Adhesive composition

Abstract

This application is, (A) Ethylene / α-olefin elastomer and (B) Functionalized ethylene / α-olefin interpolymer, (C) Rosin-based tackifier and (D) Provides an adhesive composition comprising a hydrocarbon-based tackifier.

Description

[Technical Field]

[0001] This application generally relates to adhesive compositions comprising polyolefin elastomers and rosin ester derivatives.

[0002] (cross reference) This application claims priority to U.S. Provisional Patent Application No. 63 / 579872, filed on 31 August 2023, and U.S. Provisional Patent Application No. 63 / 504983, filed on 30 May 2023, the respective contents of which are incorporated herein by reference in whole. [Background technology]

[0003] In the adhesives industry, polyolefin elastomers are commonly compounded with hydrogenated tackifiers for hot melt adhesives (HMAs) to achieve superior adhesive performance. However, hydrogenated tackifiers are expensive to manufacture and can become scarce when petroleum raw material supplies become tight. An attractive alternative to hydrogenated tackifiers is rosin-based tackifiers (tackifiers derived from rosin). Rosin-based tackifiers are derived from naturally occurring hydrocarbon secretions of many plants and are less expensive than hydrogenated tackifiers. However, rosin-based tackifiers are inherently incompatible with polyolefin elastomers. Therefore, there is a need for new adhesive compositions that offer improved compatibility between polyolefin elastomers and rosin-based tackifiers, as well as suitable adhesive performance. [Overview of the Initiative]

[0004] This application is, (A) Ethylene / α-olefin elastomer and (B) Functionalized ethylene / α-olefin interpolymer, (C) Rosin-based tackifier and (D) Provides an adhesive composition comprising a hydrocarbon-based tackifier. [Brief explanation of the drawing]

[0005] [Figure 1A] This diagram depicts the cloud point curve for blends containing AFFINITY® GA 1950 and SYLVALITE® 2200 rosin esters. [Figure 1B] This diagram depicts the cloud point curve for blends containing AFFINITY® GA 1950 and SYLVALITE® 2200 rosin esters. [Figure 2] The cloud point curves of the blends containing AFFINITY® GA 1950, AFFINITY® GA 1000R, and SYLVALITE® 2200 rosin ester tackifier and hydrogenated hydrocarbon tackifier in a 1:1 ratio, as described in Examples 9, 10, and 11 of the Invention, are plotted. [Figure 3] The cloud point curves for AFFINITY® GA 1950, AFFINITY® GA 1000R, and SYLVALITE® 2200 rosin ester tackifiers and hydrogenated hydrocarbon tackifiers in a 1:1 ratio, as described in Examples 9, 10, and 11 of the Invention, are plotted, along with the control cloud point curves for AFFINITY® GA 1950 and SYLVALITE® 2200 rosin esters. [Figure 4] Table 8 illustrates the increase in the cloud point (°C) of the adhesive formulations of the invention. [Figure 5] Table 8 describes two regions of cloud point behavior as a function of the rosin ester tackifier for the adhesive formulations of the invention. [Figure 6] Table 8 describes the cloud point of the blended compositions as a function of the GA 1000R polymer, based on TST results, for the adhesive formulations of the invention.

[0006] definition Unless otherwise stated, implied by the context, or customary in the art, all parts and percentages are based on weight, and all test methods are current as of the filing date of this disclosure.

[0007] Any reference to the Periodic Table of Elements refers to the Periodic Table of Elements published by CRC Press, Inc., 1990–1991. References to element groups in this table refer to a new notation for numbering groups. For the purposes of U.S. patent practice, any referenced patent, patent application, or publication is incorporated by reference in its entirety (or an equivalent U.S. version is incorporated by reference) particularly with respect to definition disclosures (to the extent that they do not conflict with any definitions specifically provided herein) and general knowledge in the art. Numerical ranges disclosed herein include all values ​​from the lower limit to the upper limit (including the lower and upper limits). Ranges containing explicit values ​​(e.g., 1 or 2, or 3–5, or 6 or 7) include any subrange between any two explicit values ​​(e.g., 1–2, 2–6, 5–7, 3–7, 5–6, etc.).

[0008] An adhesive composition is a mixture of components capable of bonding together target substrates under the application of heat and / or pressure. A non-limiting example of a suitable adhesive composition is a hot melt adhesive (HMA) composition. A hot melt adhesive (HMA) composition is a mixture of components capable of bonding together target substrates under the application of heat, or more typically, heat and pressure.

[0009] The term "alkyl group" refers to an organic radical derived from an aliphatic hydrocarbon by removing one hydrogen atom from it. Alkyl groups may be linear, branched, cyclic, or a combination thereof. In embodiments, alkyl groups are C1-C 20 It is an alkyl group.

[0010] The term "composition" refers to a mixture of materials containing the composition, as well as reaction and decomposition products formed from the materials of the composition.

[0011] The terms "comprising," "including," "having," and their derivatives are not intended to exclude the presence of any additional components, steps, or procedures, whether or not specifically disclosed. To avoid any doubt, all compositions claimed through the use of the term "comprising" may contain any additional additives, adjuvants, or compounds, whether polymeric or otherwise, unless otherwise specified. In contrast, the term "consisting essentially of" excludes any other components, steps, or procedures, except those that are not essential to the operability, from the scope of any subsequent recitation. The term "consisting of" excludes any component, step, or procedure not specifically described or enumerated.

[0012] An "ethylene polymer" or "ethylene-based polymer" is a polymer that contains a majority amount of polymerized ethylene based on the weight of the polymer and optionally may contain at least one comonomer. An "ethylene-based interpolymer" is an interpolymer that contains a majority amount of ethylene and at least one comonomer in polymerized form based on the weight of the interpolymer. Preferably, the ethylene-based interpolymer is a random interpolymer (i.e., including a random distribution of its monomeric constituents). Non-limiting examples of suitable ethylene-based interpolymers are ethylene plastomers / elastomers.

[0013] An "ethylene / α-olefin interpolymer" is an interpolymer that contains a majority amount of polymerized ethylene and at least one α-olefin based on the weight of the interpolymer. An "ethylene / α-olefin copolymer" is an interpolymer that contains a majority amount of polymerized ethylene and an α-olefin as only two monomer types based on the weight of the copolymer.

[0014] "Ethylene plastomer / elastomer" is a substantially linear or linear ethylene / α-olefin copolymer containing units derived from ethylene and units derived from at least one C3-C 10 α-olefin comonomer, or at least one C4-C8 α-olefin comonomer, or at least one C6-C8 α-olefin comonomer, and having a uniform short-chain branching distribution. The ethylene plastomer / elastomer has a density of 0.870 g / cc, or 0.880 g / cc, or 0.890 g / cc to 0.900 g / cc, or 0.902 g / cc, or 0.904 g / cc, or 0.909 g / cc, or 0.910 g / cc, or 0.917 g / cc. Non-limiting examples of ethylene plastomers / elastomers include AFFINITY™ plastomers and elastomers (available from The Dow Chemical Company), EXACT™ Plastomers (available from ExxonMobil Chemical), Tafmer™ (available from Mitsui), Nexlene™ (available from SK Chemicals Co.), and Lucene™ (available from LG Chem Ltd.).

[0015] The term "heteroatom" refers to an atom other than carbon or hydrogen. Non-limiting examples of suitable heteroatoms include F, Cl, Br, N, O, P, B, S, Si, Sb, Al, Sn, As, Se, and Ge. The terms "hydrocarbyl" and "hydrocarbon" refer to substituents containing only atoms of hydrogen and carbon, including branched or unbranched, saturated or unsaturated, cyclic, polycyclic, or acyclic species. Non-limiting examples include alkyl groups, cycloalkyl groups, alkenyl groups, alkadienyl groups, cycloalkenyl groups, cycloalkadienyl groups, aryl groups, and alkynyl groups.

