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    • 专利摘要:
    THERMOFUSIBLE ADHESIVE COMPOSITION A hot-melt adhesive that is composed of a metallocene-catalyzed polyethylene polymer, a hydrogenated styrenic block copolymer, a taching resin, and a solid plasticizer. The preferred polyethylene polymer is an ethylene-octene copolymer, and the preferred styrenic block copolymer is a styrene-ethylene-butylene-styrene having less than 30% styrene content. The preferred solid plasticizer is glycerol tribenzoate or 1,4-cyclohexane dimethanol dibenzoate.
    公开号:BR112013025928B1
    申请号:R112013025928-0
    申请日:2012-04-09
    公开日:2021-02-09
    发明作者:Michael D. Vitrano；Kevin Stafeil；Tsebaot Hailemichael
    申请人:Bostik, Inc.；
    IPC主号:
    专利说明:

    BACKGROUND OF THE INVENTION
    The present invention relates to hot-melt adhesives, and more specifically to a hot-melt adhesive which is composed of a metallocene-catalyzed polyethylene polymer, a hydrogenated styrenic block copolymer, a taching resin, and a solid plasticizer.
    Historically, adhesive formulators have endeavored to transmit low viscosity, fast setting speed, superior adhesion, and cold flow and / or reduced blockage to their products. Many of these properties are mutually exclusive using conventional raw materials and formulation techniques. This invention details a new way in which a hotmelt formulator can transmit low viscosity, fast setting speed, superior adhesion, and cold flow and / or reduced blocking to its products without compromising other properties.
    Adhesives used to laminate thin and / or porous substrates, such as non-woven fabrics used in the construction of disposable diapers, cannot exhibit cold flow, blockage or migration. Adhesives based on traditional ethylene / vinyl acetate (EVA) copolymers, amorphous polyalpha-olefins (APAO) and styrenic block copolymer (SBC) used to laminate or bond thin and / or porous substrates typically struggle with the balance of reducing flow cold, migration and / or blocking, while increasing adhesion properties.
    Adhesives used in applications where substrates are laminated are often required to adhere to a wide variety of surface characteristics (treatments, recycled content, porosity). The substrates themselves can also vary in physical characteristics, such as stiffness, density and chemical makeup. As a result, adhesives must be formulated to overcome these obstacles. Consequently, adhesive formulators are constantly evaluating new materials and new formulation strategies to develop an adhesive with the widest possible application window. The application window of an adhesive is defined as the ability of an adhesive to overcome the deficiencies and / or variables of manufacturing an application. The present invention details a new way in which a thermofusible formulator can maximize beneficial properties for lamination applications.
    Historically, formulators of adhesives have had to balance fast-pick speed with adhesion. Quick-grip adhesives have worse adhesion. Increasing the adhesion properties of a traditionally formulated low viscosity adhesive will also cause that adhesive to exhibit more cold flow and / or blockage. Cold flow being defined as the tendency of the adhesive to flow or "creep" under low pressure at relatively low temperatures. Blocking is defined as the unwanted adhesion of a coated adhesive to substrates with which it comes into contact during shipping and / or storage.
    Over the years, adhesive formulators have used a variety of different polymers as well as other additives in their formulations to achieve a balance of these attributes. These polymers include, but are not limited to, polyolefins (ethylene or propene based polymers), styrenic based copolymers (both saturated and unsaturated medium blocks), functionalized polyolefins (ethylene or propylene copolymers with oxygen-containing monomers), or APAOs (copolymers of ethylene, propene or butene), and EVA (ethylene vinyl acetate).
    It is also known to use solid plasticizers in hot melt adhesives. For example, both US5,026,756 and US5091454 discuss the use of solid plasticizers, specifically 1,4-cyclohexane dimethanol benzoate in hotmelt adhesives. They are both directed to the use of solid plasticizers in EVA-based adhesives, although there is also an example in each of a product based on SIS and one based on a polyamide. No mention is made of polyethylene or SEBS as polymer bases for adhesives. US5,624,986 as well as US5,853,864 and US5,627,229 discuss the use of solid plasticizers, but all of them refer to adhesives that flow cold for a period of time before solidifying. End uses include high moisture resistant diaper cores, palletizing adhesives and cigarette bags. Examples include EVA, SBC polymers and the like, but do not mention metallocene-catalyzed polyalphaolefins. US6,582,829 discloses ethylene / alpha-olefin combinations and block copolymers used in hotmelt adhesives, but does not talk about combinations with solid plasticizers. US6.034.159 discloses a binding adhesive made from a SIS block copolymer, taching resin, a high melting synthetic wax, a solid benzoate plasticizer, and up to 15% of a compatible polymer, which may include polymers ethylene-based.
    US5,747,573 discloses a thermosetting compound composed of an amorphous polyalphaolefin, a solid benzoate plasticizer, and a tachifier. SUMMARY OF THE INVENTION
    The invention is based on the use of a polyolefin polymer based on metallocene catalyst technology, a tachifier, a styrenic block copolymer, and a solid plasticizer.
