Polyurethane composition with low plasticiser migration

Abstract

A composition having at least one polyisocyanate and/or at least one isocyanate-group-containing polyurethane polymer and at least one latent hardener having aldimino group(s) of formula (I)—as an elastic adhesive, sealant or coating, which is applied on at least one plasticiser migration sensitive substrate and/or is provided with at least one covering layer and a composite obtained therefrom. The method is characterized in that porous material or stress-crackforming plastics can be used without restriction as substrates and very different materials can be used without restriction as covering layers, without the occurrence of damage associated with plasticiser migration from the composition, such as bleeding, discoloring, spotting, softening, swelling or detachment.

Claims

1. A method comprising applying a composition as an elastic adhesive, sealant, or coating to at least one substrate that is configured to be sensitive to plasticizer migration and/or at least one outer layer that is configured to be sensitive to plasticizer migration, the composition comprising at least one polyisocyanate and/or at least one polyurethane polymer containing isocyanate groups and at least one latent hardener having aldimino group(s) of the formula (I) ##STR00020## where Z is a radical of the formula (II) ##STR00021## where R is a branched alkyl radical having 10 to 14 carbon atoms.

2. The method as claimed in claim 1, wherein the at least one substrate is a porous material or a stress crack-forming plastic.

3. The method as claimed in claim 1, wherein the at least one outer layer is or cures to form a polymeric material.

4. The method as claimed in claim 3, wherein the at least one outer layer is a sealing layer or an adhesive layer or a coating or a protective film.

5. The method as claimed in claim 1, wherein the at least one latent hardener having aldimino group(s) of the formula (I) is a polyaldimine of the formula (III) ##STR00022## where n is 2 or 3 and A is an n-valent hydrocarbyl radical optionally containing ether oxygen and having a molecular weight in a range of from 28 to 6′000 g/mol.

6. The method as claimed in claim 5, wherein A has an average molecular weight in a range of from 170 to 470 g/mol.

7. The method as claimed in claim 1, wherein the at least one latent hardener having aldimino group(s) of the formula (I) is a reaction product having aldimino group(s) of the formula (V) ##STR00023## where A′ is a divalent aliphatic or cycloaliphatic or arylaliphatic hydrocarbyl radical optionally containing ether oxygen or amine nitrogen and having a molecular weight in a range of from 28 to 500 g/mol, and X is O or S or NR.sup.0 where R.sup.0 is a hydrogen radical or is a hydrocarbyl radical which has 1 to 30 carbon atoms and optionally contains at least one carboxylic ester, nitrile, nitro, phosphonic ester, sulfone or sulfonic ester group or aldimino group of the formula (I).

8. The method as claimed in claim 1, wherein the composition comprises a mixture including two or more latent hardeners having aldimino group(s) of the formula (I) in which each latent hardener has a Z that is a radical of the formula (II) and an R that is selected from linear or branched decyl, undecyl, dodecyl, tridecyl, and tetradecyl radicals.

9. The method as claimed in claim 1, wherein the composition comprises the at least one polyurethane polymer containing isocyanate groups.

10. The method as claimed in claim 9, wherein the composition further comprises a catalyst.

11. The method as claimed in claim 1, wherein the composition further comprises at least one plasticizer.

12. The method as claimed in claim 1, wherein the composition is a one-component composition.

13. A bonding composite or sealing composite or coating composite obtained from the method as claimed in claim 1, comprising the optionally cured composition and the substrate adhering to the composition and/or the outer layer adhering to the composition.

14. The composite as claimed in claim 13, wherein it is an elastic seal and comprises either a substrate sensitive to plasticizer migration, the cured composition adhering thereon, optionally a further substrate adhering to the composition, and optionally an outer layer adhering to the composition; or a substrate, the cured composition adhering thereon, an outer layer adhering to the composition, and optionally a further substrate adhering to the composition.

15. The composite as claimed in claim 13, wherein it is an elastic adhesive bond and comprises either a) a first substrate sensitive to plasticizer migration, the cured composition adhering thereon, and a second substrate adhering to the composition; or b) a first substrate, the cured composition adhering thereon, a second substrate adhering to the composition, and an outer layer adhering to the composition; or c) a first substrate, the cured composition adhering thereon, an outer layer adhering to the composition, and a second substrate bonded to the outer layer.

