PSA of renewable origin with temperature-stable adhesive power

Abstract

Heat-curable adhesive composition: (a) a polyurethane composition (A) of formula: ##STR00001## (i) in which R.sup.1 is a hydrocarbon-based radical; R.sup.2 is a polyester block; R.sup.3 is a linear C1-C3 alkylene radical; R.sup.4 and R.sup.5 are a C1-C4 alkyl; m is an integer such that the molar mass of the said polyurethanes is 900-27 000 Da; p=0, 1 or 2;
obtained by producing polyester diols by polycondensation of: (i) dimerized fatty acids with an acid number of 190-200 mg KOH/g with a C2-C44 diol optionally having O or S; or (ii) dimerized fatty alcohols with a hydroxyl number of 200-220 mg KOH/g with a C4-C44 dicarboxylic acid optionally having O or S; (b) 22-62% of a compatible tackifying resin (B); and (c) 0.01-3% of a crosslinking catalyst (C). Self-adhesive support obtained by preheating the adhesive composition, coating onto a support layer and then curing. Manufacture of self-adhesive labels and/or tapes.

Claims

1. A heat-curable adhesive composition comprising: (a) from 35% to 75% weight/weight of a composition (A) comprising at least 90% weight/weight of polyurethanes bearing hydrolysable alkoxysilane end groups of formula (I): ##STR00011## in which: R.sup.1 represents a divalent hydrocarbon-based radical comprising from 5 to 15 carbon atoms which may be aromatic or aliphatic, and linear, branched or cyclic; R.sup.2 represents a divalent polyester block which is derived from a polyester diol of formula R.sup.2(OH).sub.2 by replacing each of the two hydroxyl groups with a free valency; R.sup.3 represents a linear divalent alkylene radical comprising from 1 to 3 carbon atoms; R.sup.4 and R.sup.5, in each case, independently, represent a linear or branched alkyl radical of 1 to 4 carbon atoms; m is an integer such that the number-average molar mass of the polyurethanes of formula (I) is between 900 Da and 27 kDa; and p is an integer equal to 0, 1 or 2; wherein composition (A) is obtained via a process that comprises preparing a composition (A-1) of polyester diols of formula R.sup.2(OH).sub.2 by reacting via a polycondensation reaction: (i) one or more dimerized fatty acids included in a composition (A-1-1) with an acid number I.sub.A of between 190 and 200 mg KOH/g with one or more diols comprising from 2 to 44 carbon atoms and optionally one or more heteroatoms chosen from oxygen and sulfur; or (ii) one or more dimerized fatty alcohols included in a composition (A-1-2) with a hydroxyl number I.sub.OH of between 200 and 220 mg KOH/g with one or more dicarboxylic acids comprising from 4 to 44 carbon atoms and optionally one or more heteroatoms chosen from oxygen and sulfur; such that said composition (A-1) has a hydroxyl number I.sub.OH of between 15 and 35 mg KOH/g and a Brookfield viscosity measured at 80 C. of less than 10 Pa.Math.s; (b) from 22% to 62% weight/weight of a compatible tackifying resin (B) with a number-average molar mass of between 200 Da and 10 kDa; and (c) from 0.01% to 3% weight/weight of a crosslinking catalyst (C).

2. The heat-curable adhesive composition according to claim 1, wherein when composition (A-1) of polyester diols of formula R.sup.2(OH).sub.2 is obtained according to variant (i), composition (A-1-1) is a composition comprising from 95% to 98% of dimerized fatty acids with an acid number I.sub.A of between 194 and 198 mg KOH/g.

3. The heat-curable adhesive composition according to claim 1, wherein when composition (A-1) of polyester diols of formula R.sup.2(OH).sub.2 is obtained according to variant (ii), composition (A-1-2) is a composition comprising at least 96% of aliphatic dimerized fatty alcohols with an I.sub.OH of between 202 and 212 mg KOH/g.

4. The heat-curable adhesive composition according to claim 1, wherein composition (A-1) of polyester diols of formula R.sup.2(OH).sub.2 has a hydroxyl number I.sub.OH of between 16 and 25 mg KOH/g and a Brookfield viscosity measured at 80 C. of less than 6 Pa.Math.s.

5. The heat-curable adhesive composition according to claim 1, wherein R.sup.1 is chosen from one of the following divalent radicals, of which the formulae below reveal the two free valencies: ##STR00012## ##STR00013## ##STR00014## ##STR00015## e) (CH.sub.2).sub.6.

