JP6028309B2 - Polyolefin adhesive composition containing a nucleating agent for improved cure time - Google Patents

Description

CROSS REFERENCE TO RELATED APPLICATIONS This application claims the benefit of US Provisional Patent Application No. 61 / 713,182, filed on October 12, 2012, and US Patent Application No. 61 / 609,020, filed March 9, 2012. Related to the issue.
The present invention relates to a polyolefin adhesive composition comprising one or more nucleating agents for improving the cure time of the finished adhesive.

Historically, packaging grade hot melt adhesive ("HMA") formulations include a base polymer and one or more waxes and tackifiers. In addition to basic adhesive bond strength performance, HMA cure time is an important parameter for packaging grade HMA. This is because lower cure times allow for faster packaging line speeds.
The cure time is the minimum time interval after the two substrates are bonded that the cohesive strength of the bond is stronger than the joint stress (often referred to as the pop open force). Thus, cure time represents the time required to cool the HMA and obtain a good bond. The open time is the maximum time interval after which the second support adheres to the molten adhesive and a good bond is formed after application of liquid HMA. In general, once the adhesive is cooled to a certain temperature, it is no longer possible to make a bond. Typically, HMA formulators attempt to design HMA formulations with long open times and short cure times, but that balance is difficult to achieve.
Conventional HMA formulations contain up to 30% wax to obtain good cure times. However, the wax is not involved in the actual adhesive performance, and removing the wax increases the overall adhesive performance.

  It would therefore be desirable to provide a hot melt adhesive formulation that requires less wax, preferably requires little or no wax, and requires a higher base polymer loading.

These challenges and / or other challenges are addressed by the methods and products disclosed herein.
In one aspect, an adhesive as compared to a polyolefin composition comprising a homopolymer of propylene or a copolymer of propylene and ethylene or a C ₄ -C ₁₀ alpha-olefin, and the same adhesive composition except that a nucleating agent is absent An adhesive composition is provided comprising a nucleating agent effective to reduce the cure time for the composition. The nucleating agent may be an organometallic salt. The adhesive composition has a Dot T-Peel of 1 Newton or more on kraft paper.
In another aspect, a polyolefin composition comprising a homopolymer of propylene or a copolymer of propylene and ethylene or C ₄ -C ₁₀ alpha-olefin is bonded to the same adhesive composition except that a nucleating agent is absent. And an nucleating agent effective to reduce the cure time for the agent composition, wherein the nucleating agent has a crystallization temperature higher than the crystallization temperature of the inorganic solid particle or polyolefin composition. It is an organic component. The adhesive composition has a point T-peeling greater than 1 Newton on kraft paper.
In yet another aspect, compared to a polyolefin composition comprising a homopolymer of propylene or a copolymer of propylene and ethylene or a C ₄ -C ₁₀ alpha-olefin, compared to the same adhesive composition except that a nucleating agent is absent. An adhesive composition is provided comprising a nucleating agent effective to reduce the cure time for the adhesive composition by at least 10%. The adhesive composition has a point T-peeling greater than 1 Newton on kraft paper.
These and other aspects of the present invention are described in greater detail in the following detailed description and illustrated in the accompanying drawings.

It is a graph which shows the various adhesive composition construction intensity | strength of time. 2 is a graph showing a differential scanning calorimetry cooling curve for composition F in Table 1. FIG. 2 is a graph showing a differential scanning calorimetry cooling curve for composition F in Table 1. FIG.

Disclosed herein is an adhesive formulation that allows enhanced adhesion and provides excellent cure time while maintaining long open times. In any embodiment, these formulations allow for the use of higher polymer loadings in the finished adhesive, thereby providing increased bond strength. In doing so, the formulation can reduce the adhesive density and provide a path to reduce the mass and volume of adhesive that needs to be applied in the packaging line. By reducing the adhesive volume, the curing time can be further improved due to the fact that the reduced amount of heat requires less cooling time.
The formulations disclosed herein can provide improved cure times while maintaining long open times due to the incorporation of nucleating agents in the adhesive formulation. In any embodiment, the blend may comprise a propylene homopolymer or a polyolefin comprising propylene and ethylene or a C ₄ -C ₁₀ alpha-olefin copolymer. In any embodiment, the polyolefin composition may comprise a copolymer of propylene and ethylene.
In any embodiment, the nucleating agent reduces the cure time for the adhesive composition, preferably by at least 10%, compared to the same adhesive composition, except in the absence of the nucleating agent. It may be effective. In any embodiment, the nucleating agent may be effective to increase the initial crystallization temperature of the polyolefin composition relative to the adhesive composition in the absence of the nucleating agent. In any embodiment, the nucleating agent may be effective to increase the initial crystallization temperature of the polyolefin composition by at least 10 ° C. relative to the adhesive composition in the absence of the nucleating agent.
In any embodiment, the nucleating agent may be a metal salt. In any embodiment, the nucleating agent may be an organic compound having a crystallization temperature that is higher than the crystallization temperature of the polyolefin composition. In any embodiment, the nucleating agent may be selected from the group consisting of sodium benzoate, talc, glycerol alkoxide salts, cyclic carboxylates, bicyclic carboxylates, glycerolates, and hexahydrophthalates. Good. In any embodiment, the nucleating agent comprises a salt of bicyclo [2.2.1] heptanedicarboxylate.
It is advantageous that the improvement in cure time allowed by the formulations disclosed herein can be achieved using reduced amounts of wax, or more preferably with little or no wax. . In any embodiment, the adhesive composition may comprise no more than about 25% wax, or no more than about 5% by weight wax, or may be substantially free of wax.
The formulations disclosed herein are widely applicable to multi-modal polymer blends having a combination of properties that are beneficial for use in adhesive compositions. In general, the nucleating agent may be used with a polyolefin composition having a multimodal polymer blend comprising at least two polymers having a blend heat difference of about 20 J / g or greater, or about 30 J / g or greater. For example, a nucleating agent reduces the cure time of a multimodal polymer blend in which one polymer has a heat of fusion of about 50 J / g or less and the second polymer has a heat of fusion of about 30 J / g or more. Can be used to For example, a nucleating agent has one polymer having a heat of fusion of about 65 J / g to about 85 J / g and a second polymer having a heat of fusion of about 10 J / g to about 30 J / g. It can be used to reduce the cure time of multimodal polymer blends. Nucleating agents can also reduce the cure time of multimodal polymer blends where one polymer has a heat of fusion of 80 J / g or more and the second polymer has a heat of fusion of about 50 J / g or less. Can be used. Nucleating agents can also reduce the cure time of multimodal polymer blends where one polymer has a heat of fusion greater than 50 J / g and the second polymer has a heat of fusion less than about 15 J / g. Can be used. In any embodiment, the weight ratio of the first polymer to the second polymer present in the blend is from 10:90 to 90:10, or from 20:80 to 80:20, or from 30:70 to 70:30. Or 40:60 to 60:40.