[0016] An "interpolymer" is a polymer prepared by the polymerization of at least two different types of monomers. Therefore, the general term interpolymer includes copolymers (used to refer to polymers prepared from two different types of monomers) and polymers prepared from two or more different types of monomers.

[0017] An "olefin polymer" or "polyolefin" is a polymer containing a majority of polymerized olefin monomers, such as ethylene or propylene (based on the weight of the polymer), and optionally containing at least one comonomer. Non-limiting examples of olefin polymers include ethylene polymers and propylene polymers.

[0018] A "polymer" is a polymer compound prepared by polymerizing monomers, whether of the same or different types. Therefore, the general term "polymer" encompasses the terms "homopolymer" (used to refer to polymers prepared from only one type of monomer, with the understanding that trace amounts of impurities can be incorporated into the polymer structure) and "interpolymer," as defined below. Trace amounts of impurities, such as catalyst residues, can be incorporated into and / or within the polymer.

[0019] As used herein, the term "fully hydrogenated" refers to a hydrogenation level greater than 90%. As used herein, the term "partially hydrogenated" refers to a hydrogenation level between 50% and 90%. As used herein, the term "unhydrogenated" refers to a hydrogenation level less than 50%. The hydrogenation level can be determined by those skilled in the art, for example, by proton (1H) NMR. [Modes for carrying out the invention]

[0020] As discussed above, there is a strong desire among adhesive compounders and suppliers to provide end users with increasingly available bio-derived or more sustainably sourced components. Rosin ester tackifiers have a lower carbon footprint than conventional hydrocarbon tackifiers. However, polyolefins such as AFFINITY®GA are not inherently compatible with rosin ester tackifiers, but they have good compatibility with hydrogenated hydrocarbon tackifiers.

[0021] The applicants have surprisingly found that specific combinations of components, such as rosin ester tackifiers and hydrogenated hydrocarbon tackifiers, combined with polyolefin elastomers and functionalized polyolefin compatibilizers, result in significant improvements in blend compatibility.

[0022] Therefore, this application is, (A) Ethylene / α-olefin elastomer and (B) Functionalized ethylene / α-olefin interpolymer, (C) Rosin-based tackifier and (D) Provides an adhesive composition comprising a hydrocarbon-based tackifier.

[0023] Ethylene / α-olefin elastomer In one embodiment, the composition further comprises A) an ethylene / α-olefin interpolymer, and further comprises an ethylene / α-olefin copolymer. Preferred α-olefins include, but are not limited to, C3-C20 α-olefins, preferably C3-C10 α-olefins. More preferred α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene, and more preferably propylene, 1-butene, 1-hexene, and 1-octene.

[0024] In one embodiment, the ethylene / α-olefin interpolymer and further copolymer of component A have a melt viscosity of 40,000 cP or less, further 30,000 cP or less, further 20,000 cP or less, and further 10,000 cP or less at 350°F (177°C). Preferred α-olefins are considered above.

[0025] In one embodiment, the ethylene / α-olefin interpolymer and further copolymer of component A have a melt viscosity of 2,000 cP or more, more specifically 3,000 cP or more, more specifically 4,000 cP or more, and more specifically 5,000 cP or more at 350°F (177°C). Preferred α-olefins are considered above.

[0026] In one embodiment, the ethylene / α-olefin interpolymer and further copolymer of component A have a melt viscosity of 2,000 cP to 40,000 cP, further 3,000 cP to 30,000 cP, further 4,000 cP to 20,000 cP, and further 5,000 cP to 10,000 cP at 350°F (177°C). Preferred α-olefins are considered above.

[0027] In one embodiment, the ethylene / α-olefin interpolymer and further copolymer of component A have a molecular weight distribution (Mw / Mn) of 3.5 or less, further 3.0 or less, further 2.5 or less, and further 2.3 or less. In a further embodiment, the ethylene / α-olefin interpolymer is an ethylene / α-olefin copolymer. Preferred α-olefins are considered above.

[0028] In one embodiment, the ethylene / α-olefin interpolymer and further copolymer of component A have a molecular weight distribution (Mw / Mn) of 1.1 or more, further 1.3 or more, further 1.5 or more, and further 1.7 or more. In a further embodiment, the ethylene / α-olefin interpolymer is an ethylene / α-olefin copolymer. Preferred α-olefins are considered above.

[0029] In one embodiment, the ethylene / α-olefin interpolymer and further copolymer of component A have a weight-average molecular weight distribution (Mw) of 40,000 g / mol or less, further 30,000 g / mol or less, and further 25,000 g / mol or less. Preferred α-olefins are considered above.

[0030] In one embodiment, the ethylene / α-olefin interpolymer and further copolymer of component A have a weight-average molecular weight distribution (Mw) of 2000 g / mol or more, more specifically 3000 g / mol or more, and more specifically 4000 g / mol or more. Preferred α-olefins are considered above.

[0031] In one embodiment, the ethylene / α-olefin interpolymer and further copolymer of component A have a melt index (I2 or MI) of 400 g / 10 min or more, more specifically 600 g / 10 min or more, and even more specifically 800 g / 10 min or more, or a calculated melt index (I2 or MI). Preferred α-olefins are considered above.

[0032] In one embodiment, the ethylene / α-olefin interpolymer and further copolymer of component A have a melt index (I2 or MI) of 2000 g / 10 min or less, more preferably 1500 g / 10 min or less, and more preferably 1200 g / 10 min or less, or a calculated melt index (I2 or MI). Preferred α-olefins are considered above.

[0033] In one embodiment, the ethylene / α-olefin interpolymer and further copolymer of component A have a crystallinity percentage of 40 percent or less, more preferably 30 percent or less, and more preferably 20 percent or less, as determined by DSC. Preferred α-olefins are considered above.

[0034] In one embodiment, the ethylene / α-olefin interpolymer and further copolymer of component A have a crystallinity percentage of 2 percent or more, more preferably 5 percent or more, and more preferably 10 percent or more, as determined by DSC. Preferred α-olefins are considered above.

[0035] In one embodiment, the ethylene / α-olefin interpolymer and further copolymer of component A have a density of 0.855 g / cc or more, more specifically 0.860 g / cc or more, and more specifically 0.865 g / cc or more. Preferred α-olefins are considered above.

[0036] In one embodiment, the ethylene / α-olefin interpolymer and further copolymer of component A have densities of 0.900 g / cc or less, further 0.895 g / cc or less, further 0.890 g / cc or less, and further 0.885 g / cc or less. Preferred α-olefins are considered above. Preferred α-olefins are considered above.

[0037] In one embodiment, the ethylene / α-olefin interpolymer and further copolymer of component A are present at 0.855 g / cm³. 3 ~0.900g / cm 3 Furthermore, 0.860 g / cm³ 3 ~0.895g / cm 3 Furthermore, 0.865 g / cm³ 3 ~0.890g / cm 3 It has the density of . Preferred α-olefins are considered above. Preferred α-olefins are considered above.

[0038] In one embodiment, the ethylene / α-olefin interpolymer and further copolymer of component A is a uniformly branched linear interpolymer and further copolymer, or a uniformly branched substantially linear interpolymer and further copolymer. Preferred α-olefins are considered above.