16. The composite as claimed in claim 13, wherein it is an elastic coating and comprises a substrate, the cured composition adhering thereon, and an outer layer adhering to the composition.

17. The method as claimed in claim 2, wherein the porous material is selected from the group consisting of wood, paper, cardboard, gypsum, mortar, fiber cement, concrete, and natural stone.

18. The method as claimed in claim 17, wherein the natural stone is marble, granite, gneiss, limestone, or sandstone.

Description

EXAMPLES

(1) Adduced hereinafter are working examples which are intended to elucidate the invention described in detail. It will be appreciated that the invention is not restricted to these described working examples.

(2) Aldehydes Used:

(3) Aldehyde-1: Fractionated reaction mixture obtained from formylation, catalyzed by means of HF—BF.sub.3, of C.sub.10-14-alkylbenzene, containing mainly branched 4-(C.sub.10-14-alkyl)benzaldehydes. (mean aldehyde equivalent weight 290 g/eq)

(4) 2,2-Dimethyl-3-lauroyloxypropanal (284.4 g/mol)

(5) Benzaldehyde (106.1 g/mol)

(6) p-tert-Butylbenzaldehyde (162.2 g/mol)

(7) 3-Phenoxybenzaldehyde (198.2 g/mol)

(8) Aldehyde-1 is a mixture of aldehydes of the formula (VI), whereas 2,2-dimethyl-3-lauroyloxypropanal, benzaldehyde, p-tert-butylbenzaldehyde and 3-phenoxybenzaldehyde do not conform to the formula (VI).

(9) Preparation of Aldimines:

(10) The amine value (including aldimino groups) was determined by means of titration (with 0.1 N HClO.sub.4 in acetic acid versus crystal violet).

(11) The viscosity was measured with a thermostated Rheotec RC30 cone-plate viscometer (cone diameter 50 mm, cone angle 1°, cone tip-plate distance 0.05 mm, shear rate 10 s.sup.−1).

(12) Aldimine A1:

(13) 50.00 g of aldehyde-1 were initially charged in a round-bottom flask under a nitrogen atmosphere. While stirring, 13.93 g of 3-aminomethyl-3,5,5-trimethylcyclohexylamine were added and then the volatile constituents were removed at 80° C. and a reduced pressure at 10 mbar. A light yellow, odorless and pH-neutral liquid having a viscosity at 20° C. of 21.3 Pa.Math.s and an amine value of 150.1 mg KOH/g was obtained.

(14) Aldimine A2:

(15) 50.00 g of aldehyde-1 were initially charged in a round-bottom flask under a nitrogen atmosphere. While stirring, 13.58 g of hexane-1,6-diamine solution (70% by weight in water) were added and then the volatile constituents were removed at 80° C. and a reduced pressure of 10 mbar. A light yellow, odorless and pH-neutral liquid having a viscosity at 20° C. of

(16) 1.0 Pa.Math.s and an amine value of 161.6 mg KOH/g was obtained.

(17) Aldimine A3:

(18) 50.00 g of aldehyde-1 were initially charged in a round-bottom flask under a nitrogen atmosphere. While stirring, 11.14 g of 1,3-bis(aminomethyl)benzene were added and then the volatile constituents were removed at 80° C. and a reduced pressure at 10 mbar. A pale yellow, odorless and pH-neutral liquid having a viscosity at 20° C. of 2.6 Pa.Math.s and an amine value of 155.7 mg KOH/g was obtained.

(19) Aldimine A4:

(20) 50.00 g of aldehyde-1 were initially charged in a round-bottom flask under a nitrogen atmosphere. While stirring, 11.63 g of 1,3-bis(aminomethyl)cyclohexane were added and then the volatile constituents were removed at 80° C. and a reduced pressure at 10 mbar. A light yellow, odorless and pH-neutral liquid having a viscosity at 20° C. of 6.1 Pa.Math.s and an amine value of

(21) 153.0 mg KOH/g was obtained.

