Polyurethane-vinyl hybrid polymers, methods of making them and their use

Abstract

Described are polyurethane-vinyl hybrid polymers, methods of making them and their use. The hybrid polymers are made from an anionic polyurethane and a polymerizable vinyl compound, wherein the polymerizable vinyl compound is selected from methylene malonates, methylene beta-ketoesters and methylene beta-diketones. The hybrid polymers can be used as binder in structural adhesives, as binder in pressure-sensitive adhesives, as binder in laminating adhesives, as binder in contact adhesives, as binder in ink, as binder in paints, as binder in coatings, as binder for fiber bonding, as binder for particle bonding or as binder in high cohesion adhesive tapes.

Claims

1. A polyurethane-vinyl hybrid polymer comprising, in reacted form, at least one anionic polyurethane and at least one polymerizable vinyl compound, wherein the polymerizable vinyl compound is selected from the group consisting of methylene malonates, methylene beta-ketoesters and methylene beta-diketones; and wherein a) the polyurethane-vinyl hybrid polymer is formed by first coating a substrate with an aqueous anionic polyurethane dispersion and subsequently overcoating with the polymerizable vinyl compound wherein the ratio of anionic groups of the polyurethane to vinyl groups of the polymerizable vinyl compound is greater than 1:9; or b) wherein the polyurethane-vinyl hybrid polymer is formed in an aqueous dispersion.

2. The polyurethane-vinyl hybrid polymer according to claim 1, wherein the molar ratio of the anionic groups of the polyurethane to the vinyl groups of the polymerizable vinyl compound is greater than 1:1.

3. The polyurethane-vinyl hybrid polymer according to claim 1, wherein the polyurethane has an amount of anionic groups from 50 mmol/kg to 500 mmol/kg based on dry material, and wherein the anionic groups are selected from the group consisting of carboxylate groups, sulfonate groups and phosphate groups.

4. The polyurethane-vinyl hybrid polymer according to claim 1, wherein the Polyurethane has an amount of anionic groups from 50 mmol/kg to 500 mmol/kg based on dry material, and wherein the anionic groups are carboxylate groups.

5. The polyurethane-vinyl hybrid polymer according to claim 1, wherein the anionic polyurethane comprises, in reacted form: a) one or more diisocyanates, b) one or more polyesterdiols with molar mass of greater than 500 to 5000 g/mol, and/or one or more polyetherdiols with molar mass of from 240 to 5000 g/mol, c) one or more diols having carboxylic acid groups, and d) optionally one or more further mono- or polyfunctional compounds which differ from a)-c) and have reactive groups, selected from the group consisting of alcoholic hydroxy groups, primary amino groups, secondary amino groups, and isocyanate groups.

6. The polyurethane-vinyl hybrid polymer according to claim 1, wherein the anionic polyurethane has a glass transition temperature, prior to polymerization of the polymerizable vinyl compound, below 0 C.

7. The polyurethane-vinyl hybrid polymer according to claim 1, wherein the polymerizable vinyl compound is a methylene malonate having a formula
R.sup.1OC(O)C(CCH.sub.2)C(O)OR.sup.2, or wherein the polymerizable vinyl compound is a methylene beta-ketoester having a formula
R.sup.1C(O)C(CCH.sub.2)C(O)OR.sup.2, or wherein the polymerizable vinyl compound is a methylene beta-diketone having a formula
R.sup.1C(O)C(CCH.sub.2)C(O)R.sup.2, wherein R.sup.1 and R.sup.2 are each independently C1-C15 alkyl, C2-C15 alkenyl, halo-(C1-C15 alkyl), C3-C6 cycloalkyl, halo-(C3-C6 cycloalkyl), heterocyclyl, heterocyclyl-(C1-C15 alkyl), aryl, aryl-(C1-C15 alkyl), heteroaryl or heteroaryl-(C1-C15 alkyl), or alkoxy-(C1-15 alkyl), each of which may be optionally substituted by C1-C15 alkyl, halo-(C1-C15 alkyl), C3-C6 cycloalkyl, halo-(C3-C6 cycloalkyl), heterocyclyl, heterocyclyl-(C1-C15 alkyl), aryl, aryl-(C1-C15 alkyl), heteroaryl, C1-C15 alkoxy, C1-C15 alkylthio, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, ester or sulfonyl; or wherein R.sup.1 and R.sup.2 are taken together with the atoms to which they are bound to form a 5-7 membered heterocyclic ring which may be optionally substituted by C1-C15 alkyl, halo-(C1-C15 alkyl), C3-C6 cycloalkyl, halo-(C3-C6 cycloalkyl), heterocyclyl, heterocyclyl-(C1-C15 alkyl), aryl, aryl-(C1-C15 alkyl), heteroaryl, C1-C15 alkoxy, C1-C15 alkylthio, hydroxyl, nitro, azido, acyloxy, carboxy, ester or sulfonyl.