[0039] In one embodiment, the ethylene / α-olefin interpolymer of component A is a uniformly branched linear interpolymer, and furthermore, a copolymer.

[0040] In one embodiment, the ethylene / α-olefin interpolymer of component A is a uniform, branched, substantially linear interpolymer, or even a copolymer.

[0041] Some examples of ethylene / α-olefin copolymers include AFFINITY® GA polyolefin plastomers available from The Dow Chemical Company and LICOCENE performance polymers from Clariant. Some preferred examples of ethylene / α-olefin copolymers include AFFINITY® GA 1900, AFFINITY® GA 1950, AFFINITY® GA 1875, and XUS 38628.00, all available from The Dow Chemical Company. Other examples of ethylene / α-olefin interpolymers suitable for the present invention include the ultra-low molecular weight ethylene polymers described in U.S. Patents 6,335,410, 6,054,544, and 6,723,810, which are fully incorporated herein by reference, respectively.

[0042] Functionalized ethylene / α-olefin interpolymer In one embodiment, component B is an anhydride and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer, and furthermore, an anhydride and / or carboxylic acid-functionalized grafted ethylene / α-olefin copolymer. Preferred α-olefins include, but are not limited to, C3-C20 α-olefins, preferably C3-C10 α-olefins. More preferred α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene, and more preferably propylene, 1-butene, 1-hexene, and 1-octene.

[0043] In one embodiment, the anhydride and / or carboxylic acid functionalized ethylene / α-olefin interpolymer of Component B has a density of 0.857 g / cc or more, further 0.860 g / cc or more, and further 0.865 g / cc or more. In a further embodiment, the anhydride and / or carboxylic acid functionalized ethylene / α-olefin interpolymer is an anhydride and / or carboxylic acid functionalized ethylene / α-olefin copolymer. Some preferred α-olefins are considered above.

[0044] In one embodiment, the anhydride and / or carboxylic acid functionalized ethylene / α-olefin interpolymer of Component B has a density of 0.892 g / cc or less, further 0.890 g / cc or less, and further 0.885 g / cc or less. In a further embodiment, the anhydride and / or carboxylic acid functionalized ethylene / α-olefin interpolymer is an anhydride and / or carboxylic acid functionalized ethylene / α-olefin copolymer. Some preferred α-olefins are considered above.

[0045] In one embodiment, the anhydride and / or carboxylic acid functionalized ethylene / α-olefin interpolymer of Component B has a density of 0.855 g / cc to 0.890 g / cc, further 0.855 g / cc to 0.885 g / cc, and further 0.855 g / cc to 0.880 g / cc (1 cc = 1 cm 3 )). In a further embodiment, the anhydride and / or carboxylic acid functionalized ethylene / α-olefin interpolymer is an anhydride and / or carboxylic acid functionalized ethylene / α-olefin copolymer. Some preferred α-olefins are considered above.

[0046] In one embodiment, the anhydride and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer of component B has densities of 0.857 g / cc to 0.892 g / cc, further 0.860 g / cc to 0.890 g / cc, and further 0.865 g / cc to 0.885 g / cc. In further embodiments, the anhydride and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer is an anhydride and / or carboxylic acid-functionalized ethylene / α-olefin copolymer. Several preferred α-olefins are considered above.

[0047] If the density of component B is greater than 0.895 g / cc, the adhesion of the final composition is reduced due to the increased rigidity of the polymer.

[0048] In one embodiment, the anhydride and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer of component B contains 0.5% by weight or more, more specifically 0.7% by weight or more, and more specifically 0.9% by weight or more of anhydride and / or carboxylic acid functional groups, based on the weight of the polymer. In further embodiments, the anhydride and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer is an anhydride and / or carboxylic acid-functionalized ethylene / α-olefin copolymer. Several preferred α-olefins are considered above.

[0049] In one embodiment, the anhydride and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer of component B contains 0.9 to 1.5 weight percent, more precisely 0.9 to 1.4 weight percent, and more precisely 0.9 to 1.3 weight percent of anhydride and / or carboxylic acid functional groups, based on the weight of the polymer. In further embodiments, the anhydride and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer is an anhydride and / or carboxylic acid-functionalized ethylene / α-olefin copolymer. Several preferred α-olefins are considered above.

[0050] In one embodiment, the ethylene / α-olefin elastomer and the functionalized ethylene / α-olefin interpolymer are present in a ratio of 4:1. Component B has a melt viscosity of 40,000 cP or less, more preferably 30,000 cP or less, more preferably 20,000 cP or less, and more preferably 15,000 cP or less at 350°F (177°C). In further embodiments, the anhydrous and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer is an anhydrous and / or carboxylic acid-functionalized ethylene / α-olefin copolymer. Several preferred α-olefins are considered above.

[0051] In one embodiment, the anhydride and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer of component B has a melt viscosity of 2,000 cP or more, more preferably 3,000 cP or more, more preferably 4,000 cP or more, and more preferably 5,000 cP or more at 350°F (177°C). In further embodiments, the anhydride and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer is an anhydride and / or carboxylic acid-functionalized ethylene / α-olefin copolymer. Several preferred α-olefins are considered above.

[0052] In one embodiment, the anhydride and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer of component B has a melt viscosity of 2,000 cP to 50,000 cP, more specifically 3,000 cP to 40,000 cP, more specifically 4,000 cP to 30,000 cP, and more specifically 5,000 cP to 20,000 cP at 350°F (177°C). In further embodiments, the anhydride and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer is an anhydride and / or carboxylic acid-functionalized ethylene / α-olefin copolymer. Several preferred α-olefins are considered above.

[0053] In one embodiment, the anhydride and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer of component B has a molecular weight distribution (Mw / Mn) of 5.0 or less, more preferably 4.0 or less, and more preferably 3.0 or less. In further embodiments, the anhydride and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer is an anhydride and / or carboxylic acid-functionalized ethylene / α-olefin copolymer. Several preferred α-olefins are considered above.

[0054] In one embodiment, the anhydride and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer of component B has a molecular weight distribution (Mw / Mn) of 1.5 or more, more specifically 2.0 or more, and more specifically 2.5 or more. In further embodiments, the anhydride and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer is an anhydride and / or carboxylic acid-functionalized ethylene / α-olefin copolymer. Several preferred α-olefins are considered above.

[0055] In one embodiment, the anhydride and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer of component B has a molecular weight distribution (MWD) of 1.5 to 5.0, moreover 2.0 to 4.0, and moreover 2.2 to 3.0. In further embodiments, the anhydride and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer is an anhydride and / or carboxylic acid-functionalized ethylene / α-olefin copolymer. Several preferred α-olefins are considered above.

[0056] In one embodiment, the anhydride and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer of component B has a weight-average molecular weight (Mw) of 50,000 g / mol or less, more preferably 40,000 g / mol or less, and more preferably 30,000 g / mol or less. In further embodiments, the anhydride and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer is an anhydride and / or carboxylic acid-functionalized ethylene / α-olefin copolymer. Several preferred α-olefins are considered above.

[0057] In one embodiment, the anhydride and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer of component B has a weight-average molecular weight (Mw) of 2000 g / mol or more, more specifically 3000 g / mol or more, and more specifically 4000 g / mol or more. In further embodiments, the anhydride and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer is an anhydride and / or carboxylic acid-functionalized ethylene / α-olefin copolymer. Several preferred α-olefins are considered above.

[0058] In one embodiment, the anhydride and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer of component B has a melt index (I2) of 300 g / 10 min or more, more specifically 400 g / 10 min or more, and even more specifically 500 g / 10 min or more, or a calculated melt index (I2). In further embodiments, the anhydride and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer is an anhydride and / or carboxylic acid-functionalized ethylene / α-olefin copolymer. Several preferred α-olefins are considered above.

