FI65287C - RESTLOEST I TORRT TILLSTAOND AVDRAGBAR PUBLIC ADJUSTMENTS - Google Patents

Description

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Patent meddelat T (51) Kv.ikP / hta.3 D 06 N 7/00 FINLAND I —FI N LAN D (21) Pwenttihtlwmu · - P «t« nt »n» ölcnlnj Θ02266 (22) H »k * mJ »P« v * - Ameknlnpdaf IT. 07.80 ^ * (23) AHuipUvt — Glltl | h «tsda | IT. 07.80 (41) Interpreters (ulkbahal - BIMt offmtllf 20. 01. 8l

Patent and Registration Office * (44) Niht * vtk * ip «non j * kuL | uUuu« m p * m.—

Patent · och rcgisterstyrelMn ’AiwMan uthgd och utl. * Krtft« o public · ™) 30.12.83 (32) (33) (31) Pyr * «tty« TuoHcui-B.jIrd priority 19 · 07. 79

Federal Republic of Germany Förbundsrepubliken Tyskland (DE) P 2929228.2 (71) Wolff Walsrode AG, D-3030 Walsrode-Banlitz, Federal Republic of Germany Förbundsrepubliken Tyskland (DE) (72) Eugen Reinhardt, Walsrode, Walsrabowski, Klaus Szablikowski

Wolfgang Mross, Walsrode, Lutz Hoppe, Walsrode,

Federal Republic of Germany-Förbundsrepubliken Tyskland (DE) (7 * 0 Oy Kolster Ab (5 * 0 Residual dry-wall coverings -Restlöst i torrt tillst & nd avdragbar vaggbeklädnad

The present invention relates to dry-removable, if desired gluable, wall coverings, the back surface of which is provided with a hydrophobic multicomponent layer and, if desired, a water-activatable adhesive layer.

The technique today uses to make wall coverings, especially wallpaper, hydrophobic. According to DE-PS 1 635 623, the textile web is made hydrophobic by means of a wax containing zirconium salts. In the second step, an amount of cationic acrylate resin emulsion of 100-150 g / m 2 is then applied to the fabric to obtain a fabric wallpaper that retains its dimensions against water, water vapor and mechanical effects. After application of the water-activated adhesive layer, the wallpaper to be glued directly, but removed in a dry state without residue, is obtained.

2 65287

Commercially available, dry-release wallpapers are also provided with a hydrophobic layer on the back surface to ensure their dimensional stability when gluing. However, these wallpapers must be allowed to swell for at least 15 minutes after application of commercial wallpaper pastes, otherwise sufficient adhesion of the wallpaper will not be achieved. This swelling time can be considerably shortened if the wallpaper raw paper is provided with a hydrophobic layer according to the invention.

The present invention thus relates to dry-release, optionally gluable wall coverings, the back surface of which is provided with a hydrophobic multicomponent layer and possibly a water-activatable adhesive layer and which is characterized in that the multicomponent layer contains 1.30-85% by weight, preferably 60-80% by weight of a copolymer containing a) 25-75% by weight, preferably 30-70% by weight of vinylidene chloride units, b) 10-50% by weight, preferably 15-35% by weight of ethyl acrylate units and c) 10-50% by weight, preferably 15-35% by weight of methyl acrylate units, 2. 0.30% by weight of a copolymer containing d) 85-65% by weight, preferably 80-70% by weight % C 1-4 alkyl acrylate units and e) 35-15% by weight, preferably 20-30% by weight of aliphatic C 1-5 monoolefin units or aromatic olefin units, 3.15-70% by weight, preferably 20-35% by weight commercial wax with a pour point of at least 40 ° C (according to DIN 51556 n), preferably a fluorinated polymer compound, 4. 0.05-2.5% by weight, preferably 0.1-1.0% by weight of an impregnating agent, preferably an organic silicone compound, 5. 0.05-5% by weight, preferably 0.3-3.0% by weight of a conventional flow improver and 6. 0-5% by weight, preferably 0-3% by weight of a conventional thickener and a mixture of 1) -6) and a) -c) and d) -e) the amounts in each case are 100% by weight.

3 65287

The hydrophobic multicomponent layer is preferably applied as an aqueous dispersion to a wallcovering, preferably wallpaper raw paper, wherein the solids proportions of the dispersion ingredients in the dispersion correspond to the above weight percentages. Known application means are an adhesive brush / squeegee, rollers or an adhesive press. Preliminary tests can be used to easily determine which concentration or viscosity is most suitable for each mode of application. Preferably, the back surface of the wall covering should have 1-10 g / m, especially 3-7 g / m of hydrophobic layer. Excessive machine-dependent foaming can be prevented by the addition of suitable antifoaming agents. After application of the dispersion, the paper web is dried in a dryer (e.g. by means of infrared radiation, gas radiator, heated rollers, etc.).

Thus, the hydrophobically made wallcovering, preferably wallpaper raw paper, can be printed according to known methods and glued with commercial pastes.

In this case, it has been necessary to allow the pasted wallpaper to swell for at least 15 minutes in order to obtain a "slackness" resembling a moist leather surface when using the hitherto known wallpaper which can be removed without residual dryness. Only then can it be glued.