  The formulations disclosed herein have a point T-peeling greater than 1 Newton on kraft paper. As used herein, point T-peel is about 1 square inch when the specimen is compressed with two 1 inch x 3 inch (2.54 cm x 7.62 cm) support cutouts under a 500 gram load. Measured in accordance with ASTM D 1876, except that it is made by mating with an adhesive point having a volume that occupies an area (1 inch = 2.54 cm). Once made, all specimens may be pulled apart when testing side by side at a rate of 2 inches / minute with a device that measures the applied breaking force. The maximum force obtained for each sample tested is the point T-peel. One Newton's point T-peel may be considered the minimum performance requirement for the adhesive. In general, adhesive compositions that exhibit measurable fiber tear have a point T-peel of at least 1 Newton.

A. Polyolefin Composition The polymers used in any of the polyolefin compositions of the present invention are propylene, ethylene, C ₄ -C ₂₀ linear or branched olefins, and diolefins (particularly C ₄ -C ₁₀ olefins). It is preferably derived from one or more monomers selected from the group consisting of: As used herein, the term “monomer” or “comonomer” can refer to the monomer used to form the polymer, ie, the unreacted chemical compound in its pre-polymerized form, and it can be used for the polymer. Can represent the monomer after it has been incorporated (also referred to herein as “[monomer] -derived unit”), which is due to the polymerization reaction less hydrogen atoms than it has before the polymerization reaction Typically.
It is preferred that the polymer is primarily propylene. Preferred comonomers include ethylene, butene, hexene, and octene, with ethylene being the most preferred comonomer. For propylene-based polymers, the crystallinity and heat of fusion of the polymer are affected by the comonomer content and the ordered distribution of the comonomer within the polymer. In general, increased levels of comonomer will reduce the crystallinity afforded by crystallization of stereoregular propylene derived sequences.
The comonomer content and order distribution of the polymer can be determined by methods known to those skilled in the art using ¹³ C nuclear magnetic resonance (NMR). The comonomer content in different molecular weight ranges is determined by methods known to those skilled in the art (Fourier Transform Infrared in conjunction with GPC samples as described in Wheeler and Willis et al., Applied Spectroscopy, 1993, 47, 1128-1130. Spectroscopic analysis (including FTIR). For propylene ethylene copolymers containing more than 75% by weight of propylene, the comonomer content (ethylene content) of such polymers can be measured as follows: a thin uniform film is pressed at a temperature of about 150 ° C. or higher; Attached to Perkin Elmer PE 1760 infrared spectrometer. The entire spectrum of the sample from 600 cm-1 to 4000 cm-1 is recorded, and the ethylene monomer mass% can be calculated by the following formula: ethylene mass% = 82.585-111.987X + 30.045X2, where X is 1155 It is the ratio of the peak height at cm-1 to the peak height at 722 cm-1 or 732 cm-1 (whichever is higher). For propylene ethylene copolymers having a propylene content of 75% by weight or less, the comonomer (ethylene) content can be measured using procedures described in the Wheeler and Willis literature. Various test methods including GPC measurement methods and methods for measuring ethylene content by NMR and DSC measurements are described in US Pat. No. 6,525,157, which is hereby incorporated by reference in its entirety.

Preferred polymers are semicrystalline propylene based polymers. In any embodiment, the polymer may have a relatively low molecular weight, preferably no more than about 100,000 g / mol. In any embodiment, the polymer may comprise a comonomer selected from the group consisting of ethylene and linear or branched C ₄ -C ₂₀ olefins and diolefins. In any embodiment, the comonomer may be ethylene or a C ₄ -C ₁₀ olefin.
The term “polymer” as used herein includes, but is not limited to, homopolymers, copolymers, interpolymers, terpolymers, etc., and alloys and blends thereof. Furthermore, the term “copolymer” as used herein is meant to include polymers having two or more monomers, optionally with other monomers, and may represent interpolymers, terpolymers, and the like. The term “polymer” as used herein also includes impact copolymers, block copolymers, graft copolymers, random copolymers and alternating copolymers. The term “polymer” should further include all possible geometric forms unless specifically stated otherwise. Such forms may include isotactic symmetry, syndiotactic symmetry and random symmetry.
“Polypropylene” as used herein includes propylene homopolymers and copolymers or mixtures thereof. Products comprising one or more propylene monomers polymerized with one or more additional monomers may more commonly be known as random copolymers (RCP) or impact copolymers (ICP). Impact copolymers are also known in the art as heterophasic copolymers. “Propylene-based” as used herein includes propylene alone or in combination with one or more comonomers, where propylene is the major component (ie, greater than 50 mole% propylene). It is meant to include any polymer. In any embodiment, the polymer may be a propylene-based elastomer. The term “elastomer” as used herein refers to elasticity, ie the ability to recover shape after deformation, is above its glass transition temperature at room temperature, and is preferably at least 80%, or more preferably at least Represents a polymer that exhibits an elongation at break of 100%, or more preferably at least 200%.