[0059] In one embodiment, the anhydride and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer of component B has a melt index (I2) or calculated melt index (I2) of 1500 g / 10 min or less, more specifically 1200 g / 10 min or less, and even more specifically 1000 g / 10 min or less. In further embodiments, the anhydride and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer is an anhydride and / or carboxylic acid-functionalized ethylene / α-olefin copolymer. Several preferred α-olefins are considered above.

[0060] In one embodiment, the anhydride and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer of component B has a crystallinity percentage of 40 percent or less, more preferably 35 percent or less, more preferably 30 percent or less, more preferably 25 percent or less, and more preferably 20 percent or less, as determined by DSC. In further embodiments, the anhydride and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer is an anhydride and / or carboxylic acid-functionalized ethylene / α-olefin copolymer. Several preferred α-olefins are considered above.

[0061] In one embodiment, the anhydride and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer of component B has a crystallinity percentage of 2 percent or more, more preferably 5 percent or more, and more preferably 10 percent or more, as determined by DSC. In further embodiments, the anhydride and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer is an anhydride and / or carboxylic acid-functionalized ethylene / α-olefin copolymer. Several preferred α-olefins are considered above.

[0062] Suitable functionalized copolymers include MAH grafted copolymers (e.g., AFFINITY® GA 1000R polyolefin plastomers available from The Dow Chemical Company).

[0063] The anhydrous and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer of component B may include a combination of two or more embodiments described herein.

[0064] The anhydrous and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer of component B may include a combination of two or more embodiments described herein.

[0065] The base polymer used to form the anhydrous and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer is an ethylene / α-olefin copolymer. The following embodiments may also be applied to the ethylene / α-olefin interpolymer of component A.

[0066] In one embodiment, the ethylene / α-olefin interpolymer is an ethylene / α-olefin copolymer. Preferred α-olefins include, but are not limited to, C3-C20 α-olefins and even C3-C10 α-olefins. More preferred α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene, and even more specifically, propylene, 1-butene, 1-hexene, and 1-octene.

[0067] In one embodiment, the ethylene / α-olefin interpolymer has a melt viscosity of 50,000 cP or less, more specifically 40,000 cP or less, and more specifically 30,000 cP or less at 350°F (177°C). In a further embodiment, the ethylene / α-olefin interpolymer is an ethylene / α-olefin copolymer. Suitable α-olefins are considered above.

[0068] In one embodiment, the ethylene / α-olefin interpolymer has a melt viscosity of 2,000 cP or more, more specifically 4,000 cP or more, and even more specifically 5,000 cP or more at 350°F (177°C). In a further embodiment, the ethylene / α-olefin interpolymer is an ethylene / α-olefin copolymer. Suitable α-olefins are considered above.

[0069] In one embodiment, the ethylene / α-olefin interpolymer has a melt viscosity of 2,000 cP to 20,000 cP, moreover 4,000 cP to 16,000 cP, and moreover 5,000 cP to 10,000 cP at 350°F (177°C). In a further embodiment, the ethylene / α-olefin interpolymer is an ethylene / α-olefin copolymer. Suitable α-olefins are considered above.

[0070] In one embodiment, the ethylene / α-olefin interpolymer has a molecular weight distribution (Mw / Mn) of 5.0 or less, more specifically 4.0 or less, and more specifically 3.0 or less. Furthermore, the ethylene / α-olefin interpolymer has a molecular weight distribution of 1.1 to 3.5, more specifically 1.1 to 3.0, and more specifically 1.1 to 2.5. In a further embodiment, the ethylene / α-olefin interpolymer is an ethylene / α-olefin copolymer. Preferred α-olefins are considered above.

[0071] In one embodiment, the ethylene / α-olefin interpolymer has a melt index (I2 or MI) of 500 g / 10 min or more, more specifically 800 g / 10 min or more, and more specifically 1000 g / 10 min or more, or a calculated melt index (I2 or MI). In a further embodiment, the ethylene / α-olefin interpolymer is an ethylene / α-olefin copolymer. Suitable α-olefins are considered above.

[0072] In one embodiment, the ethylene / α-olefin interpolymer has a melt index (I2 or MI) or a calculated melt index (I2 or MI) of 2500 g / 10 min or less, more specifically 2000 g / 10 min or less, and more specifically 1500 g / 10 min or less. In a further embodiment, the ethylene / α-olefin interpolymer is an ethylene / α-olefin copolymer. Suitable α-olefins are considered above.

[0073] In one embodiment, the ethylene / α-olefin interpolymer has a crystallinity percentage of 40 percent or less, more precisely 30 percent or less, and more precisely 20 percent or less, as determined by DSC. In further embodiments, the ethylene / α-olefin interpolymer is an ethylene / α-olefin copolymer. Preferred α-olefins are considered above.

[0074] In one embodiment, the ethylene / α-olefin interpolymer has a crystallinity percentage of 2 percent or more, more specifically 5 percent or more, and more specifically 10 percent or more, as determined by DSC. In a further embodiment, the ethylene / α-olefin interpolymer is an ethylene / α-olefin copolymer. Preferred α-olefins are considered above.

[0075] In one embodiment, the ethylene / α-olefin interpolymer has a crystallinity percentage of 2 to 30 percent, more precisely 5 to 25 percent, and more precisely 10 to 20 percent, as determined by DSC. In a further embodiment, the ethylene / α-olefin interpolymer is an ethylene / α-olefin copolymer. Preferred α-olefins are considered above.

[0076] In one embodiment, the ethylene / α-olefin interpolymer has a density of 0.855 g / cc or more, more specifically, 0.860 g / cc or more, and more specifically, 0.865 g / cc or more. In further embodiments, the ethylene / α-olefin interpolymer is an ethylene / α-olefin copolymer. Suitable α-olefins are considered above.

[0077] In one embodiment, the ethylene / α-olefin interpolymer has a density of 0.895 g / cc or less, more specifically 0.890 g / cc or less, and more specifically 0.880 g / cc or less. In further embodiments, the ethylene / α-olefin interpolymer is an ethylene / α-olefin copolymer. Suitable α-olefins are considered above.

[0078] In one embodiment, the ethylene / α-olefin interpolymer is 0.855 g / cm³. 3 ~0.890g / cm 3 Furthermore, 0.860 g / cm³ 3 ~0.885g / cm 3 Furthermore, 0.865 g / cm³ 3 ~0.880g / cm 3 It has a density of . In further embodiments, the ethylene / α-olefin interpolymer is an ethylene / α-olefin copolymer. Suitable α-olefins are considered above.

[0079] Some examples of ethylene / α-olefin copolymers include AFFINITY® GA polyolefin plastomers available from The Dow Chemical Company and LICOCENE® performance polymers from Clariant. Other examples of ethylene / α-olefin polymers suitable for the present invention include the ultra-low molecular weight ethylene polymers described in U.S. Patents 6,335,410, 6,054,544, and 6,723,810, which are fully incorporated herein by reference, respectively.

[0080] In one embodiment, the ethylene / α-olefin interpolymer is a uniformly branched linear interpolymer and further copolymer, or a uniformly branched substantially linear interpolymer and further copolymer. Suitable α-olefins are considered above.

[0081] In one embodiment, the ethylene / α-olefin interpolymer is a uniformly branched linear interpolymer, and furthermore, a copolymer. Suitable α-olefins are considered above.

