to control the application method and properties of the transfer coating applied to the substrate. These are in particular the aforementioned lakes for covering power improvers such as aluminosilicates, colorants such as carbon black, in particular basic dyes in the form of gallic acid derivatives such as Pr1ntan from OibaGeigy.

The materials of the individual coatings of the transfer ribbon of the present invention are generally defined via the adhesion tension between the contact adhesive coating and the transfer coating (work of adhesion corresponding to the Geuzole equation: K, L, W).
olf' Physik and Ohemie der
Springer
(see Velagl 957, pl 64) is higher than that between the auxiliary carrier and the transfer coating to satisfy the tx5 basic requirement. If, in special cases, this is not fulfilled, a suitable anti-adhesive agent must be applied to the auxiliary carrier in order to fulfill this basic requirement. Another requirement is taken into account in such cases that the transfer coating formed on the substrate is non-adhesive to other materials, especially the paper with which it comes into contact.

Therefore, the transfer ribbon of the present invention can be effectively used with the following adhesive tension conditions, where the symbol S is the adhesive tension ratio between the various materials, i.e., the paper/contact adhesive coating,
"2 stands for transfer coating/touch adhesive coating, S3 stands for transfer coating/auxiliary carrier, S4 stands for transfer coating/a, S5 stands for touch adhesive coating/auxiliary carrier, the following requirements are taken into account: s
, is higher than S3, s2 is higher than s3, s5 is smaller than S2, and S5 is smaller than s3bo Furthermore, the free surface of a transfer coating applied to a substrate, especially paper, must not have outward adhesion. ie, S4 is zero or close to zero.

In other words, the applied transfer coating must not be tacky when in contact with the hand or paper.A feature of the advantageous process for producing the transfer ribbon of the invention is the conventional use of a suitable plastics solution containing said tear aid. The method is applied in the form of a flexible film to an auxiliary carrier, for example with a doctor blade, the solvent is evaporated by raising the temperature, and then the aqueous dispersion containing the tactile adhesive is applied in a conventional manner, such as with a lid blade or roll coater. by applying the binder-containing transfer coating formed, followed by evaporation of the water.

When using the transfer ribbon according to the invention, it is advantageous to use commercially available applicators which are capable of roll-transferring the transfer coating with the contact adhesive and at the same time winding up the auxiliary carrier. This makes it possible to handle the transfer ribbon according to the invention particularly easily. The applicator is formed by a commercially available manual instrument. A particularly suitable device of this type is a so-called hand roller, in which a supply spool wrapped with transfer ribbon is arranged in an easily grippable casing, the ribbon being led out from an applicator leg projecting from the casing, and from which the ribbon is guided into the casing. is returned to the take-up spool.

Appropriate gearing between the spools within the casing ensures that the transfer ribbon is properly tensioned at all times. To use the transfer ribbon, the user picks up the casing and
The outer peelable ribbon coating, which is passed over the end edge by the applicator leg, is crimped against the substrate to be transferred (eg, a typed paper sheet to be modified). During crimping, the user moves the instrument relative to the substrate, thereby transferring, for example, an opaque or fluorescent coating to the substrate, and the flexible auxiliary carrier is unwound from the supply stool and wound onto a take-up spool.

The transfer ribbon of the present invention is particularly suitable for use as a correction tool for the purpose of covering and correcting erroneously typed text markings, drawings, in offices, schools and homes. Another use for transfer ribbons is the colored marking of surfaces, documents and/or signs, where transfer IJ f
The fon has a transfer coating containing colored pigments. Another use is the highlighting of text points, symbols or drawing descriptions. For this purpose, the transfer coating is particularly transparent and colored with a daylight fluorescent colorant. In all the examples of use mentioned here, the application is carried out dry, ie there is no bleeding of liquid coatings and no evaporation of harmful solvents, so immediate retyping of the scales is particularly advantageous. Thus, with the transfer ribbon of the present invention, for example, a concealing coating can be applied easily, quickly and uniformly to a substrate. If the transfer coating of the transfer ribbon of the invention is transparent, ie, does not contain coating pigments, for example, it can be used for mere coatings without coloring effects and for preserving or protecting prints that are sensitive to effects such as visual effects.

Example: The invention will now be explained by way of example.

Example 1: To form a colorant-containing transfer coating, the following dispersion is first prepared: Solvent-soluble polyurethane (Permuthane U 4
924) (isopropyl alcohol/toluene mixing ratio 1
: 25% in 1) 19.0 parts by weight Impropatool 10.0 Toluene
35.0 Rake (Printan)
G) l, Q tt Ethyl cellulose NZ (tearing aid) 1.0〃 Titanium dioxide (Kronos RN 34) 29. O
tt aluminosilicate P820 (hiding power improver) 5.0
〃 Carbon black (Pr1ntex 14 Q V)
(Colorant) 0.01 〃 io, o, oi 〃 The above coating material was coated with a doctor blade V in 18. li'/m2
was applied to a silicone paper carrier in an amount of . The solvent was then evaporated by passing hot air at about 100°C. Near acrylate tactile adhesive (plastic dispersion vp859/6 of Frθ1hoff) (acrylic ester copolymer) 66 in which an aqueous dispersion having the following composition was applied to the surface of a colorant-containing concealing coating using a V-futa brake. .9 parts by weight water
33.0 Wetting agent or surfactant (B7kw) 0.1 100.0 The tactile adhesive was applied with a doctor blade r to a thickness of 29/m2. Moisture was then evaporated by passing hot air at about 100°C.

