DE2332758A1 - SELF-ADHESIVE MATERIAL - Google Patents

Description

Patent attorney Dipl.-Phys. Gerhard Lied! 8 Munich 22 Steinsdorfstr. 21-22 Tel. 29 84

B 6139

NIPPON KAKOH SEISHI K.K. No. 5-27, Akasaka, 2-chome, Minato-ku, Tokyo, 107, JAPAN

Self-adhesive material

The invention relates to a self-adhesive material, in particular in Form of a self-adhesive film. This material is intended to apply to an object that has a smooth surface, for example a polished glass plate, a plate made of plastic or a steel plate and / or on an object that is micro-roughened or has a small roughened surface, for example a matt-finished glass plate and paper without additional adhesive

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can be glued. In addition, the self-adhesive material should be repeated can be glued on and removed from the surface again ..

Various self-adhesive materials or substances are known and; has been manufactured. Usually has a self-adhesive material a base body in the form of a sheet, for example made of paper, regenerated cellulose film, plastic film or a Metal foil on which an adhesive, for example in the form of a natural or synthetic rubbers or a synthetic resin or a release paper, is provided. Although now

Known rubber adhesives have a high adhesive force Adhesives, however, have the disadvantage that they are only slightly weatherproof and are heat-resistant. Furthermore, after the self-adhesive material has been applied to the article, it can be removed from the article can no longer be peeled off without a part of the adhesive, in particular rubber adhesive, remaining on the surface of the article. Resin adhesives such as acrylic type are excellent in adhesive strength and weather resistance, but grows their adhesive strength increases over time, so that after a certain time it is very difficult to remove the self-adhesive material from the surface remove the object again. In some cases the adhesive material is in a cracked or torn form or broken shape. Another disadvantage of a conventional adhesive material is that when it is in the form of rolls or stacked sheets or sheets, the pressure due to its own weight results in a cold flow of the adhesive, from the adhesive layer towards the edge. This process takes place in particular during transport or during storage and leads to block formation.

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Other adhesive materials are made by extrusion, coating or coating a heat-gelled compound comprising 100 parts by weight of polyvinyl chloride and 50: 100 parts of a plasticizer contained on a release paper or base paper body. Such an adhesive material has a self-adhesive property and can be applied to an object that has a smooth surface, for example a plastic body and a coated or Colored steel without additional glue, can be glued on and then peeled off from these surfaces. The plasticizer or plasticizer in this adhesive material penetrates into the surface of the object, from which a discoloration and sometimes cracking on the surface of the article also results. In addition, such an adhesive material can admittedly the smooth surface of an object only stuck on a few times and peeled off again and cannot be glued to a slightly roughened (micro-roughened) surface. That’s what is missing adhesive force required for this. For example, with paper, wood or frosted glass, the adhesive strength decreases over time, and due to the volatilization and migration of the plasticizer or plasticizing.

The object of the invention is therefore to provide a self-adhesive material show this on an object with a smooth surface without additional Glues can be glued on, with a repeated It should be possible to peel it off the surface of the object and stick it back on.

This task is performed by a self-adhesive material, in particular in the form of a self-adhesive film, which is characterized according to the invention by a graft polymer, which with a

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Vi nylchloridmonomer is grafted.

The graft polymer with the grafted vinyl chloride monomer can be used alone or as a mixture of two or more substances, which are selected from the group ethylene-vinyl acetate copolymer / Vi nyl chloride graft polymer (hereinafter referred to as "E VA / VC graft polymer" referred to), polyvinyl ether / vinyl chloride graft polymer and polyacrylic ester / vinyl chloride graft polymer can be used.

Further advantages of the invention are that the self-adhesive Material no migration or no penetration of the plasticizer or plasticizing into the surface of the object or discoloration or cracking on the surface of the object.

In addition, the adhesive force is high and the self-adhesive material can not only on smooth surfaces, but also on objects that have a slightly roughened or micro-roughened surface, without additional adhesive can be applied. In addition, it can be repeatedly peeled off the surface and stuck on.

Furthermore, shows the self-adhesive material according to the invention no cold flow when rolled or stacked.

In addition, the weather resistance is improved. That means, that the adhesive strength is not reduced even at room temperature.

The self-adhesive material according to the invention can for example As a sticky note, a protective wrapper or the like. Can be used.

The invention is explained in conjunction with the accompanying drawing

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Hang explained with preferred embodiments. Show it:

Fig. 1 is an enlarged cross-section of a self-adhesive material and

Fig. 2 is an enlarged cross section of another embodiment ^u shape of the self-adhesive material.

