ADHESIVE BASED ON A SPECIAL POLYURETHANE UREA, AND PRODUCTION AND USE THEREOF

Abstract

The invention relates to an adhesive that can be produced from an aqueous polyurethane urea dispersion, containing an amorphous polyurethane urea, which can be obtained by reacting at least A) an aliphatic polyisocyanate component having an average isocyanate functionality of 1.8 and 2.6; B) a polymeric polyether polyol component; C) an amino-functional chain extender component having at least two isocyanate-reactive amino groups, containing at least one amino-functional compound C1) that has no ionic or ionogenic groups, and/or an amino-functional compound C2) that has ionic or ionogenic groups; D) optionally, further hydrophilizing components that are different from C2); E) optionally, hydroxy-functional compounds having a molecular weight of 62 to 399 mol/g; F) optionally, further polymeric polyols that are different from B); G) a compound that has exactly one isocyanate-reactive group, or a compound that has more than one isocyanate-reactive group, wherein only one of the isocyanate-reactive groups reacts with the isocyanate groups present in the reaction mixture under the selected reaction conditions; and H) optionally, an aliphatic polyisocyanate component having an average isocyanate functionality of >2.6 and 4, wherein together, the components B) and F) contain 30 wt % of component F) based on the total mass of components B) and F). The invention further relates to an adhesive layer and to a product comprising the adhesive, to a method for producing the adhesive layer, to a special polyurethane urea, and to the use of the adhesive.

Claims

1. An adhesive producible from an aqueous polyurethaneurea dispersion comprising an amorphous polyurethaneurea obtainable by reacting at least A) an aliphatic polyisocyanate component having an average isocyanate functionality of 1.8 and 2.6, B) a polymeric polyetherpolyol component, C) a amino-functional chain extender component having at least 2 isocyanate-reactive amino groups, containing at least one amino-functional compound C1) that does not have any ionic or ionogenic groups and/or an amino-functional compound C2) that has ionic or ionogenic groups, D) optionally further hydrophilizing components different than C2), E) optionally hydroxy-functional compounds having a molecular weight of 62 to 399 mol/g, F) optionally further polymeric polyols that are different than B), G) a compound having exactly one isocyanate-reactive group or a compound having more than one isocyanate-reactive group, where only one of the isocyanate-reactive groups reacts with the isocyanate groups present in the reaction mixture under the reaction conditions chosen, and H) optionally an aliphatic polyisocyanate component having an average isocyanate functionality of >2.6 and 4, where components B) and F) together contain 30% by weight of component F), based on the total mass of components B) and F).

2. The adhesive as claimed in claim 1, wherein component A) is isophorone diisocyanate, hexamethylene diisocyanate or a mixture of isophorone diisocyanate and hexamethylene diisocyanate.

3. The adhesive as claimed in claim 1, wherein component B) contains or consists of poly(propylene glycol) polyetherpolyols.

4. The adhesive as claimed in claim 1, wherein component B) contains or consists of a mixture of poly(propylene glycol) polyetherpolyols, where the poly(propylene glycol) polyetherpolyols differ by at least 100 g/mol in their number-average molecular weights.

5. The adhesive as claimed in claim 1, wherein component B) has an average molar mass within a range from 400 to 4000 g/mol.

6. The adhesive as claimed in claim 1, wherein the polyurethaneurea is obtainable by preparing isocyanate-functional polyurethane prepolymers a) from components A), B) and optionally D) and/or C2), and optionally compounds E) and/or H), and the free NCO groups thereof are then wholly or partially reacted with the amino-functional chain-extender component C), and also component G) and optionally component D).

7. The adhesive as claimed in claim 1, wherein the polyurethaneurea has a Tg25 C.

8. An adhesive layer (100) comprising at least one first layer (110) comprising at least one first surface (120) and at least one first further surface (130), where the first surface (120) runs essentially parallel to the first further surface (130), wherein the first layer (110) includes an adhesive as claimed in claim 1.

9. The adhesive layer (100) as claimed in claim 8, wherein the adhesive layer (100) is at least partly covered on its first surface (120) at least by a first further layer (140).

10. The adhesive layer (100) as claimed in claim 8, wherein the adhesive layer (100) is at least partly covered on its first further surface (130) at least by a second further layer (150).