The resulting transfer ribbon was immediately suitable for covering typed characters on paper. I was able to apply the IJ bong quickly and evenly and immediately retype over it. It was applied using a commercially available Han-Roller.

Example 2: Example 1 was modified by using the following formulation to form a colorant-containing transfer coating: Polyurethane (Bayer
Desmolac 2100) 5.0 parts by weight Methyl ethyl ketone 60.0 Toluene
28.6 〃Maxilonbri
llant-flavin 1Q GFF (BASF
)1.0 Ba5onyl-Rot 54 Q (BASF)
Q, 4 ttTitanium dioxide (Kronos R
N34) 29. Ott aluminosilicate P 820
(Degussa) 5.0 Ethylcellulose N 7 (Hercules) 1.
0 The transfer coating of the obtained transfer ribbon has good hiding power,
It was colored (orange) and showed no fluorescence.

Example 3: Example 1 was modified by using the following formulation to form a colorant-containing transfer coating.
Vitel F]! : 7[][]-Goodyθar
) 4-0 parts by weight Methyl ethyl ketone 30.0 Toluene
3LO White pigment, zinc sulfide (Sachtolith L-8achtleben)
25.0 Ethyl cellulose N 7 (Hercu
les) 1-0 〃Blaze Oran
ge'r15 (Dayglo) 9.0 〃
The transfer coating of the obtained transfer ribbon has good hiding power,
It was colored (orange) and showed fluorescence.

Example 4: Example 1 was modified by using the following formulation to form a colorant-containing transfer coating: Styrene-isoprene-styrene copolymer (0ar
iplex T R1107-8hexl) 4-
7 parts by weight methyl ethyl ketone 4.2.0
〃Toluene 42.0 〃Red
glo 5olable Toner GF13 (R
edglo) 0.8 parts by weight Ethylcell O-su N 22 (Hercules) 1.
0〃 Aluminum stearate A1ugθl TM01 (B
11rlocher) 3. Q
tt silicic acid (Aerosil 200-Deguss
a) 1. Q // The transfer coating of the obtained transfer ribbon was transparent and colored (orange).

Example 5: Example 1 was modified by using the following formulation to form a colorant-containing transfer coating: Vinylpropionate-based polymer dispersion (Propionfan 6D-BASF
) 2 [1,3 parts by weight Titanium dioxide (K″ronos
RNOX) 3 Q, Q tt Aluminosilicate P820 5.0 11 Water
28.5 /1Wal
Ocel MW5QGB (Wolff & Q
O, N 1.0 〃Isoproper tool
14.0 Aqueous solution of halogenated organic compound not containing silicone (foam suppressant 5F-Hi: 1chst
AG) 1.0 parts by weight Sodium dioctyl sulfosuccinate (Luten
sit ABO/wetting agent-BASF) Q, 5 n
The transfer coating of the obtained transfer ribbon has good hiding power,
It was white.

Claims (1)

Claims: 1. having an auxiliary carrier and a tactile adhesive coating, wherein a binder-containing transfer coating is disposed between the auxiliary carrier and the tactile adhesive coating; A flexible multilayer transfer ribbon with stronger adhesion, characterized in that the binder-containing transfer coating contains a tearing aid in the form of a soluble cellulose derivative. 2. The transfer ribbon of claim 1, wherein the tear aid is present in the transfer coating in an amount of 0.5 to 5% by weight. 6. The transfer ribbon according to claim 1 or 2, wherein the cellulose derivative is ethylcellulose. 4. Any one of claims 1 to 3, wherein the auxiliary carrier comprises plastic and/or silicone coated paper.
Transfer ribbon as described in section. 5. Transfer ribbon according to any one of claims 1 to 4, wherein the transfer coating contains polyurethane as a binder. 6. The transfer ribbon according to claim 5, wherein the polyurethane is an aliphatic one-component polyurethane. 7. A transfer ribbon according to any one of claims 1 to 6, wherein a colorant is present in the transfer coating. 8. The transfer ribbon according to claim 7, wherein the colorant is a pigment. 9. The transfer ribbon according to claim 8, wherein the pigment for the purpose of correction is a white pigment with high hiding power. 10. The transfer ribbon according to claim 8, wherein the pigment is an organic or inorganic colored pigment. 11. To emphasize the display of text characters or figures,
8. The transfer ribbon of claim 7, wherein the colorant is a fluorescent dye. 12. Transfer ribbon according to any one of claims 1 to 11, in which when a basic dye is added, the transfer coating comprises a lake for this dye. 13. The ratio of the thickness of the contact adhesive coating and the transfer coating is 1:4 ~
13. The transfer ribbon according to claim 1, wherein the transfer ribbon has a ratio of 1:12. 14. The transfer ribbon according to claim 13, wherein the thickness ratio is 1:8 to 1:10. 15. A plastic solution containing a tearing aid in the form of a soluble cellulose derivative is applied by a conventional applicator to a flexible auxiliary carrier, the temperature being raised to evaporate the solvent, and then an aqueous dispersion containing a tactile adhesive. A method for making a flexible multilayer transfer ribbon, characterized in that a liquid is applied by a conventional applicator to the formed transfer coating, and the water is allowed to evaporate. 16. The method according to claim 15, wherein the method is rolled up into a manual instrument.