In any embodiment, the polyolefin composition may include one or more propylene-based polymers, which are from about 5 mol% to about about selected from propylene and C ₂ and C ₄ -C ₁₀ α-olefins. Up to 30 mol% of one or more comonomers. In any embodiment, the α-olefin comonomer unit may be derived from ethylene, butene, pentene, hexene, 4-methyl-1-pentene, octene, or decene. Although the embodiments described below are described with respect to ethylene and hexene as α-olefin comonomers, the embodiments are equally applicable to other copolymers with other α-olefin comonomers. In this regard, the copolymer may be referred to simply as a propylene-based polymer with respect to ethylene or hexene as the α-olefin.
In any embodiment, the polyolefin composition is at least about 5 mol%, at least about 6 mol%, at least about 7 mol%, or at least about 8 mol%, or at least about 10 mol%, or at least about 12 mol%. Ethylene-derived units or hexene-derived units may be included. In these or other embodiments, the copolymer is up to about 30 mol%, or up to about 25 mol%, or up to about 22 mol%, or up to about 20 mol%, or up to about 19 mol%, or about 18 It may contain up to mol%, or up to about 17 mol% of ethylene derived units or hexene derived units, where mass% is based on the total amount of propylene derived units and α-olefin derived units. In other words, the polyolefin composition has at least about 70 mol%, or at least about 75 mol%, or at least about 80 mol%, or at least about 81 mol% propylene derived units, or at least about 82 mol% propylene derived units, Or in these or other embodiments, the copolymer may be up to about 95 mol%, or up to about 94 mol%, or up to about 93 mol%, or Up to about 92 mol%, or up to about 90 mol%, or up to about 88 mol% of propylene-derived units may be included, where weight percent is based on the combined amount of propylene-derived units and α-olefin derived units. . In any embodiment, the polyolefin composition comprises from about 5 mol% to about 25 mol% ethylene derived units or hexene derived units, or from about 8 mol% to about 20 mol% ethylene derived units or hexene derived units, Or from about 12 mol% to about 18 mol% ethylene derived units or hexene derived units.

Polyolefin compositions may be characterized by their melting point (Tm), which can be measured by differential scanning calorimetry (DSC). For the purposes of this specification, the maximum of the maximum temperature peak is considered to be the melting point of the polymer. The “peak” in this situation is defined as the change in the general slope of the DSC curve (heat flow vs. temperature) from positive to negative, forming a maximum without any shift at the baseline, in which case the DSC curve is endothermic. Are plotted as indicated by the positive peak.
In any embodiment, the Tm (as measured by DSC) of the polyolefin composition may be less than about 115 ° C, or less than about 110 ° C, or less than about 100 ° C, or less than about 90 ° C. In any embodiment, the Tm of the polyolefin composition may be greater than about 25 ° C, or greater than about 30 ° C, or greater than about 35 ° C, or greater than about 40 ° C.
In one or more embodiments, the first crystallization temperature (Tc1) (as measured by the viscosity curve) of the polyolefin composition is less than about 100 ° C., or less than about 90 ° C., or less than about 80 ° C., or about Less than 70 ° C, or less than about 60 ° C, or less than about 50 ° C, or less than about 40 ° C, or less than about 30 ° C, or less than about 20 ° C, or less than about 10 ° C. In this or other embodiments, the Tc1 of the polyolefin composition is greater than about 0 ° C., or greater than about 5 ° C., or greater than about 10 ° C., or greater than about 15 ° C., or about 20 Higher than ℃.
In other embodiments, the lower limit of Tc1 of the polyolefin composition may be 0 ° C., 5 ° C., 10 ° C., 20 ° C., 30 ° C., 40 ° C., 50 ° C., 60 ° C., and 70 ° C., and the Tc 1 upper limit temperature. May be 100 ° C, 90 ° C, 80 ° C, 70 ° C, 60 ° C, 50 ° C, 40 ° C, 30 ° C, 25 ° C, and 20 ° C, and ranges from any lower limit to any upper limit .

In one or more embodiments, the second crystallization temperature (Tc2) (as measured by DSC) of the polyolefin composition is less than about 100 ° C., or less than about 90 ° C., or less than about 80 ° C., or about 70 Less than or less than about 60 ° C, or less than about 50 ° C, or less than about 40 ° C, or less than about 30 ° C, or less than about 20 ° C, or less than about 10 ° C. In this or other embodiments, the Tc2 of the polymer is greater than about 0 ° C, or greater than about 5 ° C, or greater than about 10 ° C, or greater than about 15 ° C, or greater than about 20 ° C. Is also expensive.
In other embodiments, the lower Tc2 limit of the polyolefin composition may be 0 ° C, 5 ° C, 10 ° C, 20 ° C, 30 ° C, 40 ° C, 50 ° C, 60 ° C, and 70 ° C, and the Tc2 upper limit temperature. May be 100 ° C, 90 ° C, 80 ° C, 70 ° C, 60 ° C, 50 ° C, 40 ° C, 30 ° C, 25 ° C, and 20 ° C, and ranges from any lower limit to any upper limit .
In one or more embodiments, the polyolefin composition is from about 0.85 g / cm ³ to about 0.92 g / cm ³ , or from about 0.86 g / cm ³ to about 0.90 g, as measured by the ASTM D-792 test method at room temperature. up / cm ^3, or from about 0.86 g / cm ³ may have a density of up to about 0.89 g / cm ^3.
In one or more embodiments, the semi-crystalline polymer is from about 5,000 g / mol to about 500,000 g / mol, or from about 7,500 g / mol to about 300,000 g / mol, or from about 10,000 g / mol to about 200,000 g. May have a weight average molecular weight (Mw) of up to / mol or from about 25,000 g / mol to about 175,000 g / mol.
Techniques for measuring molecular weight may be found in US Pat. No. 4,540,753 (Cozewith, Ju, and Verstrate) and Macromolecules, 1988, 21, page 3360 (Verstrate et al.). For example, molecular weight may be measured by size exclusion chromatography (SEC) by using a Waters 150 gel permeation chromatograph equipped with a differential refractive index detector and calibrated using polystyrene standards.