(22) Aldimine A5:

(23) 50.00 g of aldehyde-1 were initially charged in a round-bottom flask under a nitrogen atmosphere. While stirring, 17.21 g of 4,4′-diaminodicyclohexylmethane were added and then the volatile constituents were removed at 80° C. and a reduced pressure at 10 mbar. A light yellow, odorless and pH-neutral liquid having a viscosity at 20° C. of 59.6 Pa s and an amine value of 140.2 mg KOH/g was obtained.

(24) Aldimine A6:

(25) 50.00 g of aldehyde-1 were initially charged in a round-bottom flask under a nitrogen atmosphere. While stirring, 8.85 g of 1,4-phenylenediamine were added and then the volatile constituents were removed at 80° C. and a reduced pressure at 10 mbar. An orange-brown, odorous and pH-neutral liquid having a viscosity at 20° C. of 4.9 Pa.Math.s and an amine value of 163.0 mg KOH/g was obtained.

(26) Aldimine A7:

(27) 25.00 g of aldehyde-1 were initially charged in a round-bottom flask under a nitrogen atmosphere. While stirring, 8.60 g of 2-(2-aminoethoxy)ethanol were added and then the volatile constituents were removed at 80° C. and a reduced pressure at 10 mbar. A pale yellow, odorous and pH-neutral liquid having a viscosity at 20° C. of 0.4 Pa.Math.s and an amine value of 142.9 mg KOH/g was obtained.

(28) Aldimine A8:

(29) 25.00 g of aldehyde-1 were initially charged in a round-bottom flask under a nitrogen atmosphere. While stirring, 14.02 g of 3-aminomethyl-3,5,5-trimethylcyclohexanol were added and then the volatile constituents were removed at 80° C. and a reduced pressure at 10 mbar. A pale yellow, odorless and pH-neutral liquid having a viscosity at 20° C. of 34.3 Pa.Math.s and an amine value of 122.3 mg KOH/g was obtained.

(30) Aldimine R1:

(31) 50.00 g of 2,2-dimethyl-3-lauroyloxypropanal were initially charged in a round-bottom flask under a nitrogen atmosphere. While stirring, 13.93 g of 3-aminomethyl-3,5,5-trimethylcyclohexylamine were added and then the volatile constituents were removed at 80° C. and a reduced pressure at 10 mbar. A pale yellow, odorless liquid having an amine value of 153.0 mg KOH/g was obtained.

(32) Aldimine R2:

(33) 50.00 g of 2,2-dimethyl-3-lauroyloxypropanal were initially charged in a round-bottom flask under a nitrogen atmosphere. While stirring, 13.88 g of hexane-1,6-diamine solution (70% by weight in water) were added and then the volatile constituents were removed at 80° C. and a reduced pressure at 10 mbar. An almost colorless, odorless liquid having an amine value of 165.0 mg KOH/g was obtained.

(34) Aldimine R3:

(35) 50.00 g of 2,2-dimethyl-3-lauroyloxypropanal were initially charged in a round-bottom flask under a nitrogen atmosphere. While stirring, 11.39 g of 1,3-bis(aminomethyl)benzene were added and then the volatile constituents were removed at 80° C. and a reduced pressure at 10 mbar. An almost colorless, odorless liquid having an amine value of 160.9 mg KOH/g was obtained.

(36) Aldimine R4:

(37) 50.00 g of 2,2-dimethyl-3-lauroyloxypropanal were initially charged in a round-bottom flask under a nitrogen atmosphere. While stirring, 9.05 g of 1,4-phenylenediamine were added and then the volatile constituents were removed at 80° C. and a reduced pressure at 10 mbar. A light brown, odorless liquid having an amine value of 167.6 mg KOH/g was obtained.

(38) Aldimine R5:

(39) 24.46 g of 2,2-dimethyl-3-lauroyloxypropanal were initially charged in a round-bottom flask under a nitrogen atmosphere. While stirring, 8.60 g of 2-(2-aminoethoxy)ethanol were added and then the volatile constituents were removed at 80° C. and a reduced pressure at 10 mbar. An almost colorless, odorless liquid having an amine value of 144.3 mg KOH/g was obtained.