8. The polyurethane-vinyl hybrid polymer according to claim 1, wherein the polymerizable vinyl compound has a formula: ##STR00009## wherein R.sup.1 and R.sup.2 are each independently C1-C15 alkyl, C2-C15 alkenyl, halo-(C1-C15 alkyl), C3-C6 cycloalkyl, halo-(C3-C6 cycloalkyl), heterocyclyl, heterocyclyl-(C1-C15 alkyl), aryl, aryl-(C1-C15 alkyl), heteroaryl or heteroaryl-(C1-C15 alkyl), or alkoxy-(C1-15 alkyl), each of which may be optionally substituted by C1-C15 alkyl, halo-(C1-C15 alkyl), C3-C6 cycloalkyl, halo-(C3-C6 cycloalkyl), heterocyclyl, heterocyclyl-(C1-C15 alkyl), aryl, aryl-(C1-C15 alkyl), heteroaryl, C1-C15 alkoxy, C1-C15 alkylthio, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, ester or sulfonyl; or wherein R.sup.1 and R.sup.2 are taken together with the atoms to which they are bound to form a 5-7 membered heterocyclic ring which may be optionally substituted by C1-C15 alkyl, halo-(C1-C15 alkyl), C3-C6 cycloalkyl, halo-(C3-C6 cycloalkyl), heterocyclyl, heterocyclyl-(C1-C15 alkyl), aryl, aryl-(C1-C15 alkyl), heteroaryl, C1-C15 alkoxy, C1-C15 alkylthio, hydroxyl, nitro, azido, acyloxy, carboxy, ester or sulfonyl; [A]- represents (CR.sup.AR.sup.B).sub.n, (CR.sup.AR.sup.B).sub.nO(CO)(CH.sub.2).sub.1-15(CO)O(CR.sup.AR.sup.B).sub.n, (CH.sub.2).sub.n[CY](CH.sub.2).sub.n, a polybutadienyl linking group, a polyethylene glycol linking group, a polyether linking group, a polyurethane linking group, an epoxy linking group, a polyacrylic linking group, or a polycarbonate linking group; each instance of R.sup.A or R.sup.B is independently H, C.sub.1-C.sub.15 alkyl, C.sub.2-C.sub.15 alkenyl, or a moiety represented by the formula: ##STR00010## wherein L is a linking group selected from the group consisting of alkylene, alkenylene, haloalkylene, cycloalkylene, cycloalkylene, heterocyclylene, heterocyclyl alkylene, aryl-alkylene, heteroarylene, heteroaryl-(alkylene), and alkoxy-(alkylene), each of which may be optionally branched and each of which may be optionally substituted by alkyl, haloalkyl, cycloalkyl, halo cycloalkyl, heterocyclyl, heterocyclyl-(alkyl), aryl, aryl-(alkyl), heteroaryl, C.sub.1-C.sub.15 alkoxy, C.sub.1-C.sub.15 alkylthio, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, ester, each of which may be optionally branched; R.sub.3 is independently selected from the group defined in R.sub.2 above; [CY] represents an alkyl, alkenyl, haloalkyl, cycloalkyl, halo cycloalkyl, heterocyclyl, heterocyclyl-(alkyl), aryl-(alkyl), heteroaryl or heteroaryl-(alkyl), or alkoxy-(alkyl) group; n is an integer from 1 to 25; m is an integer from 1 to 25; and each instance of Q represents O or a direct bond.

9. The polyurethane-vinyl hybrid polymer according to claim 1, wherein the polymerizable vinyl compound has a formula
R.sup.1OC(O)C(CCH.sub.2)C(O)OR.sup.2, wherein R.sup.1 and R.sup.2 are each independently C1-C10 alkyl; or wherein the polymerizable vinyl compound has a formula ##STR00011## wherein R.sup.1 and R.sup.2 are each independently C1-C10 alkyl, and A is selected from the group consisting of C1-C10 alkylene and X-Ph-Y, wherein X and Y are each independently C1-C10 alkylene.

10. The polyurethane-vinyl hybrid polymer according to claim 1, wherein the polyurethane-vinyl hybrid polymer is contained in an aqueous dispersion.