6. The heat-curable adhesive composition according to claim 1, wherein R.sup.1 is ##STR00016##

7. The heat-curable adhesive composition according to claim 1, wherein R.sup.3 is methylene or n-propylene; R.sup.4 and R.sup.5 each independently represent methyl or ethyl; and/or p equals 0 or 1.

8. The heat-curable adhesive composition according to claim 1, wherein tackifying resin (B) is chosen from: (iii) rosins of natural or modified origin and hydrogenated, dimerized or polymerized derivatives thereof or derivatives esterified with monoalcohols or polyols; or (v) terpenic resins in the presence of Friedel-Crafts catalysts.

9. The heat-curable adhesive composition according to claim 1, wherein said composition comprises: (a) from 40% to 65% weight/weight of composition (A), (b) from 33% to 58% weight/weight of tackifying resin (B), and (c) from 0.45% to 2.5% weight/weight of crosslinking catalyst (C).

10. The heat-curable adhesive composition according to claim 1, further comprising a polymer of formula (V): ##STR00017## in which: R.sup.6 represents a divalent hydrocarbon-based radical comprising from 5 to 15 carbon atoms, which is aromatic or aliphatic, and linear, branched or cyclic; R.sup.7 represents a linear or branched divalent alkylene radical comprising from 1 to 4 carbon atoms; R.sup.8 represents a linear divalent alkylene radical comprising from 1 to 3 carbon atoms; R.sup.9 and R.sup.10, in each case, independently, represent a linear or branched alkyl radical of 1 to 4 carbon atoms; q is an integer such that the number-average molar mass of a polyether block of formula [OR.sup.7].sub.q is between 300 Da and 30 kDa; r is either equal to zero or to a non-zero integer such that the number-average molar mass of the polymer of formula (V) is between 600 Da and 60 kDa; and s is an integer equal to 0, 1 or 2, wherein the amount of said polymer of formula (V) is up to 15% weight/weight.

11. The heat-curable adhesive composition according to claim 10, wherein in the polymer of formula (V) r equals 0.

12. The heat-curable adhesive composition according to claim 10, wherein in the polymer of formula (V): R.sup.7 is isopropylene; R.sup.8 is methylene; s=0 or 1; and R.sup.9 and R.sup.10 each represent methyl.

13. The heat-curable adhesive composition according to claim 1, wherein said composition has a Brookfield viscosity measured at 100 C. of between 9 and 100 Pa.Math.s.

14. A self-adhesive support that is obtained via a process comprising: (a) preheating the adhesive composition as defined in claim 1 to a temperature of between 50 and 130 C., and then (b) coating said adhesive composition on a support layer, and then (c) curing said adhesive composition, by heating the support thus coated to a temperature of between 50 and 150 C.

15. A one-sided or two-sided self-adhesive label or tape comprising the self-adhesive support of claim 14.

16. The heat-curable adhesive composition according to claim 1, wherein wherein composition (A) is obtained via a process comprising: (a) preparing a composition (A-1) of polyester diols of formula R.sup.2(OH).sub.2 by reacting via a polycondensation reaction: (i) one or more dimerized fatty acids included in a composition (A-1-1) with an acid number I.sub.A of between 190 and 200 mg KOH/g with one or more diols comprising from 2 to 44 carbon atoms and optionally one or more heteroatoms chosen from oxygen and sulfur; or (ii) one or more dimerized fatty alcohols included in a composition (A-1-2) with a hydroxyl number I.sub.OH of between 200 and 220 mg KOH/g with one or more dicarboxylic acids comprising from 4 to 44 carbon atoms and optionally one or more heteroatoms chosen from oxygen and sulfur; such that said composition (A-1) has a hydroxyl number I.sub.OH of between 15 and 35 mg KOH/g and a Brookfield viscosity measured at 80 C. of less than 10 Pa.Math.s; (b) preparing a composition (A-2) comprising at least 90% weight/weight of polyurethanes bearing hydroxyl end groups by reacting polyester diol Composition (A-1) with diisocyanate of formula (II):
NCOR.sup.1NCO(II) in amounts corresponding to a ratio of the molar equivalent of the number of NCO/OH functions of between 0.3 and 0.7, to obtain polyurethanes bearing hydroxyl end groups of formula (III): ##STR00018## in which m is less than or equal to 10; and (c) preparing composition (A) comprising at least 90% weight/weight of polyurethanes bearing alkoxysilane end groups of formula (I) by reacting Composition (A-2) of polyurethanes bearing hydroxyl end groups with an isocyanatosilane of formula (IV):
NCOR.sup.3Si(R.sup.4)p(OR.sup.5).sub.3-p(IV) in an amount corresponding to a ratio of the molar equivalent of NCO/OH functions of between 0.90 and 1.05.