    The invention provides thermofusible adhesive formulations, preferably composed of a polyethylene polymer based on metallocene catalyst technology, taching resin, a styrenic block copolymer, and a solid plasticizer. These formulations provide superior hot adhesion, adhesion characteristics, resistance to blocking and / or cold flow, and fast setting speed compared to traditional EVA, APAO and SBC adhesives. Applications include, but are not limited to, disposable aprons, heat-reactive tapes, diapers, sanitary napkins, cardboard box and carton seals, book binding, general assembly, and filtration.
    Consequently, in one aspect, a hot melt adhesive composition is provided comprising: (a) about 20% to 60% by weight of a metallocene-catalyzed polyolefin polymer; (b) about 15% to 65% by weight of a tachyting resin; (c) about 2% to 20% by weight of a styrenic block copolymer; and (d) about 2% to 25% by weight of a solid plasticizer.
    In another aspect, the polyolefin is a polyethylene polymer.
    In yet another aspect, the metallocene-catalyzed polyethylene polymer is an ethylene copolymer and a C4 to C8 alpha-olefin comonomer. The comonomer is preferably butene-1 or octene-1. The ethylene-based copolymer has a melt index greater than 100 g / 10 minutes, preferably greater than 200 g / 10 minutes, and more preferably greater than 500 g / 10 minutes. The ethylene-based copolymer is most preferably present in the range of about 30% to about 60% by weight, and is most preferably present in the range of about 40% to about 60% by weight.
    In yet another aspect, the tachyting resin is selected from aliphatic and cycloaliphatic petroleum hydrocarbon resins, hydrogenated aliphatic and cycloaliphatic petroleum resins, hydrogenated aromatic petroleum hydrocarbon resins, petroleum-derived hydrocarbon resins aliphatic / aromatic, hydrocarbon resins hydrogenated aliphatic / aromatic petroleum carbons, aromatic modified cycloaliphatic resins, hydrogenated aromatic modified cycloaliphatic resins, polyterpene resins, copolymers and terpene polymers of natural terpenes, and mixtures thereof. Preferably, the taching resin has a softening point equal to or greater than 90 ° C, and is present in the range of about 30% to about 60% by weight.
    In yet another aspect, the styrenic block copolymer is present in an amount of about 2% to about 20% by weight, preferably from about 2% to about 15% by weight, and most preferably about 2% about 12% by weight and is selected from styrene-butadiene (SB), styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-isoprene (SI), styrene-isoprene-butadiene -styrene (SIBS), styrene-ethylene-butylene-styrene (SEBS), styrene-ethylene-butylene (SEB), styrene-ethylene-propylene-styrene (SEPS), styrene-ethylene-propylene (SEP) and styrene-ethylene- ethylene-propylene-styrene (SEEPS). Preferably, the styrenic block copolymer is a SIS, SEBS, SEPS, SEP or SEEPS. In addition, its styrene content is preferably about 10% to about 30% by weight, more preferably about 10% to about 20% by weight. Most preferably, the styrenic block copolymer is a SEPS having a styrene content of about 13% by weight.
    In yet another aspect, the plasticizer has a softening point equal to or greater than 60 ° C, and is preferably selected from glycerol tribenzoate and 1,4-cyclohexane dimethanol dibenzoate.
    Since the adhesive composition of the present invention will typically be used in spray applications, its Brookfield viscosity measured at 325 ° F (162.8DC) should be 20,000 centipoise (cP) or less, preferably 15,000 cP or less, and more preferably 10,000 cP or less. DESCRIPTION OF THE INVENTION
    It has been found that a combination of a polyolefin polymer, preferably a polyethylene polymer, based on a metallocene catalyst technology, a tachifier, a styrenic block copolymer, and a solid plasticizer can be incorporated into thermofusible adhesive formulas that will display fast pick-up speed, improved hot grip and increased adhesion characteristics, while resisting blocking and cold flow.
    More recently, metallocene catalysis has been used to make polyolefins with more precisely adapted properties. For example, the molecular weight of the polymer can be controlled in a way that was not possible with the older Ziegler-Natta catalysts. Ethylene-based polymers can be made using high levels of comonomer, such as butene-1 and octene-1, to produce polymers with very low levels of crystallinity and density. These polymers have been used to make hot-melt adhesives with more desirable properties than those based on previous generations of polyolefins. Examples of such metallocene polymers include Affinity® and Engage® polymers from Dow Chemical Company. Polymers and adhesives of this type are described in US Patents 6,107,430 and 6,319,979, both of which are specifically incorporated herein by reference.
