Stabilization of hot melt adhesives

Abstract

The present invention pertains to a stabilized hot melt adhesive containing a) one or more hot melt adhesive materials and b) a stabilizer composition. The one or more hot melt adhesive materials a) include a polyolefin, a styrene-isoprene-styrene block co-polymer, a styrene-butadiene-styrene block co-polymer, a polyacrylate, an acryl-copolymer, an ethylene vinyl acetate, a polyamide, a polyester, a polyurethane, a polyimide, a silane terminated polyolefin, a silane terminated poly-ether, and a silane terminated polyurethane. The stabilizer composition includes a component (B), which is a polymeric sterically hindered amine, and a component (C), which is a specific sterically hindered phenol.

Claims

1. A stabilized hot melt adhesive, comprising a) one or more hot melt adhesive materials selected from the group consisting of a polyolefin, a styrene-isoprene-styrene block co-polymer, a styrene-butadiene-styrene block co-polymer, a polyacrylate, a styrene-ethylene-butadiene-styrene acryl-copolymer, an ethylene vinyl acetate, a polyamide, a polyester, a polyurethane, a polyimide, a silane terminated polyolefin, a silane terminated polyether, and a silane terminated polyurethane; and b) a stabilizer composition comprising components (B) and (C), wherein (B) is a polymeric sterically hindered amine selected from the group consisting of: ##STR00009## ##STR00010## ##STR00011## ##STR00012##  wherein n=5−8, and wherein (C) is sterically hindered phenol selected from the group consisting of: ##STR00013## ##STR00014## ##STR00015## ##STR00016## ##STR00017##

2. The stabilized hot melt adhesive according to claim 1, wherein the stabilizer composition consists of components (B) and (C).

3. The stabilized hot melt adhesive according to claim 1, wherein a weight ratio between components (B) and (C) is between 1:5 and 5:1.

4. The stabilized hot melt adhesive according to claim 1, wherein the component (B) is at least one selected from the group consisting of: ##STR00018## ##STR00019##

5. The stabilized hot melt adhesive according to claim 1, wherein the component (B) is: ##STR00020##

6. The stabilized hot melt adhesive according to claim 1, wherein the component (C) is at least one selected from the group consisting of: ##STR00021## ##STR00022## ##STR00023##

7. The stabilized hot melt adhesive according to claim 1, wherein the component (C) is at least one selected from the group consisting of: ##STR00024##

8. The stabilized hot melt adhesive according to claim 1, wherein the stabilizer composition further comprises: one or more additives selected from the group consisting of a phosphite, a thioether, a secondary arylamine, a hydroxyl-amine based stabilizer, a UV-absorber, and an inorganic stabilizer.

9. A method of stabilizing a hot melt adhesive against degradation by one or more of light, oxygen and heat, the method comprising: adding a stabilizer composition to one or more hot melt adhesive materials selected from the group consisting of a polyolefin, a styrene-isoprene-styrene block co-polymer, a styrene-butadiene-styrene block co-polymer, a polyacrylate, a styrene-ethylene-butadiene-styrene acryl-copolymer, an ethylene vinyl acetate, a polyamide, a polyester, a polyurethane, a polyimide, a silane terminated polyolefin, a silane terminated polyether, and a silane terminated polyurethane, wherein the stabilizer composition comprises components (B) and (C), wherein (B) is a polymeric sterically hindered amine selected from the group consisting of: ##STR00025## ##STR00026##  wherein n=5−8, and wherein (C) is sterically hindered phenol selected from the group consisting of: ##STR00027## ##STR00028## ##STR00029## ##STR00030##

10. A stabilized hot melt adhesive, comprising a) one or more hot melt adhesive materials selected from the group consisting of a polyolefin, a styrene-isoprene-styrene block co-polymer, a styrene-butadiene-styrene block co-polymer, a polyacrylate, a styrene-ethylene-butadiene-styrene acryl-copolymer, an ethylene vinyl acetate, a polyamide, a polyester, a polyurethane, a polyimide, a silane terminated polyolefin, a silane terminated polyether, and a silane terminated polyurethane; and b) a stabilizer composition comprising components (B) and (C), wherein (B) is a polymeric sterically hindered amine selected from the group consisting of: ##STR00031## ##STR00032##  wherein n=5−8, and wherein (C) is sterically hindered phenol selected from the group consisting of: ##STR00033## ##STR00034## ##STR00035## ##STR00036##

11. The stabilized hot melt adhesive according to claim 10, wherein the stabilizer composition consists of components (B) and (C).

