HK1243115A1 - Hot melt adhesive compositions that include semi-crystalline propylene polymer and wax and articles including the same - Google Patents

Description

Hot melt adhesive compositions comprising semi-crystalline propylene polymers and waxes and articles comprising the same

Background

The present invention relates to the preparation of hot melt adhesive compositions comprising a semi-crystalline propylene polymer and a wax.

Hot melt adhesive compositions typically include a polymer and a tackifier and in some cases a wax or oil. Hot melt adhesives for packaging should exhibit good bond formation, heat resistance and thermal stability and fast set times to be commercially useful. It is difficult to formulate propylene polymer based hot melt adhesive compositions that exhibit the performance properties that must be met for the packaging adhesive to be commercially useful. Tackifiers can, for example, cause discoloration and charring of the hot melt adhesive. Waxes have a detrimental effect on the bond formation of polypropylene hot melt adhesive compositions. This is particularly true for waxes with high crystallinity. Oils are known to reduce the setting speed of hot melt adhesive compositions. Oil can also bleed out of the hot melt adhesive composition and cause undesirable staining of the substrate to which it is bonded.

It is desirable to obtain a hot melt adhesive composition based on propylene polymers that exhibits good adhesion at low and high temperatures, thermal stability, fast set time and very low to no oil stain and oil migration.

SUMMARY

In one aspect, the present invention is directed to a hot melt adhesive composition comprising at least 55% by weight of an unmodified, semi-crystalline propylene polymer comprising at least 50% by weight propylene, at least 15% by weight of a first non-functionalized wax, and a second wax different from the first wax. In some embodiments, the hot melt adhesive composition includes greater than 20% by weight wax.

In another aspect, the present invention is directed to a hot melt adhesive composition comprising at least 55% by weight of a semi-crystalline propylene polymer comprising at least 50% by weight propylene and greater than 20% by weight of a wax, the wax comprising from 0% by weight to no greater than 10% by weight of a functionalized wax, based on the weight of the hot melt adhesive composition, and the composition exhibiting a set time of no greater than 2 seconds. In one embodiment, the wax includes a first wax and a second wax different from the first wax.

In some embodiments, the hot melt adhesive composition includes no greater than 10 wt-% tackifier.

In one embodiment, the second wax comprises a functionalized wax.

In another embodiment, the semi-crystalline propylene polymer is a metallocene catalyzed propylene polymer. In some embodiments, the semi-crystalline propylene polymer has a heat of fusion of from 15J/g to not greater than 50J/g. In one embodiment, the semi-crystalline propylene polymer has a heat of fusion of from 15J/g to no greater than 45J/g.

In another embodiment, the first non-functionalized wax has a melting point greater than 80 ℃. In some embodiments, the first non-functionalized wax has a melting point greater than 100 ℃. In other embodiments, the first non-functionalized wax has a melting point greater than 115 ℃. In one embodiment, the second wax has a melting point greater than 115 ℃. In some embodiments, the first non-functionalized wax has a melting point greater than 115 ℃ and the composition exhibits a set time of no greater than 2 seconds. In some embodiments, the first non-functionalized wax has a melting point greater than 115 ℃ and the second wax has a melting point greater than 115 ℃.

In some embodiments, the composition exhibits a set time of no greater than 5 seconds. In other embodiments, the composition exhibits a set time of no greater than 2 seconds.

In one embodiment, the composition exhibits a resistance to thermal stress of greater than 71 ℃. In other embodiments, the composition exhibits a thermal stress resistance greater than 76 ℃. In some embodiments, the composition exhibits a resistance to thermal stress of greater than 71 ℃ and a set time of no greater than 2 seconds. In one embodiment, the composition exhibits resistance to thermal stress of greater than 71 ℃ and a set time of no greater than 2 seconds, and the first non-functionalized wax comprises at least one of a polyethylene wax and a fischer-tropsch wax, and the second wax comprises a non-functionalized polypropylene wax, a maleated polyethylene wax, a maleated polypropylene wax, or a combination thereof.

In another embodiment, the composition exhibits greater than 25% fiber tear at-18 ℃ (fibertear) and greater than 25% fiber tear at 60 ℃. In other embodiments, the composition exhibits greater than 25% fiber tear at 4 ℃ and greater than 25% fiber tear at 60 ℃. In still other embodiments, the composition exhibits greater than 25% fiber tear at 4 ℃ and greater than 25% fiber tear at 71 ℃.

In one embodiment, the hot melt adhesive composition further comprises an oil, polybutene, or a combination thereof. In other embodiments, the hot melt adhesive composition further comprises a tackifier. In one embodiment, the hot melt adhesive composition includes no greater than 7 wt-% tackifier.

In some embodiments, the composition exhibits a viscosity of no greater than 2000 centipoise at 177 ℃. In other embodiments, the composition exhibits a viscosity of no greater than 1200 centipoise at 177 ℃.

In one embodiment, the first non-functionalized wax comprises a polyethylene wax and the second wax comprises a non-functionalized polypropylene wax, a maleated polyethylene wax, a maleated polypropylene wax, or a combination thereof. In some embodiments, the first non-functionalized wax exhibits a melting point greater than 115 ℃ and includes at least one of a polyethylene wax and a fischer-tropsch wax, and the second wax includes a maleated polyethylene wax, a maleated polypropylene wax, or a combination thereof. In other embodiments, the first non-functionalized wax comprises a polyethylene wax and the second wax comprises a maleated polyethylene wax, a maleated polypropylene wax, or a combination thereof.

In some embodiments, the hot melt adhesive composition includes 55 wt% to about 84 wt% of the semi-crystalline propylene polymer, about 20 wt% to about 35 wt% of the first non-functionalized wax, and about 1 wt% to about 10 wt% of the second wax. In one embodiment, the composition exhibits a set time of no greater than 2 seconds. In other embodiments, the composition exhibits a set time of no greater than 1 second.

In other embodiments, the hot melt adhesive composition comprises 60% to about 80% by weight polypropylene polymer.

In one embodiment, the semi-crystalline propylene polymer comprises a propylene-alpha olefin copolymer. In another embodiment, the semi-crystalline propylene polymer comprises a propylene-hexene copolymer, propylene-octene, propylene-butene copolymer, propylene-ethylene copolymer, or combinations thereof. In some embodiments, the semi-crystalline propylene polymer exhibits a viscosity of no greater than 2,000cP at 190 ℃. In other embodiments, the semi-crystalline propylene polymer exhibits a viscosity of no greater than 1200cP at 190 ℃. In another embodiment, the hot melt adhesive composition exhibits a resistance to thermal stress of greater than 71 ℃, greater than 25% fiber tear at-18 ℃ and greater than 25% fiber tear at 60 ℃.

In another embodiment, the composition exhibits a viscosity of no greater than 1500 centipoise at 149 ℃.

In another aspect, the present invention provides a package comprising the hot melt adhesive composition described herein, a first substrate comprising fibers, and a second substrate comprising fibers, the second substrate being bonded to the first substrate by the adhesive composition. In one embodiment, the adhesive exhibits fiber tear adhesion to at least one of the first substrate and the second substrate at-18 ℃ and at 60 ℃.

In another aspect, the present disclosure is directed to a hot melt adhesive composition comprising at least 40% by weight of an unmodified, semi-crystalline propylene polymer comprising at least 50% by weight propylene, at least 15% by weight of a non-functionalized wax comprising a first non-functionalized wax and a second non-functionalized wax different from the first non-functionalized wax, and no greater than 8% by weight of an ethylene-ethylenically unsaturated ester copolymer. In one embodiment, the adhesive composition further comprises an elastomeric block copolymer comprising styrene. In some embodiments, the elastomeric block copolymer is selected from the group consisting of styrene-ethylene/butylene-styrene block copolymers, styrene-ethylene/propylene-styrene block copolymers, and combinations thereof.