[0082] In one embodiment, the ethylene / α-olefin interpolymer is a uniformly branched, substantially linear interpolymer, and even a copolymer. Suitable α-olefins are considered above.

[0083] The terms “uniform” and “uniformly branched” are used in relation to ethylene / α-olefin interpolymers in which α-olefin comonomers are randomly distributed within a given polymer molecule, and all polymer molecules have the same or substantially the same comonomer-to-ethylene ratio.

[0084] Uniformly branched linear ethylene interpolymers are ethylene-based polymers that lack a measurable amount of long-chain branching but have short-chain branching derived from comonomers polymerized to the interpolymer, uniformly distributed both within the same polymer chain and between different polymer chains. These ethylene / α-olefin interpolymers have a linear polymer backbone, lack measurable long-chain branching, and have a narrow molecular weight distribution. Polymers of this class are disclosed, for example, by Elston in U.S. Patent No. 3,645,992, and subsequent processes for producing such polymers using bis-metallocene catalysts have been developed, for example, as shown in European Patent No. 0129368, European Patent No. 0260999, U.S. Patent No. 4,701,432, U.S. Patent No. 4,937,301, U.S. Patent No. 4,935,397, U.S. Patent No. 5,055,438, and International Publication No. 90 / 07526, which are incorporated herein by reference, respectively. As discussed, uniformly branched linear ethylene interpolymers lack long-chain branching, similar to linear low-density polyethylene polymers or linear high-density polyethylene polymers. Commercial examples of uniformly branched linear ethylene / α-olefin interpolymers include TAFMER® polymers from Mitsui Chemical Company, and EXACT® and EXCEED® polymers from ExxonMobil Chemical Company.

[0085] Uniformly branched, substantially linear ethylene / α-olefin interpolymers are described in U.S. Patents 5,272,236, 5,278,272, 6,054,544, 6,335,410, and 6,723,810, which are incorporated herein by reference, respectively. Substantially linear ethylene / α-olefin interpolymers have long-chain branches. These long-chain branches have the same comonomer distribution as the polymer backbone and can be approximately the same length as the polymer backbone. "Substantially linear" typically refers to polymers substituted with, on average, "0.01 long-chain branches per 1000 total carbons" to "3 long-chain branches per 1000 total carbons." The length of the long-chain branches is longer than the carbon length of the short-chain branches formed from the incorporation of one comonomer into the polymer backbone.

[0086] Some polymers can be substituted with "0.01 long-chain branches per 1000 total carbon atoms" to "3 long-chain branches per 1000 total carbon atoms," further to "0.01 long-chain branches per 1000 total carbon atoms" to "2 long-chain branches per 1000 total carbon atoms," and further to "0.01 long-chain branches per 1000 total carbon atoms" to "1 long-chain branch per 1000 total carbon atoms."

[0087] Substantially linear ethylene / α-olefin interpolymers form a unique class of homogeneously branched ethylene-based polymers. As considered above, they are substantially different from the known class of conventional homogeneously branched linear ethylene / α-olefin interpolymers, and furthermore, they are not in the same class as conventional heterogeneous "Ziegler-Natta catalyst-polymerized" linear ethylene polymers (e.g., ultra-low density polyethylene (ULDPE), linear low density polyethylene (LLDPE), or high density polyethylene (HDPE) produced using the techniques disclosed by Anderson et al. in U.S. Patent No. 4,076,698), nor are they in the same class as high-pressure free-radical initiated highly branched polyethylenes such as low density polyethylene (LDPE), ethylene-acrylic acid (EAA) copolymers, and ethylene vinyl acetate (EVA) copolymers.

[0088] The uniformly branched, substantially linear ethylene / α-olefin interpolymers useful in this invention exhibit excellent processability despite having a relatively narrow molecular weight distribution. Surprisingly, the melt flow ratio (I10 / I2) of substantially linear ethylene interpolymers according to ASTM D 1238 can be varied broadly and essentially independently of the molecular weight distribution (Mw / Mn or MWD). This surprising behavior is in contrast to conventional uniformly branched linear ethylene interpolymers, such as those described by Elston in U.S. Patent No. 3,645,992, and conventional heterogeneously branched "Ziegler-Natta catalyst polymerized" linear polyethylene interpolymers, such as those described by Anderson et al. in U.S. Patent No. 4,076,698. Unlike substantially linear ethylene interpolymers, linear ethylene interpolymers (whether uniformly or heterogeneously branched) exhibit a change in I as the molecular weight distribution increases. 10 It possesses rheological properties such that the / I2 value also increases.

[0089] Long chain branching is, 13This can be determined using 13C nuclear magnetic resonance (NMR) spectroscopy and quantified using Randall's method (Rev. Macromol. Chem. Phys., C29(2&3), 1989, pp. 285-297). Two other methods are gel permeation chromatography, coupled with a low-angle laser light scattering detector (GPCLALLS), and gel permeation chromatography, coupled with a differential viscometer detector (GPC-DV). The use of these techniques for long-chain branching detection, and the underlying theory, is well documented in the literature. For example, see Zimm, B.Hand; Stockmayer, WH, J. Chem. Phys., 17, 1301 (1949), and Rudin, A., Modern Methods of Polymer Characterization, John Wiley & Sons, New York (1991), pp. 103-112.

[0090] In contrast to "substantially linear ethylene polymers," "linear ethylene polymers" mean that the polymer lacks measurable or demonstrable long-chain branching, i.e., the polymer is substituted with fewer than 0.01 long-chain branches on average per 1000 total carbon atoms.

[0091] Rosin ester This composition contains a rosin ester. “Rosin ester” refers to a polymer in which, in its polymerized form, contains rosin and optionally one or more dienes, whose polymer structure is then esterified with one or more polyols, and whose esterified polymer structure is then optionally hydrogenated. As an ester, a rosin ester contains at least one ester group having an oxygen atom, thereby excluding tackifiers composed solely of hydrogen and carbon atoms. “Polyol” is an alcohol containing at least two hydroxyl groups (-OH).

[0092] Rosin is a hydrocarbon secretion from many plants, particularly conifers such as Pinus palustris and Pinus caribaea. Natural rosin typically consists of a mixture of seven or eight rosinic acids and other trace components. Rosin is commercially available and can be obtained from pine trees by distillation of oily resin (gum rosin, the residue of the distillation), by extraction of pine stumps (wood rosin), or by fractionation of tall oil (tall oil rosin). Rosin is a mixture of rosinic acids, which are carboxylic acids. These naturally occurring rosins may preferably be mixtures and / or isomers of monocarboxylic tricyclic rosinic acids, usually containing about 20 carbon atoms. Tricyclic rosinic acids differ mainly in the position of the double bond. Rosin acid may be at least one of levopimaric acid, neoabietic acid, pulsed phosphoric acid, abietic acid, dehydroabietic acid, seco-dehydroabietic acid, tetrahydroabietic acid, dihydroabietic acid, pimaric acid, pulsed phosphoric acid, and isopimaric acid, or mixtures, isomers, and / or derivatives thereof. Non-limiting examples of suitable rosins include gum rosin, wood rosin, tall oil rosin, and combinations thereof.