In one or more embodiments, the polyolefin composition is measured at 190 ° C. and measured according to ASTM D-3236 from about 100 cP to about 1,000,000,000 cP, or from about 1,000 cP to about 100,000,000 cP, or from about 2,000 cP. Up to about 10,000,000 cP, or from about 2,500 cP to about 7,500,000 cP, or from about 3,000 cP to about 5,000,000 cP, or from about 3,500 cP to about 3,000,000 cP, or from about 4,000 cP to about 1,000,000 cP, or from about 4,500 cP Viscosities up to about 750,000 cP, or about 5,000 cP to about 500,000 cP, or about 5,500 cP to about 450,000 cP, or about 6,000 cP to about 400,000 cP (also referred to as Brookfield viscosity or melt viscosity) You may have.
In one or more embodiments, the polyolefin composition may be characterized by its viscosity at 190 ° C. In one or more embodiments, the semi-crystalline polymer is at least about 100 cP (centipoise), or at least about 500 cP, or at least about 1,000 cP, or at least about 1,500 cP, or at least about 2,000 cP, or at least about 3,000 cP. Or at least about 4,000 cP, or at least about 5,000 cP. In these or other embodiments, the polyolefin composition is less than about 100,000 cP, or less than about 75,000 cP, or less than about 50,000 cP, or less than about 25,000 cP, or less than about 20,000 cP, or less than about 15,000 cP, Alternatively, it may be characterized by a viscosity at 190 ° C. of less than about 10,000 cP, or less than about 5,000 cP, and ranges from any lower limit to any upper limit are contemplated.

In any embodiment, one or more polymers described herein are blended with another polymer, eg, another polymer described herein, to form a physical blend of polymers, preferably multimodal. A polymer blend may be produced. As used herein, the term “blend” refers to a mixture of two or more polymers. The term “multimodal” as used herein is based on at least one chemical or physical property in which each species is selected from the group consisting of molecular weight, melt viscosity, comonomer content, heat of fusion, and crystallinity. Represents a blend of two or more different polymer species that can be distinguished from other species present in the blend.
In any embodiment, the first and second polymers of the blend may have a heat of fusion difference of about 20 J / g or greater, or more preferably about 30 J / g or greater. In any embodiment, the first polymer may have a heat of fusion of about 50 J / g or greater and the second polymer may have a heat of fusion of about 30 J / g or less. For example, the first polymer may have a heat of fusion of about 65 J / g to about 85 J / g and the second polymer has a heat of fusion of about 10 J / g to about 20 J / g. Also good. Each of the first polymer and the second polymer may independently be a homopolymer of propylene or a copolymer of propylene and ethylene or C ₄ -C ₁₀ olefins. In any embodiment, each polymer in the blend may have a propylene content greater than 50 mole percent.
Particularly advantageous adhesive properties are obtained by using multimodal polymer blends using exceptionally low crystalline propylene based polymers in combination with higher crystalline propylene based polymers. In any embodiment, the exceptionally low crystalline propylene-based polymer may be a homopolymer of propylene or a copolymer of propylene and ethylene or a C ₄ -C ₁₀ olefin, and not greater than about 15 J / g Has heat of fusion. In any embodiment, the exceptionally low crystalline propylene-based polymer may be a homopolymer of propylene or a copolymer of propylene and ethylene, butene, hexene, or octene. In any embodiment, the exceptionally low crystalline propylene-based polymer may be a homopolymer of propylene or a copolymer of propylene and ethylene. In any embodiment, an exceptionally low crystalline propylene-based polymer may have a propylene content greater than 50 mole percent.

In any embodiment, the higher crystalline propylene-based polymer blended with an exceptionally low crystalline propylene-based polymer is a homopolymer of propylene or propylene and ethylene or a C ₄ -C ₁₀ olefin. It may be a copolymer and has a heat of fusion of about 50 J / g or more, or 55 J / g or more, or 60 J / g or more, or 65 J / g or more, or 75 J / g or more. In an exemplary embodiment, the higher crystalline propylene-based polymer has a heat of fusion of about 65 J / g to about 85 J / g. In any embodiment, the higher crystalline propylene-based polymer may be a homopolymer of propylene or a copolymer of propylene and ethylene, butene, hexene, or octene. In any embodiment, the higher crystalline propylene-based polymer is a homopolymer of propylene or a copolymer of propylene and ethylene. In any embodiment, the higher crystalline propylene-based polymer may have a propylene content greater than 50 mole percent.
In addition, particularly advantageous adhesive properties are obtained by using exceptionally crystalline propylene-based polymers in combination with lower crystalline propylene-based polymers. In any embodiment, the exceptionally crystalline propylene-based polymer may be a homopolymer of propylene or a copolymer of propylene and ethylene or a C ₄ -C ₁₀ olefin, and not less than about 80 J / g Has heat of fusion. In any embodiment, the highly crystalline propylene-based polymer may be a homopolymer of propylene or a copolymer of propylene and ethylene, butene, hexene, or octene. In any embodiment, the highly crystalline propylene-based polymer is a homopolymer of propylene or a copolymer of propylene and ethylene. In any embodiment, the highly crystalline propylene-based polymer may have a propylene content greater than 50 mol%.
In any embodiment, the lower crystalline propylene-based polymer that is blended with the exceptionally crystalline propylene-based polymer is a homopolymer of propylene or propylene and ethylene or a C ₄ -C ₁₀ olefin. It may be a copolymer and has a heat of fusion of about 50 J / g or less, or more preferably about 25 J / g or less. In an exemplary embodiment, the lower crystalline propylene-based polymer has a heat of fusion of about 10 J / g to about 20 J / g. In any embodiment, the lower crystalline propylene-based polymer may be a homopolymer of propylene or a copolymer of propylene and ethylene, butene, hexene, or octene. In any embodiment, the lower crystalline propylene-based polymer is a homopolymer of propylene or a copolymer of propylene and ethylene. In any embodiment, the lower crystalline propylene-based polymer may have a propylene content greater than 50 mole percent. In any embodiment, the lower crystalline propylene-based polymer has a heat of fusion of 45 J / g or less, 40 J / g or less, 35 J / g or less, or 30 J / g or less.
The relative weight percent of the polymer in the blend may vary depending on the application of the hot melt adhesive formulation. In any embodiment, the higher crystalline polymer is about 10% to about 90% of the polymer blend, or about 20% to about 80% of the polymer blend, or about 30% to about 70% of the polymer blend, or It may be about 40% to about 60% of the polymer blend.