In Fig. 1 is a release paper 3, which is on a base paper 1 a Has release layer 2, coated or covered with a self-adhesive film or foil 4, so that a self-adhesive material 11 is formed. Depending on the use, patterns 6 and 7 are printed or raised.

In Fig. 2, the release paper 3 is with the release layer 2 on one Base paper 1 coated or covered with a self-adhesive film or foil 4. There is a base sheet on it, with or without glue or a cover sheet 5 is placed, which comes to lie on the self-adhesive film 4. This creates another embodiment of a self-adhesive material 12 is formed. The patterns 6 and 7 are applied to the base sheet 5, either printed or raised depending on the intended use.

When using the self-adhesive material 11 or 12, self-adhesive sheets 8, 9 are peeled off the release paper 3 and put on glued to the surface of an object.

In Fig. 3 is a self-adhesive film or a self-adhesive sheet applied as a layer or as a coating to the base sheet or cover sheet 5 without additional adhesive. This results in a wide

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Another embodiment of a self-adhesive material 13, the self-adhesive material 13 results in a self-adhesive sheet 10, which is used as such.

The base paper 1, which is used for the release paper 3, and on the surface of which the release agent is applied, contains a paper with a smooth surface, for example one with one side a covering material or paper coated with clay, a tracing paper, a parchment paper, wood-free paper and art paper. The release agents for the release layer 2 contain synthetic resins such as polyethylene, polypropylene, polyamide, saturated or unsaturated Polyester resins, urea alkyd resin, phenolic resin and silicone resin. Such release agents are applied to the base paper with or without an edge layer, such as polyvinyl alcohol, starch and carboxymethyl ^ cellulose, applied.

As already mentioned above, the graft polymer is with the grafted vinyl chloride monomer used for the self-adhesive film according to the invention. The graft polymer is alone or used as a mixture, the mixture of two or more of the materials EVA / VC graft polymer, polyvinyl ether / vinyl chloride pf graft polymer and polyacrylic ester / vinyl chloride graft polymer consists. Of these graft polymers, the EVA / VC graft polymer is preferred for the self-adhesive film 4. The weight ratio of the vinyl chloride to the EVA copolymer in this EVA / VC graft polymer is 20 to 80: 80 to 20, while that of ethylene to vinyl acetate is 20 to 60: 80 to 40. The relationship continues from vinyl chloride to EVA copolymer preferably 40 to 60: to 40, while that of ethylene to vinyl acetate is 30 to 60: 70 to 40.

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These graft polymers are applied to the release paper 3 or the base sheet 5 independently applied so that a self-adhesive material is obtained. However, if these graft polymers contain plasticizers are used, the self-adhesive film has a higher adhesive strength as a graft polymer alone. Any plasticizer known in the art of polyvinyl chloride conversion can be used for this purpose and is compatible with the above-mentioned graft polymer is to be used. The plasticizer can be used alone or in admixture and can be selected from various liquid organic Connections must be selected. Typical examples of this are phthalates, for example ditutyl phthalate, di-η-octyl phthalate, di-isooctyl phthalate and di (2-ethylhexyl) phthalate; dibasic acid esters, such as, for example, di (2-ethylhexyl) adipate, di (2-ethylhexyl) sebacate (Sebacic acid ester) and di (2-ethylhexyl) azelate; Phosphates, for example Tri (2-ethylhexyl) phosphate, diphenyl-2-ethylhexyl phosphate and triphenyl phosphate; Polyester, e.g. polypropylene adipate (adipic acid ester) and polypropylene sebacate (sebacic acid ester); Butyl phtharyl butyl glycolate and methyl acetyl ricinolate. Such plasticizers can be mixed in small amounts with the graft polymer. In order to get an optimal result, the plasticizer is in one Ratio of 5 parts by weight or more, based on 100 parts of the graft polymer, mixed with the graft polymer. For the self-adhesive material that is to be glued to a finely roughened (micro-roughened) surface becomes the plasticizer in one Ratio of 20 parts by weight or more, based on 100 parts by weight of the graft polymer, admixed. If more than 100 parts of the plasticizer are added for 100 parts of the graft polymer, the plasticizer migrates into the surface of the object, from which discoloration results. The migration of the plasticizer is different, however, and depends on the graft polymer and on the