11. A product (200), wherein the product (200) includes an adhesive as claimed in claim 1 and additionally has at least one of the following features: at least one substrate (210), at least one component (220) including at least one component surface (230).

12. The product (200) as claimed in claim 11, wherein the product (200) is selected from the group consisting of a plaster, a (wound) dressing, a tape, a dressing, a stoma pouch, a medical device, an automobile or a combination of at least two of these or is at least a constituent of these end products.

13. An aqueous polyurethaneurea dispersion comprising an amorphous polyurethaneurea obtainable by reacting at least A) an aliphatic polyisocyanate component having an average isocyanate functionality of 1.8 and 2.6, B) a polymeric polyetherpolyol component, C) an amino-functional chain extender component having at least 2 isocyanate-reactive amino groups, containing at least one amino-functional compound C1) that does not have any ionic or ionogenic groups and/or an amino-functional compound C2) that has ionic or ionogenic groups, D) optionally further hydrophilizing components different than C2), E) optionally hydroxy-functional compounds having a molecular weight of 62 to 399 mol/g, F) optionally further polymeric polyols that are different than B), G) a compound having exactly one isocyanate-reactive group or a compound having more than one isocyanate-reactive group, where only one of the isocyanate-reactive groups reacts with the isocyanate groups present in the reaction mixture under the reaction conditions chosen, and H) an aliphatic polyisocyanate component having an average isocyanate functionality of 2.6 and 4, where components B) and F) together contain 30% by weight of component F), based on the total mass of components B) and F).

14. A process for producing an adhesive layer, comprising the steps of: I) applying a polyurethaneurea in form of an aqueous polyurethaneurea dispersion as claimed in claim 13 to a first further layer (140) to obtain a precursor (300), II) thermally treating the precursor (300) from step I) at temperatures within a range from 20 C. to 200 C. to form the adhesive layer (100).

15. The process as claimed in claim 14, comprising at least one of the following further steps: III) detaching the adhesive layer (100) from the first further layer (140); IV) transferring the adhesive layer (100) from the first further layer (140) to a second further layer (150); V) covering the adhesive layer (100) with a second further layer (150) on the first surface (120) of the first layer (110); VI) covering the adhesive layer (100) with a second further layer (150) on the first further surface (130) of the first layer (110); VII) transferring the adhesive layer (100) from the first further layer (140) to a substrate (210); VIII) transferring the adhesive layer (100) from the first further layer (140) to at least a portion of a component surface (230) of a component (220); IX) transferring the adhesive layer (100) from the first further layer (140) to a third further layer (160).

16. The use of an adhesive as claimed in claim 1 for securing a product on an article or on the skin of a living being.

Description

FIGURES

[0287] The invention is illustrated in detail by the figures which follow, but without being restricted thereto.

[0288] FIG. 1: schematic diagram of an adhesive layer of the invention;

[0289] FIG. 2: schematic diagram of an adhesive layer of the invention on a first further layer;

[0290] FIG. 3: schematic diagram of an adhesive layer of the invention between a first further layer and a second further layer;

[0291] FIG. 4: schematic diagram of an adhesive layer of the invention on a substrate and covered by a second further layer;

[0292] FIG. 5: schematic diagram of an adhesive layer of the invention on a component and covered by a second further layer;

[0293] FIG. 6: schematic diagram of a transfer of an adhesive layer of the invention from a first further layer to a third further layer;

[0294] FIG. 7: schematic diagram of a process of the invention for production of an adhesive layer.

[0295] FIG. 1 shows, in schematic form, an inventive adhesive layer 100 in the form of a first layer 110 that has a first surface 120 and a further surface 130. The adhesive layer 100 is produced, for example, as described in use example 1. The thickness of the adhesive layer 100 is between 50 and 200 m.

[0296] FIG. 2 shows the same adhesive layer 100 in the form of a first layer 110 as in FIG. 1, with the difference that the first surface 120 has been covered by a first further layer 140. In this case, the first further layer 140, in terms of its dimensions, is larger than the adhesive layer 100. However, this is not absolutely necessary. The first further layer 140 is formed from a paper having a silicone coating.