Nucleating Agent As used herein, the term “ nucleating agent ” refers to a component that, when added to an adhesive composition, increases the temperature at which the polyolefin composition begins to solidify or crystallize from a molten state. While not being bound by theory, it is believed that such components that are compatible with the polyolefin composition form nucleation sites that promote the placement and crystallization of the polyolefin polymer molecules adjacent to the nucleation sites. In any embodiment, the nucleating agent may be solid particles having a size suitable to promote the nucleating effect. In any embodiment, the nucleating agent may be a polymer that is compatible with the polyolefin and that crystallizes at a higher temperature than the polyolefin and promotes the nucleating effect when the adhesive composition cools from the molten state. .

In any embodiment, the nucleating agent may be selected from the group consisting of sodium benzoate, talc, glycerol alkoxide salts, cyclic carboxylates, bicyclic carboxylates, glycerolates, and hexahydrophthalates. Good. As nucleating agents, HYPERFORM ^™ additives such as HPN-68, HPN-68L, HPN-20, HPN-20E, MILLAD ^™ additive (eg MILLAD ^™ 3988) (Milken Chemicals, Spartanburg, SC) and Organic phosphates such as NA-11 and NA-21 (Amfine Chemicals, Allendale, NJ). In any embodiment, the nucleating agent may comprise at least one bicyclic carboxylate. In any embodiment, the nucleating agent is bicycloheptane dicarboxylic acid, disodium salt, such as bicyclo [2.2.1] heptane dicarboxylate. In any embodiment, the nucleating agent may be a blend of components including bicyclo [2.2.1] heptanedicarboxylate, disodium salt, 13-docosenamide, and amorphous silicon dioxide. In any embodiment, the nucleating agent may be cyclohexanedicarboxylic acid, calcium salt or cyclohexanedicarboxylic acid, a blend of calcium salt and zinc stearate.
In any embodiment, the nucleating agent may be a metal salt of formula (I).

Formula (I)

In the formula, R ^{1 to} R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 9 carbon atoms, an amino group, 1 to 9 An alkylamine group having a carbon atom, a halogen atom, a phenyl group, or a formula R-(R '-O) n-- (wherein R is an alkyl group having 1 to 3 carbon atoms, R Is an alkylene group having 2 or 3 carbon atoms, and n is an integer of 1 to 4, and any two alkyl groups of R ^{1 to} R ¹⁰ are bonded to each other. May be linked to form a carbocycle having 3 to 6 carbon atoms, and R ¹ and R ² have a trans or cis configuration with each other. Examples of R ^{1 to} R ¹⁰ in formula (I) representing a metal salt are methyl group, ethyl group, propyl group, methoxy group, ethoxy group, methylamino group, ethylamino group, dimethylamino group, diethylamino group, fluorine atom , Chlorine atom, bromine atom and iodine atom. Examples of groups represented by the formula R-(R '-O) n- included in formula (I) are as follows: CH3-(CH2CH2--O)-, CH3 ( CH2CH2--O) 2--, CH3 (CH2CH2--O) 3--, CH3 (CH2CH2--O) .sub.4--, C2H5-(CH2CH2--O)-, C2H5 (CH2CH2- -O) 2--, C2H5 (CH2CH2--O) 3--, C3H7-(CH2CH2-)-, C3H7 (CH2CH2--O) 2--, C3H7 (CH2CH2--O) 3-- CH3-(CH (CH3) CH2--O)-, CH3 (CH (CH3) CH2--O) 2--, C2H5-(CH (CH3) CH2--O)-, and C2H5 (CH (CH3) CH2--O) 2--.
R ^{1 to} R ¹⁰ are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, such as a methyl group, an ethyl group, and a propyl group. A more preferred metal salt is calcium 1,2-cyclohexanedicarboxylate represented by the following formula.

Further examples of metal salts represented by formula (I) are:

In order to improve the dispersibility of the metal salt in the adhesive composition of the present invention, the metal salt may be combined with a dispersant. Examples of dispersants are aliphatic acids, for example aliphatic acids having 10 to 24 carbon atoms, alkyl esters of such aliphatic acids, alkali metal salts or alkaline earth metal salts of such aliphatic acids , Alcohols having 10 to 30 carbon atoms, polyalcohols, and esters of such polyalcohols. Of these, metal salts of aliphatic acids are preferred.
Examples of alkali metals are sodium, potassium and lithium, and examples of alkaline earth metals are calcium, magnesium and zinc. Examples of polyalcohols are glycerin, ethylene glycol, propylene glycol, pentaerythritol, dipentaerythritol, tripentaerythritol, and sorbitol.
The metal salt is preferably in a particulate form, which is usually 0.01 to 10 μm, preferably 0.01 to 5 μm, as measured with a laser diffraction particle size distribution measuring device, for example, a HELOS ^™ measuring device (Sympatech GmbH) Preferably it has an average particle diameter of 0.01-3 μm.
In any embodiment, the calcium 1,2-cyclohexanedicarboxylate may be a commercially available metal salt, such as HYPERFORM ^™ HPN-20E (a trademark of Milliken), which contains 66% by weight calcium Contains 1,2-cyclohexanedicarboxylate as the main component.

B. Special Embodiments The present invention can also be understood with respect to the following specific embodiments.
Paragraph A:
A polyolefin composition comprising a homopolymer of propylene or a copolymer of propylene and ethylene or C ₄ -C ₁₀ alpha-olefins,
An adhesive composition comprising a nucleating agent effective to reduce the cure time of the adhesive composition by at least 10% compared to the same adhesive composition except in the absence of the nucleating agent,
The adhesive composition, wherein the adhesive composition has a point T-peel of 1 Newton or more on kraft paper.
Paragraph B: The adhesive composition of Paragraph A, wherein the nucleating agent is a metal salt.
Paragraph C: The adhesive composition of Paragraph A, wherein the nucleating agent is an organic compound having a crystallization temperature higher than the crystallization temperature of the polyolefin composition.
Paragraph D: The adhesive composition of any of Para. AC, wherein the nucleating agent is effective to increase the initial crystallization temperature of the polyolefin composition relative to an adhesive composition in the absence of the nucleating agent.
Paragraph E: The adhesion of any of Paragraph AD, wherein the nucleating agent is effective to increase the initial crystallization temperature of the polyolefin composition by at least 10 ° C relative to the adhesive composition in the absence of the nucleating agent. Agent composition.

