This invention relates to hot-melt pressure- sensitive adhesive compositions having a novel co bina- tion of properties. More specifically, the invention relates to blends of plasticizing oils and compatible tackifiers with substantially amorphous or semicrystal- line olefin copolymers containing a C, to C_- linear α- olefin and 15 to 60 mole percent of a CV to C- _ linear α-olefin which are useful as hot-melt, pressure-sensitive adhesives. Description of the Prior Art

In U.S. Patent 3,95^,697 propylene/higher α- olefin copolymers containing -40 to 60 mole percent higher α-olefin and having melt viscosities up to 75,000 cp (measured by ASTM D1238) were coated by hot-melt tech¬ niques on backing materials and they were disclosed as having good pressure-sensitive adhesive properties. Copolymers with melt viscosities greater than 75,000 are difficult to coat and the coatings have striations in them. In fact, the copolymers with melt viscosities greater than 75.000 cp. have not been useful as pressure- sensitive hot-melt adhesives. Summary of the Invention In accordance with our invention we have found that the coatability and adhesive properties of amor¬ phous or semi-crystalline olefin copolymers containing a C-, to C_- linear α-olefin and 15 to 60 mole percent of a higher α-olefin of 6 to 10 carbon atoms, the copolymers having a melt viscosity of 5.000 to 1,000,000 cp. at

190 C. can be substantially improved by blending the co¬ polymers with a plasticizing oil and a compatible tackifying resin. The addition of the plasticizing oil and tackifying resin to copolymers having a melt viscos- ity greater than 75,000 cp. results in a blend having

an unexpected increase in the shear failure time in ad¬ dition to substantial increases in probe tack and peel adhesion values compared to the unmodified copolymers of comparable melt viscosities. Detailed Description of the Invention

The hot-melt pressure-sensitive adhesive com¬ positions of our invention contain

1) 98 to 25 weight percent of an amorphous or semi- crystalline copolymer containing a C^ to C,- linear α-olefin and 15 to 60 mole percent of a higher linear α-olefin of 6 to 10 carbon atoms, the copoly¬ mer having a melt viscosity of 5 ₃ 000 to 1,000,000 cp. at 190°C.

2) 1 to 6θ weight percent of a compatible tackifying resin, and

3) 1 to 25 weight percent of a plasticizing oil.

The plasticizing oils that are used in our adhesives are compatible with the α-olefin copolymers and tackifying resinε. Preferred plasticizing oils are highly paraffinic or napthenic petroleum fractions that can be used as synthetic rubber extenders. A typical plasticizing oil is known as Schellflex 371- Other hydrocarbon plasticizing oils can be used, such as low molecular weight oils derived from a CV hydrocarbon fraction, low molecular weight polyisobutylenes, poly¬ merized DAC-B oils and liquid polyterpenes. Operable plasticizing oils can also be esters, such as esters derived from aromatic or aliphatic acids having a boiling point above 275 C. at 7β0 mm pressure. Useful esters include tris(2-ethylhexyl) trimellitate, bis(2-ethyl- hexyl) phthalate, bis(2-ethylhexyl) terephthalate, di- butyl sebacate, bis(2-ethylhexyl) adipate, 2,2,--tri- methyl-l,3-pentanediol diisobutyrate and methyl abietate. Operable concentrations of the plasticizing oils are from 1 to 25 weight percent. The preferred range is 5 to 15 weight percent.

The compatible tackifying resins useful in the adhesive compositions of this invention can be a hydro¬ carbon resin such as DAC-B hydrocarbon resin prepared according to the process disclosed in U.S. Patent 3_701,76θ as well as other hydrocarbon resins, polyter- penes or synthetic polyterpenes, and the like. One such DAC-B hydrocarbon tackifying resin is a hydrocarbon res¬ in having a softening point of 100 C. and available com¬ mercially as Resin H-100 from Eastman Chemical Products, Inc. Other hydrocarbon tackifying resins can be prepared by the polymerization of monomers consisting primarily of olefins and diole ins and include, for example, the residual by-product monomers resulting from the manufac¬ ture of isoprene. These hydrocarbon tackifying resins typically exhibit a Ring and Ball softening point of from 8θ C. to 135 C; an acid number of 0-2, a saponifi- cation value of less than 1; and an iodine value of 30 to 100. Examples of such commercially available resins based on a C^-olefin fraction of this type are "Wing- tack" 95 and "Wingtack" 115 tackifying resins sold by Goodyear Tire and Rubber Company, the Sta-Tac and Beta- prene A or H resins sold by Reichhold Chemical Corpora¬ tion, Arkon resins sold by Arakawa Forest Chemical Industries, and Escorez resins sold by Exxon Chemical Co.