12. The stabilized hot melt adhesive according to claim 10, wherein a weight ration between components (B) and (C) is between 1:5 and 5:1.

13. The stabilized hot melt adhesive according to claim 10, wherein the component (B) is at least one selected from the group consisting of: ##STR00037## ##STR00038##

14. The stabilized hot melt adhesive according to claim 10, wherein the component (B) is at least one selected from the group consisting of: ##STR00039##

15. The stabilized hot melt adhesive according to claim 10, wherein the component (C) is at least one selected from the group consisting of: ##STR00040## ##STR00041## ##STR00042##

16. The stabilized hot melt adhesive according to claim 10, wherein the component (C) is at least one selected from the group consisting of: ##STR00043##

17. The stabilized hot melt adhesive according to claim 10, wherein the stabilizer composition further comprises: one or more additives selected from the group consisting of a phosphite, a thioether, a secondary arylamine, a hydroxyl-amine based stabilizer, a UV-absorber, and an inorganic stabilizer.

18. A method of stabilizing a hot melt adhesive against degradation by one or more of light, oxygen and heat, the method comprising: adding a stabilizer composition to one or more hot melt adhesive materials selected from the group consisting of a polyolefin, a styrene-isoprene-styrene block co-polymer, a styrene-butadiene-styrene block co-polymer, a polyacrylate, a styrene-ethylene-butadiene-styrene acryl-copolymer, an ethylene vinyl acetate, a polyamide, a polyester, a polyurethane, a polyimide, a silane terminated polyolefin, a silane terminated polyether, and a silane terminated polyurethane, wherein the stabilizer composition comprises components (B) and (C), wherein (B) is a polymeric sterically hindered amine selected from the group consisting of: ##STR00044## ##STR00045##  and wherein (C) is a sterically hindered phenol selected from the group consisting of: ##STR00046## ##STR00047## ##STR00048## ##STR00049##

19. The stabilized hot melt adhesive according to claim 1, wherein the hot melt adhesive comprises a polyolefin, and wherein the polyolefin is selected from the group consisting of an amorphous poly-alpha-olefin and a metallocene based polyolefin.

20. The stabilized hot melt adhesive according to claim 1, wherein the hot melt adhesive comprises a polyolefin, and wherein the polyolefin is a metallocene based polyolefin.

21. The stabilized hot melt adhesive according to claim 10, wherein the hot melt adhesive comprises a polyolefin, and wherein the polyolefin is selected from the group consisting of an amorphous poly-alpha-olefin and a metallocene based polyolefin.

22. The stabilized hot melt adhesive according to claim 10, wherein the hot melt adhesive comprises a polyolefin, and wherein the polyolefin is a metallocene based polyolefin.

Description

(1) Accordingly, in a first aspect the present invention relates to a hot melt adhesive comprising a) one or more hot melt adhesive materials selected from the group consisting of polyolefins such as amorphous poly-alpha-olefins, metallocene based polyolefins, styrene-isoprene-styrene (SIS) block co-polymer, styrene-butadiene-styrene (SBS), styrene-ethylene-butadiene-styrene (SEBS) block co-polymer, polyacrylate, acryl-copolymer, ethylene vinyl acetate, polyamide, polyester, polyurethane, polyimide, silane terminated polyolefin, silane terminated polyether and silane terminated polyurethane; and b) a stabilizer composition comprising or consisting of two or three of components (A), (B) and (C), wherein (A) is a sterically hindered amine (HALS) selected from the group consisting of:

(2) ##STR00001## wherein R═H, CH.sub.3 or OC.sub.8H.sub.17

(3) ##STR00002## ##STR00003## (B) is a polymeric sterically hindered amine (HALS) selected from the group consisting of:

(4) ##STR00004## ##STR00005## (C) is a sterically hindered phenol selected from the group consisting of:

(5) ##STR00006## ##STR00007## ##STR00008##

(6) In a preferred embodiment, the stabilizer composition as described herein comprises or consists of components (A) and (C). In this embodiment, the weight ratio between components (A) and (C) preferably is between 1:5 and 5:1.

(7) In another preferred embodiment, the stabilizer composition as described herein comprises or consists of components (B) and (C). In this embodiment, the weight ratio between components (B) and (C) preferably is between 1:5 and 5:1.