In other aspects, the present disclosure provides a hot melt adhesive composition comprising at least 40% by weight of an unmodified, semi-crystalline propylene polymer comprising at least 50% by weight propylene, at least 15% by weight of a non-functionalized wax, from 0% to no greater than 10% by weight of a functionalized wax, and from 1% to 10% by weight of an elastomeric block copolymer comprising styrene.

In some embodiments, the adhesive composition includes at least 45 wt% unmodified, semi-crystalline propylene polymer. In other embodiments, the adhesive composition includes at least 50 weight percent unmodified, semi-crystalline propylene polymer. In other embodiments, the adhesive composition includes at least 55 wt% unmodified, semi-crystalline propylene polymer.

In other embodiments, the adhesive composition includes 45 wt.% to about 70 wt.% unmodified, semi-crystalline propylene polymer, about 20 wt.% to about 35 wt.% non-functionalized wax, and about 1 wt.% to about 10 wt.% functionalized wax.

In other embodiments, the unmodified, semi-crystalline propylene polymer exhibits a heat of fusion from 15J/g to no greater than 50J/g.

In one embodiment, the first non-functionalized wax comprises a polyethylene wax, a fischer-tropsch wax, or a combination thereof. In some embodiments, the first non-functionalized wax has a melting point greater than 100 ℃. In other embodiments, the second non-functionalized wax has a melting point greater than 115 ℃.

In one embodiment, the adhesive composition further comprises a functionalized wax. In some embodiments, the first non-functionalized wax comprises a polyethylene wax, a fischer-tropsch wax, or a combination thereof, and the functionalized wax comprises a maleated polyethylene wax, a maleated polypropylene wax, or a combination thereof.

In some embodiments, the first non-functionalized wax has a melting point greater than 100 ℃. In other embodiments, the first non-functionalized wax has a melting point greater than 100 ℃ and the second non-functionalized wax has a melting point greater than 110 ℃.

In some embodiments, the adhesive composition includes greater than 20% by weight of the wax.

In another embodiment, the adhesive composition exhibits a set time of no greater than 2 seconds. In other embodiments, the adhesive composition exhibits a set time of no greater than 1.5 seconds. In other embodiments, the adhesive composition exhibits a set time of no greater than 1 second.

In some embodiments, the adhesive composition exhibits a resistance to thermal stress of greater than 60 ℃, greater than 50% fiber tear at 4 ℃ and greater than 50% fiber tear at 60 ℃, and a set time of no greater than 2 seconds. In other embodiments, the adhesive composition exhibits a resistance to thermal stress of greater than 60 ℃, greater than 50% fiber tear at 4 ℃, greater than 50% fiber tear at 60 ℃, and a set time of no greater than 1.5 seconds. In another embodiment, the adhesive composition exhibits a resistance to thermal stress of greater than 71 ℃, greater than 50% fiber tear at 4 ℃, greater than 50% fiber tear at 71 ℃, and a set time of no greater than 1.5 seconds. In another embodiment, the adhesive composition exhibits a resistance to thermal stress of greater than 71 ℃, greater than 50% fiber tear at-18 ℃, greater than 50% fiber tear at 71 ℃, and a set time of no greater than 1.5 seconds.

In other embodiments, the adhesive composition further comprises an oil, polybutene, or a combination thereof.

In another embodiment, the adhesive composition exhibits a viscosity of no greater than 2000 centipoise at 177 ℃. In other embodiments, the adhesive composition exhibits a viscosity of no greater than 1500 centipoise at 149 ℃.

In other embodiments, the adhesive composition includes from 50 wt% to about 65 wt% of the unmodified, semi-crystalline polypropylene polymer.

In other embodiments, the unmodified, semi-crystalline propylene polymer exhibits a viscosity of no greater than 1200cP at 190 ℃.

In another embodiment, the unmodified, semi-crystalline propylene polymer comprises an unmodified, metallocene-catalyzed, semi-crystalline propylene polymer, an unmodified, non-metallocene heteroaryl-catalyzed, semi-crystalline propylene polymer, or a combination thereof.

In another embodiment, the unmodified, semi-crystalline propylene polymer comprises an unmodified, metallocene-catalyzed, semi-crystalline propylene copolymer, an unmodified, non-metallocene heteroaryl-catalyzed, semi-crystalline propylene copolymer, or a combination thereof.

In other embodiments, the adhesive composition further comprises 15 wt% to 30 wt% tackifier.

In another aspect, the present invention provides a package comprising any of the hot melt adhesive compositions disclosed above, a first substrate comprising fibers, and a second substrate comprising fibers, the second substrate being bonded to the first substrate by the adhesive composition.

The present invention proposes a semicrystalline propylene polymer based hot melt adhesive composition showing fast setting time, thermal stability and good adhesion at low and high temperatures.

Other features and advantages will be apparent from the following description of the preferred embodiments and from the claims.

Glossary

In connection with the present invention, these terms have the following meanings:

the term "wax" as used herein refers to a polymer or oligomer having a heat of fusion of greater than 60 joules/gram and a viscosity of no greater than 750 centipoise (cP) at 190 ℃.

The term "semi-crystalline polymer" refers to a polymer having a heat of fusion of greater than 10J/g to no greater than 60J/g and a viscosity of at least 750cP at 190 ℃.

The term "unmodified polymer" refers to a polymer that has not been modified in the presence of a free radical initiator.

The term "non-functionalized wax" refers to a wax that does not contain polar functional groups.

The term "functionalized wax" refers to a wax having at least one polar functional group.

Detailed description of the invention

The hot melt adhesive composition includes at least 40% by weight of a semi-crystalline propylene polymer including at least 50% by weight propylene and a wax. The hot melt adhesive composition exhibits a fast set time: preferably a set time of not more than 5 seconds, not more than 3 seconds, not more than 2 seconds, not more than 1.5 seconds or even not more than 1 second. The hot melt adhesive composition also exhibits tear adhesion to the fibers of the fibrous packaging material at low and high temperatures. The hot melt adhesive composition preferably exhibits greater than 25%, greater than 30%, greater than 40%, greater than 45%, greater than 50% or even greater than 70% fiber tear at 4 ℃, -18 ℃, or even at-29 ℃, and greater than 25%, greater than 30%, greater than 40%, greater than 45%, greater than 50% or even greater than 70% fiber tear at 60 ℃ or even at 71 ℃.

The hot melt adhesive composition also exhibits good resistance to thermal stress, preferably at least 54 ℃, at least 60 ℃, at least 66 ℃, at least 71 ℃ or even at least 76 ℃.

The hot melt adhesive composition preferably exhibits a viscosity of no greater than 5000cP, no greater than about 3000cP, no greater than about 2000cP, no greater than about 1500cP, no greater than about 1200cP, or even no greater than about 1000cP at 177 ℃, and a viscosity of no greater than about 3000cP, no greater than about 2000cP, or even no greater than about 1000cP at 190 ℃. The hot melt adhesive composition can be formulated to exhibit a viscosity of no greater than 2000cP, no greater than about 1500cP, no greater than about 1300cP, or even no greater than about 1200cP at 149 ℃ or even at 135 ℃.

The hot melt adhesive composition also exhibits good thermal stability. Two measures of thermal stability are viscosity change over time and the presence of charring. After conditioning at 177 ℃ for 200 hours, the hot melt adhesive composition preferably exhibits a viscosity change of no more than 20% or even no more than 10% relative to its initial viscosity at 177 ℃ and exhibits minimal or even no charring and skinning, i.e. the formation of a skin on the surface of the composition.

The hot melt adhesive composition also preferably exhibits an initial Gardner color of no greater than 3, no greater than 2, or even no greater than 1.

Semi-crystalline propylene polymers

The propylene polymers are semi-crystalline and exhibit a heat of fusion of greater than 10 joules/gram (J/g) to no greater than 60J/g, from about 15J/g to about 50J/g, or even from about 15J/g to about 45J/g. The propylene polymer exhibits a viscosity at 190 ℃ of at least 750cP, no greater than 5,000cP, no greater than 4,000cP, no greater than 3,000cP, no greater than 2,000cP, or even no greater than 1,000 cP.