Paragraph F: The nucleating agent may be selected from the group consisting of sodium benzoate, talc, glycerol alkoxide salts, cyclic carboxylates, bicyclic carboxylates, glycerolates, and hexahydrophthalates, paragraph AE Any adhesive composition of.
Paragraph G: The adhesive composition of Paragraph F, wherein the nucleating agent comprises a salt of bicyclo [2.2.1] heptanedicarboxylate.
Paragraph H: The adhesive composition of any of Paragraph AG, wherein the adhesive composition comprises up to about 25% by weight wax.
Paragraph I: The adhesive composition of any of Paragraph AH, wherein the adhesive composition comprises up to about 5% by weight wax.
Paragraph J: The adhesive composition of any of Paragraph AG, wherein the adhesive composition is substantially free of wax.
Paragraph K: The adhesive composition of any of Paragraph AJ, wherein the polyolefin composition comprises a copolymer of propylene and ethylene.
Paragraph L: The adhesive composition of any of Paragraph AK, comprising a multimodal polymer blended with a polyolefin composition.
Paragraph M: The blended multimodal polymer comprises a first polymer and a second polymer, wherein the first polymer is a copolymer of propylene and ethylene or a C ₄ -C ₁₀ olefin, and the second polymer is propylene and ethylene. Or the adhesive composition of paragraph L, which is a copolymer of C ₄ -C ₁₀ olefins.

Paragraph N: The adhesive composition of Paragraph M, wherein the first polymer and the second polymer have a heat of fusion difference of about 20 J / g or greater.
Paragraph O: The adhesive composition of Paragraph N, wherein the difference in heat of fusion between the first polymer and the second polymer is about 30 J / g or greater.
Paragraph P: The adhesive composition of Paragraph N, wherein the first polymer has a heat of fusion of about 50 J / g or greater and the second polymer has a heat of fusion of about 30 J / g or less.
Paragraph Q: of Paragraph P wherein the first polymer has a heat of fusion of about 65 J / g to about 85 J / g and the second polymer has a heat of fusion of about 10 J / g to about 30 J / g. Adhesive composition.
Paragraph R: The adhesive composition of Paragraph Q, wherein the first polymer has a heat of fusion of about 80 J / g or greater and the second polymer has a heat of fusion of about 50 J / g or less.
Paragraph S: The adhesive composition of Paragraph O, wherein the first polymer has a heat of fusion of about 50 J / g or greater and the second polymer has a heat of fusion of about 15 J / g or less.
Paragraph T:
A polyolefin composition comprising a homopolymer of propylene or a copolymer of propylene and ethylene or C ₄ -C ₁₀ alpha-olefins;
An adhesive composition comprising a nucleating agent effective to reduce the cure time for the adhesive composition as compared to the same adhesive composition except that the nucleating agent is absent,
The nucleating agent is an inorganic component or an organic component having a crystallization temperature higher than the crystallization temperature of the polyolefin composition, and the adhesive composition has a point T-peeling of 1 Newton or more on kraft paper. The adhesive composition.
Paragraph U:
A polyolefin composition comprising a homopolymer of propylene or a copolymer of propylene and ethylene or C ₄ -C ₁₀ alpha-olefins;
An adhesive composition comprising a nucleating agent effective to reduce the cure time of the adhesive composition as compared to the same adhesive composition except that the nucleating agent is absent,
The adhesive composition wherein the nucleating agent is an organometallic salt and the adhesive composition has a point T-peel of 1 Newton or more on kraft paper.
Paragraph V: Any adhesive composition of Paragraph AU, wherein the nucleating agent is present in an amount of 200 to 5000 ppm.

Six adhesive compositions (AF) were made by preheating the ingredients to 180 ° C. in a glass beaker and blended by simple manual stirring using a spatula. The composition of each adhesive is listed in Table 1. Unless otherwise specified, numerical values are expressed in mass%. Each of the compositions was analyzed to determine its open time, cure time, fiber tear under freezing and freezing, and viscosity. The results of this analysis are also reported in Table 1.
The following terms used in this example have the following meanings.
“PBE1” is a propylene-based elastomer having a viscosity of 1122 mPas at 190 ° C. and a heat of fusion of 45 J / g.
“PBE2” is a propylene-based elastomer having a viscosity of 865 mPas at 190 ° C. and a heat of fusion of 41 J / g.
“Linxer ^™ 127” is a polyolefin adhesive base polymer resin available from ExxonMobil Chemical Company.
“Escolen ^™ UL 40028” is an ethylene vinyl acetate copolymer resin available from ExxonMobil Chemical Company.
“Escolen ^™ UL 02528” is an ethylene vinyl acetate copolymer resin available from ExxonMobil Chemical Company.