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9 η ■: ■ " τ co

Conditions under which the self-adhesive material is used. The maximum amount of plasticizer must therefore be determined taking into account the graft polymer and the conditions under which the self-adhesive material is used. For example, if the self-adhesive material is to be used at a room temperature of up to 50 C, the maximum amount of plasticizer is 75 parts by weight in an EVA / VC graft polymer, 100 parts in the polyvinyl ether / VC graft polymer and 60 parts in the polyacrylic ester / VC- Graft polymer. On the other hand, when the self-adhesive material is used at a temperature above 50 ° C., particularly successively at 60 ° C., the amount of the plasticizer in the self-adhesive composition must be below 20 parts because of migration. If, under these conditions, the self-adhesive material is to be adhered to the finely roughened (micro-roughened) surface of an object, the plasticizer is used in conjunction with a tackifying agent. The self-adhesive composition then consists of the graft polymer, the plasticizer and the tackifying agent. The tackifying agent should preferably be compatible with the graft polymer and the plasticizer. However, it is also possible to use a tackifying agent which is compatible either with the graft polymer or with the plasticizer. The tackifying agent used in the invention includes rosin, modified rosin and its derivatives such as glycerin ester rosin, pentaerythritol ester rosin, polyterpene rosin, modified terpene such as terpene phenol, aliphatic hydrocarbon resin and phenolic resin such as alkyl phenolic resin Phenolic resin. Such tackifying agents are used alone or in admixture. The amount of tackifying agent used has a ratio of

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5 to 200 parts for 100 parts of the graft polymer. The amount of mixture must, however, depend on the type of graft polymer to be determined. For example, there are 5 to 150 parts in an EVA / VC graft polymer, 40 to 200 parts in a polyvinyl ether / VC graft polymer and 5 to 120 parts in a polyacrylic ester / VC graft polymer to use. The plasticizer for the self-adhesive composition in this self-adhesive material is the same as described above. To get an optimal result, the amount of the plasticizer used with the tackifying agent is preferably 5 parts or more. the Maximum amount of plasticizer is the same as above in connection with the self-adhesive composition containing the Graft polymer and contains the plasticizer, has been described.

The self-adhesive film according to the invention can be a heat stabilizer, a lubricant, an ultraviolet absorber, a pigment and the like. Contain.

Examples of the heat stabilizer are stearates such as dibasic Lead stearate, zinc, calcium and barium stearate; Dibutyltin di-maleate, Dibutyltin dilulate and epoxidized soybean oil. The stabilizer prevents the self-adhesive film from breaking down during extrusion and calendering or when applying or coating as a solution.

Examples of the lubricants are stearylamide, methylene-bis-stearylamide, Paraffin wax, stearic acid and glycerol mono-oleate. Metal soaps such as lead, cadmium, zinc stearate have the properties of both heat stabilizer and lubricant, so that they can also be used as lubricants. At-

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Games of the pigment are titanium dioxide, aluminum hydroxide, calcium carbonate and the like ..

The self-adhesive composition is applied to the release paper 3 or the base sheet 5 is applied in various ways, for example by calendering, extrusion or by coating. if When calendering or extrusion is used, the self-adhesive composition is ground or kneaded in a roller mill. Then a self-adhesive film of 50μ to 200μ thick is formed at a temperature of 100 ° C to 140 ° C and then on the release paper 3 or the base sheet 5 applied as a layer. When coating agents, for example air, brushes, reverse rollers, doctor blades are used, the self-adhesive composition is applied in the form of a solution to the release paper or the base sheet and dried at a temperature of 100 C to 140 ° C, wherein the self-adhesive composition is gelled at the same time. Coating with a solution is preferably used if the self-adhesive film should have a thickness of below 50 μ.

Examples of the solvent that in such a solution for coating is used are cyclohexanone, tetrahydrofuran, dioxane, benzene, mono- and di-chlorobenzene, nitrobenzene, toluene, xylene, dimethylformamide, Ethylene dichloride, trichlorethylene, tetrachlorethylene, Acetone, methyl ethyl ketone, methyl acetate, ethyl acetate, butyl acetate and cellulose acetate. The amount of solvent used in the preparation of the coating solution is used, is 300 to 1,000 parts by weight per 100 parts of graft polymer, with less solvent a more viscous solution results, which causes difficulties in the coating work, while a larger amount of solvent produces a thinner solution which has only poor film-forming properties.

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The thickness of the self-adhesive film that is on the release paper or is made on the base sheet is preferably 10 to 200 µ; a thinner film is not advantageous in practice because of the low adhesive strength and a film thicker than 200 μ does not guarantee any further advantages.

In this way one obtains the self-adhesive material according to the invention, as shown in Figs. The self-adhesive material in FIG. 1 can be printed and / or it can, as a function raised spots on the self-adhesive film are caused by conventional means due to the intended use. When using the self-adhesive sheet 8 is detached or peeled off from the release paper 3 and stuck onto the surface of the object. In Fig. 3, the self-adhesive material becomes the self-adhesive sheet 10, which is used for protection or covering, as shown is used.