The propylene polymer preferably exhibits a glass transition temperature (Tg) of no greater than-10 ℃, no greater than-20 ℃, or even no greater than-30 ℃.

Useful propylene polymers include, for example, polypropylene homopolymers (i.e., 100 mole percent propylene), propylene copolymers (i.e., copolymers, terpolymers, and higher polymers), mixtures of at least two different propylene polymers including, for example, blends comprising polypropylene homopolymers and propylene copolymers, blends comprising different polypropylene homopolymers, blends comprising different propylene copolymers, and various combinations thereof. Useful propylene polymers also include, for example, modified, unmodified, grafted and ungrafted propylene polymers, unimodal propylene polymers, multimodal propylene polymers and combinations thereof. The term "multimodal" refers to a polymer having a multimodal molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) as determined by Size Exclusion Chromatography (SEC). When the SEC trace has more than one peak or inflection point (i.e., two or more inflection points), there is a multimodal molecular weight distribution. An inflection point is a point at which the sign of the second derivative changes (e.g., from negative to positive, or vice versa). The term "unimodal" means that the polymer has a unimodal molecular weight distribution (Mw/Mn) as determined by SEC. When the SEC trace has only one peak, there is a monomodal molecular weight distribution.

Useful propylene copolymers are derived from propylene and alpha-olefin comonomers (e.g., alpha-olefin monomers having at least 2 carbon atoms, at least 4 carbon atoms, 4 carbon atoms to 8 carbon atoms, and combinations of such monomers). Examples of suitable classes of alpha-olefin comonomers include mono alpha-olefins (i.e., one unsaturated double bond) and higher alpha-olefins (e.g., dienes (e.g., 1, 9-decadiene)). Useful alpha-olefin monomers include, for example, ethylene, butene, pentene, hexene, heptene, octene, nonene, decene, dodecene, 4-methyl-pentene-1, 3,5, 5-trimethyl-hexene-1, 5-ethyl-1-nonene, and combinations thereof. Specific examples of suitable propylene- α -olefin copolymers include propylene-ethylene, propylene-butene, propylene-hexene, propylene-octene, and combinations thereof.

The propylene copolymer preferably comprises at least 1 wt%, at least 2 wt%, at least about 5 wt%, at least about 10 wt%, no greater than 50 wt%, no greater than about 40 wt%, no greater than 30 wt%, no greater than 20 wt%, no greater than 17 wt%, no greater than 15 wt%, or even no greater than 10 wt% alpha-olefin comonomer, and at least 50 wt%, at least about 60 wt%, no greater than 99 wt%, no greater than 98 wt%, no greater than 95 wt%, no greater than 90 wt%, about 50 wt% to about 99 wt%, about 60 wt% to about 99 wt%, or even about 70 wt% to about 99 wt% propylene.

Useful propylene polymers include propylene polymers made using a variety of catalysts, including, for example, single site catalysts (e.g., metallocene catalyzed propylene polymers)), multiple single site catalysts, non-metallocene heteroaryl catalysts, and combinations thereof. Other suitable polymers include polymers made by grafting amorphous propylene polymers onto semi-crystalline polymers, examples of which and methods of making are disclosed in, for example, U.S. Pat. No. 7,541,402 (abhara et al) and incorporated herein. The propylene polymer may comprise isotactic polypropylene blocks and atactic polypropylene blocks.

Suitable propylene polymers are available under various trade names, including, for example, VISTAMAXX 8880 propylene-ethylene copolymer, VISTAMAXX 8816 propylene-hexene copolymer, and LINXAR propylene-hexene copolymer from ExxonMobil Chemical Company (Houston, Texas), including LINXAR 127, and LICOCENE propylene-ethylene copolymer from Clariant Int' l ltd. (Muttenz, Switzerland), including, for example, LICOCENE PP 1502 TP, PP1602 TP, and PP 2602 TP.

The hot melt adhesive composition includes at least 40 wt%, at least 45 wt%, at least 50 wt%, at least 55 wt%, not greater than about 84 wt%, not greater than about 80 wt%, not greater than about 75 wt%, about 70 wt%, not greater than about 65 wt%, not greater than about 60 wt%, about 40 wt% to about 84 wt%, about 45 wt% to about 80 wt%, or even about 45 wt% to about 60 wt% propylene polymer.

Wax

The hot melt adhesive composition includes at least two different waxes (e.g., at least two different non-functionalized waxes, at least two different functionalized waxes, a functionalized wax, and a non-functionalized wax, and combinations thereof). The hot melt adhesive composition includes at least 15 wt%, greater than 20 wt%, 20 wt% to 35 wt%, at least 15 wt% to about 35 wt%, greater than 15 wt% to about 35 wt%, or even about 15 wt% to about 30 wt% wax.

Non-functionalized waxes

Useful non-functionalized waxes have a melting point of at least 50 ℃, at least 60 ℃, at least 80 ℃, at least 100 ℃, or even at least 115 ℃ and a heat of fusion of greater than 60J/g or even greater than 70J/g. Examples of suitable non-functionalized waxes include polyolefin waxes (e.g., polypropylene waxes and polyethylene waxes), fischer-tropsch waxes, paraffin waxes, microcrystalline waxes, metallocene waxes, and combinations thereof (e.g., a combination of two non-functionalized waxes each having a melting point of at least 115 ℃). The hot melt adhesive composition preferably includes at least 15 wt%, greater than 20 wt%, at least 15 wt% to about 35 wt%, greater than 15 wt% to about 35 wt%, or even about 15 wt% to about 30 wt% non-functionalized wax.

Useful polyethylene waxes are commercially available under various trade names, including, for example, the trade name of the EPOLENE series from Westlake chemical corporation (Houston, Texas), including, for example, EPOLENE N-21 and N-14 polyethylene waxes, the trade name of the BARRECO series from Baker Hughes Inc. (Sun Land, Texas), including, for example, BARRECO C4040 polyethylene waxes, the trade name of the AC series from Honeywell Int' l Inc. (Morristown, New Jersey), including, for example, A-C8 and A-C9 polyethylene waxes, the trade name of the POLYWAX series from Baker Hughes (Houston, Texas), including POLYWAX 3000 polyethylene waxes, and CWP 400 polyethylene waxes from SSI CHUSEI, Inc. (Pasedena, Texas). The hot melt adhesive composition may include from 0 wt% to about 35 wt%, at least 1 wt%, at least 7 wt%, at least 10 wt%, from about 1 wt% to about 30 wt%, from about 1 wt% to about 25 wt%, from about 5 wt% to about 20 wt%, or even from about 5 wt% to about 15 wt% polyethylene wax.

Useful polypropylene waxes are commercially available under various trade names including, for example, EPOLENE N-15 from Westlake Chemical, Honeywell Int 'l inc, Honeywell AC1089, and LICOCENE6102 from Clariant Int' ltd. (Muttenz, Switzerland). The hot melt adhesive composition may include from 0 wt% to about 35 wt%, from about 1 wt% to about 25 wt%, or even from about 1 wt% to about 20 wt% polypropylene wax.

Useful Fischer-Tropsch waxes are commercially available under various trade names, including, for example, those from the BARER Hughes Inc. (Suralland, Texas), including, for example, BARRECO PX-100 and PX-105 Fischer-Tropsch waxes, those from the SHELLWAX series of ShellMalaysia Ltd. (Kuala Lumpur, Malaysia), including, for example, SHELLWAX AXSX100 and SX105 Fischer-Tropsch waxes, those from the VESONIK Industries AG (Germany), including, for example, VESOSAX 2050 Fischer-Tropsch waxes, and those from the SASOLWAX series of Sasol Wax North America Corporation (Hayward, California), including, for example, SASOLWAX H105, C80, H1, and H4 Fischer-Tropsch waxes. The hot melt adhesive composition may include from 0 wt% to about 35 wt%, at least 1 wt%, at least about 5 wt%, from about 1 wt% to about 30 wt%, from about 1 wt% to about 25 wt%, from about 5 wt% to about 10 wt%, or even from about 4 wt% to about 8 wt% fischer-tropsch wax.