[0093] A "diene" is an unsaturated hydrocarbon containing two double bonds between carbon atoms. A diene can be a conjugated, unconjugated, linear, branched, or cyclic hydrocarbon diene having 6 to 15 carbon atoms. Non-limiting examples of suitable dienes include branched acyclic dienes such as 1,4-hexadiene, 1,6-octadiene, 1,7-octadiene, 1,9-decadiene, 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, 3,7-dimethyl-1,7-octadiene, and mixed isomers of dihydromyricene and dihydroosynene; monocyclic alicyclic dienes such as 1,3-cyclopentadiene, 1,4-cyclohexadiene, 1,5-cyclooctadiene, and 1,5-cyclododecadiene; and polycyclic alicyclic condensed and crosslinked ring dienes such as tetrahydroindene, methyltetrahydroindene, dicyclopentadiene, and bicyclo-(2,2,1)-hepta-2,5-diene; and 5-methylene-2-norbornene. Examples include alkenyls, alkylides, cycloalkenyls, and cycloalkylidene norbornenes such as e, MNB), 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene, norbornadiene, 5-ethylidene-2-norbornene (ENB), 5-vinylidene-2-norbornene (VNB), 5-methylene-2-norbornene (MNB), and dicyclopentadiene (DCPD), as well as combinations thereof.Further non-limiting examples of suitable dienes include 4-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 5,7-dimethyl-1,6-octadiene, 3,7,11-trimethyl-1,6,10-octatriene, 6-methyl-1,5-heptadiene, 1,3-butadiene, 1,6-heptadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,5-cyclododecadiene, and bicyclo[2.2.1]hepta-2,5-diene (no Examples include dien (diene), tetracyclododecene, butadiene, dicyclopentadiene, vinylnorbornene, mixed isomers of dihydromyricene and dihydroosinene, tetrahydroindene, methyltetrahydroindene, 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene, and combinations thereof. In embodiments, the diene is DCPD.

[0094] Rosin acids derived from natural sources also include rosins modified by polymerization, isomerization, disproportionation, and hydrogenation, i.e., rosin mixtures. Rosin acids may include those described in U.S. Patents 6,900,274, 6,875,842, 6,846,941, 6,344,573, 6,414,111, 4,519,952, and 6,623,554. Preferred rosins are tall rosins, which are isomer mixtures mainly composed of C20 condensed ring monocarboxylic acid hydrocarbons, represented by levopimar acid and abietic acid. Any type of rosin may be used, including tall oil rosins, gum rosins, and wood rosins. Suitable examples of commercially available rosins include tall oil rosins such as Sylvalite® 2200, Sylvaros® 85, Sylvaros® 90, or Sylvaros® 95 from Kranton Chemical. Other suitable examples of rosin esters include FORAL® 105-E, FORALYN® 90, FORAL-AX-E®, PERMALYN® 6110 from Eastman Chemical Company, and KTP 95® from Komotac.

[0095] Hydrocarbon tackifiers This composition contains hydrocarbon resin tackifiers. These hydrocarbon tackifiers are mainly produced from petroleum by-products of naphtha crackers. The three main types are C5 aliphatic, C9 aromatic, and DCPD alicyclic resins. Any type of hydrocarbon resin tackifier may be used based on commercial availability. Examples of suitable commercially available hydrocarbon tackifiers include C9 resin: Regalite® R1125, DCPD resin: Examples include ESCAREZ (trademark) and Regalite (trademark) T1140, C5 resin, and Eastotac (trademark) H-100W resin.

[0096] additives The compositions of the present invention may further contain waxes. Examples of waxes include, but are not limited to, paraffin wax, microcrystalline wax, high-density low-molecular-weight polyethylene wax, polypropylene wax, pyrolysis wax, by-product polyethylene wax, Fischer-Tropsch wax, Fischer-Tropsch oxide wax, and functionalized waxes such as hydroxystearamide wax and fatty amide wax. It is common in the art to use the term “synthetic high-melting-point wax” to include high-density low-molecular-weight polyethylene wax, by-product polyethylene wax, and Fischer-Tropsch wax. Other waxes include those described in U.S. Patents 6,335,410, 6,054,544, and 6,723,810, all incorporated herein by reference. Preferred waxes include, but are not limited to, SASOL® waxes (e.g., SASOLWAX® H1 from Sasol Wax Company) and Fischer-Tropsch wax. In one embodiment, the composition contains 10 to 40 weight percent, more precisely 10 to 35 weight percent, and more precisely 10 to 30 weight percent of wax, based on the weight of the composition.

[0097] Typically, the polymers used in the present invention are treated with one or more stabilizers, such as antioxidants currently supplied by BASF, e.g., IRGANOX® 1010, IRGANOX® 1076, and IRGAFOS® 168. The polymers are typically treated with one or more stabilizers before extrusion or other melting processes. Other polymer additives include, but are not limited to, UV absorbers, antistatic agents, pigments and dyes, nucleating agents, fillers, slip agents, flame retardants, plasticizers, processing aids, lubricants, stabilizers, smoke suppressants, viscosity modifiers, and anti-tack agents. The compositions of the present invention may also contain one or more thermoplastic polymers. In one embodiment, the composition contains 0.2 to 20 weight percent, more specifically 0.10 to 10 weight percent, and more specifically 0.5 to 5 weight percent of a tackifier, based on the weight of the composition.

[0098] The compositions of the present invention may further contain oil. The oil is typically used to reduce the viscosity of the adhesive. If used, the oil will typically be present in an amount of less than 50 weight percent, preferably less than 20 weight percent, and more preferably less than 10 weight percent, based on the weight of the composition. Examples of oils of an exemplary class include, but are not limited to, white mineral oil (e.g., KAYDOL® oil available from Witco), SHELLFLEX® 371 naphthenic oil (available from Shell Oil Company), and CALSOL® 5550 (naphthenic oil from Calumet Lubricants).

[0099] Purpose The compositions of the present invention can be prepared by standard melt-blending procedures. In particular, maleic anhydride grafted polymers or blends, tackifiers, and other components can be melt-blended until a homogeneous mixture is obtained. Any mixing method that produces a homogeneous blend without decomposing the adhesive components, such as a container equipped with a stirrer and an optional heating mechanism, is satisfactory. The adhesive can be supplied in the form of pellets, pillows, chiclets, drags, or any other desired configuration.

[0100] The compositions of the present invention may also be used in a variety of applications, including but not limited to sealing cases and cartons, automobiles, graphic arts, nonwoven fabrics, panel assemblies, high-performance tapes, contact hot-melt adhesives, cardboard coatings, inks, personal care and cosmetics, sealants, colorants and additive concentrates, carpet tape adhesives, woodworking adhesives, and profile wrap adhesives.

[0101] Test method melt viscosity Melt viscosity is measured according to ASTM D 3236 (350°F) using a Brookfield Digital Viscometer (Model DV-III, Version 3) and a disposable aluminum sample chamber. The spindle used is generally an SC-31 hot-melt spindle, suitable for measuring viscosities in the range of 10 to 100,000 centipoise. The sample (polymer or adhesive composition) is poured into the chamber, which is then inserted into a Brookfield Thermosel and secured in place. The sample chamber has a notch at the bottom that fits into the bottom of the Brookfield Thermosel to ensure that the chamber is not rotated when the spindle is inserted and rotating. The sample (about 8 to 10 grams of resin) is heated to the required temperature until the molten sample is about 1 inch below the top of the sample chamber. The viscometer device is lowered, and the spindle is submerged in the sample chamber. The lowering continues until the bracket of the viscometer is aligned on the Thermosel. The viscometer is powered on and set to operate at a shear rate that leads to torque readings within the range of 40-60 percent of the total torque capacity, based on the viscometer's rpm output. Readings are acquired every minute for approximately 15 minutes, or until the value stabilizes, at which point the final reading is recorded.