Also other suitable tackifying resins are the terpene polymers such as the polymeric, resinous mat¬ erials obtained by polymerization and/or copolymeriza- tion of terpene hydrocarbons such as the alicyclic, monocyclic, and bicyclic ...onoterpenes and their mix¬ tures, including alloocimene, carene, isomerized pin- ine, pinene, dipentene, terpinene, terpinolene, limo- nene, terpentine, and various other terpenes. Parti¬ cularly useful starting materials are terpene mixtures containing at least 20 percent by weight beta-pinene

__] _

and/or limonene or dipentene (racemic limonene) _. , and the "sulfate terpentine" obtained as a by-product in the sulfate pulping process. Commercially available resins of the terpene type include the Zonarez terpene B-Series and 7000 Series resins from Arizona Chemical

Corp. and Nirez resins from Reichhold Chemical Corp. The typical properties reported .'"or the Zonarez terpene resins include Ring and Ball softening points of 55 to 125 C. (ASTK E-28-67), color of 2 to 3 (Gardner 1963, 50% -In hep- tane), acid number of less than 1 (ASTM D-.65-59), sapon- ification number of less than 1 (ASTM .D-.6*4-59) and spec¬ ific gravity at 25°C. of 0.96 to 0.99 (ASTM D1963-61) •

The hydrocarbon resins, polyterpenes, or other compatible tackifying resins can be used either alone or in combination. The operable concentration of these tack¬ ifying resins is 1 to 60 weight percent. The preferred concentration range for these compatible tackifying resins is 10 to 50 weight percent. Incompatible tacki¬ fying resins such as those based on wood rosin esters or polyindene are not useful in the practice of this invention since blends containing them are grainy and hazy. Furthermore, the presence of the incompatible tackifying resins reduces the tack of the copolymers to a very low level. The base copolymers for the blends of this in¬ vention may be made according to the procedure described in U.S. Patent 3,954,697- Operable melt viscosity limits for these copolymers include 5,000 cp up to 1,000,000 cp, with the preferred melt viscosity range being 15,000 cp to 850,000 cp at 190°C. Such copoly¬ mers contain 15-60 mole percent higher-1-olefin. Co¬ polymers containing -40 to 60% higher 1-olefin are es¬ sentially amorphous while those containing less than 0% higher 1-olefin are partially crystalline. C-ener- ally, the semicrystalline copolymers have heats of

O PI fa wl ^p δ ^"~

fusi.on of 4 calories/gram as measured on samples which have been annealed in an oven at 7Q°C. for periods of about 2 to 2*4 hours.

The "apparent heat of fusion" (ΔH _f ) of a poly- mer, as defined here, is the total amount of latent heat in cal./gram involved in the melting of all crystalline phases of a crystallizable polymer. ΔH _f values are readily obtained using thermal analytical instruments, such as the Perkin-Elmer DSC-2 Differential Scanning Calorimeter or the Du Pont Model 990 Thermal Analyzer with differential scanning calorimeter cell. One method for determining ΔH _f is also described in the Journal of Applied Polymer Science, 20, 1209 (1976). Measurement of H _f is also described in Du Pont Thermal Analysis Bulle- tin No. 900-8 (1965). Qualitatively, it is possible to compare the degree of crystallinity of polymers by com¬ paring their ΔH _f values.

Copolymers useful in the practice of this in¬ vention are readily prepared using titanium trichloride based catalysts. In general, preferred results have been achieved by using catalyst systems which provide poor stereoregulation in the polymerization of propylene or ϊ-butene. Combinations of Et-,A1 with AATiCl-, with Al/Ti molar ratios ranging from about 1:1 to 5:1 have been found to be quite useful. It is also generally desirable to conduct the polymerization at relatively high temperatures such as from about 110 to about 170 C.

Although not preferred, catalysts which pro¬ vide highly stereoregular propylene homopolymer may also be used to copolymerize propylene or 1-butene or 1-pentene, with hexene, heptene, octene, nonene, and decene. Examples of highly stereospecific catalysts (for the polymerization of propylene) which may be used include EtAlCl ₂ /Bu ₃ N/TiCl ₃ , EtAlCl ₂ /HPT/TiCl ₃ , and Et ₂ AlCl/HPT/TiCl,, catalysts (B -,N = tributylamine; HPT = tributylamine; HPT = hexamethyl-phosphoric tri- amide), and the polymerizations may be conducted at

te peratures as low as about 70 C.

The following test methods are the ones used to evaluate the hot-melt, pressure-sensitive adhesives of this invention. 1. The melt viscosities of the adhesives are determined according to ASTM Procedure D1238 or in a Brookfield Thermosel Viscometer made by Brookfield Engineering Laboratories, Inc.

2. The glass transition temperatures of the ad- hesives are determined using a differential scanning calorimeter (Perkin-Elmer DSC-2 in¬ strument) operating over the range of -70 C. to +200°C.

3. The Ring and Ball softening points of the tackifying resins are determined according to ASTM Procedure E28.

-4. The probe tack values of the coated tapes are determined according to the method as described by Testing Machines, Inc., Amityville, New York the- manufacturer of the Polyken Probe Tack

Tester (Model TMIδO-2). The probe tack values are determined at 23 C. with the Polyken Probe

Tack Tester using a 0.5 cm diameter probe, 100

2 g/cm contact pressure, two-second contact time, and 2 cm/second separation speed.

5. The l8θ peel adhesion values of the coated tapes are determined according to the Pres¬ sure Sensitive Tape Council's PSTC-1 test. The amount of adhesive residue left on the stainless steel testing panels when the bonds are tested is also noted.