[0297] FIG. 3 shows an adhesive layer 100 in the form of a first layer 110, as shown in FIGS. 1 and 2, with the difference that a first further layer 140 is disposed on the first surface 120 and a second further layer 150 is disposed on the first further surface 130 of the first layer 110. In both cases, the surface dimensions of the first further layer 140 and the second further layer 150 are larger than those of the first layer 110.

[0298] FIG. 4 shows a product 200 including an adhesive layer 100 in the form of a first layer 110, with a substrate 210 disposed on the first surface 120 and a first further layer 140 in the form of a paper atop the first further surface 130. The paper is preferably siliconized. The substrate 210 in this case is a weave, preferably a cotton weave, in order to form a plaster 200 together with the adhesive layer 100. Alternatively, the substrate 210 may also be a polymer and be configured in the form of a pouch in order to form an ostomy 200 together with the adhesive layer 100. The paper 140 is removed before utilization of the product 200 in order to secure the product 200, either the plaster 200 or the ostomy 200 here, to the skin of a patient by contacting the adhesive layer 100 with the skin of the patient.

[0299] FIG. 5 shows a product 200 in the form of a component 220 that has an adhesive layer 100 in the form of a first layer 110 on its component surface 230. Here too, the adhesive layer 100 is protected by a first further layer 140, for example in the form of a paper, before this paper layer 140 is removed prior to the bonding of component 222 to another article or the skin of a patient. The component 220 may, for example, be an electronic component 270, such as a sensor 270, for example a blood pressure sensor, a pulse sensor, a moisture sensor or a temperature sensor, or a combination of at least two of these. In this case, the sensor 270 is protected from the environment by a thermoplastic polyurethane layer 240. Before application of the product 200 to the skin of a patient, the paper layer 140 is removed.

[0300] FIG. 6 shows, in schematic form, the transfer 180 of an adhesive layer 100 in the form of a first layer 110 from a first further layer 140, for example in the form of a paper layer 140, to a third further layer 160. For this purpose, the first further layer 160 is moved toward the adhesive layer 100 in the direction of the arrow 170 and contacted therewith at the first further surface 130. Subsequently or simultaneously, the first further layer 140 is removed from the first surface 120 of the adhesive layer 100. This can be effected, for example, by simply pulling away the first further layer 140 by hand. After the adhesive layer 100 has been transferred from the first further layer 140 to the third further layer 160, the third further layer 160 fully covers the adhesive layer 110 on the first further surface 130 and projects beyond the two-dimensional extent of the adhesive layer 100. The projection of the third further layer 160 facilitates the removal of the third further layer 160 on use of the adhesive layer 100 for its end use.

[0301] FIG. 7 shows a schematic of the process for producing the adhesive layer 100. In a first step I) 250, a polyurethaneurea in the form of an aqueous polyurethaneurea dispersion as described in use example 1 is applied to a first further layer 140, a release paper from Felix Schller with the Y5200 name here, to form a precursor 300 with the aid of by means of an Erichsen drawdown bar (300 m) in a wet film thickness of 300 m. In step II) 260, the precursor 300 is converted to the adhesive layer 100 by thermal treatment at 40 C. for 20 minutes and at 130 C. for 3 minutes.

EXAMPLES

[0302] The invention is illustrated in detail by the examples which follow, but without being restricted thereto. The expression film as also used in some standards is used synonymously with the adhesive layer used in the rest of the description, especially the first layer.

[0303] Methods:

[0304] Unless indicated otherwise, all percentages are based on weight and the total amount or on the total weight of the compositions.

[0305] Unless stated otherwise, all analytical measurements relate to measurements at temperatures of 23 C.

[0306] Solids contents were ascertained in accordance with DIN EN 3251 by heating a weighed sample to 105 C. to constant weight. At constant weight, the solids content was calculated by reweighing the sample.

[0307] Unless explicitly mentioned otherwise, NCO values were determined by volumetric means to DIN-EN ISO 11909.

[0308] The check for free NCO groups was conducted by means of IR spectroscopy (band at 2260 cm.sup.1).

[0309] The viscosities reported were determined by means of rotary viscometry to DIN 53019 at 23 C. with a rotary viscometer from Anton Paar Germany GmbH, Ostfildern, DE (1 Pa s=1 N/m.sup.4*s).