Useful paraffins are available under various trade names, including, for example, PARVAN 1580 and 1520 paraffins from ExxonMobil Chemical Company (Houston, Texas) and CALUMET FR-6513 from Calumet Specialty products & targets, LP (Indianapolis, Indiana). The hot melt adhesive composition may include from 0 wt% to about 35 wt%, from about 1 wt% to about 25 wt%, from about 1 wt% to about 20 wt%, or even from about 0 wt% to about 15 wt% paraffin wax.

Functionalized waxes

Useful functionalized waxes have a melting point of at least 50 ℃, at least 60 ℃, at least 80 ℃, at least 100 ℃, or even at least 115 ℃, and a heat of fusion of greater than 60J/g or even greater than 70J/g. Examples of suitable functionalized waxes include functionalized polypropylene waxes (e.g., maleated polypropylene waxes and oxidized polypropylene waxes), functionalized polyethylene waxes (e.g., maleated polyethylene waxes and oxidized polyethylene waxes), polar waxes, functionalized stearamide waxes (e.g., hydroxystearamide, N- (2-hydroxyethyl) -12-hydroxystearamide, N '-ethylene bis 12-hydroxystearamide and 12-hydroxystearic acid, N' ethylene-bis stearamide), and combinations thereof. Useful commercially available functionalized waxes include, for example, A-C597P, A-C596P and A-C1325 maleated polypropylene waxes and A-C573 maleated polyethylene waxes, both available from Honeywell Int' l Inc. (Morristown, New Jersey), and Westlake E43 maleated polypropylene waxes available from Westlake Chemical Corporation (Houston, Texas).

The functionalized wax may be present in the hot melt adhesive composition in an amount of about 0 wt% to no greater than 10 wt%, about 1 wt% to no greater than 10 wt%, about 0.2 wt% to about 5 wt%, about 1 wt% to about 4 wt%, about 2 wt% to about 3.5 wt%, no greater than 2 wt%, or even no greater than 1 wt%. Optionally, the hot melt adhesive composition is free of functionalized wax.

Oil

The hot melt adhesive composition optionally includes an oil. Useful classes of oils include, for example, petroleum-based naphthenic oils (napthenic petroleum-based oils), paraffinic oils (e.g., naphthenic oils), mineral oils, animal oils, vegetable oils, synthetic oils, derivatives of oils, glycerides of fatty acids, and combinations thereof.

Commercially available OILs that may be used include KAYDOL OIL from sonneborn (tarrytown New york), KRYSTOL 550 mineral OIL from Petrochem Carless Limited (Surrey, England), and CALSOL 550 naphthenic OIL from calumet specialty Products Partners, LP (Indianapolis, Indiana).

The hot melt adhesive composition optionally includes from 0 wt% to not greater than about 20 wt%, not greater than about 15 wt%, not greater than about 12 wt%, from about 0.5 wt% to about 10 wt%, from about 1 wt% to about 10 wt%, or even from about 2 wt% to about 5 wt% oil.

Polybutylene

The hot melt adhesive composition optionally includes polybutene having a weight average molecular weight of no greater than about 2000 g/mole. Useful polybutenes are available under various trade names including, for example, TPC595 from the TPC Group (Houston Texas), the trade name of the INDOOL series from Ineos Europe, Limited (Belgium), and the trade name of the PARAPOL series from the ExxonMobil chemical Company (Houston, Texas).

The hot melt adhesive composition optionally includes 0 wt.% to not greater than about 20 wt.%, not greater than about 15 wt.%, not greater than about 12 wt.%, about 0.5 wt.% to about 10 wt.%, about 1 wt.% to about 10 wt.%, or even about 2 wt.% to about 5 wt.% polybutene.

Tackifier

The hot melt adhesive composition optionally includes a tackifier. Useful tackifiers exhibit a Tg of no greater than 90 ℃, no greater than 80 ℃, no greater than 70 ℃, no greater than 60 ℃, or even no greater than 50 ℃ and a ring and ball softening point of less than about 160 ℃. Suitable classes of tackifiers include, for example, aromatic, aliphatic, and cycloaliphatic hydrocarbon resins, mixed aromatic and aliphatic modified hydrocarbon resins, aromatic modified aliphatic hydrocarbon resins, and hydrogenated versions thereof; terpenes, modified terpenes, and hydrogenated forms thereof; natural rosins, modified rosins, rosin esters, and hydrogenated versions thereof; low molecular weight polylactic acid; and combinations thereof. Examples of natural and modified rosins that may be used include gum rosin, wood rosin, tall oil rosin, distilled rosin, hydrogenated rosin, dimerized rosin, and polymerized rosin. Examples of useful rosin esters include, for example, glycerol esters of xanthene resin (palle wood rosin), glycerol esters of hydrogenated rosin, glycerol esters of polymerized rosin, pentaerythritol esters of natural and modified rosins, including pentaerythritol esters of xanthene resin, hydrogenated rosin, tall oil rosin, phenolic modified rosin pentaerythritol esters, and combinations thereof. Examples of useful polyterpene resins include polyterpene resins having a softening point of about 10 ℃ to about 160 ℃ as determined by ASTM method E28-58T, copolymers and terpolymers of hydrogenated polyterpene resins and natural terpenes (e.g., styrene-terpene, alpha-methylstyrene-terpene, and vinyltoluene-terpene), and combinations thereof. Examples of useful aliphatic and cycloaliphatic petroleum hydrocarbon resins include aliphatic and cycloaliphatic petroleum hydrocarbon resins having a ring and ball softening point of about 10 ℃ to 160 ℃, hydrogenated derivatives thereof, and combinations thereof. Suitable aliphatic and cycloaliphatic petroleum hydrocarbon resins include, for example, branched, unbranched, and cyclic C5 resins, C9 resins, and C10 resins.

Useful tackifiers are available under various trade names including, for example, those from the ESCOREZ series of ExxonMobil Chemical Company (Houston, Texas), including, for example, ESCOREZ 1310LC, ESCOREZ5400, ESCOREZ 567, ESCOREZ 5415, ESCOREZ 5600, ESCOREZ 5615 and ESCOREZ 5690, those from the EASTman Chemical Company (Kingsport, Tennessee), including, for example, Eastac H-100R, EATAC H-100L and EASTOTAC H130W, those from the WINGTValley HSC (Exton, Pennsylvania), including, for example, WINGTACK 86, WINGTEXACK TRA and WINGTACK 95, those from the Cray Valley HSC (Exton, Tennsylvania), those from the COGTACK series including, for example, COCOREAZ series including, and those from the GmARKAALL series including, for example, REKANTEastEAN series including, REJOBORE AGZ and REJOBE series including, ESORE series including, ESCORE AGZ from EastEANZ and REGALN REGALITE R, including RESINALL R1030.

Useful tackifiers that are liquid at room temperature (i.e., 20 ° F to 22 ° F) include, for example, REGALREZ 1018 hydrocarbon resin from Eastman Chemical Company, piccolostic a5 hydrocarbon resin from Eastman Chemical Company, and WINGTACK 10 from Cray Valley (Exton, Pennsylvania).

The hot melt adhesive composition optionally includes at least about 1 wt%, at least 5 wt%, at least about 10 wt%, at least about 15 wt%, at least about 20 wt%, not greater than about 40 wt%, not greater than about 35 wt%, not greater than about 30 wt%, not greater than about 25 wt%, from about 15 wt% to about 30 wt%, or even from about 20 wt% to about 25 wt% tackifier.

For some hot melt adhesive compositions that include at least 55 wt% of a semi-crystalline polypropylene polymer, useful amounts of the optional tackifier include from about 0 wt% to not greater than about 30 wt%, from 1 wt% to not greater than about 30 wt%, from about 1 wt% to about 20 wt%, from about 1 wt% to about 15 wt%, from about 1 wt% to about 10 wt%, not greater than about 7 wt%, or even not greater than about 0.5 wt%.