6. The shear adhesion failure times of the coated tapes are determined according to the Pressure Sensitive Tape Council's PSTC-7 test. 7. The bleed-through (staining) resistance of the

adhesives is determined by coating the adhes¬ ives from the melt (190°C.) 0.001 to 0.002 inches thick on 60 pound Kro ekote paper with a heated doctor blade. The coated paper tapes are then aged at 70°C. in a forced draft oven, and the degree of bleed-through on the paper backing is visually observed periodically up to four weeks .

8. The thermal stabilities of the adhesives are determined by heating the adhesives to 177°C. in the presence of air for 24 hours in a Brook¬ field Thermosel viscometer. As a measure of thermal stability, the melt viscosities of the adhesives are determined with the viscometer at 177°C. after 1, 4, 8, 12 and 24 hours and differences from the initial melt viscosity are noted. Char and film formation are also noted.

9. The compatibilities of the various base copoly¬ mers with the tackifying resins (and plasti- cizing oils) are determined by melting samples

^' of each blend between glass microscope slides. The temperature of the melt is raised to 150 C, photomicrographs are made, and phase separa¬ tion (if any) is noted. 10. Heat of fusion by Differential Scanning Calori- etry.

In order to meet the requirements for a wide range of hot-melt, pressure-sensitive adhesive applica¬ tions, the adhesives of this invention generally have properties which fall within the following ranges: Glass transition temperature, C 0 to -40 Probe tack, g. 400 to 1500

Peel adhesion, pound/inch 1 to ^* 10

Shear adhesion failure time, minutes ^200 toτ>-10,000 The following examples show the unpredicted and surprising advantages obtained when compatible

tackifiers and plasticizing oils are used as modifiers according to the teachings of this invention. For ex¬ ample, the addition of compatible tackifiers and plas¬ ticizing oils to substantially amorphous or semicrys- talline olefin copolymers of at least one α-olefin selected from propylene, 1-butene, and 1-pentene and at least one higher α-olefin of 6 to 10 carbon atoms and having a melt viscosity of about 5,000 to 1,000,000 cp at 190 C. provides adhesives having unexpectedly high shear adhesion failure time in addition to high probe tack and peel adhesion values relative to unmodified copolymers of comparable melt viscosities. It should be noted that the values obtained will depend somewhat on the degree of homogenization of the blend as well as on the thickness and smoothness of the polymer coat¬ ing. Thus, the pressure-sensitive properties of the blends of this invention may vary by as much as 10-25 depending on the blend method and on the quality of the coating. The pressure-sensitive adhesive compositions of this invention are prepared by blending together the compatible tackifiers and plasticizing oils with the co¬ polymers in the melt at a temperature of 160°C. to 200 C. until a homogeneous blend is obtained. Various methods of blending materials of this type are known to the art and any method that produces a homogeneous blend is sat¬ isfactory. These components blend easily in the melt and a heated vessel equipped with a stirrer is all that is required. In addition to the polyolefin, tackifier and plasticizing oil, it is desirable for the hot-melt pressure-sensitive adhesive composition to contain 0.1 to 1.5 percent by weight, preferably 0.25 percent to 1.0 percent by weight, of one or more stabilizers or antioxidants. Antioxidants that are^effective for each of the various components can be used. Such antioxidants include, for example, "Ionox" 220 and 330 [tris(di-t-

_ Q _

butyl-p-hydroxybenzyl)-trimethylbenzene], "Dalpac" 4C2 [2,6-di(t-butyl)-p-cresol], "Naugawhite" (alkylated bisphenol), "Butyl Zimate" (zinc dibutyl diethiocarba- mate), and "Ethyl" 702 [ , '-methylene bis(2,6-di-tert- butylphenol)] . A particularly effective antioxidant is Irganox 1010 which is identified as pentaerythritol te- trakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] . There are numerous uses for the pressure-sen¬ sitive adhesives of the present invention. ^' One such use is in the construction of women's sanitary napkins. A strip of the pressure-sensitive ^' adhesive may be applied to the polyethylene shield of the napkin and then pro¬ tected by a release sheet. At the time of use, the re¬ lease sheet is removed and the napkin is held in place by adhering the pressure-sensit.ive adhesive to the under¬ garment, thus eliminating the need for belts and pins. Removal of the napkin is quick as it strips cleanly from the garment.

Another use of the adhesives of this invention is in the construction of floor tiles having a preapplied adhesive for the do-it-yourself market. The pressure- sensitive adhesive is thinly coated onto the undersurface of such floor tiles and covered with a protective re¬ lease sheet. Quick and permanent installation of the floor tiles is accomplished by removing the release sheet and pressing the tile into place. This technique of installing floor tiles can be extended to other types of coverings such as wall tiles and ceiling tiles. Other major uses for the pressure-sensitive adhesives include their use on tapes and labels.