17. The heat-curable adhesive composition according to claim 1, wherein R.sup.3 is methylene or n-propylene; R.sup.4 and R.sup.5 each independently represent methyl or ethyl; and p equals 0 or 1.

18. The heat-curable adhesive composition according to claim 10, wherein the polymer of formula (V) has a number-average molar mass ranging from 30 to 40 kDa and a viscosity, measured at 23 C., ranging from 30 to 37 Pa.Math.s.

19. The heat-curable adhesive composition according to claim 10, wherein the polymer of formula (V) has a polydispersity index ranging from 1 to 2.

20. The heat-curable adhesive composition according to claim 16, wherein composition (A-1) of polyester diols of formula R.sup.2(OH).sub.2 is prepared by reacting, via a polycondensation reaction, one or more dimerized fatty acids included in a composition (A-1-1) with an acid number I.sub.A of between 190 and 200 mg KOH/g with one or more diols comprising from 2 to 44 carbon atoms and optionally one or more heteroatoms chosen from oxygen and sulfur.

21. The heat-curable adhesive composition according to claim 16, wherein composition (A-1) of polyester diols of formula R.sup.2(OH).sub.2 is prepared by reacting, via a polycondensation reaction, one or more dimerized fatty alcohols included in a composition (A-1-2) with a hydroxyl number I.sub.OH of between 200 and 220 mg KOH/g with one or more dicarboxylic acids comprising from 4 to 44 carbon atoms and optionally one or more heteroatoms chosen from oxygen and sulfur.

Description

EXAMPLE A (REFERENCE)

Preparation of a Composition (A) Comprising at Least 90% Weight/Weight of Polyurethanes Bearing Hydrolysable Alkoxysilane End Groups of Formula (I), Obtained from Tripropylene Glycol and from a Dimerized Fatty Acid Chloride Composition Prepared from Pripol 1013

(1) 1st Step:

(2) Preparation (According to Variant (i)) of a Composition (A-1) with a Hydroxyl Number I.sub.OH Equal to 18 mg KOH/g and Comprising at Least 90% Weight/Weight of Polyester Diols Obtained by Condensation of Tripropylene Glycol and of Dimerized Fatty Acid Chlorides Derived from Pripol 1013:

(3) 572 g (1 mol) of the fatty acid dimer composition Pripol 1013 with an acid number of 196 mg KOH/g are placed in a jacketed 2 liter reactor equipped with a stirrer, a heating means, a thermometer, a condenser and connected to a vacuum pump, and the system is brought to 85 C. under a reduced pressure of 20 mbar with a stream of nitrogen over 1 hour in order to dehydrate it.

(4) The fatty acid dimer composition, dehydrated and cooled to 40 C. beforehand, is diluted in 500 ml of dichloromethane and 250 g of thionyl chloride (2.10 mol) are then added at room temperature (23 C.). After stirring for 2 hours at room temperature, the dichloromethane and the excess thionyl chloride are removed by distillation under a reduced pressure of 20 mbar.

(5) 600 g of a dimerized fatty acid chloride composition with an acid number of 196 mg KOH/g are obtained.

(6) 542 g (0.89 mol) of this dimeric fatty acid chloride composition and 192.3 g (1.00 mol) of tripropylene glycol (I.sub.OH of 584 mg KOH/g) are placed in a jacketed 1 liter reactor. The reaction medium is then brought to 120 C. under cover of nitrogen, with mechanical stirring and under a partial vacuum of 10 mbar to remove the HCl formed. The condensation reaction is continued for about 6 hours until the reaction of the acid chloride composition is complete.

(7) Once the reaction is complete, the reaction medium is cooled to about 85 C., the residual acidity is neutralized with sodium bicarbonate and the medium is then filtered.

(8) 672 g of a composition with a hydroxyl number I.sub.OH equal to 18 mg KOH/g, a Brookfield viscosity measured at 80 C. of 4295 mPa.Math.s and comprising at least 90% weight/weight of polyester diols are obtained.