Additive agent

The hot melt adhesive composition optionally includes various additional components including, for example, antioxidants, stabilizers, additional polymers, adhesion promoters, ultraviolet light stabilizers, rheology modifiers, corrosion inhibitors, colorants (e.g., pigments and dyes), fillers, flame retardants, nucleating agents, and combinations thereof.

Useful antioxidants include, for example, pentaerythritol tetrakis [3, (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2' -methylenebis (4-methyl-6-tert-butylphenol) phosphite, including, for example, tris- (p-nonylphenyl) -phosphite (TNPP) and bis (2, 4-di-tert-butylphenyl) 4,4' -diphenylene-diphosphonite, distearyl-3, 3' -thiodipropionate (DSTDP), and combinations thereof. Useful antioxidants are available under various trade names, including, for example, those of the IRGANOX series, including, for example, IRGANOX 1010, IRGANOX 565, and IRGANOX 1076 hindered phenolic antioxidants, and IRGAFOS168 phosphite antioxidants, all available from BASF Corporation (Florham Park, New Jersey), and ETHYL 7024, 4' -methylenebis (2, 6-di-tert-butylphenol), available from Albemarle Corporation (Baton Rouge, Louisiana). When present, the adhesive composition preferably includes from about 0.1% to about 2% by weight antioxidant.

Additional polymers that can be used include, for example, homopolymers, copolymers, and terpolymers, thermoplastic polymers including, for example, other polyolefins (e.g., high viscosity propylene ethylene polymers), ziegler-natta catalyzed amorphous polyalphaolefins (e.g., amorphous propylene ethylene polymers), and combinations thereof), elastomers including, for example, elastomeric block copolymers (e.g., elastomeric block copolymers including styrene (e.g., styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene/butylene-styrene, styrene-ethylene/propylene-styrene, and combinations thereof), metallocene-based elastomeric block copolymers, and combinations thereof), and functionalized versions and combinations thereof.

The high viscosity polymer exhibits a viscosity greater than 100,000 at 121 ℃. Additional high viscosity polyolefin polymers that may be used include, for example, high viscosity amorphous polyalphaolefins, high viscosity crystalline polyolefins, high viscosity semi-crystalline polyolefins, and combinations thereof. Suitable high viscosity polyolefins are available from the trade names of the L-MODU series of Idemitsu Kosan Co., Ltd (Japan), including, for example, L-MODUS400, S600 and S901 propylene homopolymers, and VISTA AX propylene-ethylene copolymers from ExxonMobil Chemical Company (Houston, Texas), including, for example, VISTA AX 6202, 3980 and 2330.

Ziegler-Natta catalyzed amorphous polyalphaolefin polymers are available under various trade names, including, for example, the REXTAC series trade names available from Rextac LLC (Odessa, Texas) and the EASTOFLEX and AERAFIN series trade names from Eastman Chemical Company (Kingsport Tennessee).

The hot melt adhesive composition optionally includes a polyolefin polymer that is not greater than about 10 wt%, about 1 wt% to not greater than about 7 wt%, or even not greater than about 5 wt% of a non-semicrystalline propylene polymer.

Useful elastomeric block copolymers are available under various trade names, including, for example, Kraton G1657 styrene-ethylene/butylene-styrene block copolymer and G1652 styrene-ethylene/propylene-styrene block copolymer from Kraton Polymers u.s.llc (Houston, Texas), and VECTOR 4411 styrene-isoprene-styrene block copolymer from TSRC Dexco Polymers LP (taipeiccity, Taiwan r.o.c). The hot melt adhesive composition optionally includes from about 1 wt% to about 10 wt%, or even from about 4 wt% to about 10 wt% of a block copolymer including styrene.

The hot melt adhesive composition is preferably free of ethylene-ethylenically unsaturated ester copolymers such as ethylene vinyl acetate, ethylene acrylate, ethylene methacrylate, and ethylene butyl acrylate. When present in the hot melt adhesive composition, the ethylene-ethylenically unsaturated ester copolymer is preferably present in an amount of less than 8 wt%, no greater than 5 wt%, no greater than 3 wt%, or even no greater than 1 wt%.

Use of

The hot melt adhesive composition can be applied to or incorporated into a variety of articles including, for example, fibers, substrates made from fibers (e.g., virgin fibers), recycled fibers, synthetic polymer fibers (e.g., nylon, rayon, polyester, acrylic, polypropylene, polyethylene, polyvinyl chloride, polyurethane), cellulosic fibers (e.g., natural cellulosic fibers such as wood pulp), natural fibers (e.g., cotton, silk, and wool), and glass fibers, and combinations thereof), release liners, porous substrates, cellulosic substrates, sheet materials (e.g., paper and fiber sheets), paper products, woven and nonwoven webs (e.g., webs made from fibers (e.g., yarns, threads, filaments, microfibers, blown fibers (blon fibers) and spun fibers (spun fibers)), perforated films, and combinations thereof), tape backings (tape backings), and combinations thereof.

The hot melt adhesive composition can be used to bond a variety of substrates including, for example, chipboard, coated chipboard, paperboard, fiberboard, virgin and recycled kraft, high and low density kraft, chipboard, treated and coated kraft and chipboard, and corrugated forms thereof, clay coated cardboard stock (clay coated chipboard stock), composites, leather, fibers and substrates made from fibers (e.g., virgin fibers, recycled fibers, synthetic polymer fibers, cellulosic fibers, and combinations thereof), release liners, porous substrates (e.g., woven webs, nonwoven webs, and perforated films), cellulosic substrates, sheets (e.g., paper and fiber sheets), paper products, tape backings, and combinations thereof.

The hot melt adhesive composition can be used to bond a first substrate to a second substrate in a variety of uses and configurations, including, for example, packaging, bags, boxes, cartons, cases, trays, multi-layer bags, articles including accessories (e.g., a straw attached to a beverage box), ream wrap, cigarettes (e.g., plug wrap), filters (e.g., pleated filters and filter frames), bookbindings, paper products including, for example, paper towels (e.g., multipurpose towels), toilet tissue, facial tissue, wipes, tissue, towels (e.g., paper towels), and combinations thereof.

The hot melt adhesive composition can be applied to a substrate in any useful form, including, for example, as a coating (e.g., continuous coating and discontinuous coating (e.g., random, pattern, or array)), as beads, as a film (e.g., continuous and discontinuous films), and combinations thereof, using any suitable application method, including, for example, slot coating, spray coating (e.g., spiral spray coating, random spray coating, and random fiberization (e.g., melt blowing)), foaming, extrusion (e.g., bead application, fine line extrusion, single screw extrusion, and twin screw extrusion), reel application, non-contact coating, gravure printing, engraved roll, roll coating, transfer coating, screen printing, flexographic printing, "on-demand" application methods, and combinations thereof.

In on-demand hot melt application systems (which are also referred to as "tank free" and "tank less" systems), the hot melt composition is fed in a solid state (e.g., pellets) into a relatively small heating vessel (as opposed to conventional hot melt application systems that include a tank) where the hot melt composition is melted and, typically shortly thereafter, the molten liquid is applied to a substrate. In on-demand systems, relatively large amounts of hot melt compositions generally do not remain molten for long periods of time. In many existing on-demand systems, the volume of the molten hot melt composition is no greater than about 1 liter or even no greater than about 500 milliliters, and the hot melt composition remains molten for a relatively short period of time, including, for example, less than 2 hours, less than 1 hour, or even less than 30 minutes. Suitable hot melt on demand adhesive application systems include, for example, the InvisiPac Tank-Free HotMelt Delivery System from Graco Minnesota Inc. (Minneapolis, Minnesota) and the Free HotMelt Dispensing System from Nordson Corporation (Westlake, Ohio). On-demand hot melt adhesive application systems are described in U.S. patent publication nos. 2013-0105039, 2013-0112709, 2013-0112279 and 2014-0042182 and U.S. patent No.8,201,717 and incorporated herein.

The invention will now be described by way of the following examples. All parts, ratios, percentages, and amounts specified in the examples are by weight unless otherwise specified.