    Ethylene-based olefin copolymers and at least one α-olefin are a component of the adhesive. These copolymers are manufactured by metallocene catalysts. One embodiment of the invention uses such ethylene-based copolymers or terpolymers together with C4 to C2-α-olefins. The comonomers that can be added in addition to ethylene are the olefinic unsaturated monomers known to be copolymerizable with ethylene.
    They involve particularly straight or branched C4 to C20 α-olefins, such as butene, hexene, methylpentene, octene, cyclic unsaturated compounds, such as norbornene or norbornadiene, asymmetrically substituted ethylene derivatives, where C1 to C12 alkyl groups are suitable substitutes; as well as unsaturated carboxylic acids or carboxylic acid anhydrides.
    The adhesive contains about 20 to 60 weight percent of the metallocene-based polyolefin polymer, more preferably about 30% to about 60% by weight, and most preferably about 40% to about 60% by weight . The polymer preferably has a relatively high melt index when conducted according to ASTM 1238 using a temperature of 190 ° C and a weight of 2.16 kg. Preferably, the melt index is greater than 100 g / 10 minutes, more preferably greater than 200 g / 10 minutes and most preferably greater than 500 g / 10 minutes. Two classes of ethylene / octene copolymers that are particularly useful are Affinity GA 1900 and Affinity GA 1950, which have flow rates of 1000 g / 10 minutes and 500 g / 10 minutes, respectively. These polymers are available from Dow Chemical Company.
    The adhesives of the invention contain a taching resin in combination with a metallocene-catalyzed thermoplastic polyolefin, styrenic block copolymer and solid plasticizer. Tachyting resins are selected for a specific degree of compatibility with the polymer and plasticizer.
    Tachyting or tachyting resins that are used in the hot melt adhesives of the present invention are those that extend adhesive properties and improve specific adhesion. As used herein, the term "taching resin" includes: (a) aliphatic and cycloaliphatic oil hydrocarbon resins having softening points by the Ring and Ball method from 10 ° C to 160 ° C, as determined by the ASTM E28 method , the latest resins resulting from the polymerization of monomers consisting primarily of aliphatic and / or cycloaliphatic olefins and diolefins; also included are hydrogenated aliphatic and cycloaliphatic petroleum hydrocarbon resins; examples of such commercially available resins based on such a C5 olefin fraction are Piccotac 95 taching resin sold by Hercules Corp, and Escorez 1310LC, sold by ExxonMobil Chemical Company. (b) aromatic petroleum hydrocarbon resins and their hydrogenated derivatives; (c) hydrocarbon resins derived from aliphatic / aromatic petroleum and the hydrogenated derivatives thereof; (d) aromatic modified cycloaliphatic resins and their hydrogenated derivatives; (e) polyester pen resins having a softening point of about 10 ° C to about 140 ° C, the latter resins generally resulting from the polymerization of terpene hydrocarbons, such as the monoterpene known as pinene, in the presence of catalysts Friedel-Crafts at moderately low temperatures; also included are hydrogenated polyesterpen resins; and (f) copolymers and terpolymers of natural terpenes, for example, styrene / terpene, o-methyl styrene / terpene and vinyl toluene / terpene.
    Mixtures of two or more of the tachyting resins described above may be required for some formulations. Although a range of 15% to 65% by weight of tachyting resin can be used, the preferred amount is from about 30% to about 60% by weight. Tachyting resins which are useful for the present invention may perhaps include polar tachyting resins, however, the choice of available polar tachyting resins is limited, in view of the fact that many of the polar resins appear only partially compatible with the polyolefin polymers.
    As noted above, tachyting resins that are useful within the scope of the present invention comprise about 15% to 65% by weight. Preferably, the tachyting resins can be selected from any of the relatively non-polar types, which are commercially available. Preferred resins include aliphatic petroleum hydrocarbon resins, examples of which are based on C5 olefins, such as Hercotac 1148, available from Eastman Chemical. Aromatic modified C5 resins, such as Piccotac 9095, available from Eastman Chemical, or Wingtack STS, available from Cray Valley Chemicals are also preferred. Other preferred resins are based on hydrogenated dicyclopentadiene (DCPD) or aromatically modified derivatives thereof. Examples of such resins are Escorez 5400 and Escorez 5600, respectively, sold by Exxon / Mobil Chemical Company. The Ring & Ball Softening Point, as determined by ASTM E-28, of the tachyting resin (s) must be greater than 70 ° C, preferably greater than 80 ° C and most preferably greater than 90 ° C, but not greater than 140 ° C and preferably not greater than 125 ° C.
    A plasticizer is broadly defined as a typically organic composition that can be added to rubbers and other resins to improve extrudability, flexibility, workability, or stretch. Typical plasticizers in adhesives are plasticizer oils that are liquid at room temperature. The plasticizer used in the inventive adhesives is typically a solid composition at room temperature, having a Ring & Ball softening point of at least 45 ° C. Preferably, the plasticizer composition has a ring & ball softening point of at least 60 ° C. Increasing softening points (60 ° - 130 ° C) can assist in improving heat resistance or preventing glue failure at high temperatures.