(9) The proportion of starting materials of renewable origin in composition (A-1) thus obtained is 74% weight/weight.

(10) 2nd Step:

(11) Preparation of a Composition (A-2) Comprising at Least 90% Weight/Weight of Polyurethanes Bearing Hydroxyl End Groups of Formula (III):

(12) 190.14 g of the composition obtained in the first step (containing a total equivalent number of OH functions equal to 61 mmol) are placed in a closed 250 ml reactor equipped with a stirrer, heating means and a thermometer, and connected to a vacuum pump. The system is heated to 85 C. and maintained at a reduced pressure of 20 mbar for 1 hour to dehydrate the polyester polyols.

(13) The following are then introduced into the reactor maintained at atmospheric pressure and brought to a temperature of 90 C.: 20 mg of a bismuth/zinc carboxylate catalyst (Borchi Kat VP0244 from the company Borchers GmbH), and 3.4 g of isophorone diisocyanate (or IPDI, with a titre of 37.6% weight/weight of NCO group), containing 30.52 mmol of NCO functions.

(14) The amounts introduced thus correspond to an NCO/OH mole ratio equal to 0.5.

(15) The polyaddition reaction is continued for 3 hours until consumption of the NCO functions of the isophorone diisocyanate is complete (detected by the disappearance of the NCO band on infrared analysis).

(16) 193.56 g of a composition (A2-2) with a content of OH functions of 0.158 mmol/g and comprising at least 90% of polyurethanes bearing hydroxyl end groups are obtained.

(17) The proportion of starting materials of renewable origin in composition (A-2) thus obtained is 72.7% weight/weight.

(18) 3rd Step:

(19) Production of Composition (A) Comprising at Least 90% Weight/Weight of Polyurethanes Bearing Hydrolysable Alkoxysilane End Groups of Formula (I):

(20) 6.45 g of gamma-isocyanato-n-propyltrimethoxysilane (with a titre of 19.9% weight/weight of NCO groups), i.e. 30.58 mmol of NCO corresponding to an NCO/OH ratio equal to 1, are placed in the reactor of the second step.

(21) The reactor is then maintained under an inert atmosphere at 100 C. for 1.5 hours until reaction is complete (detected by the disappearance of the NCO band on infrared analysis).

(22) 200.01 g of a composition that is viscous at room temperature, with a viscosity at 100 C. of 16 850 mPa.Math.s (measured with a Brookfield viscometer with a No. 27 needle rotating at a rate of 20 rpm) comprising at least 90% weight/weight of polyurethanes bearing hydrolysable alkoxysilane end groups of formula (I) are obtained.

(23) The weight proportion of this composition that is obtained from renewable starting materials is 70.3% weight/weight.

EXAMPLE B (REFERENCE)

(24) Preparation of a Composition (A) Comprising at Least 90% Weight/Weight of Polyurethanes Bearing Hydrolysable Alkoxysilane End Groups of Formula (I), Obtained from 3-Methyl-1,5-Pentanediol and from a Dimerized Fatty Acid Chloride Composition Prepared from Pripol 1013

(25) The first step of Example A is repeated with 118.2 g (1.00 mol) of 3-methyl-1,5-pentanediol (I.sub.OH of 950 mg KOH/g) and 537 g (0.88 mol) of the dimerized fatty acid chloride composition with an acid number of 196 mg KOH/g.

(26) 594 g of a composition (A-1) with a hydroxyl number I.sub.OH equal to 22.5 mg KOH/g, a Brookfield viscosity measured at 80 C. of 5536 mPa.Math.s and comprising at least 90% weight/weight of polyester diols are obtained.

(27) The second and then the third step are subsequently repeated, adapting the amounts of reagents so as to maintain an NCO/OH ratio equal, respectively, to 0.5 and 1.

(28) A composition that is viscous at room temperature, with a viscosity at 100 C. of 22 700 mPa.Math.s (measured with a Brookfield viscometer at 100 C., with a No. 27 needle rotating at a rate of 20 rpm), is obtained.

(29) This composition comprises at least 90% weight/weight of polyurethanes bearing hydrolysable alkoxysilane end groups of formula (I).

(30) The weight proportion of this composition that is obtained from renewable starting materials is 78.9% weight/weight.