Examples

Test procedure

The test procedures used in the examples include the following. All ratios and percentages are by weight unless otherwise indicated. Unless otherwise specified, these procedures are carried out at room temperature (i.e., ambient temperature of about 20 ℃ to about 25 ℃) and ambient humidity (i.e., 30% to 70%).

Method for determining molecular weight

Molecular weights (Mn, Mw and Mz) were determined using Polymer Labs PL-GPC220 high temperature size exclusion chromatography (HT-SEC) run at 160 ℃ with 1,2, 4-Trichlorobenzene (TCB) as the mobile phase. The system contained three PL gel mixed B columns in series and was equipped with a Refractive Index (RI) detector. SEC was run at an injection volume of 100 microliters at a flow rate of 1.0 ml/min. All HT-SEC samples were prepared at a concentration of 4.0 mg/ml. Molecular weights were calculated from the Mark-Houwink relationship using known polystyrene standards. For polystyrene, the Mark-Houwink parameters are K0.000121 and α 0.707; for polypropylene, the Mark-Houwink parameters are K0.000190 and α 0.725. Results are reported in grams per mole (g/mole).

Viscosity test method

The viscosity was determined according to ASTM D-3236 (10/31 1988) entitled "Standard Test Method for applied viscosity of Hot melt additives and Coating Materials" using a Brookfield viscometer, a Brookfield Thermosel heated sample cell, and a 27 spindle. Results are reported in centipoise (cP).

Solidification time test method

A bead of the adhesive composition, measured as 5.08cm x0.24cm, was applied to a first substrate of RockTenn 56SK-23ME-56SK high performance 44 pound ECT 87% virgin liner (virgininer board) using a MEC ASM-15N hot melt adhesion simulator at 177 ℃.2 seconds after the adhesive bead was applied to the first substrate, the adhesive bead was contacted with a second substrate of RockTenn 56SK-23ME-56SK high performance 44 pound ECT 87% virgin liner, which was then pressed against the first substrate at a pressure of 0.21MPa for a period of time (referred to herein as the compression time). The bond simulator timer is started when the substrate is compressed. After a pre-programmed compression time, the instrument separates the two substrates by pulling the second substrate in the Z-direction and holding the first substrate in a fixed position, and measures the force required to separate the substrates and the amount of fiber tear present on the adhesive composition. Samples were run in triplicate at each compression time. Initially, the compression time was 0.5 seconds. If the three samples fail to exhibit greater than 50% fiber tear for each sample, the compression time is increased by 0.1 seconds and the test method is repeated until greater than 50% fiber tear is noted for all three samples. Set time was recorded as the compression time for these three samples to achieve greater than 50% fiber tear upon separation. The clotting time was recorded in seconds.

Thermal stress resistance test method

Thermal stress resistance was measured according to the standard IOPP T-3006 entitled "coated Test Method for Determining the Heat stress resistance of Hot Melt Adhesives" using an onset temperature of 46℃ (115F), a 200 gram load per sample and 5 adhesive samples per adhesive. After each 24 hours, the number of samples that no longer supported the weight was recorded and the temperature was increased by 2.8 ℃ (5.0 ° F). The pass temperature (passtemperature) of each adhesive, defined as the maximum temperature at which 80% of the sample remains bonded, is the resistance to thermal stress and is reported in degrees celsius (c).

Fiber tear test method

The percent fiber tear is the percentage of fiber covering the area of the adhesive after the two substrates previously bonded together by the adhesive are forcibly separated. The percent fiber tear exhibited by the adhesive composition was determined as follows. A bead of adhesive composition measuring 15.24cm (6 inches) x0.24cm (3/32 inches) was applied to a first substrate of ROCKTENN 56SK-23ME-56SK 44 pound ECT 87% virgin liner using a ROCKTENN adhesion simulator at a specified application temperature. 2 seconds after the adhesive bead was applied to the first substrate, the adhesive bead was contacted with a second substrate of RockTenn 56SK-23ME-56SK 44 pound ECT 87% virgin liner, which was pressed against the adhesive and first substrate at a pressure of 0.21MPa (30 pounds per square inch (psi)) for 2 seconds. The resulting construct was then conditioned at room temperature for at least 4 hours, and then at the specified test temperature for at least 12 hours. The constructed substrates are then separated from each other by pulling the two substrates apart from each other by hand at the conditioning temperature (e.g., immediately after removing the sample from the conditioning chamber). The surface of the binder composition was observed and the percent surface area of the binder composition covered by the fibers was determined and recorded. A minimum of five samples were prepared and tested for each hot melt adhesive composition. Results are reported in% fiber tear.

Thermal stability test method

A 200 gram sample of the hot melt adhesive composition was placed in a glass beaker (no lid) and conditioned in a temperature controlled forced air oven at 177 ℃ for 200 hours. The molten sample was removed from the oven. The molten sample was observed for the presence of gels, surface skinning and charring. The observations were recorded.

The samples were then tested according to the viscosity test method and the measured viscosity was expressed in centipoise.

Thermal stability is determined by the change in viscosity and the presence or absence of charring or skinning.

Melting point test method

The melting Point is determined according to ASTM D-3461 entitled "Standard Test Method for Soft Forming Point of Asphal and Pitch (Method Cup and Ball Method)" with a heating rate of 2 ℃ per minute.

Gardner color

The samples (in the melt state) were tested to determine the Gardner color by comparing the sample colors against a Gardner color standard as set forth in ASTM D-1544. The comparison was performed using a Gardner Delta comparator equipped with an illuminator available from Pacific Scientific (Bethesda, Maryland). Results are reported as values relative to the Gardner color standard.

Examples 1 to 4

The hot melt adhesive compositions of examples 1-4 were prepared by combining the amounts (wt%) and types of LINXAR 127 propylene-hexene copolymer (ExxonMobil Chemical Company, Houston, Texas) specified in Table 1, wax, oil and antioxidant and heating them to 175 ℃ to 190 ℃ with mixing.

The hot melt adhesive compositions of examples 1-4 were tested according to the viscosity, set time, resistance to thermal stress and fiber tear test methods. The results are reported in table 1.

TABLE 1

Examples	1	2	3	4
					LINXAR 1271	71.8	72	77	71
CALSOL 5502	5	9.8	0	7.8
					EPOLENE N-213	15	15	19.8	18
EPOLENE N-154	5	0	0	0
					WESTLAKE E-435	3	3	3	3
IRGANOX 10106	0	0.2	0.2	0.2
					EVERNOX 107	0.2	0	0	0
IRGANOX 10768	0	0	0	0
					Viscosity @177 ℃ (cP)	966	680	940	735
Setting time (seconds)	1.0	1.7	1.1	1.4
					Resistance to thermal stress (. degree.C.)	57	63	>85	79
-29℃	80	55	92	94
					-18℃	80	80	98	100
4℃	100	98	100	100
					49℃	100	NT	NT	NT
54℃	NT	100	100	100
					60℃	100	100	100	100
66℃	NT	98	NT	NT
					71℃	NT	86	93	91

1 ═ LINXAR 127 propylene-hexene copolymer having a density of 0.860 g/cc, a viscosity of 825cP at 190 ℃ and a peak melting temperature of 125 ℃ (ExxonMobil Chemical Company, Houston, Texas)

2 ═ CALSOL 550 naphthenic oils (Calumet Specialty Products Partners, LP, Indianapolis, Indiana)

EPOLENE N-21 polyethylene wax (Westlake Chemical Corporation, Houston, Texas)

4-EPOLENE N-15 Polypropylene wax (Westlake Chemical Corporation)

5-WESTLAKE E-43 maleic anhydride modified Polypropylene wax (Westlake Chemical Corporation)

6-IRGANOX 1010 hindered phenolic antioxidant (BASF Corporation, Florham Park, New Jersey)

EVERNOX 10 hindered phenolic antioxidant (Evershift Chemical, Taichung, Taiwan)

IRGANOX 1076 hindered phenolic antioxidant (BASF Corporation, Florham Park, New Jersey)

NT ═ untested

Examples 5 to 8

The hot melt adhesive compositions of examples 5-8 were prepared by combining the amounts (wt%) and types of LINXAR 127 propylene-hexene copolymer (ExxonMobil Chemical Company, Houston, Texas) specified in Table 2, wax, oil, antioxidant and tackifier and heating them to 175 ℃ to 190 ℃ with mixing.