(40) Aldimine R6:

(41) 33.43 g of benzaldehyde were initially charged in a round-bottom flask under a nitrogen atmosphere. While stirring, 25.55 g of IPDA were added and then the volatile constituents were removed at 80° C. and a reduced pressure at 10 mbar. What was obtained was a light yellow, intensely odorous liquid having an amine value of 314.1 mg KOH/g, which crystallized after a few days.

(42) Aldimine R7:

(43) 27.87 g of p-tert-butylbenzaldehyde were initially charged in a round-bottom flask under a nitrogen atmosphere. While stirring, 13.93 g of IPDA were added and then the volatile constituents were removed at 80° C. and a reduced pressure at 10 mbar. What was obtained was a light yellow, intensely odorous, highly viscous liquid having an amine value of 236.2 mg KOH/g, which crystallized after a few days. The viscosity at 80° C. was 23.7 Pas.

(44) Aldimine R8:

(45) 34.06 g of 3-phenoxybenzaldehyde were initially charged in a round-bottom flask under a nitrogen atmosphere. While stirring, 13.93 g of IPDA were added and then the volatile constituents were removed at 80° C. and a reduced pressure at 10 mbar. What was obtained was a light yellow, highly viscous liquid with low odor and having an amine value of 203.8 mg KOH/g, which crystallized after a few days. The viscosity at 80° C. was 5.1 Pas.

(46) The aldimines A1 to A6 are polyaldimines of the formula (III); the aldimines R1 to R4 and R6 to R8 serve as a comparison.

(47) The aldimines A7 and A8 are aldimines of the formula (IV); the aldimine R5 serves as a comparison.

(48) Preparation of Polymers Containing Isocyanate Groups

(49) Polymer P1:

(50) 300.0 g of polyoxypropylenepolyoxyethylenediol (Desmophen® L300, from Covestro; OH number 190.0 mg KOH/g) and 228.8 g of isophorone diisocyanate (Vestanat® IPDI, Degussa) were reacted by a known method at 60° C. to give an NCO-terminated polyurethane polymer which is liquid at room temperature and has a content of free isocyanate groups of 8.35% by weight.

(51) Polymer P2:

(52) 590 g of polyoxypropylenediol (Acclaim® 4200, from Covestro; OH number 28.5 mg KOH/g), 1180 g of polyoxypropylenepolyoxyethylenetriol (Caradol® MD34-02, from Shell; OH number 35.0 mg KOH/g) and 230 g of isophorone diisocyanate (Vestanat® IPDI, Degussa) were reacted by a known method at 80° C. to give an NCO-terminated polyurethane polymer which is liquid at room temperature and has a content of free isocyanate groups of 2.10% by weight.

(53) Polymer P3:

(54) 3080 g of polyoxypropylenediol (Acclaim® 4200, from Covestro; OH number 28.5 mg KOH/g), 1540 g of polyoxypropylenepolyoxyethylenetriol (Caradol® MD34-02, from Shell; OH number 35.0 mg KOH/g) and 385 g of tolylene diisocyanate (Desmodur® T 80 P, Covestro) were reacted at 80° C. by a known method to give an NCO-terminated polyurethane polymer which is liquid at room temperature and has a content of free isocyanate groups of 1.50% by weight.

(55) Polymer P4:

(56) 4000 g of polyoxypropylenediol (Acclaim® 4200, from Covestro; OH number 28.5 mg KOH/g) and 520 g of diphenylmethane 4,4′-diisocyanate (Desmodur® 44 MC L, from Covestro) were reacted by a known method at 80° C. to give an NCO-terminated polyurethane polymer which is liquid at room temperature and has a content of free isocyanate groups of 1.85% by weight.

(57) Preparation of Reaction Products:

(58) Reaction Product U1:

(59) 60.00 g (about 115.3 mmol of NCO) of polymer P1, 15.82 g (about 40.4 mmol) of aldimine A7 and 0.05 g of Coscat® 83 were mixed in a honey jar under argon and then left to react in an air circulation oven at 60° C. for 16 hours. A clear reaction product which is liquid at room temperature and has aldimine and isocyanate groups was obtained.