This invention can be further illustrated by the following examples. EXAMPLE 1

Poly(56-propylene-co-44-[l-hexene_]) £20 g; 100,000 cp at 190°C. by ASTM D1238 using a Tinius Olsen

Melt Indexer with, an Q,Q4-inch orifice and 2160 g weight], 16 g of Wingtack 95 tackifying resin syn¬ thetic polyterpene hydrocarbon type tackifying resin based on a C_- olefin fraction; Ring and Ball softening point = 100+5 C, iodine number = 30, specific gravity = 0.93); 4 g of Shellflex 371 plasticizing oil: and 0.1 g of Irganox 1010 antioxidant ( entaerythritol tetrakisl3-(.3,5-ditertbutyl-4-hydroxyphenyl)propicnate]) were melt blended at 175°C. for 30 minutes under an atmosphere of nitrogen. Shellflex 371 is a plasticizing oil sold by Shell Oil Company. The oil has a specific gravity at 6θ°F. (15°C.) of 0.9007, a boiling point range of 710-865°F. (376-462°C. ) , a refractive index at 20 C. of 1.4908 and having a carbon atom analysis of 3$ aromatic carbon, 4$ napthenic carbon and 53$ paraf¬ finic carbon. The clear compatible blend was removed from the mixer and allowed to cool to 23 C, the blend was very tacky to the touch. The melt viscosity of the blend was 23,200 cp at 190°C. A sample of the blend was maintained at 177 C. for 24 hours in contact with air. The sample did not change in melt viscosity during this period and it did not show any evidence of char formation or film forma¬ tion on the surface of the melt. The melt is clear and compatible.

The blend was coated from the melt (190°C.) 0.001 +0.0002 inch thick onto Mylar film (0.001 inch thick) using a heated doctor blade. The resulting pres¬ sure-sensitive tapes were transparent and had a probe tack value of 1190 g/0.5 cm diameter probe and a l8θ peel adhesion value of 6.1 pounds/inch-width after the tapes were aged for 24 hours at 23°C. and 50$ relative humidity. No adhesive residue was left when the coated tapes were peeled from the stainless steel test panels. The tapes had shear adhesion failure times of greater

than 1,660 minutes when using a 1000 g static load per square inch of bond area. The probe tack and l8θ° peel adhesion values were not changed when tapes were aged for one week at 50 C. Coated tapes made using 60 pound Kromekote paper were aged in an oven at 7Q C. for four weeks. These aged paper tapes showed no evidence of bleed-through. Similarly good results were achieved using Wingtack 115 tackifying resin (Ring and Ball sof¬ tening point = 115-120°C.-, molecular weight = 1400 to 1500) instead of Wingtack 95. EXAMPLE 2

The procedure of Example 1 was repeated except that 20 g of poly(8θ-propylene-co-20-[l-hexene_]) having a melt viscosity of 30,000 cp at 190 C. was blended with 16 g of Wingtack 95 and 4 g of Shellflex 371 oil to pre¬ pare a blend having a melt viscosity of 4,800 cp at 190 C. Pressure-sensitive tapes made with this blend had a probe tack value of 1030 g/0.5 cm diameter probe, a peel adhesion value of 6.3 pounds/inch, and a shear adhesion failure time of 7100 minutes. Similarly good results can be obtained using a poly(8θ-[l-butene]-co- 20-[l-hexene]) instead of the poly(8θ-propylene-co-20- [1-hexene]) . EXAMPLE 3 The procedure of Example 1 was repeated except that 20 g of poly(68-propylene-co-32-[l-hexene]) having a melt viscosity of 22,500 cp at 190°C. was melt blended with 16 g of Wingtack 95 resin and 4 g of Shellflex 371 oil to provide a blend with a melt viscosity of 4,070 cp at 190°C. (by Brookfield Thermosel method). This blend was compatible and pressure-sensitive tapes made with this blend had a probe tack value of 1060 g/Q.5 cm dia¬ meter probe, a peel adhesion value of 7-3 pounds/inch, and a shear adhesion failure time of 5120 minutes. Si - ilarly good results can be obtained using a poly(70-

[l-pentene]-co-30-[l-hexene]) instead of the poly(68- propylene-co-32-[l-hexene]) . EXAMPLE 4

The procedure of Example 1 was repeated except that 20 g of poly(54-propylene-co-46-[l-hexene3) having a melt viscosity of 23,690 cp at 190°C. by (ASTM D1238) was melt blended with 16 g of Wingtack 95 resin and 4 g Shellflex 371 oil to provide a blend with a melt vis¬ cosity of 4,170 cp at 190°C. (by Brookfield Thermosel method) . This blendwas compatible and pressure sensi¬ tive tapes made from this blend had a probe tack value of 1280 g/0.5 cm diameter probe, peel adhesion value of 7.3 pounds/inch, and a shear adhesion failure time of 19 minutes. EXAMPLE 5

The procedure of Example 1 was repeated except that 20 g of a poly(78-propylene-co-22-[l-hexene]) hav¬ ing a melt viscosity of 135,000 cp at 190°C. (by ASTM D1238) v/as blended with 16 g of Wingtack 95 resin and 4 g Shellflex 371 oil to provide a blend having a melt viscosity of 24,200 cp at 190°C. (by Brookfield Ther¬ mosel method) . Pressure-sensitive tapes made with this blend had a probe tack value of 1050 g/0.5-cm diameter probe, a peel adhesion value of 6.4 pounds/inch, and a shear adhesion failure time of >10,000 minutes. EXAMPLE 6