The hot melt adhesive compositions of examples 5-8 were tested according to the viscosity, set time, resistance to thermal stress and fiber tear test methods. The results are reported in table 2.

TABLE 2

ESCOREZ5400 cycloaliphatic hydrocarbon resin having a Tg of 52 ℃ (ExxonMobil)

Corporation,Houston,Texas)

Examples 9 to 13

The hot melt adhesive compositions of examples 9-13 were prepared by combining the amounts (wt%) and types of LINXAR 127 propylene-hexene copolymer (ExxonMobil Chemical Company, Houston, Texas) specified in Table 3, wax, oil (when present), and antioxidant and heating them to 175 ℃ to 190 ℃ with mixing.

The hot melt adhesive compositions of examples 9-13 were tested according to at least one of the viscosity, set time, resistance to thermal stress and fiber tear test methods. The results are reported in table 3.

TABLE 3

10 ═ POLYWAX 3000 polyethylene wax (Baker Hughes, Houston, Texas)

11-SX-105 Fischer-Tropsch wax (Shell Malaysia Ltd., Kuala Lumpur, Malaysia)

12 ═ FR-6513 paraffin (Calumet Specialty Products Partners, LP, Indianapolis, Indiana)

Examples 14 to 17

The hot melt adhesive compositions of examples 14-17 were prepared by combining the amounts (wt%) and types of components specified in table 4 and heating them to 175 ℃ to 190 ℃ with mixing.

The hot melt adhesive compositions of examples 14-17 were tested according to at least one of viscosity, set time, resistance to thermal stress, and fiber tear test methods. The results are reported in table 4.

TABLE 4

13-VISTA MAX 8880 metallocene catalyzed propylene-ethylene copolymer (ExxonMobil chemical company, Houston, Texas)

14-VISTA MAX 3980FL metallocene catalyzed polypropylene elastomer (ExxonMobil)

15-VISTA MAX 6202 propylene-ethylene copolymer (ExxonMobil)

16-KRATON G1657 styrene-ethylene-butylene-styrene Block copolymer (Kraton polymers LLC, Houston, Texas)

17 ═ ESCOREZ 5637 aromatic modified alicyclic hydrocarbon resin (ExxonMobil)

18 ═ AC 596P maleated polyethylene wax (Honeywell Int' l Inc., Morristown, New Jersey)

19 ═ SARAWAX SX105 Fischer-Tropsch wax (Shell Malaysia Ltd., Kuala Lumpur, Malaysia)

Examples 18 and 19

The hot melt adhesive compositions of examples 18 and 19 were prepared by combining the amounts (wt%) and types of components specified in table 5 and heating them to 175 ℃ to 190 ℃ with mixing.

The hot melt adhesive compositions of examples 18 and 19 were tested according to at least one of viscosity, set time and fiber tear test method. The results are reported in table 5.

TABLE 5

Examples 20 to 22

The hot melt adhesive compositions of examples 20-22 were prepared by combining the amounts (wt%) and types of components specified in table 6 and heating them to 175 ℃ to 190 ℃ with mixing.

The hot melt adhesive compositions of examples 20-22 were tested according to at least one of viscosity, set time, and fiber tear test methods. The results are reported in table 6.

TABLE 6

20＝RESINAL R1030(Resinall Corp,Severn,North Carolina)

Other embodiments are within the claims. All documents cited herein are incorporated in their entirety.

1. A hot melt adhesive composition comprising at least 40% by weight of an unmodified, semi-crystalline propylene polymer comprising at least 50% by weight propylene, at least 15% by weight of a non-functionalized wax comprising a first non-functionalized wax and a second non-functionalized wax different from the first non-functionalized wax, and no greater than 8% by weight of an ethylene-ethylenically unsaturated ester copolymer.

2. A hot melt adhesive composition comprising at least 40 wt% of an unmodified, semi-crystalline propylene polymer comprising at least 50 wt% propylene, at least 15 wt% of a non-functionalized wax, 0 wt% to no greater than 10 wt% of a functionalized wax, and 1 wt% to 10 wt% of an elastomeric block copolymer comprising styrene.

3. A hot melt adhesive composition comprising at least 55 weight percent of a semi-crystalline propylene polymer comprising at least 50 weight percent propylene and greater than 20 weight percent of a wax comprising a first wax, a second wax different from the first wax, and from 0 weight percent to no greater than 10 weight percent of a functionalized wax, based on the weight of the hot melt adhesive composition, the hot melt adhesive composition exhibiting a set time of no greater than 2 seconds.

4. The hot melt adhesive composition of any of paragraphs 1 and 3, further comprising an elastomeric block copolymer comprising styrene.

5. The hot melt adhesive composition of any of paragraphs 2 and 4, wherein the elastomeric block copolymer is selected from the group consisting of styrene-ethylene/butylene-styrene block copolymers, styrene-ethylene/propylene-styrene block copolymers, and combinations thereof.

6. The hot melt adhesive composition of any of paragraphs 1-5, comprising at least 45% by weight unmodified, semi-crystalline propylene polymer.

7. The hot melt adhesive composition of any of paragraphs 1-5, comprising at least 50% by weight of the unmodified, semi-crystalline propylene polymer.

8. The hot melt adhesive composition of any of paragraphs 1-5, comprising at least 55% by weight of the unmodified, semi-crystalline propylene polymer.

9. The hot melt adhesive composition of any of paragraphs 1 to 8, wherein the first non-functionalized wax comprises a polyethylene wax, a Fischer-Tropsch wax, or a combination thereof.

10. The hot melt adhesive composition of any of paragraphs 1-9, wherein the first non-functionalized wax has a melting point greater than 100 ℃.

11. The hot melt adhesive composition of any of paragraphs 1 to 10, wherein the second non-functionalized wax has a melting point greater than 115 ℃.

12. The hot melt adhesive composition of any of paragraphs 1-11, further comprising a functionalized wax.

13. The hot melt adhesive composition of paragraph 12, wherein the first non-functionalized wax comprises a polyethylene wax, a fischer-tropsch wax, or a combination thereof, and the functionalized wax comprises a maleated polyethylene wax, a maleated polypropylene wax, or a combination thereof.

14. The hot melt adhesive composition of any of paragraphs 1,2, and 4-13, comprising greater than 20 wt% wax.

15. The hot melt adhesive composition of any of paragraphs 1,2, and 4-15, wherein the unmodified, semi-crystalline propylene polymer has a heat of fusion of from 15J/g to no greater than 50J/g.

16. The hot melt adhesive composition of any of paragraphs 1,2, and 4-15, wherein the composition exhibits a set time of no greater than 2 seconds.

17. The hot melt adhesive composition of any of paragraphs 1 to 16, wherein the composition exhibits a resistance to thermal stress of greater than 60 ℃ and a set time of no greater than 2 seconds.

18. The hot melt adhesive composition of any of paragraphs 1-17, wherein the composition exhibits a resistance to thermal stress of greater than 60 ℃, greater than 50% fiber tear at 4 ℃ and greater than 50% fiber tear at 60 ℃ and a set time of no greater than 1.5 seconds.

19. The hot melt adhesive composition of any of paragraphs 1-17, wherein the composition exhibits a resistance to thermal stress of greater than 71 ℃, greater than 50% fiber tear at 4 ℃ and greater than 50% fiber tear at 71 ℃ and a set time of no greater than 1.5 seconds.

20. The hot melt adhesive composition of any of paragraphs 1-17, wherein the composition exhibits a resistance to thermal stress of greater than 71 ℃, greater than 50% fiber tear at-18 ℃ and greater than 50% fiber tear at 71 ℃ and a set time of no greater than 1.5 seconds.