EXAMPLE C (REFERENCE)

Preparation of a Composition (A) Comprising at Least 90% Weight/Weight of Polyurethanes Bearing Hydrolysable Alkoxysilane End Groups of Formula (I), Obtained from Pripol 2033 and from 3-Methyl-1,5-Pentanedicarboxylic Acid Chloride

(31) The first step of Example A is repeated with 159.3 g (0.87 mol) of 3-methyl-1,5-pentanedicarboxylic acid chloride, and 542 g (1.00 mol) of fatty alcohol dimer Pripol 2033 (I.sub.OH of 207 mg KOH/g).

(32) 625.4 g of a composition with a hydroxyl number I.sub.OH equal to 22.5 mg KOH/g, a Brookfield viscosity measured at 80 C. of 5640 mPa.Math.s and comprising at least 90% weight/weight of polyester diols are obtained.

(33) The second and then the third step are subsequently repeated, adapting the amounts of reagents so as to maintain an NCO/OH ratio equal, respectively, to 0.5 and 1.

(34) A composition that is viscous at room temperature, with a viscosity at 100 C. of 21 150 mPa.Math.s (measured with a Brookfield viscometer at 100 C. with a No. 27 needle rotating at a rate of 20 rpm), is obtained.

(35) This composition comprises at least 85% weight/weight of polyurethanes bearing hydrolysable alkoxysilane end groups of formula (I).

(36) The weight proportion of this composition that is obtained from renewable starting materials is 70.3% weight/weight.

EXAMPLE 1 (ACCORDING TO THE INVENTION)

1) Preparation of a Heat-Curable Adhesive Composition Based on the Composition of Polyurethanes Bearing Hydrolysable Alkoxysilane End Groups of Example A

(37) The composition presented in the following table is prepared by first introducing the tackifying resin Dertoline G2L into a glass reactor under vacuum, with stirring and heated to about 130 C. Next, once the resin has completely melted, composition (A) of Example A is added.

(38) The mixture is stirred under vacuum for 45 minutes and then cooled to 100 C. The mixture is stirred under vacuum for 20 minutes and then cooled to 80 C. The catalyst (K-Kat 5218) is then introduced at the same time as the antioxidants Irganox 245 and Irganox 1010. The desiccant (Silquest A-174) is added if necessary, and the mixture is then maintained under vacuum and with stirring for a further 10 minutes.

(39) The Brookfield viscosity of the composition thus obtained is indicated in the table.

(40) The weight proportion of this composition that is obtained from renewable starting materials is calculated from: the weight proportion of the composition of Example A that is obtained from renewable starting materials, weighted by the content of the said composition in the composition of the present example and from the content in the composition of the present example of Dertoline G2L, which is itself 100% of renewable origin.

(41) The weight proportion obtained by calculation is indicated as a weight/weight percentage in the table.

2) Preparation of a PET Support Layer Coated with the Cured Composition, at a Basis Weight Rate Equal to 50 g/m2

(42) A polyethylene terephthalate (PET) rectangular sheet 50 m thick and 20 cm by 40 cm in size is used as support layer.

(43) The composition obtained in 1) is preheated to a temperature close to 100 C. and is placed in a cartridge, from which a bead is extruded which is deposited close to the edge of the sheet parallel to its width.

(44) The composition contained in this bead is then spread over the entire surface of the sheet, so as to obtain a uniform layer of substantially constant thickness. A film spreader (also known as a filmograph) is used to do this, which is moved from the edge of the sheet to the opposite edge. A layer of composition corresponding to a basis weight of 50 g/m.sup.2 is thus deposited, which represents a thickness of about 50 m.

(45) The PET sheet thus coated is then placed in an oven at 120 C. for 8 minutes for curing of the composition, and is then laminated onto a protective non-stick layer consisting of a rectangular sheet of silicone film of the same dimensions.

(46) The PET support layer thus obtained is subjected to the tests described below.

(47) Peel Test at 180 on a Stainless-Steel Plate:

(48) The adhesive power is evaluated by the peel test at 180 on a stainless-steel plate as described in FINAT method No. 1, published in the FINAT 6th edition Technical Manual, 2001. FINAT is the international federation of self-adhesive label manufacturers and transformers. The principle of this test is as follows.