    The solid plasticizer serves to improve hot adhesion and specific adhesion, while increasing the setting speed, but also decreasing the amount of pressure sensitivity. Historically, liquid plasticizers, waxes, and / or other thinners have been used to modify hot adhesion, adhesion and viscosity properties, but liquid plasticizers increase pressure sensitivity and soften the adhesive, which in turn increases the blocking and overflow (bleed through).
    A useful class of plasticizers used in the invention comprises a cycloaliphatic or aromatic ester of a benzene dicarboxylic acid. Such plasticizers are prepared by forming an ester from a cycloaliphatic or aromatic alcohol, such as cyclohexanol, phenol, naphthol, or other alcohol monohydroxy compounds having 5 to 12 carbon atoms. Ester compounds are formed from dicarboxylic acid compounds, typically phthalic acids. Phthalic acids that can be used in plasticizers are 1,2-benzene dicarboxylic acids, 1,3-benzene dicarboxylic acid (isophthalic acid), or 1,4-benzene dicarboxylic acid (terephthalic acid). Preferred plasticizers in this class comprise dicyclohexyl phthalate or diphenyl phthalate. Most preferably, dicyclohexyl orthophthalate is used.
    A second class of useful plasticizers comprises an aromatic carboxylic acid ester of a cycloaliphatic polyfunctional alcohol having from 2 to 10 hydroxy groups. Specific examples of preferred hydroxy compounds include 1,4-cyclohexane dimethanol, and other useful cycloaliphatic polyfunctional hydroxyl compounds. Aromatic carboxylic acids that can be used with cycloaliphatic polyfunctional alcohols to form this class of ester plasticizer compounds of the invention typically have at least one aromatic group and at least one carboxyl function. Representative acids include benzoic acid, naphthanoic acid, and 4-methyl benzoic acid.
    The most preferred plasticizer is a solid with a softening point by the Ring & Ball method above 60 ° C and belongs to the class of plasticizers called benzoates. Specific examples include glycerol tribenzoate with a softening point of 71 ° C and cyclohexane dimethanol dibenzoate compounds. A 1,4-cyclohexane dimethanol dibenzoate is exemplified and has a softening point of 118 ° C. It is available from Eastman Chemical under the name Benzoflex 352.
    Other solid plasticizers are known and can be used in the formulations of the present invention. These include sucrose benzoate, glycerol benzoate, among others. However, it is desirable for the solid plasticizer to have a softening point greater than 60 ° C.
    The amount of the solid plasticizer can vary widely from as low as 2% to as much as 25%, preferably about 2% to about 20%, and most preferably about 2% to about 15% by weight.
    Any type of elastomeric block copolymer can be used in a hotmelt adhesive formula according to the present invention, and can be incorporated into the composition in amounts of about 2% to about 20% by weight, preferably about 2% at about 15% by weight, and most preferably from about 2% to about 12% by weight. Among the useful elastomeric block copolymers are those having structure AB, AB- A, A- (BA) nB, or (AB) nY, where A comprises a polyvinyl aromatic block, having a Tg greater than 80 ° C, B comprises a medium rubber block, having a Tg less than -10 ° C, Y comprises a multivalent compound, and n is an integer of at least 3.
    Examples of the latter block copolymers conventionally used in hotmelt adhesive compositions are styrene block copolymers (SBC) and include styrene-butadiene (SB), styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-styrene isoprene (SI), styrene-isoprene-butadiene-styrene (SIBS), styrene-ethylene-butylene-styrene (SEBS), styrene-ethylene-butylene (SEB), styrene-ethylene-propylene-styrene (SEPS), styrene-ethylene -propylene (SEP) and styrene-ethylene-ethylene-propylene-styrene (SEEPS or hydrogenated SIBS). Although the total styrene content of polymers can be up to 51% by weight of the polymer, and since polymers can have more than two A blocks for optimal performance, the total A block should be less than or equal to about 45 % by weight of the polymers, and, more preferably, is less than or equal to 35% by weight of the polymer. In an S-B-S (styrene-butadiene-styrene) copolymer, the preferred molecular weight is about 50,000 to 120,000, and the preferred styrene content is about 20 to 45% by weight. In an S-1-S (styrene-isoprene-styrene) copolymer, the preferred molecular weight is about 100,000 to 200,000 and the preferred styrene content is about 1435% by weight. Hydrogenation of the middle blocks of butadiene produces medium blocks of rubber that are typically converted to medium blocks of ethylene-butylene and is referred to as a SEBS polymer. The most preferred polymers are block copolymers SIS, SEBS and SEPS and SEEPS containing less than 30% styrene. Particularly preferred is the SEBS polymer referred to as Kraton 1657, which can be obtained from limited Kraton Performance Polymers. It is a SEBS block copolymer with a styrene content of 12% by weight and a solution viscosity (20% by weight in toluene) of 1500 centipoise at 25 ° C.