“Sasor Wax ^™ C80” is a Fischer-Tropsch wax having a melting point of 80 ° C. available from Sasor Wax (South Africa), a division of Sasor Limited.
“Sasor Wax ^™ H1” is a Fischer-Tropsch wax having a melting point of 98 ° C. available from Sasor Wax (South Africa), a division of Sasor Limited.
“Milken ^™ HPN 20e” is a metal salt of 1,2-cyclohexanedicarboxylate available from Milliken Chemicals, a division of Milliken & Company.
“Escollets ^™ 2206LC” is an aromatic modified aliphatic hydrocarbon resin having a softening point of 92 ° C. available from ExxonMobil Chemical Company.
“MAPP 40” has a softening point of 300-350 ° F (149-177 ° C), a viscosity of 200-400 cPs at 150 ° C, and an acid number of 40-50 available from SSI Chusei in Pasadena, Texas It is a maleated polypropylene.
“AC ^™ 596” is a propylene maleic anhydride copolymer available from Honeywell Specialty Adhesives.
“Irganox ^™ 1010” is a hindered phenol antioxidant available from BASF SE Corporation, Ludwigshafen, Germany.
“Fiber tear” describes the bond strength of the adhesive to the support and was measured at room temperature (RT) and −18 ° C. Fiber tear is a visual measurement of the amount of paper support fibers that are attached to the bond after the support has been torn. 100% fiber tear means that the adhesive is stronger than the support and 100% of the adhesive is covered by the support fibers. 0% fiber tear means that the adhesive does not bond at all and simply leaves the support. Fiber tear was measured by bonding the support together with the adhesive after the molten adhesive (180 ° C.) was dropped onto one of the supports with an eye dropper. The second support was placed on the adhesive and a 500 g weight was placed on the second support for further application. The adhesive was cooled at baseline temperature for at least 1 hour. The support was then torn and the adhesive was inspected for fiber tear.

“Curing time” is defined as the minimum retention time to build a bond agglomeration that requires greater than 10 kg force to break the bond. The cure time was measured by bonding the support together with the adhesive after the molten adhesive (180 ° C.) was dropped onto one of the supports with an eye dropper. The second support was placed on the adhesive and a 500 g weight was placed on the second support for further application. After a predetermined interval of time, the second support is removed and checked for fiber tear. If no fiber tear was seen, longer intervals of time were attempted. This continued until fiber tear was seen. This length of time was reported as the cure time.
“Opening time” is defined as the maximum opening time after which it remains possible to build a bond stronger than a force of 10 kg. The open time was measured by bonding the support together with an adhesive after the molten adhesive (180 ° C.) was dropped onto one of the supports with an eye dropper. The second support was placed on the adhesive and a 500 g weight was placed on the second support for further application. The bonded specimens were examined to determine the longest period of time that allowed at least 50% fiber tearing between proper adhesion of the adhesive to one surface and engagement of the second surface.

As can be seen in Table 1, the compositions containing nucleating agents (Compositions E and F) exhibited cure time performance equal to the desired performance mark cure time performance. Notably, such performance was obtained without using Fischer-Tropsch wax and without using higher polymer loadings. Open time and fiber tear performance were also exceptional for Compositions E and F.
The peel force as a function of application time for each of the adhesive blends is shown in FIG. As seen in FIG. 1, an adhesive composition containing a nucleating agent quickly builds strength after about 0.7 seconds of application. This phenomenon is affected by the crystallization of the organic component of the metal salt as the adhesive cools, and as the adhesive composition cools, it crystallizes the base polymer of the adhesive composition, which in turn begins at sites adjacent to the nucleating agent. And promote solidification. Thus, the presence of the nucleating agent increases the initial crystallization temperature of the polyolefin composition relative to the adhesive composition in the absence of the nucleating agent, for example, by at least 2 ° C, 3 ° C, 5 ° C, or 7 ° C. Can do. As shown in FIGS. 2 and 3, the presence of a nucleating agent in composition F increased the initial crystallization temperature of the composition (relative to composition D) from 90.26 ° C. to 97.62 ° C. In any embodiment, the nucleating agent has an initial crystallization temperature of the polyolefin composition relative to the adhesive composition in the absence of the nucleating agent, for example, at least 2 ° C, 3 ° C, 5 ° C, or 7 ° C. May be provided in an amount effective to ascend only.
Certain embodiments and features have been described using numerical upper limit sets and numerical lower limit sets. It should be appreciated that ranges from any lower limit to any upper limit are contemplated unless otherwise indicated. Certain lower limits, upper limits and ranges appear in one or more claims below. All numerical values are given as “about” or “approximate” and take into account experimental error and variations as expected by one skilled in the art.