The procedure of Example 1 was repeated except that 20 g of poly(71-propylene-co-29-[l-hexene_]) having a melt viscosity of 75,000 cp at 19 ^* 0°C. (by ASTM DI238) was blended with 16 g of Wingtack 95 resin and 4 g of Shellflex 371 oil to provide a blend having a melt vis¬ cosity of 12,000 cp at 190°C. (by Brookfield Thermosel method). Pressure-sensitive tapes made with this blend had a probe tack value of 1110 g/0.5-cm diameter probe, a peel adhesion value of 6.5 pounds/inch, and a shear

adhesion failure time of 8150 minutes. EXAMPLE 7

The procedure of Example 1 was repeated except that 20 g of poly(69-propylene-co-31-[l-hexene]) having a melt viscosity of 202,000 cp at 190°C. (by ASTM D1238) was blended with 16 g of Wingtack 95 resin and 4 g of Shellflex 371 oil to provide a blend having a melt vis¬ cosity of 51,200 cp at 190°C. (by Brookfield Thermosel method) . Pressure-sensitive tapes made with this blend had a probe tack value of 990 g/0.5-cm diameter probe, a peel adhesion value of 6.6 pounds/inch, and a shear adhesion failure time of 8150 minutes. EXAMPLE 8

The procedure of Example 1 v/as repeated except that 32 g of poly(50-propylene-co-50-[l-hexene]) having a melt viscosity of 240,000 cp at 190°C. (by ASTM D1238) was blended with . g of Wingtack 95 and -4 g of Shellflex 371 oil to prepare a blend having a melt viscosity of 74,400 cp at 190°C. (by ASTM D1238 method). Pressure- sensitive tapes made with this blend had a probe tack value of 570 g/0.5-cm diameter probe, a peel adhesion value of 3-0 pounds/inch, and a shear failure time of 2320 minutes. EXAMPLE 9 The procedure of Example 1 was repeated except that 26 g of poly(50-propylene-co-50-[l-hexene]) having a melt viscosity of 240,000 cp at 190°C. (by ASTM D1238 method) was blended with 6 g of Wingtack 95 and 8 g of Shellflex 371 oil to prepare a blend having a melt vis- cosity of 24,200 cp at 190°C. (by ASTM D1238 method). Pressure-sensitive tapes made with this blend had a probe tack value of 580 g/0.5-cm diameter probe, a peel adhesion value of 2.2 pounds/inch, and a shear adhesion failure time of 4770 minutes.

EXAMPLE 10

The procedure of Example 1 was repeated except that 26 g of poly(50-propylene-co-50-ri-hexene]) having a melt viscosity of 240,000 cp at 190°C. (by ASTM D1238 method) was blended with 10 g of Wingtack 95 and 4 g of Shellflex 371 oil to prepare a blend having a melt vis¬ cosity of 31,000 cp at 190°C. (by ASTM D1238 method). Pressure-sensitive tapes made with this blend had a probe tack value of 820 g/0.5-cm diameter probe, a peel adhesion value of 3-0 pounds/inch, and a shear adhesion failure time of 2640 minutes. EXAMPLE 11

The procedure of Example 1 was repeated except that 20 g of poly(50-propylene-co-50-[l-hexene]) having a melt viscosity of 240,000 cp at 190°C. (by ASTM D1238 method) was blended with 16 g of Wingtack 95 and 4 g of Shellflex 371 oil to prepare a blend having a melt vis¬ cosity of 14,400 cp at 190°C. (by ASTM D1238 method). Pressure-sensitive tapes made with this blend had a probe tack value of 960 g/0.5-cm diameter probe, a peel adhesion value of 5.1 pounds/inch, and a shear adhesion failure time of 38OO minutes. EXAMPLE 12

The procedure of Example 1 was repeated except that 18 g of poly(50-propylene-co-50-[l-hexene]) having a melt viscosity of 240,000 cp at 190°C. (by ASTM D1238 method) v/as blended with 14 g of Wingtack 95 and 8 g of Shellflex 371 oil to prepare a blend having a melt vis¬ cosity of 5880 cp at 190°C. (by ASTM D1238 method). Pressure-sensitive tapes made with this blend had a probe tack value of 790 g/0. 5- ^~~ - diameter probe, a peel adhesion value of 3-5 pounds/inch, and a shear adhesion failure time of 4560 minutes. EXAMPLE 13 The procedure of Example 1 v/as repeated except

that 26 g of poly(47-propylene-co-53-[l-hexene]) having a melt viscosity of 19,600 cp at 190°C. (by ASTM D1238 method) was blended with 10 g of Wingtack 95 and 4 g of Shellflex 371 oil to prepare a blend having a melt vis¬ cosity of 3770 cp at 190°C. (by ASTM D1238 method). Pressure-sensitive tapes made with this blend had a probe tack value of 910 g/0.5-cm diameter probe, a peel adhesion value of 4.2 pounds/inch, and a shear adhesion failure time of 130 minutes. EXAMPLE 14

The procedure of Example 1 was repeated except that 26 g of poly(48-propylene-co-52-[l-hexene_]) having a melt viscosity of 100,000 cp at 190°C. (by ASTM D1238 method) was blended with 10 g of Wingtack 95 and 4 g of Shellflex 371 oil to prepare a blend having a melt vis¬ cosity of 14,830 cp at 190°C. (by ASTM D1238 method). Pressure-sensitive tapes made with this blend had a probe tack value of 970 g/0.5-cm diameter probe, a peel adhesion value of 4.0 pounds/inch, and a shear adhesion failure time of 670 minutes. EXAMPLE 15