On the other hand, if the self-adhesive material should also have improved printability and treatability, the self-adhesive composition is coated or coated on the release paper. Then a Base sheet, for example paper, a regenerated cellulose film or cellulose foil, woven or non-woven cloth, art paper, a metal foil or a synthetic resin film which contains a thermoplastic synthetic resin, such as vinyl chloride resin, acrylic resin, Polyamide, polystyrene, saturated polyester and the like. Applied as a layer. If paper, cloth or a resin film, what low Adhesive or adhesive properties are used, it is necessary to use a specific adhesive or a specific adhesive to use and / or a specific treatment, for example

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surface oxidation. Such adhesives are the solution type and examples thereof are nitrile, polychloroprene, polyvinyl acetate, epoxy resin and polyurethane resin. They can too be of the emulsion type. Examples of this are ethylene / vinyl acetate, Copolymer and vinyl chloride / vinyl acetate copolymer. The glue of the solution type may contain a crosslinking agent such as toluene diisocyanate to increase the adhesive strength.

In this way a self-adhesive material according to the invention is obtained, as shown in FIG. This material can be printed on and / or it can be used in a conventional manner depending on surveys of the intended use must be worked out on the basic sheet. The self-adhesive sheet 9 is separated from the release paper 3 peeled off and glued to the surface of an object.

Furthermore, the invention is to be explained in more detail with the aid of the following examples will.

example 1

A self-adhesive composition contains the following components:

Parts by weight

Graft polymer (50 parts of ethylene vinyl 100

acetate copolymer (55/45) grafted with 50 parts of a vinyl chloride monomer)

Stearic acid 1.3

Cadmium stearate 0.7

Barium stearate 0.7

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Di-n-octyl phthalate 20

Epoxidized soybean oil 3

The composition was kneaded in a roller mill or in a ball mill and formed in a calendering arrangement at about 110 ° C to 120 ° C into a self-adhesive film with a thickness of 100 μ and was applied as a layer on a plasticized polyvinyl chloride film (which contains a plasticizer 20 % contained) applied with a thickness of 80. Then, a release paper having an unsaturated polyester resin layer was applied to the self-adhesive film as another layer, so that a self-adhesive material was obtained. The properties of this self-adhesive material are shown in Table IV below.

Example 2

A self-adhesive composition consisted of the following components:

Parts by weight

Graft polymer (50 parts of an ethylene 100

vinyl acetate copolymer (55/45) grafted with 50 parts of a vinyl chloride monomer)

Stearic acid 1.3

Cadmium stearate 0.7

Barium steaxate 0.7

Di-n-octyl phthalate 20

Epoxidized soybean oil 3

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Titanium dioxide

Modified rosin

6.5 10

The composition was kneaded in a ball mill and added under pressure in a calender assembly at about 120 ° C to 130 ° C
molded into a film of 100 μm thickness and then coated on a lOOM · pigmented and plasticized polyvinyl chloride film (the plasticizer contained 25% ). Then, the release paper having an unsaturated polyester resin layer was laminated on the self-adhesive film to obtain the self-adhesive material. This self-adhesive material was printed on the polyvinyl chloride film.

The properties of the self-adhesive material are in the further
Table IV below.

Examples 3 and 4

The components shown in Table I below were used Coating solutions made:

Table I.

"-——_ ^ __ ^ Examples No.
Components "*""" ——-___ 3
(Weight
parts) 4th
(Weight
parts) Graft polymer (70 parts of an ethylene
vinyl acetate copolymer (45/55) ge
grafted with 30 parts of a vinyl chloride
Monomers)
Dibutyl phthalate
Hydrogenated rosin ester
Methyl ethyl ketone
Tetrahydrofuran 100
60
100
250
150 100
60
250
150

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A pigmented and plasticized polyvinyl chloride film (100 μ thick)

was coated with 50 g / m 2 (wet) of a coating solution by means of a rewind roller coated and then the coated film was dried. Then a release paper with a silicone resin layer was made laminated onto the coated film. The properties of the so obtained self-adhesive material are shown in Table IV below.

Example 5

A self-adhesive composition contained the following ingredients:

Parts by weight

Polyvinyl ether / polyvinyl chloride graft 100

polymer

Stearic acid 1.3

Cadmium stearate 0.7 _;

Bearium stearate 0.7

Dl-n-octyl phthalate 20

Pentearythritol ester rosin 40

The composition was kneaded in a ball mill and pressed into a film with a thickness of 100μ at 110.degree. C. to 120.degree. C. in a calendering arrangement. Then the composition was laminated onto a plasticized polyvinyl chloride film ( containing a plasticizer 20% ) with a thickness of 80 μ. Then, a release paper having an unsaturated polyester resin layer was laminated on the self-adhesive film, so that a self-adhesive material was obtained. the

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Properties of this self-adhesive material are in the below shown in Table IV below.