[0310] Average particle sizes (the number-average is specified) of the polyurethane dispersions were determined after dilution with deionized water by means of laser correlation spectroscopy (instrument: Malvern Zetasizer 1000, Malvern Inst. Limited).

[0311] The pH was measured by the method described in DIN ISO 976 on the undiluted sample.

[0312] Glass transition temperature T.sub.g was determined by dynamic differential calorimetry (DSC) in accordance with DIN EN 61006, Method A, using a DSC instrument (Perkin-Elmer Pyris Diamond DSC calorimeter) that was calibrated with indium and lead for determination of T.sub.g. 10 mg of the substance to be analyzed were weighed into a sealable aluminum crucible, which was sealed. Three successive runs of a heating operation from 100 C. to +150 C., heating rate 20 K/min, with subsequent cooling at cooling rate 320 K/min were undertaken, and the third heating curve was used to determine the values, T.sub.g is the temperature determined at half the height of a glass transition step.

[0313] Determination of MVTR (Moisture Vapor Transmission Rate)

[0314] MVTR is determined in accordance with DIN EN13726-2 (Part 3.2). This involves filling a metal cylinder with water as described in the DIN standard and closing it at the top end with the film to be examined or the layer to be examined. Subsequently, the total weight (beaker with water and film) is determined by means of a balance. The measurement setup is stored at 37 C. for 24 h and the weight is determined again. The loss of water that evaporates through the film is ascertained by subtraction. MVTR is reported in g/(m.sup.4*24 h).

[0315] Determination of Peel Force or Bonding Force (90 Peel Test) to DIN EN 1464

[0316] The bonding force of the adhesive layers is preferably determined by means of the determination of the peel force of the respective adhesive layer under standardized conditions from a steel strip. The peel force is determined with a tensile tester according to DIN EN ISO 527-1 and a roller peel device. The sample is prepared in accordance with DIN EN 1939. The adhesive film to be examined, or the adhesive layer, is reinforced on its reverse side with an adhesive tape (TESA4104) and cut to size of 202 cm.sup.2. The side of the adhesive layer that faces the release paper is stuck onto a methyl ethyl ketone- and acetone-clean steel strip (according to DIN EN 1939) (202 cm.sup.2) with 3 twin strokes of a 4 kg roller. 1 twin stroke corresponds to one back-and-forth movement of the roller across the entire film or the entire adhesive layer. After a contact time with the steel strip of at least 24 h, preferably after a period of 24 to 48 h, and storage under standard climatic conditions (according to DIN EN 1939 at 23 C. and 50% rel. air humidity), the peel force is determined to DIN 1464 at a peel angle of 90 with separation of the joined parts. The peeling rate is 300 mm/min. The peel force is reported in N/20 mm.

[0317] Substances and Abbreviations Used: [0318] Diaminosulfonate: NH.sub.2CH.sub.2CH.sub.2NHCH.sub.2CH.sub.2SO.sub.3Na (45% in water) [0319] PolyTHF 1000 poly(tetramethylene glycol) polyetherdiol having number-average molar mass 1000 g/mol, BASF SE, Ludwigshafen, DE [0320] PolyTHF 2000 poly(tetramethylene glycol) polyetherdiol having number-average molar mass 2000 g/mol, BASF SE, Ludwigshafen, DE [0321] PPG polypropylene glycol, Covestro AG, Leverkusen, DE. Unless stated otherwise, PPG was prepared via KOH catalysis. [0322] Desmodur N 3300 aliphatic polyisocyanate (HDI isocyanurate), NCO content about 21.8%, Covestro AG, Leverkusen, Germany [0323] Water water demineralized by ion exchanger

[0324] The isocyanate components used are commercial products from Covestro Deutschland AG, Leverkusen, DE. Further chemicals were purchased from Sigma-Aldrich Chemie GmbH, Taufkirchen, DE. Unless stated otherwise, the raw materials were used without further purification or pretreatment.