(8) In a further preferred embodiment, the stabilizer composition as described herein comprises or consists of components (A), (B) and (C). In this embodiment, the weight ratio between components (A), (B) and (C) preferably is between 8:1:1 and 1:8:1 and 1:1:8.

(9) Preferably, component (A) is selected from the group consisting of: A-(I), A-(II). A-(III), A-(V), A-(VII), A-(IX), A-(X).

(10) Even more preferably, component (A) is selected from the group consisting of: A-(I), A-(III).

(11) Preferably, component (B) is selected from the group consisting of: B-(II), B-(III), B-(IV), B-(V), B-(VI).

(12) Even more preferably, component (B) is selected from the group consisting of: B-(II), B-(IV).

(13) Preferably, component (C) is selected from the group consisting of: C-(I), C-(II), C-(III), C-(IV), C-(V), C-(VI), C-(VII), C-(VIII). C-(IX). C-(X), C-(XI). C-(XII), C-(XIII), C-(XIV).

(14) Even more preferably, component (C) is selected from the group consisting of: C-(III), C-(IV), C-(V), C-(XII), C-(XIV).

(15) In a preferred embodiment the hot melt adhesive according to the present invention comprises metallocene based polyolefins as one or more hot melt adhesive materials.

(16) In an embodiment the hot melt adhesive according to the present invention does not comprise a branched polyurethane-polyacrylate resin containing silicon resin, a branched polyurethane-silicon containing polyacrylate resin or a branched polyurethane-polyacrylate resin.

(17) Preferably, the stabilizer composition further comprises one or more additives selected from the group consisting of: phosphite such as Irgafos 12 CAS 80410-33-9, 2, 2′,2″-Nitrilo[triethyl-tris[3,3,5,5-tetra-tert.-butyl-1,1-biphenyl-2,2diyl]] phosphite, Irgafos 38 CAS 145650-60-8 Bis(2,4-di-tert.-butyl-6-methylphenyl)-ethyl-phosphite, Irgafos 126 CAS 26741-53-7 Bis-(2,4-di-tert.-butylphenol)pentaerythrtol diphosphite, Irgafos 168 CAS 31570-04-4 Tris(2,4-di-tert.-butylphenyl)phosphite, Irgafos P-EPQ CAS 119345-01-6 Tetrakis(2,4-d-tert-butylphenyl)[1,1-biphenyl]-4,4′-diylbisphosphonite, Irgafos TNPP CAS 26523-78-4 Tri-(nonylphenol)-phosphite thioether such as Irganox PS 800 CAS 123-28-4 Didodecyl-3,3′-thiodipropionate, Irgafos 802 CAS 693-36-7 3,3′-Thiodipropionic acid dioctadecylester, secondary arylamine such as Irganox 5057 CAS 68411-46-1 Benzenamine, N-phenyl-, reaction products with 2,4,4-trimethylpentene, hydroxyl-amine based stabilizers such as Irgastab FS 042 Oxidized bis(hydrogenated tallow alkyl)amines, optical brighteners such as Tinopal OB CO CAS 7128-64-5,5-thiophenediylbis(5-tert-butyl-1,3-benzoxazole), UV-absorber such as from the class of benzophenones, cyanoacrylate, formamidine, oxanilide, benzotriazols, hydroxyphenyltriazines and inorganic stabilizer.

(18) In a further aspect, the present invention relates to a method of stabilizing a hot melt adhesive against degradation by one or more of light, oxygen and heat, comprising the following steps: providing one or more hot melt adhesive materials selected from the group consisting of polyolefins such as amorphous poly-alpha-olefins, metallocene based polyolefins, styrene-isoprene-styrene (SIS) block co-polymer, styrene-butadiene-styrene (SBS), styrene-ethylene-butadiene-styrene (SEBS) block co-polymer, polyacrylate, acryl-copolymer, ethylene vinyl acetate, polyamide, polyester, polyurethane, polyimide, silane terminated polyolefin, silane terminated polyether and silane terminated polyurethane, silane terminated polyacrylate and adding a stabilizer composition as defined herein.