Examples 6 and 7

There were coating solutions of the following ingredients, which are shown in table Π, manufactured:

Table Π

^ --- ~ ^^ _ Example No. 6th
(Weight 7th
(Weight Coating solution parts) parts) Polyvinyl ether / polyvinyl chloride 100 100 Graft polymer Dibutyl phthalate 100 60 Modified rosin 200 100 Methyl ethyl ketone 300 300 Tetrahydrofuran 100 100 toluene 100 100

• J

A release paper with a silicone resin layer was coated with 150 g / m 2 (wet) of the coating solutions by means of a rewind roller coated and the coated paper was dried. Then a plasticized polyvinyl chloride film (contained 30 parts of plasticizer for 100 parts of polyvinyl chloride resin) laminated to the coated paper. The properties of the self-adhesive materials thus obtained are in Table IV below.

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Example 8

A self-adhesive composition contained the following ingredients:

Parts by weight

Polyacrylic ester / polyvinylchloride- 100

Graft polymer

Stearic acid 1.3

Cadmium stearate 0.7

Barium stearate 0.7

Di-n-octyl phthalate 5

Modified rosin 5

The composition was kneaded in a ball mill and pressed in a calendering device at about 110 ° C. to 120 ° C. to form a film with a thickness of 100 μm and then laminated onto a plasticized polyvinyl chloride film (contained a plasticizer 20%) with a thickness of 80 μm . Then, a release paper having an unsaturated polyester resin layer was laminated on the self-adhesive film, so that a self-adhesive material was obtained. The properties of this self-adhesive material are shown in Table IV below.

Examples 9 and 10

Coating solutions were prepared from the following Components shown in table ΙΠ:

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Table ΙΠ

9
(Weight 10
(Weight - "^ *" -—- ^^ example no. parts) i parts) Components 100 100 , Polyacrylic ester / polyvinyl chloride Graft polymer 60 60 Di-η-octyl phthalate 120 - Pentaerythritol ester rosin 220 200 Methyl ethyl ketone 320 140 Tetrahydrofuran 220 100 toluene

A 100 micron thick release paper with a silicone resin layer was with 150 g / m 2 (wet) of a coating solution was coated by means of a reflux roller, and then the coated paper was dried. A plasticized polyvinyl chloride film (containing 30 parts of plasticizer for 100 parts of polyvinyl chloride resin) was applied to the coated paper. laminated. The properties of the self-adhesive material thus obtained are shown in Table IV below.

Example 11

A self-adhesive composition contained the following ingredients * share:

Graft polymer (30 parts of an ethylene vinyl acetate copolymer (30/70) grafted with 70 parts of a vinyl chloride monomer)

Parts by weight 100

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-XB-

23 32758 ι, 3 ο, 7th ο, 7th 20th 3

Stearic acid cadmium stearate barium stearate di-η-octyl phthalate "Epoxidized" soybean oil

The composition was kneaded in a ball mill and pressed in a calendering device at about 110 ° C. to 120 ° C. to form a film with a thickness of 100 μm and then laminated onto a plasticized polyvinyl chloride film (contained a plasticizer 20%) with a thickness of 80 μm . Then, a release paper having an unsaturated polyester resin layer was laminated onto the self-adhesive film, thus obtaining a self-adhesive material. The properties of this self-adhesive material are shown in Table IV below.

Example 12

A coating solution was prepared from the following ingredients:

Parts by weight

Graft polymer (45 parts of an ethylene 100 vinyl acetate copolymer (30/70) grafted
with 55 parts of a vinyl chloride monomer)

Di-η-octyl phthalate 35

Dibutyl phthalate 35

Tetrahydrofuran 100

Methyl ethyl ketone 200

Toluene 100

A 100 μ thick pigmented and plasticized polyvinyl chloride film was with 50 g / m (wet) of a coating solution by means of a back

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Barrel on roller coated in front of the device and then dried. It was then a release paper with a silicone resin layer on the coated film laminated.

The properties of the self-adhesive material thus obtained are in Table IV below.

Example 13

A self-adhesive composition contained the following ingredients:

Parts by weight

Graft polymer (30 parts of an ethylene 100 vinyl acetate copolymer (60/40) grafted with 70 parts of a vinyl chloride monomer)

Stearic acid 1.3

Cadmium stearate 0.7

Barium stearate 0.7

Di-n-octyl phthalate 5

Titanium dioxide 6.5

Modified rosin 5

The composition was applied as in Example 11 and so on self-adhesive material received. The properties of this self-adhesive material are shown in Table IV below.