The procedure of Example 1 was repeated except that 26 g of poly(49-propylene-co-51-[l-hexene_]) having a melt viscosity of 290,000 cp at 190°C. (by ASTM D1238) was blended with 10 g of Wingtack 95 and 4 g of Shellflex 371 oil to prepare a blend having a melt viscosity of 43,400 cp at 190°C. (by ASTM D1238 method). Pressure- sensitive tapes made with this blend had a probe tack value of 970 g/0.5-cm diameter probe, a peel adhesion value of 3-4 pounds/inch, and a shear adhesion failure time of 3320 minutes. EXAMPLE 16

The procedure of Example 1 was repeated except that 26 g of poly(54-propylene-co-46-[l-hexene_]) having a melt viscosity of 820,000 cp at 19Q°C. (by ASTM D1238)

was blended with 10 g of Wingtack 95 and 4 g of Shellflex 371 oil to prepare a blend having a melt viscosity of 116,000 cp at 190°C. (by ASTM D1238 method). Pressure- sensitive tapes made with this blend had a probe tack value of 970 g/0.5-cm diameter probe, a peel adhesion value of 3-3 pounds/inch, and a shear adhesion failure - time of 4600 minutes. EXAMPLE 17

The procedure of Example 1 was repeated except that 20 g of poly(50-propylene-co-50-[l-hexene] ) having a melt viscosity of 300,000 cp at 190°C. (by ASTM D1238 method) was blended with 16 g of Wingtack 95 and 4 g of Eastman Plasticizer H, a DAC-B oil, to prepare a blend having a melt viscosity of 11,200 cp at 190°C. (by ASTM D1238 method) . Pressure-sensitive tapes made with this blend had a probe tack value of 1300 g/0.5-cm diameter probe, a peel adhesion value of 3-8 pounds/inch, and a shear adhesion failure time of 3050 minutes. EXAMPLE 18 The procedure of Example 1 is repeated except that 20 g of poly(50-propylene-co-50-£l-hexene_]) having a melt viscosity of 300,000 cp at 190°C. (by ASTM D1238 method) is blended with 16 g of Wingtack 95 and 4 g of Kodaflex TOTM plasticizer, trioctyl trimellitate, to prepare a blend having a melt viscosity of 9900 cp at

190°C. (by ASTM DI238 method). Pressure-sensitive tapes made with this blend had a probe tack value of 1130 g/0-5 cm diameter probe, a peel adhesion value of 4.6 pounds/inch, and a shear adhesion failure time of 2870 minutes. EXAMPLE 19

The procedure of Example 1 is repeated except that 20 g of poly(propylene-co-50-[l-hexene]) having a melt viscosity of 300,000 cp at 190°C. (by ASTM D1238 method) was blended with 16 g of Wingtack 95 tackifier

-17-

and 4 g of Wingtack 10 oil and a liquid polyterpene with a molecular weight of 490, to prepare a blend hav¬ ing a melt viscosity of 12,000 cp at 190°C. (by ASTM D1238 method) . Pressure-sensitive tapes made with this blend had a probe tack value of 9 g/0.5-cm diameter probe, a peel adhesion value of 5 - 0 pounds/inch, and a shear adhesion failure ..

EXAMPLE 20

The procedure of Example 1 is repeated except that 20 g of poly(50-propylene-co-50-[l-hexene]) having a melt viscosity of 300,000 cp at 190°C. (by ASTM DI238 method) was blended with 16 g of Wingtack 95 and 4 g of Indopol H-100 oil (low molecular weight liquid polyiso- butylene) to prepare a blend having a melt viscosity of 12,800- cp at 190°C. (by ASTM D1238 method). Pressure- sensitive tapes made with this blend had a probe tack value of 1190 g/0.5-cm diameter probe, a peel adhesion value of 6.5 pounds/inch, and a shear adhesion failure time of 4910 minutes. EXAMPLE 21

The procedure of Example 1 is repeated except that 15.4 g of poly(50-propylene-co-50-[l-hexene]) having a melt viscosity of 850,000 cp at 190°C. (by ASTM D1238 method) was blended with 15.4 g of Wingtack 95 and 9.2 g of Shellflex 371 oil to prepare a blend having a melt viscosity of 41,500 cp at 190°C. (by ASTM DI238 method). Pressure-sensitive tapes made with this blend had a probe tack value of 98O g/0.5-cm diameter probe, a peel adhe¬ sion value of 4.6 pounds/inch, and a shear adhesion fail- ure time of 71 minutes. EXAMPLE 22

The procedure of Example 1 was repeated except that 22 g of poly(50-propylene-co-50-[l-hexene]) having a melt viscosity of 850,000 cp at 190°C. (by ASTM D1238 method) was blended with 16- g of Wingtack 95 and 2 g of Shellflex 371 oil to prepare a blend having a melt vis¬ cosity of 47,600 cp at 190°C. (by ASTM D1238 method).