11. The polyurethane-vinyl hybrid polymer according to claim 1, wherein the polyurethane-vinyl hybrid polymer is semi-crystalline at room temperature and made from amorphous anionic polyurethane; or wherein the polyurethane-vinyl hybrid polymer is crystalline at room temperature and made from semi-crystalline anionic polyurethane.

12. The polyurethane-vinyl hybrid polymer according to claim 1, wherein the polymerizable vinyl compound is a methylene malonate.

13. The polyurethane-vinyl hybrid polymer according to claim 1, wherein the ratio of anionic groups of the polyurethane to vinyl groups of the polymerizable vinyl compound is greater than 1:1, and wherein the polymerizable vinyl compound is at least one methylene malonate with two or more methylene malonate groups.

14. A two-component composition comprising a first liquid composition and a second liquid composition, wherein the first liquid composition comprises at least one anionic polyurethane, and the second liquid composition comprises at least one polymerizable vinyl compound selected from the group consisting of methylene malonates, methylene beta-ketoesters and methylene beta-diketones.

15. A method of forming a polyurethane-vinyl hybrid polymer, comprising reacting at least one anionic polyurethane with at least one polymerizable vinyl compound selected from the group consisting of methylene malonates, methylene beta-ketoesters and methylene beta-diketones, wherein the reacting is performed in a liquid medium to form a one-component composition comprising at least one polyurethane-vinyl hybrid polymer; or comprising mixing a first liquid composition comprising the at least one anionic polyurethane and a second liquid composition comprising the at least one polymerizable vinyl compound to form a mixture, and subsequently applying the mixture to a substrate, wherein the formation of the polyurethane-vinyl hybrid polymer occurs at least partly after application to the substrate; or comprising forming the polyurethane-vinyl hybrid polymer by first coating a substrate with the at least one anionic polyurethane and subsequently overcoating the first coating with the at least one polymerizable vinyl compound with a molar ratio of the anionic groups of the polyurethane to the vinyl groups of the polymerizable vinyl compound of greater than 1:9.

16. A method of forming a laminate, comprising: (1) coating a polymer film with at least one anionic polyurethane; (2) storing the coated polymer film for at least 1 day; (3) overcoating the coated polymer film with at least one polymerizable vinyl compound, wherein the molar ratio of the anionic groups of the polyurethane to the vinyl groups of the polymerizable vinyl compound is greater than 1:9, and wherein the polymerizable vinyl compound is selected from the group consisting of methylene malonates, methylene beta-ketoesters and methylene beta-diketones; and wherein the polymerizable vinyl compound has at least two functional groups selected from the group consisting of a methylene malonate group, a methylene beta-ketoester group and a methylene beta-diketone group; and (4) laminating the overcoated polymer film to a substrate.

Description

EXAMPLES

(1) Monomer 1:

(2) ##STR00005##

(3) Monomer 2:

(4) ##STR00006##

(5) Monomer 3:

(6) ##STR00007##

(7) Monomer 4:

(8) ##STR00008##

Example 1 (Comparative)

(9) An aqueous polyurethane dispersion was prepared according to example 1 in WO 2006/087317 and adjusted to a solids content of 50%.

Example 2

(10) 13.6 g dispersion from example 1 are placed in a 100 ml PE bottle and diluted with 3.4 g deionized water. At room temperature 3.4 g of a solution of monomer 3, (20% w/w in monomer 1) are added dropwise under vigorous stirring. After 12 hours stirring, the reaction was completed and a solids content of 48% reached.

Example 3

(11) 13.6 g dispersion from example 1 are placed in a 100 ml PE bottle and diluted with 3.4 g deionized water. At room temperature 3.4 g of a solution of monomer 4 (20% solution in monomer 1) are added dropwise under vigorous stirring. After 12 hours stirring, the reaction was completed and a solids content of 47% reached.

Example 4

(12) 6 g dispersion from example 1 are placed in a 100 ml PE bottle and diluted with 3 g deionized water. At room temperature 3 g of a solution of monomer 3 (20% solution in monomer 1) are added dropwise under vigorous stirring. After 12 hours stirring, the reaction was completed and a solids content of 47% reached.

Example 5

(13) 13.6 g dispersion from example 1 are placed in a 100 ml PE bottle and diluted with 5.1 g deionized water. At room temperature 5.1 g of a solution of monomer 3 (20% solution in monomer 1) are added dropwise under vigorous stirring. After 12 hours stirring, the reaction was completed and a solids content of 48% reached.

(14) Performance Tests:

(15) The PSA tests were performed according to AFERA test methods 5012 and 5001, unless otherwise indicated.