Example 14
A coating solution was prepared from the following ingredients:

⁶¹³⁹ 3 ose :> : - · / 11 3 η

- ai-

2332758 Parts by weight Graft polymer (the same as in 100 Example 13) Di-η-octyl phthalate 30th Dibutyl phthalate 40 Modified rosin 100 Tetrahydrofuran 200 Methyl ethyl ketone 250 Cyclohexanone 150

The coating solution was used as in Example 12 and a pressure sensitive adhesive Material obtained in this way.

The properties of this self-adhesive material are in Table IV shown below.

Example 15

A self-adhesive composition contained the following ingredients:

Parts by weight

Graft polymer (45 parts of an ethylene 100 vinyl acetate copolymer (60/40) grafted with 55 parts of a vinyl chloride monomer) stearic acid 1.3

Cadmium stearate 0.7

Barium stearate 0.7

Di-η-octyl phthalate 20

The composition was applied as in Example 11 and thereby get a self-adhesive material.

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The properties of this self-adhesive material are also in of Table IV.

Example 16

A coating solution was prepared from the following ingredients:

Parts by weight

Graft polymer (same as in Example 15) 100 Di-η-octyl phthalate 30th Dibutyl phthalate 40 Modified rosin 150 Tetrahydrofuran 150 Methyl ethyl ketone 300 Ethyl acetate 200

The coating solution was applied as in Example 12 and thereby obtain a self-adhesive material.

The properties of this self-adhesive material are in Table IV shown.

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Table IV example

No.

Adhesiveness

Bond strength

Accelerated migration of the plasticizer

Polystyrene

Polycarbonate

20 cm

15-g / 2.5cm

13 "

2.5 "

-4-50

5.0 "

20th

5 "

250

10

120

15th

100

4-00

10

170

11

> 20

12th

3 "

100

13th

> 20 "

120

16

7 "

20th

500

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Comparison
example 1 '* 20 cm 3 g / 3 cm X Δ Comparative
example 2 1.0 cm 1500 » X Λ

Here mean:

1. Adhesion:

A self-adhesive sheet is peeled off the release paper. The self-adhesive Film of this sheet is placed on a glass plate which is inclined upwards at an angle of 1 °. Then an iron ball with a diameter of 1.06 cm and a weight of 5.5 g over the self-adhesive film, which is the test piece, rolled. The ball is rolled on 5 cm away from the upper end of the test piece and it becomes the distance that the iron ball on the test piece has traveled, measured.

2. Adhesion:

A test sample measuring 2.5 cm 15 cm or 3 cm 15 cm and the self-adhesive sheet are peeled off the release paper and subjected to the following test. The sample piece is placed on a stainless steel and pressed on by means of a 1.5 kg rubber roller, the rubber roller back and forth once is rolled. Then 3 cm of the specimen is peeled off the stainless steel. Then the specimen and the plate are attached attached the upper and lower bracket of a "Tensilon" tester and the specimen is peeled off at an angle of 180 °, specifically at a speed of 200 mm / min, and this is the resistance measured while peeling.

3. Accelerated plasticizer migration:

A self-adhesive sheet is peeled off a release paper and

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on a plastic plate, for example made of polystyrene resin or Polycarbonate resin, glued on. The sample thus obtained is then placed in an atmosphere for 50 hours at a temperature of 50.degree has, placed.

After the self-adhesive sheet is peeled off, it can be visualized Observation will determine whether the plasticizer is in the self-adhesive The sheet has penetrated or migrated into the plastic plate, namely by the cloudiness, the regression and the discoloration of the Parts that have stuck together is detected.

The results that were observed here can be divided into four classes as follows:

No plasticizer remained

Traces of the plasticizer are left O

some parts of the plasticizer remained ^

most of the plasticizer remained X

4. Comparative example 1

A coating solution was prepared from the following ingredients:

Parts by weight

Polyvinyl chloride 100

Di-n-octyl phthalate 60

Tetrahydrofuran 150

Methyl ethyl ketone 250

The coating solution was applied as in Example 3, thereby obtaining a self-adhesive material.

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5. Comparative example 2 shows the properties of an adhesive tape with an acrylic resin layer.

Example 17

A composition was made from the following ingredients:

Parts by weight

Graft polymer (50 parts of an ethylene 100

vinyl acetate copolymer (55/45) grafted

with 50 parts of a vinyl chloride monomer)

Stearic acid 1.3

Cadmium stearate 0.7

Barium stearate 0.7

The composition was kneaded in a ball mill and pressed in a calendering device at 110 ° C. to 120 ° C. to form a film with a thickness of 100 μm and laminated onto a plasticized polyvinyl chloride film (containing 20% plasticizer) with a thickness of 80 μm. Then, the release paper was laminated with an unsaturated polyester resin layer on the self-adhesive film to form a self-adhesive material. was obtained. The properties of this self-adhesive material are shown in Table V below.