To the extent a term used in a claim is not previously defined, it should be given the broadest definition given to that term as reflected in at least one printed publication or issued patent by those skilled in the art. It is. In addition, all patents, test procedures, and other documents cited in this application are to the extent that such disclosure is not inconsistent with this application, and are fully referenced for all jurisdictions where such incorporation is permitted. Incorporated into.
While the foregoing relates to embodiments of the present invention, other and further embodiments of the invention may be inferred without departing from the basic scope thereof, and the scope of the invention is defined by the following claims. Determined by range.
Another aspect of the present invention may be as follows.
[1] Polyolefin composition containing a homopolymer of propylene or a copolymer of propylene and ethylene or C ₄ -C ₁₀ alpha-olefin, and the same adhesive composition except that the nucleating agent is absent in the curing time of the adhesive composition An adhesive composition comprising a nucleating agent effective to reduce by at least 10% compared to the article,
The adhesive composition, wherein the adhesive composition has a point T-peel of 1 Newton or more on kraft paper.
[2] The adhesive composition according to [1], wherein the nucleating agent is a metal salt.
[3] The adhesive composition according to [1], wherein the nucleating agent is an organic compound having a crystallization temperature higher than the crystallization temperature of the polyolefin composition.
[4] The adhesive composition according to the above [1], wherein the nucleating agent is effective in increasing the initial crystallization temperature of the polyolefin composition relative to the adhesive composition in the absence of the nucleating agent.
[5] The adhesive according to [1], wherein the nucleating agent is effective to increase the initial crystallization temperature of the polyolefin composition by at least 2 ° C. with respect to the adhesive composition in the absence of the nucleating agent. Composition.
[6] The nucleating agent may be selected from the group consisting of sodium benzoate, talc, glycerol alkoxide salt, cyclic carboxylate, bicyclic carboxylate, glycerolate, and hexahydrophthalate, 1] The adhesive composition according to the above.
[7] The adhesive composition according to [1], wherein the nucleating agent contains a salt of bicyclo [2.2.1] heptanedicarboxylate.
[8] The adhesive composition according to [1], wherein the adhesive composition contains a wax of about 25% by mass or less.
[9] The adhesive composition according to [1], wherein the adhesive composition contains about 5% by mass or less of wax.
[10] The adhesive composition according to [1], wherein the adhesive composition does not substantially contain a wax.
[11] The adhesive composition according to the above [1], wherein the polyolefin composition contains a copolymer of propylene and ethylene.
[12] The adhesive composition according to the above [1], comprising a multimodal polymer blended with a polyolefin composition.
[13] The blended multimodal polymer includes a first polymer and a second polymer, the first polymer is a copolymer of propylene and ethylene or a C ₄ -C ₁₀ olefin, and the second polymer is propylene and ethylene Alternatively, the adhesive composition according to the above [12], which is a copolymer of C ₄ -C ₁₀ olefin.
[14] The adhesive composition according to [13], wherein the first polymer and the second polymer have a difference in heat of fusion of about 20 J / g or more.
[15] The adhesive composition according to [13], wherein the difference in heat of fusion between the first polymer and the second polymer is about 30 J / g or more.
[16] The adhesive composition according to [14], wherein the first polymer has a heat of fusion of about 50 J / g or more and the second polymer has a heat of fusion of about 30 J / g or less.
[17] The aforesaid [14], wherein the first polymer has a heat of fusion of about 65 J / g to about 85 J / g, and the second polymer has a heat of fusion of about 10 J / g to about 30 J / g. ] Adhesive composition of description.
[18] The adhesive composition according to [14], wherein the first polymer has a heat of fusion of about 80 J / g or more and the second polymer has a heat of fusion of about 50 J / g or less.
[19] The adhesive composition according to [14], wherein the first polymer has a heat of fusion of about 50 J / g or more and the second polymer has a heat of fusion of about 15 J / g or less.
[20] The adhesive composition according to [1], wherein the nucleating agent is present in an amount of 200 to 5000 ppm.
[21] A polyolefin composition comprising a homopolymer of propylene or a copolymer of propylene and ethylene or C ₄ -C ₁₀ alpha-olefins,
Nucleating agent comprising an organic component having a crystallization temperature higher than the crystallization temperature of the inorganic solid particles or the polyolefin composition thereof
An adhesive composition comprising:
The adhesive composition, wherein the adhesive composition has a point T-peel of 1 Newton or more on kraft paper.
[22] The adhesive composition according to [21], wherein the nucleating agent is present in an amount of 200 to 5000 ppm.
[23] A polyolefin composition comprising a homopolymer of propylene or a copolymer of propylene and ethylene or C ₄ -C ₁₀ alpha-olefins,
An adhesive composition comprising a nucleating agent effective to reduce the cure time of the adhesive composition as compared to the same adhesive composition except that the nucleating agent is absent,
The nucleating agent is an organometallic salt, and
The adhesive composition, wherein the adhesive composition has a point T-peel of 1 Newton or more on kraft paper.
[24] The adhesive composition according to [23], wherein the nucleating agent is present in an amount of 200 to 5000 ppm.

Claims (9)

Polyolefin composition containing a propylene homopolymer or a copolymer of propylene and ethylene or C ₄ -C ₁₀ alpha-olefins, comparing the cure time of the adhesive composition to the same adhesive composition except in the absence of a nucleating agent An adhesive composition comprising a nucleating agent effective to reduce by at least 10%,
Wherein the adhesive composition have a point T- peel of 1 Newton or more on Kraft paper, the metal salt of the adhesive composition contains no wax, and the nucleating agent is less formula (I)
Formula (I)
(In the formula (I), R ^{1 to} R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 9 carbon atoms, an amino group, 1 to 9 alkyl amine group having a carbon atom, a halogen atom, a phenyl group, or the formula R - (R '- O) n - ( wherein, R is an alkyl group having 1-3 carbon atoms R ′ is an alkylene group having 2 or 3 carbon atoms, and n is an integer of 1 to 4, and any two of R ^{1 to} R ¹⁰ The alkyl groups may be bonded to each other, thereby forming a carbocycle having 3 to 6 carbon atoms, and R ¹ and R ² have a trans or cis configuration relative to each other.)
The adhesive composition. In the formula (I), R ^{1 to} R ¹⁰ are independently of each other a hydrogen atom, a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a methylamino group, an ethylamino group, a dimethylamino group, a diethylamino group, The adhesive composition according to claim 1, which is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom . The adhesive composition according to claim 1 , wherein in formula (I), R ^{1 to} R ¹⁰ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms . The adhesive composition according to claim 1, wherein the nucleating agent is calcium 1,2-cyclohexanedicarboxylate . Polyolefin composition comprising a copolymer of propylene and ethylene, the adhesive composition according to any one of claims 1-4. Include multimodal polymers polyolefin composition is blended, the blended multimodal polymer comprises a first polymer and a second polymer, the first polymer is a copolymer of propylene with ethylene or C ₄ -C ₁₀ olefin There, the second polymer is a copolymer of propylene with ethylene or C ₄ -C ₁₀ olefin, the adhesive composition according to any one of claims 1-5. The adhesive composition according to claim 6 , wherein the first polymer and the second polymer have a difference in heat of fusion of 20 J / g or more. A polyolefin composition comprising a homopolymer of propylene or a copolymer of propylene and ethylene or C ₄ -C ₁₀ alpha-olefins, and
The following metal salt of formula (I):
Formula (I)
(In the formula (I), R ^{1 to} R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 9 carbon atoms, an amino group, 1 to 9 alkyl amine group having a carbon atom, a halogen atom, a phenyl group, or the formula R - (R '- O) n - ( wherein, R is an alkyl group having 1-3 carbon atoms R ′ is an alkylene group having 2 or 3 carbon atoms, and n is an integer of 1 to 4, and any two of R ^{1 to} R ¹⁰ Alkyl groups may be bonded together, thereby forming a carbocycle having 3 to 6 carbon atoms, and R ¹ and R ² have a trans or cis configuration relative to each other). Agent ,
An adhesive composition comprising:
The adhesive composition have a point T- peel of 1 Newton or more on Kraft paper, and the adhesive composition is free of wax, the adhesive composition. Nucleating agent is present in an amount of 200 ~ 5000 ppm, the adhesive composition according to any one of claims 1-8.