Pressure-sensitive tapes made with this blend had a probe tack value of 1066 g/0.5-cm diameter probe, a peel ad¬ hesion value of 5-8 pounds/inch, and a shear adhesion failure time of 6780 minutes. EXAMPLE 23

The procedure of Example 1 was repeated except that 20 g of poly(4θ-propylene-co-6θ-[l-hexene]) having a melt viscosity of 350,000 cp at 190°C. (by ASTM DI238 method) was blended with 16 g of Wingtack 95 and 4 g of Shellflex 371 oil to prepare a blend having a melt vis¬ cosity of 19,700 cp at 190°C. (by ASTM D1238 method). Pressure-sensitive tapes made with this blend had a probe tack value of 1270 g/0.5-cm diameter probe, a peel ad¬ hesion value of 5.8 pounds/inch, and a shear adhesion failure time of i860 minutes. EXAMPLE 24

The procedure of Example 1 was repeated except that 34 g of poly(55-propylene-co-45-[l-hexene]) having a melt viscosity of 150,000 cp at 190°C. (by ASTM DI238 method) was blended with 2 g of Wingtack 95 and 4 g of Shellflex 371 oil to prepare a blend having a melt vis¬ cosity of 48,500 cp at 190°C. (by ASTM D1238 method). Pressure-sensitive tapes made with this blend had a probe tack value of 640 g/0.5-cm diameter probe, a peel adhe- sion value of 3-9 pounds/inch, and a shear adhesion failure time of 2560 minutes. EXAMPLE 25

The procedure of Example 1 was repeated except that 20 g of poly(85-propylene-co-15-[l-hexene]) having a melt viscosity of 148,000 cp at 190°C. (by ASTM D1238 method) was blended with 16 g of Wingtack 95 and 4 g of Shellflex 371 oil to prepare a blend having a melt vis¬ cosity of 26,300 cp at 190°C. (by Brookfield Thermosel method). Pressure-sensitive tapes made with this blend had a probe tack value of 715 g/0.5-cm diameter probe,

a peel adhesion value of 5-1 pounds/inch, and a shear adhesion failure time of >10,000 minutes. A small piece of the base copolymer used in this example was annealed in an oven at 70 C. for 4 hours. This annealed sample is placed in the sample holder of a Differential Scann¬ ing Calorimeter, cooled to -70°C, and heated with a heating rate of 20 C. per minute to a maximum tempera¬ ture of 175°C. The sample has a Tg value of -15°C. and low, broad melting endotherms at 85°C. and l4θ°C. Based on the area under these two endotherms, the Δli.-, value for this copolymer was calculated to be 2.9 calories per gram. EXAMPLE 26

The procedure of Example 1 was repeated except that 15.2 g of poly(57-propylene-co-28-[l-butene]-co- 15-[l-hexene]) having a melt viscosity of 260,800 cp at 190°C (by ASTM D1238 method) was blended with 24 g of Wingtack 95 and 0.8 g of Shellflex 371 oil to prepare a blend having a melt viscosity of 17,200 cp at 190 C (by ASTM D1238 method) . Pressure-sensitive tapes made with this blend had a probe tack value of 970 g/0.5-cm diameter probe, a peel adhesion value of 5«6 pounds/inch, and a shear adhesion failure time of 2280 minutes. EXAMPLE 27 The procedure of Example 1 v/as repeated except that 20 g of poly(4θ-propylene-co-30-[l-hexene]-co-15- [l-octene]-co-15-[l-decene]) having a melt viscosity of 278,000 cp at 190°C (by ASTM D1238 method) was blended with 16 g of Eastman Resin H-100 tackifier and 4 g of Shellflex 371 oil to prepare a blend having a melt vis¬ cosity of 15,400 cp at 190°C (by ASTM D1238 method). Pressure-sensitive tapes made with this blend had a probe tack value of 910 g/0.5-cm diameter probe, a peel adhesr ion value of 5•0 pounds/inch, and a shear adhesion fail- ure time of 386O minutes.

EXAMPLE 28

The procedure of Example 1 was repeated except that 20 g of poly(45-propylene-co-10[l-butene]-co-5- [l-pentene]-co-4θ-[l-hexene]) having a melt viscosity of 243,100 cp at 190°C. (by ASTM D1238 method) is blended with 16 g of Zonarez 7100 tackifier, a polyterpene resin, and 4 g of Shellflex 371 oil to prepare a blend having a melt viscosity of 12,600 cp at 190°C. (by ASTM D1238 method) . Pressure-sensitive tapes made with this blend had a probe tack value of 1090 g/0.5-cm diameter probe, a peel adhesion value of 5-4 pounds/Inch, and a shear

adhesion failure time of 3350 minutes. EXAMPLE 29

The procedure of Example 1 was repeated except that 20 g of poly(50-propylene-co-50-£l-hexene]) having a melt viscosity of 250,000 cp at 190°C. (by ASTM D1238 method) was blended with 16 g of Wingtack 95 tackifier and 4 g of methyl abietate to prepare a blend having a melt viscosity of 12,800 cp at 190°C. (by ASTM D1238 method) . Pressure-sensitive tapes made with this blend

10 had a probe tack value of 1010 g/0.5-cm diameter probe, a peel adhesion value of 5-9 pounds/inch, and a shear adhesion failure time of 3540 minutes. Similarly good results were achieved when abietol was used instead of methyl abietate.