Example 18

A coating solution was prepared from the following ingredients:

Parts by weight

Graft polymer (same as in Example 17) 100

Di-n-octyl phthalate 9

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-2T-

Dibutyl phthalate 10

Methyl ethyl ketone 200

Tetrahydrofuran 100

Toluene .. 100

A 100 µm-thick release paper having a silicone resin layer was coated with 150 g / m 2 (wet) of the coating solution by means of a rewind roller, and the coated paper was dried. A plasticized polyvinyl chloride film (containing 30 % plasticizer) was then laminated onto the coated paper. The properties of the self-adhesive material obtained in this way are shown in Table V.

Example 19 A composition contained the following ingredients:

Parts by weight

Graft polymer (30 parts of an ethylene 100 vinyl acetate copolymer (55/45) grafted
with 70 parts of a vinyl chloride monomer)

Di-n-octyl phthalate 9

Dibutyl phthalate 10

Stearic acid 1.3

Cadmium stearate 0.7

Barium stearate 0.7

The composition was kneaded in a ball mill and in a Calendering device pressed at 110 ° C to 120 ° C to a film of 100 μ thickness and then on a plasticized polyvinyl chloride film (80 μ thick) laminated, whereby a self-adhesive material was obtained. The properties of this self-adhesive material are shown in Table V.

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3 0 9 B 8 3/1 13 Π

- 38 -

Example 20

A coating solution was prepared from the following ingredients:

Parts by weight

Graft polymer (70 parts of an ethylene - 100 vinyl acetate copolymer (55/45) grafted with 30 parts of a vinyl chloride monomer)

Methyl ethyl ketone 200

Tetrahydrofuran 100

Toluene 100

A release paper having a silicone resin layer was coated with 150 g / m 2 (wet) of the coating solution by means of a rewind roller coated and dried. The self-adhesive material thus obtained was printed on the self-adhesive film.

The properties of this material are shown in Table V.

⁶¹³⁹ 309 8 83/1130

Table V example

No.

17th

18th

19th

20th

Comparison example 3

Vogadh example 4th

Adhesiveness

(cm) 13

20th

Adhesion and peelability

(g / 3cm) 10

25th

20th

1800

residual pollution d. Glue

Accelerated migration of the plasticizer

Polystyrene

Polyvinyl] polycarbonate chloride

K)

CO

hO

cn

OO

-SO-

It means:

1. Adhesiveness;

A self-adhesive sheet is peeled off a release paper. The self-adhesive film of this sheet is directed upwards placed on a so-called "Dagrace Rolling Tester". Then an iron ball with a diameter of 0.5 cm and a weight of 1.05 g on the self-adhesive film from a point 5 cm from the top of the specimen away. The distance covered by the iron ball on the specimen is measured,

2. Adhesion:

The same procedure was used here as described in connection with Table IV.

3. Remaining dirt from adhesive on the item:

A self-adhesive sheet is peeled off a release paper and stuck on a glass plate or an acrylic butadiene styrene resin plate. The specimen thus obtained is added 200 hours in an oven which is maintained at a temperature of 6O ⁰ C. After being removed from the oven, the specimen is cooled for one hour at room temperature. Then the self-adhesive sheet is carefully peeled off and the amount of adhesive remaining on the object is visually observed. When peeling off, the peelability is checked at the same time.

Easily removable

not removable ........... X

Polluting glue - none (Q

residues on the object residues X

was standing

₆₁ 39 309 883/113 0

4. Accelerated plasticizer migration:

A self-adhesive sheet is peeled off a release paper and placed on plastic sheets, for example made of polystyrene resin, polyvinyl chloride resin and polycarbonate resin stuck on.

The specimens obtained in this way are placed in a so-called "weather meter" for 300 hours is set, introduced. After the self-adhesive sheet is taken out, it is determined by visual observation whether the plasticizer in the self-adhesive sheet has penetrated or migrated into the plastic sheets, namely by the Cloudiness, regression and discoloration of the parts to which the adhesive has adhered can be determined. The results fall in two classes, which are characterized as follows:

No plasticizer residue (O)

Most of the plasticizer remains behind X

5. Comparative example 3 is an adhesive tape with a gum layer.

6. Comparative example 4:

A coating solution was prepared from the following components nine r ^{rei e} * parts by weight

Polyvinyl chloride resin 100

Di-n-octyl phthalate 9

Dibutylphthalaf 10

Methyl ethyl ketone 200

Tetrahydrofuran 100

Toluene 100

6139 309803/1130

The coating solution was applied as in Example 18, whereby an adhesive material was obtained.