    Such block copolymers are available, for example, from Kraton Polymers, Polimeri Europa, Total Petrochemicals, Dexco and Kuraray.
    Although the examples illustrate a hotmelt adhesive comprised of a polyethylene polymer based on metallocene catalyst technology, a tachyting resin, a styrenic block copolymer and a solid plasticizer, it was found that other complementary polymers could also be used to provide desired functionality specifies, including, but not limited to, ethylene vinyl acetate copolymers, propylene / ethylene copolymers, ethylene / alpha-olefin copolymers, ethylene n-butyl acrylate copolymers, etc.
    Hotmelts of the present invention may also contain relatively small amounts of other auxiliary agents, such as plasticizer oils, waxes or other additives, as long as they do not detract from the performance of the adhesive, for example, they do not increase adhesion to any appreciable degree. If they are present, the amount of such auxiliary agents will generally be less than 10 weight percent.
    A suitable plasticizer oil useful as an auxiliary agent can be selected from the usual oils, such as mineral oil and polybutene.
    Waxes can also be used as an auxiliary agent in the adhesive composition, and are used to reduce the melt viscosity of heat-melting construction adhesives without appreciably decreasing their adhesive bonding characteristics. These waxes are also used to reduce the opening time of the composition without affecting the temperature performance.
    The wax material component of the adhesive is optional, but when included it may comprise up to about 10% by weight, preferably only up to 5% by weight of the adhesive composition.
    Among the useful wax materials are: (1) Low molecular weight polyethylene, ie 100-6000 g / mol, having a hardness value, as determined by the ASTM D-1321 method, of about 0.1 to 120 and ASTM softening points of about 66 ° C to 120 ° C; (2) Petroleum waxes, such as paraffin wax, having a softening point of about 130 ° to 170 ° F (54 ° C to 77 ° C), and microcrystalline wax having a softening point of about 135 ° to 200 ° F (57 ° C to 93 ° C), the latter softening points being determined by the ASTM D12760 method; (3) Propylene-based wax catalyzed by metallocene, such as those sold by Clariant, under the name "Licocene". (4) Wax catalyzed by metallocene or wax catalyzed by a single site such as those described in US Patents 4,914,253, 6,319,979 or WO 97/33921 or WO 98/03603. (5) Synthetic waxes made through the polymerization of carbon monoxide and hydrogen, such as Fischer-Tropsch wax; and (6) Polyolefin waxes. As used herein, the term "polyolefin wax" refers to those polymeric or long-chain entities comprised of olefinic monomer units. These materials are commercially available from Eastman Chemical Co. under the registered name "Epolene". The materials that are preferred for use in the compositions of the present invention have a softening point by the Ring and Ball method of 200 ° F (93 ° C) to 350 ° F (177 ° C).
    As it should be understood, each of these waxes is solid at room temperature. Other useful substances include fats and oils from hydrogenated fish and vegetables, such as tallow, lard, soybean oil, cottonseed oil, castor oil, etc. hydrogenated, and which are solid at room temperature by virtue of being hydrogenated, have also been found to be useful with respect to functioning as a wax material equivalent. These hydrogenated materials are often referred to in the adhesive industry as "animal or vegetable waxes".
    The adhesive also typically includes a stabilizer or antioxidant. The stabilizers that are useful in the hot melt adhesive compositions of the present invention are incorporated to help protect the polymers noted above, and thus the total adhesive system, from the thermal and oxidative degradation that normally occurs during the manufacture and application of the adhesive, as well as in the ordinary exposure of the final product to the environment. Such degradation is usually manifested by deterioration of the appearance, physical properties and performance characteristics of the adhesive. A particularly preferred antioxidant is Irganox 1010, a tetrakis (methylene (3,5-di-teri-butyl-4-hydroxyhydrocinamate)) methane manufactured by BASF, among others.
    The inventive adhesives were prepared using the following procedure:
    The adhesive composition useful in the method of the present invention can be produced using any of the techniques known in the art. A representative example of the procedure involves placing all liquid substances in an enveloped mixing boiler and preferably in a heavy mixer of the Baker-Perkins or Day type, which is equipped with rotors, and then raising the temperature of this mixture to a range of 120 ° C to 177 ° C. The solid tachyting resins and other additives are then added and melted to form a homogeneous mixture. Finally, the polymer is added and mixed until completely mixed. It must be understood that the precise temperature to be used in this step would depend on the melting point of the particular ingredients and the viscosity of the finished adhesive. The resulting adhesive composition is stirred until the polymers are completely dissolved. A vacuum is then applied to remove any trapped air.
    The following materials are used: Escorez 5600 is a hydrogenated aromatic modified cycloaliphatic hydrocarbon resin with a softening point of 100 ° C. It is available from ExxonMobil Chemical.
    Kaydol is a white mineral oil available from Sonneborn, Inc.