(19) In an even further aspect, the present invention relates to the use of a stabilizer composition as defined herein for stabilizing a hot melt adhesive against degradation by one or more of light, oxygen and heat, wherein the hot melt adhesive material is selected from polyolefins such as amorphous poly-alpha-olefins, metallocene based polyolefins, styrene-isoprene-styrene (SIS) block co-polymer, styrene-butadiene-styrene (SBS), styrene-ethylene-butadiene-styrene (SEBS) block co-polymer, polyacrylate, acryl-copolymer, ethylene vinyl acetate, polyamide, polyester, polyurethane, polyimide, silane terminated polyolefin, silane terminated polyether, silane terminated polyacrylate and silane terminated polyurethane.

(20) The present invention is further described by the following non-limiting examples.

(21) Hot Melt Formulations

(22) All materials in the following sections are added to a kneader at room temperature (RT, 25° C.). The kneader is closed and evacuated to 0,1 mbar. After that the temperature of the kneader is raised from room temperature to 155° C. At a temperature of 120° C. the kneading is started and continued for 0.5 Hrs.

(23) TABLE-US-00001 TABLE 1 Metallocene based Polyolefin HMA Type of 138281 140581.1 140581.2 Raw Material Material Supplier Wt % Wt % Wt % Affinity GA 1950 Metallocene Dow 33.3 33.3 33.3 Polyolefin Plastomer Eastotac 130 R Hydrogenated Exxon 33.3 33.3 33.3 Hydrocarbon Resin Catenex S 523 Paraffin Oil Shell 33.3 Paraflint H1 Paraffin Wax Sasol 33.3 LuwaxPE 10M Paraffin Wax BASF 33.3 Total 100 100 100 Wt % = Weight percent

(24) TABLE-US-00002 TABLE 2 SIS based HM-PSA Type of 140525 141150 142492 Raw Material Material Supplier Wt % Wt % Wt % Kraton D-1102 Linear Kraton 25 SBS/SB Polymer Kraton D 1161 PT SIS, linear Kraton 40 44 triblock Sylvalite RE 85 L Rosin Ester Arizona 44 Foral 85 E Hydrogenated Eastman 25 Rosin Ester Escorez 5300 Cycloaliphatic Exxon 50 hydrocarbon resin Eastotac H 130R Hydrogenated Eastman 25 Hydrocarbon Resin Catenex Oil S 523 paraffin oil Shell 10 12 Luwax PE 10M Paraffin wax BASF 25 Total 100 100 100
Materials used:

(25) TABLE-US-00003 Raw Material Supplier Description Affinity GA 1950 Dow Polyolefin Plastomer (PO) produced via INSITE ™ technology from Dow Plastics. Density = 0.855 g/cc, MFi = 500 Eastotac 130 R Eastman Eastotac ™ H-130R is a hydrogenated hydrocarbon resin, having a ring and ball softening point of 130° C. and a molten Gardner color of 4. Catenex S 523 Shell Shell Catenex oil is a paraffinic process oil manufactured via solvent extraction process with a refractive index of (ASTM D 1218) of 1,478 Paraflint H1 Sasol Synthetic wax made by the Fischer-Tropsch process with a congealing point 208° F. Possesses similar structure to paraffin wax, higher melting point, hardness and molecular weight. Used in hot melt adhesives LuwaxPE 10M BASF Polyethylene wax based on ethylene copolymer that contains acidic groups, melting point (DSC) 110-118° C. Kraton D-1102 Kraton Kraton D1102 K is a clear, linear triblock copolymer based on styrene and butadiene, with a polystyrene content of 28% and a Solution Viscosity (BAM 922) of cps 1100 Kraton D 1161 PT Kraton Kraton ® D-1161 polymer is a clear linear triblock copolymer based on styrene and isoprene, with bound styrene of 15% mass. Melt flow rate 200° C./5 kg (ISO 1133) 9 g/10 min Foral 85-E Eastman Hydrogenated Rosin Ester with a softening point of 80- 88° C.(Hercules Drop method) and a melt viscosity of 340 mPas at 140° C. Eastotec H-130R Eastman Eastotac ™ H-130R is a hydrogenated hydrocarbon resin, having a ring and ball softening point of 130° C. and a molten Gardner color of 4. Escorez 5300 Exxon Escorez 5300 is a water white cycloaliphatic hydrocarbon resin Mobile with a glass transition temp. of 55° C. Sylvalite RE 85 L Arizona SYLVALITE ® RE 85L RESIN is a polyol ester of rosin with a softening point, Ring & Ball, ° C. 83-87° C. EVA 2075.1 Buehnen Commercially available Ethyl-Vinyl-Acetat Hot Melt; water clear.