As the softening time cannot be determined precisely t, the so-called Cobb value method according to DIN 53 132 is used in the paper and wallpaper industry to obtain an appropriate measure of the softening time. The Cobb value is a measure of the water uptake capacity of a paper per unit time and area. The higher this value, the faster the paper absorbs water and the faster the desired so-called "slackness" is achieved in the paper. With the papers known hitherto, which can be removed dry without residues, a Cobb value of about 20 is reached after an exposure time of three minutes. In contrast, wall coverings according to the invention can have a Cobb value of 30-7Q after an exposure time of three minutes.

A water-activatable adhesive can also be applied to the hydrophobic layer to obtain adhesive wall coverings 2. The adhesive is preferably applied in an amount of 5-15 g / m and in particular 7-12 g / m. The applied adhesive is dried by means of known drying devices.

4 65287 This gives the wallpaper, which only needs to be drawn through a water bath, where it stays for a short time, for gluing, and which can later be removed alone by dry removal.

The copolymer solvents used to prepare the hydrophobic layer can be prepared according to known methods. They should preferably have molecular weights of at least 50,000.

Copolymer 2) is preferably composed of an alkyl acrylate containing a C 1 -C 4 alkyl radical, particularly preferably methyl acrylate or ethyl acrylate and aliphatic C 1 -C 4 monoolefins or aromatic monoolefins, preferably styrene.

Commercial waxes with a pour point of at least 40 ° C (DIN 51556) are used as dispersions. A wax dispersion with a density of 0.945-0.97 g / cm 3 at 15 ° C is particularly preferred, MOBILCER being particularly preferred.

As the fluorinated polymer compounds, conventional polyacrylate-based polymers known as impregnating agents are used.

Particularly preferably, a 40% by weight emulsion of a fluorinated polymer compound known as Scotchban FC 824 is used to prepare the hydrophobic layer.

Conventional silicone compounds known as flow improvers, especially siloxanes containing polyoxyalkane groups, are added to the coating dispersion. Particularly preferred (R) is Tegopren 100.

Preferably, a thickener selected from the group consisting of cellulose ether, polyvinylalkyl ether-maleic acid ester, polyalkylene oxides, polyvinylpyrrolidone copolymers is used.

Commercial wallpaper pastes based on cellulose ethers can be used as pastes. Suitable cellulose ethers are, for example, methylcellulose and carboxymethylcellulose.

The measured values mentioned in the examples were determined as follows: 1. Softening time

A 2% by weight aqueous Liis-ter solution is applied to the wallpaper. Measure the time required from application to softening of the wallpaper.

li 65287 2. Cobb value

The measurement method is used to determine the water absorption capacity of paper, cardboard or corrugated board from one surface (front or back) in each case and is described in DIN publication 53 132.

O

Determine the amount of water in grams that is absorbed from a 1 m paper surface on one side during the exposure time t (t = 3 min). After storage, the paper sample is used in a standard climate, at a temperature of 20 ° C and a relative humidity of 65% (DIN 50014) to determine the effect of water in accordance with the standard. The water intake is determined according to the weighing difference before and after the addition of 2 water and is calculated for an area of 1 m.

3. Polishing force

The removal force is used to determine the ability of the wallpaper to adhere to the substrate. A compression and traction meter type 901-001 manufactured by Fa. A.M. Erichsen GmbH, 5600 Wuppertal 2.

The wallpaper sample, which is glued to the substrate and dried for 2-3 days in air, is 29 cm wide and 39 cm long. The narrow edge of the wallpaper strip is detached 4-8 cm from the substrate and wrapped from the center around the metal frame provided with a hole, and the remaining edge of the paper from its adhesive surface is glued to the raw wallpaper paper glued to the substrate.

From the point where the metal bar has a hole, the paper is pierced and a traction device is attached to it. Removal of a 39 cm long sample by pulling is performed at a 90 ° angle to the wall.

In this case, the required traction forces are read from the above-mentioned traction device and written down.

Values less than 1 kp have been shown to mean too little removability. Values greater than 1 kp show good removability.

The following substances were used in the preparation: (R)

Mobilcer C: A 46 wt% wax dispersion with a density of 0.955 g / cm 2 (15 ° C) is sold by Mobil.

(R)

Scotchban FC 824: 40% by weight aqueous emulsion of a fluorinated polymer compound. Density 1.13 3 g / cm, manufactured by 3 M Deutschland GmbH.

_____ - · 1 - 6 65287 (R)

Tegeopren 100: Solid, silicone compound completely (100%) soluble in water and organic solvents, Density 1.0 g / cm 2 (250 ° C). Manufactured by Fa. Th. Goldschmidt.

f p \

Walocel 'MW 40,000 GB: Methylcellulose (100%), manufactured by Fa. Wolff, Walsrode AG.

(R)

Borchigel L 75: 5% w / w aqueous solution of a non-ionic polyurethane-based thickener. Manufactured by Fa. Gebr. Borchers AG, Dusseldorf.

(R)

Thickener L: 15% by weight, thickening solution of alkyl vinyl ether / maleic acid partial ester polymers, prepared by Fa. GAF GmbH, 5020 Frechen.