    Irganox 1010 is a sterically blocked phenolic antioxidant. It is available from Ciba Specialty Chemicals.
    Affinity GA 1950 is a metallocene-catalyzed ethylene / octane copolymer with a melt index of 500 grams / 10 minutes using ASTM D1238 at 190 ° C / 2.16 kg. The density is 0.874 g / cc and the crystallinity level is 18.3 percent. It is available from Dow Chemical Co.
    Affinity GA 1900 is a metallocene-catalyzed ethylene / octane copolymer with a melt index of 1000 grams / 10 minutes using ASTM D-1238 at 190 ° C / 2.16 kg. The density is 0.870 g / cc with a crystallinity level of 15.8 percent. It is available from Dow Chemical Co.
    Ateva 2842A is a copolymer of ethylene vinyl acetate with a melt index of 400 and a vinyl acetate content of 28 percent. It is available from Celanese Corporation.
    Benzoflex 352 is a solid plasticizer as previously described with a softening point of 118 ° C and is available from Eastman Chemical.
    Kraton D1193 is a styrene-isoprene-styrene block copolymer containing 24% styrene and 20% diblock. It is available from Kraton Performance Polymers.
    Kraton 1657 is a SEBS block copolymer containing 13 percent styrene and 30 percent diblock. It is available from Kraton Performance Polymers.
    Kraton D1161 is a SIS block copolymer with a styrene content of 15 percent and a diblock content of 19 percent. It is available from Kraton Performance Polymers.
    R7352 is a paraffin wax with a softening point of 150 ° F (66 ° C) and is available from Sasol Wax Americas. Sylvalite 100 is a pine oil pitch ester with a softening point of 100 ° C and is available from Arizona Chemical. Calsol 5550 is a naphthenic process oil available from Calumet Specialty Products.
    Piccotac 9095 is a modified aromatic hydrocarbon resin with a softening point of 95 ° C. It can be obtained from Eastman Chemical Co.
    Vestoplast 708 is an amorphous polyalpha-olefin available from Evonik Industries. It has a viscosity at 190 ° C of about 8,000 centipoise and a softening point by the A&B method of 106 ° C.
    Eastoflex E1060 is a polyalpha-olefin based on propylene. It has a viscosity of 6000 cP at 190 ° C and a softening point by the A&B method of 135 ° C. It is available from Eastman Chemicals.
    Escorez 2596 is a modified aromatic aliphatic hydrocarbon resin with a softening point of 96 ° C. It is available from ExxonMobil Chemical Co.
    Sukarez SU-400 is a hydrogenated aromatic / C5 / cyclic hydrocarbon resin with a softening point of 100 ° C. It is available from Kolon Industries, Inc.
    Sukarez SU-210 is a hydrogenated C5 / cyclic hydrocarbon resin with a softening point of 110 ° C. It can be obtained from Kolon Industries, Inc. Zonatac 105 is a terpene resin styrene with a softening point of 105 ° C available from Arizona Chemical Co.
    Elvax 150 is an ethylene / vinyl acetate copolymer made by DuPont. It has a 33 percent vinyl acetate content and a melt flow rate of 43 grams / 10 minutes using ASTM D-1238 at 190 ° C / 2.16 kg.
    TRSR TPE4202 is a linear SBS block copolymer with 40 percent styrene and essentially no diblock. It is manufactured by TSRC Corporation.
    The following tests were performed on the adhesives to determine viscosity, softening point, resistance to flaking and cold flow.
    The resulting hotmelt adhesives can then be applied to substrates using a variety of application techniques. Examples include hot melt glue gun, hot melt die coating, hot melt wheel coating, hot melt roller coating, molten blow coating, spiral spray and the like. In a preferred embodiment, the hotmelt adhesive is sprayed onto a substrate using spiral spray, which is a preferred technique for producing a filament spiral pattern for display and elastic construction in diaper manufacturing. In one example, a hot melt coating machine is equipped with a disk-like coating matrix that has a nozzle tip in the center. The tip is surrounded by a series of slanted holes for hot air jets to pass through. The hot melt adhesive is pumped out of the nozzle as a thin filament. The filament is then rotated by high-speed jets of hot air coming out of the holes, thus producing a helical pattern from a single strand of adhesive, which is transported to the substrate. It is not the intention of this invention to provide a complete description of spraying techniques and details can be found in the literature.
    For the present invention, preferred methods of applying the adhesive would be by spray application, more preferably aided by air. Among these techniques, the most common are spiral spraying (Controlled Fiberization ™ by Nordson), Summit ™ by Nordson, Surewrap ™ by Nordson, Omega ™ by ITW and various melt blown processes. For the present invention, the temperature at which the hotmelt adhesive is applied must be below 170 ° C, so that heat sensitive substrates are not damaged. Preferably, this temperature should be equal to or less than 160 ° C, more preferably less than 150 ° C.