21. The hot melt adhesive composition of any of paragraphs 1-20, further comprising an oil, polybutene, or a combination thereof.

22. The hot melt adhesive composition of any of paragraphs 1 to 20, wherein the composition exhibits a viscosity of no greater than 2000 centipoise at 177 ℃.

23. The hot melt adhesive composition of any of paragraphs 1-22 comprising 45 wt% to about 70 wt% unmodified, semi-crystalline propylene polymer, about 20 wt% to about 35 wt% non-functionalized wax, and 0 wt% to about 10 wt% functionalized wax.

24. The hot melt adhesive composition of any of paragraphs 1-17 and 21-23, wherein the composition exhibits a set time of no greater than 1.5 seconds.

25. The hot melt adhesive composition of any of paragraphs 1-17 and 21-23, wherein the composition exhibits a set time of no greater than 1 second.

26. The hot melt adhesive composition of any of paragraphs 1-25, comprising 50 wt.% to about 65 wt.% of the unmodified, semi-crystalline polypropylene polymer.

27. The hot melt adhesive composition of any of paragraphs 1,2, and 4-26, wherein the unmodified, semi-crystalline propylene polymer comprises an unmodified, metallocene-catalyzed, semi-crystalline propylene polymer, an unmodified, non-metallocene heteroaryl-catalyzed, semi-crystalline propylene polymer, or a combination thereof.

28. The hot melt adhesive composition of any of paragraphs 1,2, and 4-27, wherein the unmodified, semi-crystalline propylene polymer comprises an unmodified, metallocene-catalyzed, semi-crystalline propylene copolymer, an unmodified, non-metallocene heteroaryl-catalyzed, semi-crystalline propylene copolymer, or a combination thereof.

29. The hot melt adhesive composition of any of paragraphs 1,2, and 4-28, wherein the unmodified, semi-crystalline propylene polymer exhibits a viscosity of no greater than 1200cP at 190 ℃.

30. The hot melt adhesive composition of any of paragraphs 1 to 29, wherein the composition exhibits a resistance to thermal stress of greater than 60 ℃, greater than 50% fiber tear at-18 ℃ and greater than 50% fiber tear at 60 ℃.

31. The hot melt adhesive composition of any of paragraphs 1-30, wherein the composition exhibits a viscosity of no greater than 1500 centipoise at 149 ℃.

32. The hot melt adhesive composition of any of paragraphs 1-31, wherein the non-functionalized wax comprises a first non-functionalized wax and a second non-functionalized wax different from the first non-functionalized wax.

33. The hot melt adhesive composition of any of paragraphs 1-32, further comprising 15 wt% to 30 wt% tackifier.

34. A package comprising the hot melt adhesive composition of any of paragraphs 1-33, a first substrate comprising fibers, and a second substrate comprising fibers, the second substrate being bonded to the first substrate by the adhesive composition.

Claims (25)

1. A hot melt adhesive composition comprising:

at least 40% by weight of an unmodified semi-crystalline propylene polymer comprising at least 50% by weight propylene;

at least 15 wt% of a non-functionalized wax comprising a first non-functionalized wax and a second non-functionalized wax different from the first non-functionalized wax; and

not greater than 8 wt% of an ethylene-ethylenically unsaturated ester copolymer.

2. A hot melt adhesive composition comprising:

at least 40% by weight of an unmodified semi-crystalline propylene polymer comprising at least 50% by weight propylene;

at least 15 wt% of a non-functionalized wax;

0 wt% to no greater than 10 wt% of a functionalized wax; and

1 to 10 weight percent of an elastomeric block copolymer comprising styrene.

3. A hot melt adhesive composition comprising:

at least 55% by weight of a semi-crystalline propylene polymer comprising at least 50% by weight propylene; and

greater than 20 wt% wax comprising a first wax, a second wax different from the first wax, and 0 wt% to no greater than 10 wt% of a functionalized wax, based on the weight of the hot melt adhesive composition, the hot melt adhesive composition exhibiting a set time of no greater than 2 seconds,

4. the hot melt adhesive composition of any one of claims 1 and 3, further comprising an elastomeric block copolymer comprising styrene.

5. The hot melt adhesive composition of any one of claims 1 and 4, further comprising a functionalized wax.

6. The hot melt adhesive composition of any one of claims 1 to 5, comprising:

45% to about 70% by weight of an unmodified, semi-crystalline propylene polymer;

about 20 wt% to about 35 wt% non-functionalized wax; and

0 wt% to about 10 wt% functionalized wax.

7. The hot melt adhesive composition of any one of claims 1,2,4, and 5 comprising at least 45 weight percent unmodified, semi-crystalline propylene polymer.

8. The hot melt adhesive composition of any of claims 1,2, and 4-6 comprising at least 50% by weight of unmodified, semi-crystalline propylene polymer.

9. The hot melt adhesive composition of any one of claims 1 to 6 comprising at least 55% by weight of unmodified, semi-crystalline propylene polymer.

10. The hot melt adhesive composition of any of claims 1,2,4, 5, and 7-9 comprising greater than 20% by weight wax.

11. The hot melt adhesive composition of any of claims 1,2, and 4-10, wherein the unmodified, semi-crystalline propylene polymer has a heat of fusion of from 15J/g to no greater than 50J/g.

12. The hot melt adhesive composition of any of claims 1 and 4 to 11, wherein the first non-functionalized wax has a melting point greater than 100 ℃.

13. The hot melt adhesive composition of claim 12, wherein the second non-functionalized wax has a melting point greater than 115 ℃.

14. The hot melt adhesive composition of any one of claims 1 to 13, wherein the composition exhibits a resistance to thermal stress of greater than 60 ℃ and a set time of no greater than 1.5 seconds.

15. The hot melt adhesive composition of any one of claims 1 to 14, wherein the composition exhibits greater than 50% fiber tear at 4 ℃ and greater than 50% fiber tear at 60 ℃ and a set time of no greater than 1.5 seconds.

16. The hot melt adhesive composition of any one of claims 1 to 15, further comprising an oil, polybutene, or a combination thereof.

17. The hot melt adhesive composition of any one of claims 1 to 16, wherein the composition exhibits a viscosity of no greater than 2000 centipoise at 177 ℃.

18. The hot melt adhesive composition of any one of claims 1 to 17, wherein the composition exhibits a viscosity of no greater than 1500 centipoise at 149 ℃.

19. The hot melt adhesive composition of any of claims 1,2, and 4-18, wherein the non-functionalized wax comprises a polyethylene wax, a fischer-tropsch wax, or a combination thereof.

20. The hot melt adhesive composition of any one of claims 2 to 19, wherein the functionalized wax comprises a maleated polyethylene wax, a maleated polypropylene wax, or a combination thereof.

21. The hot melt adhesive composition of any of claims 1,2, and 4-19, wherein the unmodified, semi-crystalline propylene polymer comprises an unmodified, metallocene catalyzed propylene copolymer, an unmodified, non-metallocene heteroaryl catalyzed propylene copolymer, or a combination thereof.

22. The hot melt adhesive composition of any of claims 1,2, 4-8, and 10-20, comprising 50 wt% to about 65 wt% of an unmodified, semi-crystalline polypropylene polymer selected from unmodified, metallocene-catalyzed propylene copolymers, unmodified, non-metallocene heteroaryl-catalyzed propylene copolymers, or a combination thereof.

23. The hot melt adhesive composition of any one of claims 1,2, and 4-22, wherein the unmodified, semi-crystalline propylene polymer exhibits a viscosity of no greater than 1200cP at 190 ℃.

24. The hot melt adhesive composition of any one of claims 2 and 5 to 23, wherein the elastomeric block copolymer is selected from the group consisting of styrene-ethylene/butylene-styrene block copolymers, and combinations thereof.

25. A package, comprising:

the hot melt adhesive composition of any one of claims 1 to 24;

a first substrate comprising fibers; and

a second substrate comprising fibers, the second substrate being bonded to the first substrate by the adhesive composition.