(60) Reaction Product U2:

(61) 60.00 g (about 115.3 mmol of NCO) of polymer P1, 18.51 g (about 40.4 mmol) of aldimine A8 and 0.05 g of Coscat® 83 were mixed in a honey jar under argon and then left to react in an air circulation oven at 60° C. for 16 hours. A clear reaction product which is liquid at room temperature and has aldimine and isocyanate groups was obtained.

(62) Reaction Product Q1:

(63) 60.00 g (about 115.3 mmol of NCO) of polymer P1, 15.69 g (about 40.4 mmol) of aldimine R5 and 0.05 g of Coscat® 83 were mixed in a honey jar under argon and then left to react in an air circulation oven at 60° C. for 16 hours. A clear reaction product which is liquid at room temperature and has aldimine and isocyanate groups was obtained.

(64) The reaction products U1 and U2 are reaction products having aldimino group(s) of the formula (V) which also contain unconverted polymer P1. The reaction product Q1 serves as a comparison.

(65) One-Component Compositions

(66) Compositions Z1 to Z6 and Ref1 to Ref5

(67) For each composition, the ingredients specified in tables 1 and 2 were mixed in the amounts specified (in parts by weight) by means of a centrifugal mixer (SpeedMixer™ DAC 150, FlackTek Inc.) with exclusion of moisture at 3000 rpm for one minute and stored with exclusion of moisture. Each composition was tested as follows:

(68) As a measure of plasticizer migration, speck formation was determined on cardboard. For this purpose, each composition was applied to a piece of cardboard such that it had a round base area of diameter 12 mm and a height of 20 mm, and was stored under standard climatic conditions for 7 days. Around each composition, thereafter, a dark oval speck had formed on the cardboard. The dimensions thereof (height and width) were measured and reported in table 1 as Migration.

(69) Compositions Z1 to Z6 are inventive examples. Compositions Ref1 to Ref5 are comparative examples.

(70) Compositions Z1 to Z6 are suitable as elastic adhesives, sealants or especially coatings.

(71) TABLE-US-00001 TABLE 1 Composition (in parts by weight) and properties of Z1 to Z4 and Ref1 to Ref4. Composition Z1 Ref1 Z2 Ref2 Z3 Ref3 Z4 Ref4 Polymer P1 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 Chalk.sup.1 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 Silica.sup.2 1.13 1.13 1.13 1.13 1.13 1.13 1.13 1.13 Aldimine A1 R1 A2 R2 A3 R3 A6 R4 7.80 7.65 7.25 7.10 7.41 7.28 7.13 6.97 Dibutyltin dilaurate 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 solution.sup.3 Salicylic acid 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 solution.sup.4 Migration Height 80 110 45 130 110 120 65 135 [mm] Width 55 85 40 90 85 95 50 95 .sup.1ground calcium carbonate coated with fatty acid .sup.2hydrophobically modified fumed silica .sup.35% in diisodecyl phthalate .sup.45% in dioctyl adipate

(72) TABLE-US-00002 TABLE 2 Composition (in parts by weight) and properties of Z5 and Z6 and Ref5. Composition Z5 Z6 Ref5 Reaction product U1 U2 Q1 25.0 25.0 25.0 Chalk.sup.1 25.0 25.0 25.0 Silica.sup.2 1.9 1.9 1.9 Dibutyltin dilaurate solution.sup.3 2.5 2.5 2.5 Salicylic acid solution.sup.4 5.0 5.0 5.0 Migration Height 1 1 8 [mm] Width 1 1 6 .sup.1ground calcium carbonate coated with fatty acid .sup.2hydrophobically modified fumed silica .sup.35% in diisodecyl phthalate .sup.45% in dioctyl adipate
Compositions Z7 to Z20 and Ref6 to Ref12

(73) For each composition, the ingredients specified in tables 3 to 5 were mixed in the amounts specified (in parts by weight) by means of a centrifugal mixer (SpeedMixer™ DAC 150, FlackTek Inc.) with exclusion of moisture at 3000 rpm for one minute and stored with exclusion of moisture. Each composition was tested as follows:

(74) As a measure of storage stability, the Viscosity (1d RT) was determined the day after production, and the Viscosity (7d 60° C.) after storage in a closed container in an air circulation oven at 60° C. for 7 days. The viscosity was measured, at a temperature of 20° C. in each case, with a thermostated Rheotec RC30 cone-plate viscometer (cone diameter 50 mm, cone angle 1°, cone tip-plate distance 0.05 mm, shear rate 10 s.sup.−1).