Stabilizer Compositions

(26) TABLE-US-00004 TABLE 3 Stabilizer compositions 139485 Std. Cmp. Cmp. Cmp. Cmp Cmp. Inv. Inv. Inv. Inv. Exp. Compound 0 1 2 3 4 5 6 7 8 9 of formula Material phr phr phr phr phr phr phr phr phr phr C-(IV) Irganox 1010 0 0.5 0.25 C-(V) Irganox 1076 0 0.5 0.1 0.2 0.3 0.4 A-(I) Tinuvin 770 0 0.4 0.3 0.2 0.1 2:1 Mix Irganox B 215 0 0.5 C-(IV)/ Irgafos 168 1:1 Mix Irganox B 225 0 0.5 C-(IV)/ Irgafos 168 Std. = Standard for this experiment pool, i.e. without stabilization Cmp. = Comparative Example Inv. = Innovative Example Exp. = Experiment Number Phr = parts per hundred resin

(27) TABLE-US-00005 TABLE 4 Stabilizer compositions 140622 Std. Cmp. Cmp. Inv. Inv. Inv. Exp. Compound 0 1 2 3 4 5 of formula Material phr phr phr phr phr phr B-(II) Tinuvin 622 SF 0 0.3 A-(I) Tinuvin 770 0 0.15 0.15 0.1 C-(III) Irganox 1035 0 0.3 0.15 0.1 C-(XII) Irganox 1726 0 0.15 0.1

(28) TABLE-US-00006 TABLE 5 Stabilizer composition 141305 Std. Cmp. Cmp. Cmp. Cmp Inv. Inv. Inv. Exp. Compound 0 1 2 3 4 5 6 7 of formula Material phr Phr phr phr phr phr phr phr C-(V) Irganox 1076 0.3 C-(III) Irganox1035 1 0.3 0.3 C-(XIV) Irganox 565 1 B-(II) Tinuvin 622 SF 1 0.3 B-(IV) Chimasorb 944 0.3 0.3 Irgafos 168 0.3 0.3 0.3 Irganox PS 800 1

(29) TABLE-US-00007 TABLE 6 Stabilizer composition 142823 Std. Cmp Cmp Cmp Cmp Inv. Inv. Inv. Inv. Inv. Exp. Compound 1 2 3 4 5 6 7 8 9 of formula Material 0 phr phr phr phr phr phr phr phr phr A-(I) Tinuvin 770 0.6 0.2 0.2 0.2 0.2 0.3 B-(II) Tinuvin 622 0.6 0.2 0.2 0.2 B-(IIV) Chimasorb 944 0.6 C-(iV) Irganox 1010 0.6 0.2 0.3 C-(V) Irganox 1076 0.4 0.2 C-(III) Irganox 1035 0.2

(30) TABLE-US-00008 TABLE 7 Stabilizer Composition 142523 Std. Cmp. Cmp. Cmp. Inv. Inv. Inv. Exp. Compound 0 1 2 3 4 5 6 of formula Material phr phr phr phr phr phr phr A-(I) Tinuvin 770 0.5 0.5 0.33 0.33 B-(II) Tinuvin 622 0.5 0.33 0.33 C-(III) Irganox 1035 0.33 C-(IV) Irganox 1010 0.5 C-(V) Irganox 1076 0.5 0.5 0.33 Irgafos 168 0.5 Irganox PS 800 0.5

(31) TABLE-US-00009 TABLE 8 Stabilizer Composition 140747 Std. Cmp. Cmp. Cmp. Cmp. Cmp. Inv. Inv. Exp. Compound 0 1 2 3 4 5 6 7 of formula Add phr phr phr phr phr phr phr phr B-(II) Tinuvin 622 33.3 33.3 C-(XII) Irganox 1726 1 66.6 33.3 66.6 C-(V) Irganox 1076 1 0.5 C-(III) Irganox 1035 33.3 Irgafos 168 33.3 66.6 0.5 33.3

(32) TABLE-US-00010 TABLE 9 Stabilizer Composition 147802 Null B 900 Inv. Nr. 0 5  6 Irganox 1076 0 20% 60% Irgafos 168 0 80% Tinuvin 770 40

Test Results

(33) The hot melt formulation is prepared using a sigma-blade kneader. Tackifier, resins and oil or wax are placed in the 150 ml chamber of a “Werner & Pfleiderer” kneader (Type LUK 025). The kneader is evacuated and heated up. The kneader is started at a temperature of 100° C. with 100 rpm. When a temperature of 165° C. is reached kneading is continued for further 30 min.