(16) The pressure-sensitive adhesive dispersions were coated with coating weights as indicated in table 1 onto Hostaphan RN 36 (PET) film as carrier, and dried at 90 C. for 5 minutes. The PSA-coated carrier was slit to give test strips 25 mm wide.

(17) a) Shear Strength

(18) For the determination of the shear strength, the test strips were adhered with an overlap of 12.512.5 mm to sheet steel, rolled on once with a roller weighing 1 kg, and then loaded in suspension with a 1 kg weight. The shear strength (cohesion) was determined under standard conditions (23 C.; 50% relative humidity). The measure of the shear strength is the time taken for the weight to fall off; in each case, the average was calculated from 5 measurements.

(19) b) Peel Strength

(20) For the determination of the peel strength, the test strips were adhered to sheet steel. The peel strength (adhesion) was determined under standard conditions (23 C.; 50% relative humidity) by separating the test strip from the steel in an angle of 180 with a velocity of 300 mm/min and measuring the force in N/25 mm.

(21) Pressure sensitive adhesive films were prepared with the polymer dispersions from examples 1, 2, 3 and 5.

(22) Table 1 summarizes the conditions and results of the PSA testing.

(23) TABLE-US-00001 TABLE 1 Test results Shear strength Peel strength Coating weight AFERA steel AFERA steel Example [g/m.sup.2] [min] [N/25 mm] 1 comparative 60 12 60 2 Hybrid 57 120 15 3 Hybrid 58 1512 21 5 Hybrid 58 546 18

(24) Test Conditions:

(25) Carrier: Hostaphan RN 36 (biaxial oriented film of polyethylene terephthalat (PET))

(26) Liner: Siliconized paper (Steralease 43 gelb)

(27) Width: 25 mm

(28) Drying 5 min at 90 C.

(29) Test velocity: 300 mm/min

(30) Climate chamber: 23 C., 50% rel. humidity

(31) Shear strength: steel plate, overlap 12.512.5 mm, contact time 10 min, weight 1 kg

(32) Temperature: room temperature

(33) It can clearly be seen, that the hybrids show high cohesion and high adhesion to steel as aqueous pressure sensitive adhesives.

Example 6

(34) The polyurethane from example 1 was diluted with ethanol to 10% solids content. This solution was wiped on two test specimen (stainless steel) and dried. 0.2 g of a mixture of 60% monomer 1, 20% monomer 2, 20% thickener Vinnol H15/45 M (Wacker) was placed between the test specimen at an overlap area of 625 mm.sup.2 and fixed. After 48 h at room temperature a lap shear test was performed (Zwick Roell testing machine with 10 mm/min). A shear strength of 6 MPa are reached.

Example 6A (Comparative)

(35) The experiment 6 was performed with a solution of 1% Na-benzoate in ethanol as a starter instead of the PU.

(36) A shear strength of only 2 MPa are found.

Expample 7

(37) An aqueous polyurethane dispersion was prepared according to example 1 in DE 2645779 and adjusted to 39% solids content.

Example 8

(38) The dispersion from example 7 was brushed onto stainless steel plates and dried, resulting in a tack-free film (0.1 g/625 mm.sup.2). A very thin film (<0.01 g) of a solution of monomer 3 (20% w/w in monomer 1) was wiped onto one plate and the plate was pressed together with a second one (without monomer) with an overlap of 625 mm.sup.2 and fixed. After 48 h at room temperature a lap shear test was performed (Zwick Roell testing machine with 10 mm/min).

(39) A shear strength of 8.8 MPa are reached.

(40) Other lap shear samples were placed in an oven at 120 C. under air for two weeks. After two weeks at 120 C. and reconditioning to room temperature, a shear strength of still 5.8 MPa are found.

Example 9

(41) The dispersion from example 7 was brushed onto stainless steel plates and dried, resulting in a tack-free film (0.1 g/625 mm.sup.2). A very thin film (<0.01 g) of a solution of monomer 4 (20% w/w in Monomer 1) was wiped onto one plate and the plate was pressed together with a second one (without monomer) with an overlap of 625 mm.sup.2 and fixed. After 48 h at room temperature a lap shear test was performed (Zwick Roell testing machine with 10 mm/min).

(42) A shear strength of 8 MPa are reached.

Example 10 (Comparative)

(43) The dispersion from example 7 was brushed onto stainless steel plates and dried, resulting in a tack-free film (0.1 g/625 mm.sup.2). Two plates were pressed together with an overlap of 625 mm.sup.2 and fixed. After 48 h at room temperature a lap shear test was performed (Zwick Roell testing machine with 10 mm/min).

(44) A shear strength of only 2 MPa are reached.