⁶¹³⁹ 3 0 9 8 3 3/1130

Claims (17)

Claims 1. Self-adhesive material, especially in the form of a self-adhesive Film, characterized by a graft polymer which is grafted with a vinyl chloride monomer. 2. Self-adhesive material according to claim 1, characterized in that that the graft polymer alone or in a mixture of two or more of the substances selected from the group are made of an ethylene vinyl acetate copolymer / vinyl chloride graft polymer a polyvinyl ether / vinyl chloride graft polymer and a polyacrylic ester / vinyl chloride graft polymer consists. 3. Self-adhesive material according to claim 2, characterized in that that the weight ratio of vinyl chloride to the ethylene vinyl acetate copolymer in the ethylene vinyl acetate copolymer / vinyl chloride orid graft polymer is 20-80: 80-20, while that of ethylene to vinyl acetate is 20-60: 80-40. 4. Self-adhesive material according to one of the preceding claims, characterized in that the self-adhesive composition in addition to the graft polymer with the vinyl chloride ionomer is grafted, contains a plasticizer. 5. Self-adhesive material according to claim 4, characterized in that the self-adhesive composition contains 100 parts by weight of the graft polymer which is grafted with the vinyl chloride monomer and contains 1-100 parts by weight of plasticizer. 6139 309883/1130 6. Self-adhesive material according to claim 4 or 5, characterized in that that the graft polymer alone or as a mixture of two or more of the compounds selected from the Ethylene vinyl acetate copolymer / vinyl chloride graft polymer group, Polyvinyl ether / vinyl chloride graft polymer and polyacrylic ester / vinyl chloride graft polymer consists. 7. Self-adhesive material according to claim 4, characterized in that that the self-adhesive composition 100 parts by weight of ethylene vinyl acetate copolymer / vinyl chloride graft polymer and contains 1-75 weight percent plasticizers. 8. Self-adhesive material according to claim 4, characterized in that that the self-adhesive composition 100 parts by weight of polyvinyl ether / vinyl chloride graft polymer and 1-100 parts by weight Contains plasticizers. 9. Self-adhesive material according to claim 4, characterized in that that the self-adhesive composition contains 100 parts by weight of polyacrylic ester / vinyl chloride graft polymer and 1-60 parts by weight of plasticizer. 10. Self-adhesive material according to claim 6 or 7, characterized in that that the weight ratio of vinyl chloride to ethylene vinyl acetate Kopolyiherisat in ethylene vinyl acetate copolymer / vinyl chlorine id graft polymer is 20-80:80-20, while the of ethylene to vinyl acetate is 20-60: 80 -40. 11. Self-adhesive material according to one of the preceding claims, characterized in that the self-adhesive composition in addition to the graft polymer that is formed with the vinyl chloride monomer 6139 309883/1130 * is grafted, and the plasticizer contains a tackiness-imparting agent. 12. Self-adhesive material according to claim 11, characterized in that that the self-adhesive composition 100 parts by weight of the graft polymer grafted with the vinyl chloride monomer contains 5-100 parts by weight of plasticizer and 5-200 parts by weight of the adhesiveness-imparting agent. 13 * Self-adhesive material according to claim 11 or 12, characterized in that the graft polymer is used alone or as a mixture is contained by two or more compounds which are selected from the group ethylene vinyl acetate copolymer / vinyl chloride Pf graft polymer, poly vinyl ether / vinyl chloride graft polymer and polyacrylic ester / vinyl chloride graft polymer. 14. Self-adhesive material according to claim 11, characterized in that that the self-adhesive composition 100 parts by weight of ethylene vinyl acetate copolymer / vinyl chloride graft polymer Contains 5-75 parts by weight of plasticizer and 5-150 parts by weight of adhesive agent. 15. Self-adhesive material according to claim 11, characterized in that that the self-adhesive composition 100 parts by weight of polyvinyl ether / vinyl chloride graft polymer, 5-100 parts by weight Contains plasticizer and 40-200 parts by weight of adhesive agent. 16. Self-adhesive material according to claim 11, characterized in that that the self-adhesive composition 100 parts by weight of polyacrylic ester / vinyl chloride graft polymer, 5-60 parts by weight 6139 309633/1130 Plasticizer and 5-120 parts by weight of adhesive Contains funds. 17. Self-embedding material according to claim 13 or 14, characterized characterized in that the weight ratio of vinyl chloride to ethylene vinyl acetate copolymer in the ethylene vinyl acetate copolymer / Vinyl chloride graft polymer 20-80; 80 -20 while that of ethylene to vinyl acetate is 20 - 60: 80 - 40. 6139