!5 EXAMPLE 30

The procedure of Example 1 was repeated except that 20 g of poly(65-propylene-co-35-£l-hexene]) having a melt viscosity of 560,000 cp at 190°C. (by ASTM D1238 method) was blended with 16 g of Wingtack 95 and 4 g of

²⁰ Shellflex 371 oil to prepare a blend having a melt vis¬ cosity of 33,600 cp at 190°C. (by ASTM D1238 method). Pressure-sensitive tapes made with this blend had a probe tack value of 1170 g/0.5-cm diameter probe, a peel adhesion value of 6.5 pounds/inch, and a shear

² 5 adhesion failure time of greater than 10,000 minutes. EXAMPLE 31

The procedure of Example 1 was repeated except that 20 g of poly(48-propylene-co-52-£l-hexene ) having a melt viscosity of 1,000,000 cp at 190°C. (by ASTM

3° D1238 method) was blended with 16 g of Wingtack 95 and 4 g of Shellflex 371 to prepare a blend having a melt viscosity of 60,200 cp at 190°C. (by ASTM D1238 method). Pressure-sensitive tapes made with this blend had a probe tack value of 920 g/0.5-cm diameter probe, a peel

35 adhesion value of 5-5 pounds/inch, and a shear adhesion

value of 5-5 pounds/inch, and a shear adhesion failure time of 6200 minutes. EXAMPLE 32

The procedure of Example 1 was repeated except that 20 g of poly(50-propylene-co-50-£l-hexene]) having a melt__viscosity of 250,000 cp at 190°C. (by ASTM D1238 method) was blended with 16 g of Wingtack 95 and 4 g of Kaydol plasticizing oil to prepare a blend having a melt viscosity of 13,800 cp at 190°C. (by ASTM D1238 method) . Kaydol plasticizing oil is comprised essen¬ tially of paraffinic and naphthenic hydrocarbons and is sold by Witco Chemical Company. Pressure-sensitive tapes made with this blend had a probe tack value of 990 g/0.5-cm diameter probe, a peel adhesion value of 4.8 pounds/inch, and a shear adhesion failure time of 3660 minutes. EXAMPLE 33

The procedure of Example 1 was repeated except that 20 g of poly(50-propylene-co-50-£l-hexene]) having a melt viscosity of 250,000 cp at 190°C. (by ASTM D1238 method) was blended with 16 g of Wingtack 95 and 4 g of Tufflo 6204 plasticizing oil to prepare a blend having a melt viscosity of 15,500 cp at 190°C. (by ASTM D1238 method). Tufflo 6204 is a plasticizing oil consisting essentially of paraffinic and naphthenic hydrocarbons and sold by Arco Chemical Company. Pressure-sensitive tapes made with this blend had a probe tack value of 1030 g/0.5-cm diameter probe, a peel adhesion value of 5.3 pounds/inch, and a shear adhesion failure time of 4050 minutes. EXAMPLE 34

The procedure of Example 1 was repeated except that 20 g of poly(75-propylene-co-25-£l-hexene_]) having a melt viscosity of 10,500 cp at 190°C. (by ASTM D1238 method) was blended with 16 g of Wingtack 95 and 4 g of

Shellflex 371 oil to prepare a blend having a melt vis¬ cosity of 1260 cp at 190°C. (by Brookfield Thermosel method). Pressure-sensitive tapes made with this blend had a probe tack value of ll4θ g/0.5-cm diameter probe, a peel adhesion value of 5-7 pounds/inch, and a shear adhesion failure time of 3610 minutes. EXAMPLE 35

The procedure of Example 1 was repeated except that 18 g of poly(51-propylene-co-49-£l-hexene]) having a melt viscosity of 235,000 cp at 190°C. (by ASTM D1238 method) was blended with 12 g of Wingtack 95 and 10 g of Shellflex 371 oil to prepare a blend having a melt viscosity of 5500 cp at 190°C. (by ASTM D1238 method). Pressure-sensitive tapes made with this blend had a probe tack value of 690 g/0.5-cm diameter probe, a peel adhe¬ sion value of 3.6 pounds/inch, and a shear adhesion failure time of 2560 minutes. EXAMPLE 3

The procedure of Example 1 was repeated except that 20 g of poly(75-propylene-co-25-£l-hexene]) having a melt viscosity of 5000 cp at 190°C. (by ASTM D1238 method) was blended with 16 g. of Wingtack 95, and 4 g of Shellflex 371 to prepare a blend having a melt vis¬ cosity of 1275 cp at 190°C. (by Brookfield Thermosel method) . Pressure-sensitive tapes made with this blend had a probe tack value of 960 g./0.5-cm diameter probe and a peel adhesion value of 5-2 pounds/inch. EXAMPLE 37

The procedure of Example 1 was repealed except that 10 g. of poly(76-propylene-co-24-£l-hexene]) having a melt viscosity of 202,000 cp at 190°C. (by melt index method) was blended with 24 g. of Wingtack 95 and 6 g. of Shellflex 371 to prepare a blend having a melt vis¬ cosity of 2750 cp at 190°C. (by Brookfield Thermosel method). Pressure-sensitive tapes made with this blend

had a probe tack value of 439 g/0.5-cm diameter probe, a peel adhesion value of 5-6 pounds/inch, and a shear adhesion failure time of 6920 minutes.

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