[0102] Melt Index The melt index (I2 or MI) of ethylene-based polymers is measured according to ASTM D-1238, under conditions of 190°C / 2.16 kg. For high I2 polymers (I2 of 200 g / mol or more), the melt index is preferably calculated from Brookfield viscosity as described in U.S. Patent Nos. 6,335,410, 6,054,544, and 6,723,810. I2 (190°C / 2.16 kg) = 3.6126 [10 (log( η )-6.6928) / -1.1363 ]-9.3185l, where η = 350°F (177°C) is the melt viscosity in cP units.

[0103] Peeling and shear strength The peel adhesion fail temperature (PAFT) and shear adhesion failure temperature (SAFT) of adhesives were tested using ASTM D-4498. Four samples (two for PAFT and two for SAFT) were placed in a programmable oven, and then a 100g weight was attached to the PAFT samples and a 500g weight was attached to the SAFT samples. The test samples were equilibrated in a 30°C oven, and then the oven temperature was increased at a heating rate of 0.5°C / min. The failure time was recorded, and the failure temperature was calculated accordingly.

[0104] Two 6-inch x 12-inch kraft paper sheets were used for lamination. The bottom sheet had two pieces of masking tape separated by a 1-inch gap. The adhesive was spread using a bottom glass rod height-adjusted with tape. The top glass rod supplied compression. Excess adhesive was captured using silicone paper at the ends. The final bond was defined by two pieces of masking tape and was 1 inch wide. The molten adhesive was heated to 177°C and poured onto the bottom sheet. The glass rod was then quickly pulled to create the lamination. The laminated sheet was trimmed and cut transversely into "1-inch wide strips". These strips had a "1-inch x 1-inch bond" in the center. The samples were conditioned at room temperature and 54 percent RH (Relative Humidity) for 24 hours. The samples were then placed in an oven, with 100g in peel mode and 500g in shear mode. The oven temperature was increased at a rate of 30°C / hour. The samples were suspended from a switch that would activate upon sample failure, and the time and temperature were recorded by computer. Two samples were tested for PAFT and their mean failure temperatures were recorded. Two samples were tested for SAFT and their mean failure temperatures were recorded.

[0105] Thermal stress The heat stress resistance was measured according to Method T-3006 of the "Suggested Test Method for Determining the Heat Stress Resistance of Hot Melt Adhesives" prepared by the Institute of Packaging Professions (IoPP). To prepare one sample, two cardboard coupons measuring 2 inches × 3-3 / 16 inches and 2 inches × 5-1 / 2 inches (cut with longitudinally running grooves) were bonded together using an Olinger Bond Tester by applying "0.00014 lb / in adhesive". The adhesive was applied perpendicularly to the central groove of the shorter coupon, and the coupons were bonded so that the adhesive extended 3 / 4 inch from one end of the longer coupon. Six copies were prepared for each formulation. The sample was loaded into the sample holder with the shorter coupon end aligned with the edge of the sample holder. The sample was held in place using a wide plate secured by a wing nut. A 200g weight was placed 3.94 inches from the bond. The weight was secured by placing a peg on top of the weight in a hole made in the long coupon. The sample holder was then placed in a convection oven at the test temperature for 24 hours. If at least 80% of the bond did not break, the sample was considered to have passed the heat resistance test at the test temperature. The oven temperature was varied until the maximum passable heat stress resistance was determined. All new bond coupon samples were used for each test temperature (six samples for each formulation and test temperature).

[0106] Fiber tearing The percentage of fiber tearing for each adhesive sample was evaluated at three different temperatures: room temperature, -17°C, and 60°C, on ordinary cardboard (kraft cardboard) or difficult-to-bond substrates (BOPP (Biaxially Oriented Polypropylene) film laminated kraft or carton). Fiber tearing results on these two different substrates were recorded. The adhesive was heated to 350°F / 177°C and applied to substrates cut into 1 x 3 inch (25 x 76 mm) rectangular sheets. The adhesive to be tested was applied in strips approximately 5 mm / 0.2 inches wide, spreading longitudinally, and pulled downwards using a spatula or hot melt applicator. A second strip was then applied within 2 seconds and held under moderate pressure for 5 seconds to laminate.

[0107] Next, the bonds, which had been conditioned at room temperature and 54 percent RH for 24 hours, were separated at test temperatures of room temperature, -17°C, and 60°C. Each bond was tested immediately after the conditioning period was completed. The bond was torn by inserting a spatula blade under one corner and bending the corner upwards. The sample was then placed on a horizontal surface with the side having the bent corner facing upwards. With the laminate held as close as possible to a heating or cooling source to maintain the conditioning temperature, the bent corner was manually pulled as quickly as possible at an angle of approximately 45–90 degrees with respect to the longitudinal axis of each sheet to tear the adhesive bond. The percentage of torn fibers (fiber tear or FT) was estimated in 25 percent increments, i.e., 0 percent, 25 percent, 50 percent, 75 percent, and 100 percent. Unless otherwise specified, the FT test was usually repeated on five replicated samples, and the average of these five samples was reported.

[0108] density The density is measured according to ASTM D-792. The density measured is the "rapid density," meaning that the density is determined one hour after molding. The test sample is compression molded at a pressure of 10 MPa for 5 minutes at a temperature 20°C above the melting point of the polymer (dimensions of molded sample: 50 cm). 2 (×1~2mm).

[0109] Cloud point measurement The cloud point was measured using a custom temperature-scanning turbidity (TST) system that allowed for a throughput of 13 samples per run. The overall system consisted of (a) a TST heat block (Watlow EZ-ZONE) holding 13 vials connected to a temperature controller, (b) diffuse back illumination (Schott DCR IV, DC regulated 150W halogen light source) with a light panel and controller, (c) a digital camera for imaging the TST, and (d) a computer for saving images and recording data. The TST heat block consisted of (a) an aluminum block with four symmetrically distributed cartridge heaters having drilled recesses for 13 vials with cross-drilled holes for illumination, (b) a bolt-on aluminum cover plate with two cartridge heaters and small holes above each vial to allow for ventilation and insertion of thermocouples for monitoring the temperature inside the vials, (c) a 1 / 8-inch thick copper gasket (not shown in the drawing) between (a) and (b) to provide headspace clearance to avoid vial cracking, (d) a glass-filled PEEK platform on which the TST is mounted, which helps to effectively insulate the TST from the aluminum stand, and (e) control and over-temperature thermocouples inserted into the TST heat block at the center and end positions.

[0110] The following are the details of the TST method used to measure the cloud point. 1) The sample was loaded into the block. 2) The window guard was secured to the enclosure. The camera and backlight were turned on. 3) Initial images were taken using Qcapture and analyzed using Image J to ensure that the values ​​for empty cells were close to 4095. Intensity and / or exposure time were adjusted until the grayscale was approximately 200 (i.e., not fully saturated at 255). The maximum dynamic range was obtained for cloud point measurements when the samples were grouped based on similar clarity. 4) The TST program "TST 1712 software" was opened and the "HMA TST" method was executed. 5) The block was heated to an initial temperature of 180°C. 6) While heating, the temperature was monitored to ensure that the temperature controller was functioning properly. 7) The program was set to equilibrate the samples at 180°C for 5 minutes. If temperature recording was required, thermocouples were carefully inserted into the four samples, taking care to ensure that they did not extend into the imaging window. After 5 minutes, the T controller was switched to lamp-soak mode to start the cooling program. The settings for a cooling rate of 1°C / min were lamp endpoint = 45°C and lamp duration = 2:15 (hours:minutes). 8) Once completely cooled, the vial was removed from the heating block. The vial temperature and ambient temperature were recorded using an 8-channel USB-TC DAQ device, a K-type thermocouple, and Tracer DAQ Pro software (Measurement Computing). Control and upper limit temperature controller readings were manually recorded from the controller display. A sampling rate of 0.1 Hz (6 points / °C) was sufficient due to the slow cooling rate. A 165-minute acquisition duration was chosen to allow for additional temperature monitoring beyond the programmed cooling lamp. Images were automatically captured using StreamPix software (NorPix).