    The adhesive composition of the present invention can be used in a number of applications, such as, for example, in disposable non-woven hygienic articles, paper conversion, flexible packaging, woodworking, carton sealing and cardboard packaging, labeling and other mounting applications. Particularly preferred applications include construction of disposable diapers and feminine sanitary napkins, elastic affixing of adult incontinence and diaper briefs, absorbent and diaper core stabilization, diaper support sheet lamination, industrial filter material conversion, assembly of surgical gown and surgical cloth, etc. The adhesives of the present invention are particularly suitable as elastic affix and / or construction adhesives for use in disposable diapers, hygienic panties for babies and incontinence products for adults. INSTRUMENTAL CHARACTERIZATION
    Rheological analysis of the new adhesive formulations described in this invention shows a rapid increase in G '(storage module) between 30 ° C and 70 ° C. This rapid increase in G ’is characteristic of fast pick-up speed 10. This increase in modulus is greater than 2 orders of magnitude. Brookfield viscosity was tested according to ASTM Method D-3236 at 350 ° F (177 ° C), and is reported in centipoise (cP units).
    Dynamic Temperature Step Test The rheology of a given hot melt adhesive can be determined using a TA Instruments rheometer, such as an Ares 3 model. For the adhesives listed in the tables below, a temperature step procedure was used to determine the storage module, G1, at various temperatures as well as the glass transition temperature, Tg. The instrument was established at a frequency of 10 radians per second and the temperature was varied from 20 + 140 ° C to -40 ° C. The parallel plates used were 25 mm in diameter and had a span of 1.6 mm. Modulus values for 70 ° C and 30 ° C were obtained using this test methodology.
    In general, hotmelt adhesives, such as those written in this application, become non-adherent when the storage module (G1) at 25-30 ° C is greater than about 1 x 106 dynes / cm2. PERFORMANCE EVALUATION
    Bonding assessments of the adhesive formulations described in this invention show superior performance over traditional EVA, APAO and SBC adhesives. Peeling values using the new adhesive formulations described in this invention show increases in strength. This increase in peeling resistance does not come at the expense of increased blockage and / or cold flow, as is seen with adhesives traditionally formulated from EVA, APAO and SBC
    Retention of resistance to flaking at elevated temperatures of the 35 new adhesive formulations described in this invention is greatly increased compared to adhesives traditionally formulated from EVA, APAO and SBC. EXAMPLE 1
    The invention provides a hot melt adhesive composition 5 comprising a blend of the following components for use in a polypropylene non-woven substrate lamination application. Table One shows a number of examples of the prior art compared to a polyethylene polymer based on metallocene catalyst technology, a tachifier, a styrenic block copolymer and a solid plasticizer.


    Comparative Example 1 of Table 1 illustrates an EVA-based composition which, although it was relatively non-adherent when cold, did not spray well and had poor adhesion.
    Comparative Example 2 of Table 1 illustrates a composition based on SIS 5 which, although it had good spraying and had adequate adhesion, was very adherent when cold and had significant bleed through and blockage.
    Example from Patent 1 of Table 1 illustrates a polyethylene-based composition according to the present invention that not only had good spraying and was non-adherent when cold, but also had no bleed through or blockage problems. EXAMPLE 2
    The invention provides a hot melt adhesive composition comprising a blend of the following components for use as a pipe insulation adhesive for pipe insulation. Table Two shows a number of prior art examples in comparison to a polyethylene polymer based on metallocene catalyst technology, a tachifier, a styrenic block copolymer and a solid plasticizer.


    Comparative Example 1 of Table 2 illustrates an APAO based adhesive that, although it had good spraying and had adequate adhesion, was very adherent when cold and had undesirable bleed through and blockage. Comparative Example 2 in Table 2 illustrates an SIS-based adhesive that, although it had good spraying and had adequate adhesion, was very adherent when cold and had significant bleed through and blockage. Example from Patent 1 of Table 2 illustrates a polyethylene-based composition according to the present invention that not only had good spraying and was non-adherent when cold, but also had no bleed through or blocking problems. EXAMPLE 3
    The invention provides a thermofusible adhesive composition comprising a blend of the following components for use as an adhesive to adhere granular material to a PE / PP substrate. Table three shows a number of prior art examples compared to a polyethylene polymer based on a metallocene catalyst technology, a tachifier, a styrenic block copolymer and a solid plasticizer.



    Comparative Example 1 of Table 3 illustrates an EVA-based composition that, although it had good spraying and had adequate adhesion, was very adherent when cold and had significant bleed through and blockage.
    Comparative Example 2 of Table 3 illustrates a SBS-based composition that, although it had good spraying and had adequate adhesion, was very adherent when cold and had significant bleed through and blockage.
    Example from Patent 1 of Table 3 illustrates a polyethylene-based composition according to the present invention that not only had good spraying and was non-adherent when cold, but also had no bleed through or blocking problems.