(75) As a measure of the open time, the Tack-free time was determined. For this purpose, a few grams of the composition were applied to cardboard in a layer thickness of about 2 mm and, under standard climatic conditions, the time until, when the surface of the composition was gently tapped by means of an LDPE pipette, there were for the first time no residues remaining any longer on the pipette was determined.

(76) To determine the mechanical properties, each composition was poured onto a PTFE-coated film to give a film of thickness 2 mm and stored under standard climatic conditions for 7 days, and a few dumbbells having a length of 75 mm with a bar length of 30 mm and a bar width of 4 mm were punched out of the film and these were tested in accordance with DIN EN 53504 at a strain rate of 200 mm/minute for Tensile strength (breaking force), Elongation at break, Modulus of elasticity 5% (at 0.5-5% elongation) and Modulus of elasticity 50% (at 0.5-50% elongation).

(77) Appearance was assessed visually on the films produced. “Nice” was used to describe a clear, nontacky film without blisters.

(78) To determine Plasticizer migration, a composite was produced from each composition by pouring the composition out on a glass plate to give a film of thickness 2 mm, covering the surface with a strip of polyethylene film of width 20 mm, and storing this composite under standard climatic conditions for 14 days. Subsequently, the polyethylene film was pulled away from the surface of the cured composition and examined for soiling in the form of traces of escaped liquid. If no such traces were present, plasticizer migration was answered “no”, otherwise “yes”.

(79) Odor was assessed by smelling by nose at a distance of 2 cm from the freshly produced films. “No” means that no odor was perceptible.

(80) The results are reported in tables 3 to 5.

(81) Compositions Z7 to Z20 are inventive examples. Compositions Ref6 to Ref12 are comparative examples.

(82) Compositions Z7 to Z11 are especially suitable as elastic coating, compositions Z12 to Z16 are especially suitable as elastic sealant, and compositions Z17 to Z20 are especially suitable as elastic adhesive.

(83) TABLE-US-00003 TABLE 3 Composition (in parts by weight) and properties of Z7 to Z11 and Ref6. Composition Z7 Z8 Z9 Z10 Z11 Ref6 Polymer P2 80.00 80.00 80.00 80.00 80.00 80.00 Aldimine A1 A2 A3 A4 A6 R1 10.47 9.72 9.95 10.04 9.57 10.27 Salicylic acid solution.sup.1 1.50 1.50 1.50 1.50 1.50 1.50 Viscosity (1 d RT) 15.2 15.5 18.7 18.3 15.9 13.6 [Pa .Math. s] (7 d 60° C.) 17.5 21.1 28.1 23.1 18.6 16.2 Tack-free time 3 h 1 h 40′ 1 h 05′ 1 h 10′ >8 h 2 h Tensile strength [MPa] 1.42 0.95 1.01 1.21 1.07 0.98 Elongation at break 240 219 259 271 215 142 [%] Modulus of elasticity 5% 1.72 0.90 0.95 1.15 1.23 1.50 [MPa] Modulus of elasticity 0.82 0.62 0.57 0.67 0.72 0.90 50% Appearance nice nice nice nice nice nice Plasticizer migration no no no no no yes Odor no no no no no no .sup.15% in dioctyl adipate