[0111] To operate as a high-throughput instrument, macros were created for image analysis and merging of time / temperature and time / intensity data. The following basic steps were used: (a) Place all images for a given run into a folder. (b) Use an Excel® macro to create a spreadsheet list of all files in the folder. The file names include a timestamp (e.g., HMA11_2016-12-12-15-57-32-525.tif), and Excel® strings and time functions can be used to extract the time values ​​associated with each image. (c) ImageJ (available from NIH) is used to determine grayscale (GS) values ​​for all cells, one image at a time. To do this, the operator must tell the program where the light intensity should be analyzed for each sample. Thus, the operator opens the first image in the folder (at high temperature, where almost all blends are a transparent homogeneous melt) and uses the multipoint selection tool to select points in each cell (away from walls and any defects). Following this, alternating keystrokes of CTL-M (to measure GS values ​​in the running table) and CTL-SHFT-O (to open the next file in the folder) are repeated to provide a GS value table for all cells and all images relatively quickly. The operator merges the GS values ​​with the image timestamps, associates the sample ID with the vial position, and processes the temperature log data. Finally, the operator converts the timestamps to a more useful format (e.g., minutes) and calculates the average for channels 0-3 (ambient room air) and 4-7 (average vial temperature). All of these steps can be converted into an ImageJ macro for batch processing of all images. [Examples]

[0112] The polymers used in this study are listed in Table 1. The tackifiers are shown in Table 2 below.

[0113] [Table 1] a) GPC results. b) Available from The Dow Chemical Company. Ethylene / octen copolymer. c) Available from The Dow Chemical Company. Maleic anhydride (MAH) functionalized ethylene / octen copolymer. * The melt index can be calculated using the following formula (see U.S. Patent No. 6,335,410): I²(190℃ / 2.16kg) = 3.6126[10 (log( η -6.6928) / -1.1363 ]-9.3185l, where η = 350°F (177°C) is the melt viscosity (cP) in the formula.

[0114] [Table 2] a) Available from Eastman Chemical. c) Fully / highly hydrogenated. d) Not hydrogenated; see International Publication No. 2005 / 014752.

[0115] [Table 3]

[0116] Adhesive composition

[0117] [Table 4]

[0118] [Table 5]

[0119] As can be seen from Table 5, the addition of 1000R leads to a reduction in the cloud point, indicating that the addition of 1000R improves compatibility.

[0120] [Table 6]

[0121] [Table 7]

[0122] The results shown in Table 7 above indicate that the rosin ester tackifier HMA (samples CE9 and CE10) exhibited the lowest fiber tear (FT) performance. Samples CE12, CE13, CE14, and CE15 were 50 / 50 blends of rosin ester / hydrogenated tackifier blends, demonstrating that while the blend alone showed a moderate improvement in fiber tear performance, the benefit did not exceed a 25% improvement. However, the advantages of adding GA 1000R can be observed in formulations IE4, IE5, IE6, and IE7. In all cases where GA 1000R was added, the range over which good adhesive fiber tear occurred (FT > 75% was observed) was extended to a wider temperature range. For samples containing Sylvalite 2200 + GA 1000R, the best sample was Sylvalite / Eastotac H115R, which had FT > 70% across the temperature range.

[0123] [Table 8]

[0124] Table 8 summarizes a set of compositions intended to investigate the effects of rosin ester content (%) relative to total tackifier and maleic anhydride graft polymer (%) relative to total polymer on cloud point results. Examples P3-01 to P3-06 of the invention systematically vary the rosin ester tackifier from 10% to 90% of the total tackifier components, which is constant at 50% of the blend composition. As shown in the table and Figure 4, the cloud point (°C) increases slowly as the rosin ester tackifier content increases between 10% and 40%, and above 40% by weight, the rate of change in CP increases more rapidly. Figure 5 depicts two regions of cloud point behavior as a function of rosin ester tackifier. The rate of change in cloud point (slope of the line) increases when the rosin ester tackifier exceeds 40%. These results indicate that formulations containing rosin ester tackifiers with a total tackifier content of 40% or less maintain a balance of the benefits of the rosin ester tackifier and a certain degree of compatibility of the system, as measured by a low cloud point. The cloud point of pure AFFINITY GA 1950 resin is 71°C. Blends containing rosin ester tackifiers at a content of 40% or less have a lower CP by TST and exhibit preferred mixing conditions.

[0125] The effect of MAH-grafted POE (AFFINITY GA 1000R) on compatibility, as determined by the cloud point, was also investigated. The formulations and results are shown in Table 8, Examples P3-07 to P3-13 of the Invention. The data can be interpreted by the range (slope) of change in the cloud point with the addition of GA 1000R. The greatest effect is measured at levels of GA 1000R less than 10% of the total polymer. The area indicated by the green box in Figure 6 highlights the maximized benefit of GA 1000R in the evaluated compositions. As can be seen with further addition of 1000R, the cloud point continues to decrease, indicating that higher loading of 1000R improves compatibility.

Claims

1. An adhesive composition, (A) Ethylene / α-olefin elastomer, (B) Functionalized ethylene / α-olefin interpolymer, (C) Rosin-based tackifier and (D) An adhesive composition comprising a hydrocarbon-based tackifier.

2. (A) 30 to 45% by weight of the ethylene / α-olefin elastomer, (B) 0.1 to 20% by weight of the functionalized ethylene / α-olefin interpolymer, (C) 10 to 75% by weight of the rosin ester tackifier, (D) The adhesive composition according to claim 1, further comprising 10 to 75% by weight of the hydrocarbon tackifier.

3. (A) 20 to 50% by weight of the ethylene / α-olefin elastomer, (B) 1 to 10% by weight of the functionalized ethylene / α-olefin interpolymer, (C) 15 to 30% by weight of the rosin ester tackifier, (D) The adhesive composition according to claim 1, further comprising 15 to 30% by weight of the hydrocarbon tackifier.

4. The adhesive composition according to claim 1, wherein the rosin ester tackifier and the hydrocarbon tackifier are present in a 1:1 ratio.

5. The adhesive composition according to claim 1, wherein the ethylene / α-olefin elastomer and the functionalized ethylene / α-olefin interpolymer are present in a ratio of 4:

1.

6. The adhesive composition according to claim 2, wherein the rosin ester tackifier and the hydrocarbon tackifier are present in a 1:1 ratio.

7. The adhesive composition according to claim 2, wherein the ethylene / α-olefin elastomer and the functionalized ethylene / α-olefin interpolymer are present in a ratio of 4:

1.

8. The adhesive composition according to claim 1, wherein the functionalized ethylene / α-olefin interpolymer is a maleic anhydride and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer having a melt index (I2) of 1500 g / 10 min or less or a calculated melt index (I2).

9. The adhesive composition according to claim 4, wherein the functionalized ethylene / α-olefin interpolymer is a maleic anhydride and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer having a melt index (I2) of 1500 g / 10 min or less or a calculated melt index (I2).

10. The adhesive composition according to claim 5, wherein the functionalized ethylene / α-olefin interpolymer is a maleic anhydride and / or carboxylic acid-functionalized ethylene / α-olefin interpolymer having a melt index (I2) of 1500 g / 10 min or less or a calculated melt index (I2).

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