[0325] Polyurethaneurea Dispersion 1 (Comparison)

[0326] 450 g of PolyTHF 1000 and 2100 g of PolyTHF 2000 were heated to 70 C. Subsequently, a mixture of 225.8 g of hexamethylene diisocyanate and 298.4 g of isophorone diisocyanate was added, and the mixture was stirred at 100-115 C. until the NCO value had gone below the theoretical value. The finished prepolymer was dissolved with 5500 g of acetone at 50 C. and then a solution of 29.5 g of ethylenediamine, 1412 g of diaminosulfonate and 610 g of water was metered in. The mixture was stirred for a further 15 min. This was followed by dispersion by addition of 1880 g of water. Subsequently, the solvent was removed by distillation under reduced pressure, and a storage-stable dispersion was obtained; the solids content was adjusted by addition of water.

[0327] Solids content: 50%

[0328] Particle size (LCS): 276 nm

[0329] Viscosity: 1000 mPa s

[0330] Polyurethaneurea Dispersion 2 (Inventive Product)

[0331] 75 g of polypropylene glycol having a number-average molar mass of 1000 g/mol and 350 g of polypropylene glycol having a number-average molar mass of 2000 g/mol (prepared by a double metal cyanide (DMC) catalysis) were heated up to 65 C. Subsequently, a mixture of 37.6 g of hexamethylene diisocyanate and 49.7 g of isophorone diisocyanate and 2 drops of tin octanoate was added, and the mixture was stirred at 130 C. until the NCO value had gone below the theoretical value (about 90 min). The finished prepolymer was dissolved with 910 g of acetone at 50 C. and then a solution of 4.1 g of ethylenediamine, 18.0 g of diaminosulfonate, 5.8 g of diethanolamine and 80 g of water was metered in at 40 C. The mixture was stirred for a further 15 min. This was followed by dispersion by addition of 440 g of water. Subsequently, the solvent was removed by distillation under reduced pressure, and a storage-stable dispersion was obtained; the solids content was adjusted by addition of water.

[0332] Solids content: 45%

[0333] Particle size (LCS): 265 nm

[0334] Viscosity: 1300 mPa s

[0335] Polyurethaneurea Dispersion 3 (Inventive Product)

[0336] 60.0 g of polypropylene glycol having a number-average molar mass of 1000 g/mol and 280 g polypropylene glycol having a number-average molar mass of 2000 g/mol were heated up to 65 C. Subsequently, a mixture of 30.1 g of hexamethylene diisocyanate and 39.8 g of isophorone diisocyanate and 2 drops of tin octanoate was added, and the mixture was stirred at 130 C. until the NCO value had gone below the theoretical value (about 90 min). The finished prepolymer was dissolved with 730 g of acetone at 50 C. and then a solution of 3.0 g of ethylenediamine, 18.9 g of diaminosulfonate, 3.6 g of diethanolamine and 74 g of water was metered in at 40 C. The mixture was stirred for a further 15 min. This was followed by dispersion by addition of 550 g of water. Subsequently, the solvent was removed by distillation under reduced pressure, and a storage-stable dispersion was obtained; the solids content was adjusted by addition of water.

[0337] Solids content: 41%

[0338] Particle size (LCS): 160 nm

[0339] Viscosity: 365 mPa s

[0340] Polyurethaneurea Dispersion 4 (Inventive Product)

[0341] 60.0 g of polypropylene glycol having a number-average molar mass of 1000 g/mol and 280 g of polypropylene glycol having a number-average molar mass of 2000 g/mol were heated up to 65 C. Subsequently, a mixture of 27.1 g of hexamethylene diisocyanate, 35.8 g of isophorone diisocyanate and 14.0 g of Desmodur N 3300 and 2 drops of tin octanoate was added, and the mixture was stirred at 130 C. until the NCO value had gone below the theoretical value (about 90 min). The finished prepolymer was dissolved with 740 g of acetone at 50 C. and then a solution of 3.0 g of ethylenediamine, 18.9 g of diaminostilfonate, 3.6 g of diethanolamine and 74 g of water was metered in at 40 C. The mixture was stirred for a further 15 min. This was followed by dispersion by addition of 560 g of water. Subsequently, the solvent was removed by distillation under reduced pressure, and a storage-stable dispersion was obtained; the solids content was adjusted by addition of water.