(49) A specimen in the form of a rectangular strip (25 mm175 mm) is cut out of the PET support layer coated with the cured composition obtained previously. This specimen is fixed over of its length (after removal of the corresponding portion of the protective non-stick layer) to a substrate consisting of a stainless-steel plate. The assembly obtained is left for 20 minutes at room temperature. It is then placed in a traction machine that is capable, starting from the free end of the rectangular strip, of peeling or detaching the strip at an angle of 180 and with a separation rate of 300 mm per minute. The machine measures the force required to detach the strip under these conditions.

(50) The corresponding result is expressed in N/cm and indicated in the following table.

(51) Instantaneous Adhesion Test (Also Known as the Loop Test):

(52) The immediate bonding power or tack is evaluated by the instantaneous adhesion test known as the loop test, described in FINAT method No. 9, the principle of which is as follows.

(53) A specimen in the form of a rectangular strip (25 mm175 mm) is cut out of the PET support layer coated with the cured composition obtained previously. After removing all of the protective non-stick layer, the two ends of this strip are attached so as to form a loop whose adhesive layer is facing outwards. The two attached ends are placed in the movable jaw of a traction machine capable of imposing a rate of movement of 300 mm/minute along a vertical axis with possibility of travelling to and fro. The lower part of the loop placed in the vertical position is first placed in contact with a horizontal glass plate 25 mm30 mm on a square zone with a side length of about 25 mm. Once this contact is established, the direction of movement of the jaw is reversed. The immediate bonding power is the maximum value of the force required for the loop to become fully detached from the plate.

(54) The corresponding result is expressed in N/cm.sup.2 and indicated in the following table.

(55) Resistance Time of the Adhesive Seal to Static Shear at 90 C.:

(56) The maintenance at elevated temperature of the adhesive power of the PET support layer obtained previously in 2) is evaluated via a test which determines the resistance time of the adhesive seal to static shear at 90 C. Reference is made for this test to FINAT method No. 8. The principle is as follows.

(57) A specimen in the form of a rectangular strip (25 mm75 mm) is cut out of each of the previous two PET support layers. After removing all of the protective non-stick layer, a square portion with a side length of 25 mm located at the end of the adhesive strip is fixed onto a glass plate.

(58) The test plate thus obtained is introduced, by means of a suitable support, in a substantially vertical position into an oven at 90 C., the unattached part of the strip 50 mm long being below the plate. After thermal equilibration, the free part of the strip is connected to a 1 kg mass, the whole device still remaining throughout the duration of the test in the oven at 90 C.

(59) Due to the effect of this mass, the adhesive seal that fixes the strip to the plate is subjected to a shear stress. To better control this stress, the test plate is in fact placed so as to make an angle of 2 relative to the vertical.

(60) The time after which the strip detaches from the plate following rupture of the adhesive seal under the effect of this stress is noted.

(61) This time is indicated in the following table.

EXAMPLES 2 TO 6 (ACCORDING TO THE INVENTION) AND 7-8 (COMPARATIVE)

(62) Example 1 is repeated with the compositions indicated in the following table.

(63) The results obtained are also indicated in the table.

(64) TABLE-US-00001 Content in % weight/weight Ex. 7 Example 8 Ingredient Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 (comp.) (comp.) (a) Composition (A) Nature of (A) Ex. A Ex. A Ex. A Ex. A Ex. B Ex. C Ex. A Ex. A Content of (A) 61.11 51.12 41.11 38.62 38.62 38.62 20 85.0 (b) Dertoline G2L 36.16 46.15 56.16 46.50 46.50 46.50 77.27 12.27 (c) K-KAT 5218 2 2 2 0.50 0.50 0.50 2 2 GENIOSIL STP-E30 0 0 0 13.15 13.15 13.15 0 0 Irganox 245 + Irganox 1010 0.73 0.73 0.73 0.73 0.73 0.73 0.73 0.73 Silquest A-174 0 0 0 0.5 0.50 0.50 0 0 Brookfield viscosity at 100 C. 12.1 29 13.1 9.6 38.7 40 9.6 8.6 (Pa .Math. s) Weight proportion of renewable 79 82 85 73 77 73 91 72 origin (% weight/weight) Peel at 180 (N/cm) 2.9 7.2 9.1 5.9 5.2 5 0.0 0.4 Instantaneous adhesion (N/cm.sup.2) 1.7 4.1 0.4 3.5 2.9 3 0.1 0.3 Resistance time of the adhesive seal >24 hours >24 hours >24 hours >24 hours >24 hours >24 hours <6.sup. <1.sup. to static shear at 90 C.

(65) The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.

(66) From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention and, without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.