(84) TABLE-US-00004 TABLE 4 Composition (in parts by weight) and properties of Z12 to Z16 and Ref7. Composition Z12 Z13 Z14 Z15 Z16 Ref7 Polymer P3 80.00 80.00 80.00 80.00 80.00 80.00 Aldimine A1 A2 A3 A4 A6 R2 7.53 7.00 7.17 7.23 6.89 6.85 Salicylic acid solution.sup.1 1.50 1.50 1.50 1.50 1.50 0.20 Viscosity (1 d RT) 16.3 19.4 27.6 25.5 23.7 27.2 [Pa .Math. s] (7 d 60° C.) 20.6 28.0 45.3 35.8 30.0 47.3 Tack-free time 1 h 35′ 45′ 40′ 46′ 2 h 35′ 38′ Tensile strength [MPa] 0.52 1.22 1.72 0.94 1.79 0.73 Elongation at break 297 373 346 281 241 210 [%] Modulus of elasticity 5% 0.41 1.68 3.54 1.06 4.60 1.06 [MPa] Modulus of elasticity 0.21 0.74 1.07 0.57 1.42 0.59 50% Appearance nice nice nice nice nice nice Plasticizer migration no no no no no yes Odor no no no no no no .sup.15% in dioctyl adipate

(85) TABLE-US-00005 TABLE 5 Composition (in parts by weight) and properties of Z17 to Z20 and Ref8 and Ref12. Composition Z17 Z18 Z19 Z20 Ref8 Ref9 Ref10 Ref11 Ref12 Polymer P4 80.00 80.00 80.00 80.00 80.00 80.00 80.00 80.00 80.00 Aldimine A1 A2 A5 A6 R1 R4 R6 R7 R8 9.20 8.56 9.67 8.42 9.03 8.24 4.40 5.85 6.78 Salicylic acid 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 1.50 solution.sup.1 Viscosity (1 d RT) 29.4 50.0 32.0 35.7 22.1 24.7 36.5 43.8 39.9 [Pa .Math. s] (7 d 60° C.) 34.8 87.2 37.5 41.1 27.0 31.6 41.1 47.4 44.6 Tack-free time 1 h 20′ 1 h 10′ 1 h 10′ 1 h 30′ 45′ 45′ 1 h 30′ 2 h 1 h 35′ Tensile strength 1.62 2.91 3.46 2.10 1.18 4.86 1.66 1.44 0.55 [MPa] Elongation at 1240 508 803 248 1240 784 936 1674 1098 break [%] Modulus of 0.75 5.66 1.27 10.30 1.02 10.9 1.00 0.79 0.41 elasticity 5% [MPa] Modulus of 0.41 1.82 0.75 1.81 0.54 2.44 0.51 0.40 0.17 elasticity 50% Appearance nice nice nice nice nice nice nice nice nice Plasticizer no no no no yes yes no no no migration Odor no no no no no no significant significant slight .sup.15% in dioctyl adipate
Compositions Z21 and Ref13 to Ref17

(86) These compositions were produced in the same way as described for composition Z1 using the figures in table 6.

(87) As a measure of plasticizer migration, each composition was applied to a cardboard underlayer such that it had a round base area of diameter 15 mm and a height of 4 mm, and was stored under standard climatic conditions for 3 months. A dark oval speck formed around each composition on the cardboard, the dimensions of which (height and width) were measured after 7 days and after 3 months under standard climatic conditions and were reported in table 6 as Migration (7d) or (3 months).

(88) As a measure of the tendency to Stress-cracking on plastic, each composition was applied to a transparent, prestressed plastic sheet of polycarbonate (Makrolon®) having the dimensions of 150×30×2 mm so as to give rise to a coating of 30×30×2 mm in the middle of the stressed sheet. After 24 h under standard climatic conditions, the coating or the composition was removed and the sheet was examined for cracking and other visual changes. The prestressed plastic sheet was fixed in each case over a round piece of timber of diameter 12.5 mm mounted on a board such that the long side was at right angles to the round piece of timber and the narrow ends were fixed on the board. “Low” is used to describe the formation of small, slightly visible cracks of length 2 to 3 mm in the edge region of the sheet, which were present only superficially. “Significant” is used to describe a complete crack across the entire width of the sheet which was visible across the entire thickness of the sheet. In addition, very many small cracks were present here in the edge region of the sheet.

(89) Odor was assessed by smelling by nose at a distance of 2 cm from the freshly produced test specimens.

(90) Composition Z21 is an inventive example. Compositions Ref13 to Ref17 are comparative examples.