(R \

Polyox WSE 750 ': 100% by weight solid based on polyethylene oxide, manufactured by Union Carbide.

(R)

Waloran: A 50% by weight aqueous copolymer dispersion based on vinylidene chloride, ethyl acrylate and methyl acrylate, prepared by Fa. Wolff Walsrode AG.

(R)

Acronal 170 D: 45% by weight aqueous dispersion of acrylate / styrene polymer, manufactured by BASF.

(R)

Ukaphob B 486: An approximately 30% by weight aqueous dispersion for rendering wallpaper raw materials hydrophobic, prepared by Fa. Schill & Seilacher.

(R)

Auroplex: Wallpaper raw material, manufactured by Fa. Feldmiihle.

Valocel CT 30G01 ^ R ^: Carboxymethylcellulose, manufactured by

Fa. Wolff-Walsrode AG.

7 65287

Example 1 a) Preparation of dispersion

The following quantities of substances are prepared in storage vessels A-E:

Solid_i-

Storage vessel A: 1800 g Waloran ^ 900 g 73.71

Storage container B: 600 g Mobilcer 300 g 24.57

Storage vessel C: 30 g Tegoprene 20% 6 g 0.49

Storage vessel D: 15 g Scotchban ^ FC-824 6 g 0.49

Storage vessel E: 340 g of water, ±. 60 g

Thickener LtK '(15%) 9 g_0.74 2845 g dispersion 1221 g 100.00%

The solids content of the dispersion is 42.92% by weight

The contents of storage vessels B, E, A, C and D are emptied successively with stirring into a 5 liter mixing vessel, whereby as the volume and viscosity increase, the speed of the mixing device is increased to achieve complete mixing of the individual ingredients.

Homogenization of the mixture is complete after further stirring for 10 minutes.

b) Dispersion treatment

The dispersion prepared in a) is applied to Auroplex wallpaper wallpaper by means of a conventional (R) roll application device and then dried in a drying channel. After passing through the chill roll station, the coated paper is wound on rolls. The paper web speed is 5 m / min and the dispersion was applied at 4.6 g / m.

(c) Examination of coated wallpaper raw paper When disassembling the rolls of paper produced in (b), the possible adhesion properties of the individual layers of paper to each other (sticking and gluing) are observed. If no adhesion points are found, the adhesion properties are considered good.

The 3-minute Cobb value is set to 50.

A sheet of both printed and unprinted coated raw paper measuring 39 x 28 cm is coated on the back with a brush WALOCEL Universal ^ glue solution (dilution 1:50).

65287

The softening time is 5 minutes. The sheets of paper are then glued to the etherite wall. The gluing was good. After two days of drying, the sample sheets could be removed by dragging dry without residue. The attraction was measured to be 1.9 for non-printed paper and 2.9 for printed paper. Overall rating: very good.

Examples 2-5

Examples 2-5 and Comparative Example were performed according to Example 1 and the measured values are shown in the following Table 1. Examples 6-9

According to Examples 1-5, the wallpaper raw paper was rendered hydrophobic by applying a layer of 4.8-6.0 g / m 2.

The printed and unprinted wallpaper paper was then coated on the coated side with a 14% by weight solution of WALOCEL CT 30G01 (R) at a speed of 2.5 m / min using a roller applicator, dried in a drying channel and wound into a roll. The adhesive consumption was 8-12 g / m2.

A coated and uncoated paper sample measuring 39 x 29 cm was immersed in water for 8 seconds. Excess water was allowed to drip off in 2Q seconds and the sheets of paper were glued to the etherite wall. After a drying time of 2 days, the samples could be removed by dragging dry without residue. In this case, a pull-out force of 1.5-2.3 kp was measured for unprinted paper and 2.5-3.8 kp for printed paper. Overall rating: very good.

The measurement results of Examples 6-9 and Comparative Example B are shown in Table 2.

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Claims (2)

13 6 5 2 8 7 A wall covering which is permanently dry-dry, if desired glued, the back surface of which is provided with a multicomponent layer which makes it hydrophobic and, if desired, a water-activated adhesive layer, characterized in that the multicomponent layer contains: 1) 30-85% by weight of copolymer vinylidene chloride units, b) 10-50% by weight of ethyl acrylate units and c) 10-50% by weight of methyl acrylate units, 2) 0-30% by weight of a copolymer containing d) 85-65% by weight of C 1-6 alkyl acrylate units and e ) 35-15% by weight of aliphatic β-monoolefin units or aromatic olefin units, 3) 15-70% by weight of a commercial wax, preferably a fluorinated polymer compound, 4) 0.05-2.5% by weight of a conventional impregnating agent , preferably an organic silicone compound, 5) 0.05-5% by weight of a conventional flow improver and 6) 0-5% by weight of a conventional thickener, the amounts 1) to 6) and a) to c) and d) to e) in each case are 100% by weight. Wallcovering according to Claim 1, characterized in that the hydrophobicizing layer is applied in an amount of 1 to 10 g / m 2 and the adhesive 2 in an amount of 5 to 15 g / m 2.