(34) Tests are performed according to ASTM D 4499 (DIN EN ISO 10363). Results are given in Gardner color number index acc. ASTM D-6166. Higher numbers mean higher color, i.e. higher oxidation. The effectiveness of a stabilizer package can be ranked by the color number. Keeping lower numbers for a longer time mean better effectiveness of the radical scavenger package.

(35) The adhesion is tested using a probe tack tester (Testing Machines Inc., machine 80-02-01) according to ASTM D2979-95 (DIN 55405). Higher gram value means higher tack and is preferred.

(36) The viscosities are measured using a CAP 2000+ Viscometer (Brookfield) according to ASTM D 3236. Higher remaining values after the temperature aging means lesser damage to the polymer and is preferred.

(37) Results of Stabilizations

(38) TABLE-US-00011 TABLE 10 Results of stabilizing formulation 138281 with stabilizer compositions 139485 Exp. Hrs. 0 1 2 3 4 5 6 7 8 9 0 5 5 5 5 5 5 5 5 5 5 8 12 12 12 16 16 17 7 7 7 7 24 18 18 18 18 18 18 13 13 12 14 32 14 15 14 15 40 16 16 16 18 48 17 17 18 56 18 18 18 Hrs. = Hours at 177° C. according to ASTM D 4499 (Cycle I) Exp. = Experiment number

(39) TABLE-US-00012 TABLE 11 Results of stabilizing formulation 140581.1 with stabilizer compositions 140622 Exp. Hrs. 0 1 2 3 4 5 0 5 5 5 5 5 5 8 12 11 15 11 10 12 16 17 16 17 14 12 15 24 18 18 18 15 15 17 32 17 16 18 40 18 18

(40) TABLE-US-00013 TABLE 12 Results of stabilizing formulation 140581.2 with stabilizer compositions 140622 Exp. Hrs. 0 1 2 3 4 5 0 3 3 3 3 3 3 8 10 9 14 10 6 13 16 15 14 17 13 13 14 24 16 16 18 13 16 15 32 17 17 17 14 18 16 40 18 18 18 16 17 48 18 18

(41) TABLE-US-00014 TABLE 13 Results of stabilizing HMA-formulation 138281 with stabilizer compositions 142823 Exp. Hrs. 0 1 2 3 4 5 6 7 8 9 0 5 5 5 5 5 5 5 5 5 5 8 16 13 14 14 12 12 11 12 12 10 16 18 16 18 18 16 16 15 16 16 12 Probe Tack [gr] 115 0 0 0 61 120 276 412 311 186 (after 16 hrs) Viscosity [mPas] 655 593 688 668 673 783 705 795 715 766 (after 16 hrs)

(42) TABLE-US-00015 TABLE 14 Results of stabilizing HM-PSA formulation 140525 with stabilizer compositions 140747 Exp. Hrs. 0 1 2 3 4 5 6 7 0 3 3 3 3 3 3 3 3 4 18 14 15 16 16 17 13 13 8 18 18 18 18 18 17 16 12 18 Surface Skin Skin Skin

(43) TABLE-US-00016 TABLE 15 Results of stabilizing HM-PSA formulation 141150 with stabilizer compositions 141305 Exp. Hrs. 0 1 2 3 4 5 6 7 0 10 8 8 8 8 8 8 8 8 16 11 13 18 15 14 14 16 24 18 18 17 17 16 16 17 30 18 18 17 17 17

(44) TABLE-US-00017 TABLE 16 Results of stabilizing HM-PSA formulation 142492 with stabilizer composition 142523 Exp. Hrs. 0 1 2 3 4 5 6 0 8 8 8 8 8 8 8 2 10 10 10 10 10 10 10 8 13 13 13 13 13 13 13 18 18 18 18 18 18 18 18 Tack [gr] 0 0 0 0 116 275 178 (after 18 hrs)

(45) TABLE-US-00018 TABLE 17 Results of stabilizing commercial EVA-HMA 2075.1 with stabilizer composition 147802 Exp. Hrs 0 5 6 0 1 1 1 8 6 4 5 18 13 10 8