(91) TABLE-US-00006 TABLE 6 Composition (in parts by weight) and properties of Z21 and Ref13 to Ref17 Composition Ref13 Ref14 Ref15 Ref16 Ref17 Z21 Polymer P1 15.00 15.00 15.00 15.00 15.00 15.00 Chalk 15.00 15.00 15.00 15.00 15.00 15.00 Silica 1.13 1.13 1.13 1.13 1.13 1.13 Aldimine — R1 R6 R7 R8 A1 5.46 2.66 3.54 4.11 5.57 Dibutyltin dilaurate solution.sup.1 1.50 1.50 1.50 1.50 1.50 1.50 Salicylic acid solution.sup.2 3.00 3.00 3.00 3.00 3.00 3.00 Migration Height 17 37 17 16 17 18 (7 d) [mm] Width 17 41 19 16 19 19 Migration Height 25 47 28 20 20 23 (3 months) [mm] Width 25 52 28 22 21 23 Stress cracking low significant low low low low Odor none none significant significant slight none .sup.15% in diisodecyl phthalate .sup.25% in dioctyl adipate

(92) It is clear from the migration results in table 6 that the inventive composition Z21 comprising aldimine A1 has a similar to even lower tendency to plasticizer migration than the composition Ref13 without aldimine, and is at a similar level to compositions Ref15 to Ref17 with more or less odorous aldimines derived from benzaldehyde, p-tert-butylbenzaldehyde or 3-phenoxybenzaldehyde. By contrast, composition Ref14 comprising aldimine R1, which likewise contains a long-chain substituent and has a similarly high molecular weight to aldimine A1, has significant plasticizer migration.

(93) Compositions Z22 and Ref18

(94) For each composition, 100 parts by weight of SikaBone-T40 (one-component solvent-free elastic polyurethane adhesive containing 0.61% by weight of isocyanate groups and 20.75% by weight of plasticizer; from Sika) and the further ingredients specified in table 7 were mixed in the amount specified (in parts by weight) by means of the centrifugal mixer with exclusion of moisture at 3000 rpm for one minute and stored. Each composition was tested as follows: To measure the tensile shear strength (TSS), various test specimens were produced, with application of the composition between two isopropanol-degreased sheets of polycarbonate (Makrolon®) in a layer thickness of 3.2 mm and over an overlapping bonding area of 30×20 mm. The test specimens were stored/cured under standard climatic conditions for 14 days and then the tensile shear strength was determined to DIN EN 1465 at a strain rate of 10 mm/min and reported as “TSS on polycarbonate”.

(95) To measure migration on granite, two granite cuboids of dimensions 25×12×75 mm were used to produce a join having a cross section of 12×12 mm and a length of 50 mm between two such cuboids as described in DIN EN ISO 8339. Every test specimen of this kind was stored/cured under standard climatic conditions for 14 days. Subsequently, each join was compressed by 25% by means of suitable clamps (joint width compressed from 12 to 9 mm) and the join thus compressed was stored under standard climatic conditions for 14 days. Subsequently, each cuboid was assessed visually for discoloration in the granite resulting from migrated plasticizer. The average distance of the dark strip in the granite from the flanks of the join was reported as “Migration (granite)”.

(96) Tensile Strength, Elongation at Break and Stress at 100% Elongation were

(97) measured using the previously compressed test specimens, with determination of the values in accordance with DIN EN ISO 8339 under standard climatic conditions at a strain rate of 5 mm/min.

(98) The results are reported in table 7.

(99) Composition Z22 is an inventive example. Composition Ref18 is a comparative example.

(100) TABLE-US-00007 TABLE 7 Composition (in parts by weight) and properties of Z22 and Ref18. Composition Z22 Ref18 SikaBond ®-T40 100.0 100.0 Aldimine A1 2.2 — Aldimine R1 — 2.1 Salicylic acid solution.sup.1 1.2 0.3 Dioctyl adipate — 0.9 TSS on polycarbonate [MPa] 0.18 0.12 Migration (granite) [mm] 1 mm 2 mm Tensile strength [MPa] 0.29 0.19 Elongation at break 415% 433% Stress at 100% elongation [MPa] 0.21 0.14 .sup.15% in dioctyl adipate