    As can be seen from the data above in Tables 1-3, the ratio of the storage module G1 at 30 ° C to the storage module G1 at 15 70 ° C must be equal to or greater than 100, more preferably equal to or greater than 200, and more preferably equal to or greater than 500. In addition, the G1 storage module at 30 ° C must be greater than 1x106 dynes / cm2 to ensure that the adhesive is not pressure sensitive.
    权利要求:
    Claims (16)
    [0001]
    1. Composition of hot-melt adhesive, characterized by the fact that it comprises: (a) from 20% to 60% by weight of a metallocene-catalyzed polyolefin polymer; (b) from 15% to 65% by weight of a tachyting resin; (c) from 2% to 20% by weight of a styrenic block copolymer; and (d) from 2% to 25% by weight of a solid plasticizer.
    [0002]
    2. Composition according to claim 1, characterized in that said polyolefin polymer is a polyethylene polymer.
    [0003]
    Composition according to claim 2, characterized in that said polyethylene polymer is a copolymer of ethylene and a comonomer of alpha-olefin C4 to C8.
    [0004]
    4. Composition according to claim 3, characterized by the fact that said comonomer is butene-1 or octene-1.
    [0005]
    6. Composition according to claim 3 or 4, characterized in that said copolymer has a melt index greater than 100 g / 10 min, preferably greater than 200 g / 10 min, and more preferably greater than 500 g / 10 min
    [0006]
    Composition according to any one of claims 3 to 5, characterized in that it comprises 30% to 60%, preferably 40% to 60%, by weight of said polyethylene polymer.
    [0007]
    Composition according to any one of claims 3 to 5, characterized in that it comprises 30% to 60%, preferably 40% to 60%, by weight of said polyethylene polymer.
    [0008]
    8. Composition according to any one of claims 1 to 6, characterized in that said tachyting resin is selected from the group consisting of aliphatic and cycloaliphatic petroleum hydrocarbon resins, aliphatic and hydrocarbon petroleum resins hydrogenated cycloaliphatic resins, hydrogenated aromatic petroleum hydrocarbon resins, aliphatic / aromatic petroleum derivative hydrocarbon resins, hydrogenated aliphatic / aromatic petroleum resins, aromatic modified cycloaliphatic resins, hydrogenated modified cycloaliphatic resins, resins of polyesterpene, copolymers and terpolymers of natural terpenes, and mixtures thereof.
    [0009]
    9. Composition according to any one of claims 1 to 7, characterized in that said styrenic block copolymer is selected from the group consisting of styrene-butadiene (SB), styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-isoprene (SI), styrene-isoprene-butadiene-styrene (SIBS), styrene-ethylene-butylene-styrene (SEBS), styrene-ethylene-butylene (SEB), styrene-ethylene -propylene-styrene (SEPS), styrene-ethylene-propylene (SEP) and styrene-ethylene-ethylene-propylene-styrene (SEEPS).
    [0010]
    10. Composition according to claim 8, characterized in that said styrenic block copolymer has a styrene content of 10% to 30% by weight, preferably 10% to 20% by weight, and more preferably of 13% by weight.
    [0011]
    11. Composition according to any one of claims 1 to 9, characterized in that said solid plasticizer has a softening point equal to or greater than 60 ° C, and / or said tachyting resin has a softening point equal to or greater than 90 ° C.
    [0012]
    12. Composition according to any one of claims 1 to 10, characterized in that said solid plasticizer is selected from the group consisting of glycerol tribenzoate and 1,4-cyclohexane dimethanol dibenzoate.
    [0013]
    13. Composition according to any one of claims 1 to 11, characterized in that it comprises from 2% to 20% by weight of said solid plasticizer, preferably from 2% to 15% by weight.
    [0014]
    Composition according to any one of claims 1 to 12, characterized in that it has a viscosity of 20,000 centipoise or less, preferably 15,000 centipoise or less, and more preferably 10,000 centipoise or less.
    [0015]
    Composition according to any one of claims 1 to 13, characterized in that it comprises from 2% to 15% by weight of said styrenic block copolymer, preferably from 2% to 12% by weight.
    [0016]
    16. Composition according to any one of claims 1 to 14, characterized by the fact that it has a G1 storage module at 30 ° C of at least 1 x 106 dynes / cm2 (1 x 105 Pa or N / m2), and / or a ratio of storage module G1 at 30 ° C to storage module G1 at 70 ° C equal to or greater than 100, preferably equal to or greater than 200, more preferably equal to or greater than 500.
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-07-23| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-11-03| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2020-12-08| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-02-09| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 09/04/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201161473563P| true| 2011-04-08|2011-04-08|
    US61/473,563|2011-04-08|
    PCT/US2012/032773|WO2012139120A1|2011-04-08|2012-04-09|Polyolefin based hot melt adhesive containing a solid plasticizer|
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