[0342] Solids content: 42%

[0343] Particle size (LCS): 311 nm

[0344] Viscosity: 1280 mPa s

[0345] Polyurethaneurea Dispersion 5 (Inventive Product)

[0346] 60.0 g of polypropylene glycol having a number-average molar mass of 1000 g/mol and 280 g of polypropylene glycol having a number-average molar mass of 2000 g/mol were heated up to 65 C. Subsequently, a mixture of 30.1 g of hexamethylene diisocyanate and 39.8 g of isophorone diisocyanate and 2 drops of tin octanoate was added, and the mixture was stirred at 130 C. until the NCO value had gone below the theoretical value (about 90 min). The finished prepolymer was dissolved with 730 g of acetone at 50 C. and then a solution of 3.0 g of ethylenediamine, 18.9 g of diaminosulfonate, 3.6 g of diethanolamine and 74 g of water and 50 g of acetone was metered in at 40 C. The mixture was stirred for a further 15 min. This was followed by dispersion by addition of 560 g of water. Subsequently, the solvent was removed by distillation under reduced pressure, and a storage-stable dispersion was obtained; the solids content was adjusted by addition of water.

[0347] Solids content: 42%

[0348] Particle size (LCS): 263 nm

[0349] Viscosity: <50 mPa s

[0350] Polyurethaneurea Dispersion 6 (Inventive Product)

[0351] 56.3 g of polypropylene glycol having a number-average molar mass of 1000 g/mol and 262.5 g of polypropylene glycol having a number-average molar mass of 2000 g/mol were heated up to 65 C. Subsequently, 88 g of bis(4,4-isocyanatocyclohexyl)methane and 2 drops of tin octanoate were added, and the mixture was stirred at 130 C. until the NCO value had gone below the theoretical value (about 90 min). The finished prepolymer was dissolved with 730 g of acetone at 50 C. and then a solution of 38.1 g of diaminosulfonate, 2.9 g of diethanolamine and 105 g of water was metered in at 40 C. The mixture was stirred for a further 15 min. This was followed by dispersion by addition of 510 g of water. Subsequently, the solvent was removed by distillation under reduced pressure, and a storage-stable dispersion was obtained; the solids content was adjusted by addition of water.

[0352] Solids content: 42%

[0353] Particle size (LCS): 311 nm

[0354] Viscosity: 1280 mPa s

[0355] Use Example 1 (Inventive):

[0356] 100 g of the (inventive) polyurethane dispersion 2 are initially charged together with 3 g of a 10% by weight aqueous Rheolate 208 dispersion in a Speedmixer cup. Bubble-free mixing to give a polyurethaneurea composition is effected in the Speedmixer at a speed of 2750 min.sup.1 for 1 minute. After application by means of an Erichsen drawdown bar (300 m) to a release paper from Felix Schller with the Y5200 (matt) name, drying is effected at 40 C. for 20 minutes and at 130 C. for 3 min.

[0357] MVTR: 2600 g/d m.sup.2.

[0358] Bond force measurement: 35 N/20 mm

[0359] Use Example 2 (Inventive):

[0360] Film production/layer production with the (inventive) polyurethane dispersion 3 as in use example 1, but with 400 m rather than 300 m drawdown bar.

[0361] MVTR: 1950 g/d m.sup.2.

[0362] Bond force measurement: 34 N/20 mm

[0363] Use Example 3 (Inventive):

[0364] Film production/layer production with the (inventive) polyurethane dispersion 4 as in use example 1.

[0365] MVTR:.2150 g/d m.sup.2

[0366] Bond force measurement: 23 N/20 mm

[0367] Use Example 4 (Inventive):

[0368] Film production/layer production with the (inventive) polyurethane dispersion 5 as in use example 1.

[0369] WVTR: 2350 g/d m.sup.2.

[0370] Bond force measurement: 25 N/20 mm

[0371] Use Example 5 (Inventive):

[0372] Film production/layer production with the (inventive) polyurethane dispersion 6 as in use example 1.

[0373] MVTR: 1750 g/d m.sup.2.

[0374] Bond force measurement: 6 N/20 mm.

[0375] Use Example 6 (Noninventive):

[0376] Film production with the (noninventive) polyurethaneurea dispersion 1 as in use example 1, but with 400 m rather than 300 m drawdown bar and onto a release paper from Felix Schuller with the Y3200 name.

[0377] MVTR: 1650 g/d m.sup.2.

[0378] Bond force measurement: 0 N/20 mm