WO2024164133A1 - Hot melt adhesive composition and use thereof - Google Patents
Hot melt adhesive composition and use thereof Download PDFInfo
- Publication number
- WO2024164133A1 WO2024164133A1 PCT/CN2023/074722 CN2023074722W WO2024164133A1 WO 2024164133 A1 WO2024164133 A1 WO 2024164133A1 CN 2023074722 W CN2023074722 W CN 2023074722W WO 2024164133 A1 WO2024164133 A1 WO 2024164133A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hot melt
- adhesive composition
- melt adhesive
- copolymer
- weight
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 95
- 239000004831 Hot glue Substances 0.000 title claims abstract description 93
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C09J123/0815—Copolymers of ethene with aliphatic 1-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Definitions
- This invention relates to a hot melt adhesive composition and use thereof.
- the present invention relates to a hot melt adhesive composition exhibiting low melt viscosity, fast setting time, and good fiber tearing adhesive properties at various ambient temperatures.
- Hot melt adhesives are often used to bond two substrates together while in a molten state. Such adhesives are widely used for various commercial and industrial applications such as product assembly and packaging. To be commercially viable, most hot melt adhesive compositions must maintain adhesion to the substrate at room temperature and, to be suitable for use in high-speed packaging operations, the adhesive must also exhibit fast setting time. If the setting time is long, the initial strength will be insufficient, and the bonding surface of the object will bounce off.
- thermoplastic adhesive composition based on the total weight of the composition, comprising,
- styrene block copolymer (b) has a styrene content of greater than 15%by weight, based on the weight of component (b) .
- an article comprising a cured product of the hot melt adhesive composition according to the present invention.
- the hot melt adhesive composition in packaging, bags, boxes, cartons, cases, trays, multi-wall bags, articles with attachments, ream wrap, cigarettes, filters, bookbinding or paper products, preferably corrugated cartons with laminated films.
- the invention features a hot melt adhesive composition exhibiting low melt viscosity, fast setting time, and good fiber tearing adhesive properties at various ambient temperatures (from -5°C to 50°C) .
- setting time refers to the positioning time of the hot melt adhesive, and the time required for the adhesive to generate a certain strength within the curing time.
- the molecular weights refer to number average molecular weights (Mn) , unless otherwise stipulated. All molecular weight data refer to values obtained by gel permeation chromatography (GPC) , unless otherwise stipulated, e.g., according to DIN 55672.
- the hot melt adhesive composition based on the total weight of the composition, comprising,
- styrene block copolymer (b) has a styrene content of greater than 15%by weight, based on the weight of component (b) .
- the hot melt adhesive composition comprises 20%to 60%by weight of ethylene alpha-olefin copolymer based on the total weight of the hot melt adhesive composition.
- Suitable ethylene alpha-olefin copolymer is derived from at least 60 mole %, at least 65 mole %, or even at least 70 mole %ethylene, and an alpha-olefin monomer.
- the alpha-olefin monomer has at least three carbon atoms, or even from three to 20 carbon atoms, suitable examples of which include propylene, isobutylene, butene, pentene, hexene, heptene, octene, nonene, decene, dodecene, 4-methyl-1-pentene, 3-methyl pentene-1, 3, 5, 5-trimethyl-hexene-1, 5-ethyl-1-nonene, and combinations thereof.
- Examples of the ethylene alpha-olefin copolymers (A) include an ethylene/propylene copolymer, an ethylene/1-octene copolymer, an ethylene/1-butene copolymer, an ethylene/propylene/1-butene copolymer, and a functionalized ethylene alpha-olefin copolymer e.g., a carboxylic acid modified ethylene/propylene copolymer, a carboxylic acid modified ethylene/1-octene copolymer, a carboxylic acid modified ethylene/1-butene copolymer, a carboxylic acid modified ethylene/propylene/1-butene copolymer, a maleic anhydride modified ethylene/propylene copolymer, a maleic anhydride modified ethylene/1-octene copolymer, a maleic anhydride modified ethylene/1-butene copolymer, a maleic anhydride modified ethylene/propylene
- the ethylene alpha-olefin copolymer can be prepared using a variety of catalysts including, e.g., a single site catalyst (e.g., metallocene catalysts (e.g., metallocene catalyzed ethylene alpha-olefin copolymers) , constrained geometry catalysts (e.g., homogeneous linear or substantially linear ethylene alpha-olefin interpolymers prepared from ethylene and an alpha-olefin comonomer using a constrained geometry catalyst) ) , multiple single site catalysts, and combinations thereof, preferable ethylene alpha-olefin copolymers are metallocene catalyzed ethylene alpha-olefin copolymers.
- the polydispersity (Mw/Mn) of the copolymer (A) obtained by polymerizing using a metallocene catalyst is preferably from 1 to 4, more preferably from 1 to 3, and particularly preferably from 1.5 to 3.
- the ethylene alpha-olefin copolymers exhibit melt viscosity less than or equal to 20000 cP at 177°C, preferably from 3000 cP to 18000cP at 177°C.
- the ethylene alpha-olefin copolymers exhibit a melt index of from about 1 g/10 minutes (min) to 2500 g/10 min, at 190 °C using a 2.16 kilogram (kg) weight as measured according to ASTM D1238.
- Useful ethylene alpha-olefin copolymers are commercially available under of a variety of trade designations including, e.g., the AFFINITY series of trade designations from Dow, including, e.g., AFFINITY GA 1875, AFFINITY GA 1900, and AFFINITY GA 1950 ethylene-1-octene copolymers, AFFINITY GA 1000R maleic anhydride-modified ethylene-octene copolymer, the INFUSE series of trade designations from DOW including INFUSE 9807 ethylene-ethylene-propylene copolymer, the SABIC POE series of trade designations from Saudi Basic Industries Corp.
- the hot melt adhesive composition comprises 20%to 60%by weight of an ethylene alpha-olefin copolymer based on the total weight of the hot melt adhesive composition.
- the ethylene alpha-olefin copolymer provides the polymer base to the hot melt adhesive composition; therefore the weight percentage shall be at least 20%, otherwise the adhesion property of the cured product will be deprived, preferably the component (a) is present in an amount of more than 25%to 60%, more preferably 30%to 60%by weight of the hot melt adhesive composition.
- the hot melt adhesive composition comprises 1%to less than 15%by weight of a styrene block copolymer based on the total weight of the hot melt adhesive composition, wherein the styrene block copolymer has a styrene content of greater than 15%based on the weight of component (b) .
- the component (b) may include an aromatic vinyl polymer block and a saturated midblock, preferably a hydrogenated conjugated diene polymer block.
- the blocks can be arranged in a variety of configurations including, e.g., linear, branched, radial, star and combinations thereof.
- the aromatic vinyl polymer block can be derived from a variety of aromatic vinyl compounds including, e.g., styrene, alpha-methylstyrene, beta-methylstyrene, o-, m-, p-methylstyrene, t-butylstyrene-2, 4, 6-trimethylstyrene, monofluorostyrene, difluorostyrene, monochlorostyrene, dichlorostyrene, methoxystyrene, 1, 3-vinylnaphthalene, vinylanthracene, indene, acenaphthylene, and combinations thereof.
- aromatic vinyl compounds including, e.g., styrene, alpha-methylstyrene, beta-methylstyrene, o-, m-, p-methylstyrene, t-butylstyrene-2, 4, 6-trimethylstyrene, monofluorosty
- the hydrogenated diene polymer block can be derived from a variety of diene-containing compounds including, e.g., isoprene, butadiene, hexadiene, 2, 3-dimethyl-1, 3-butadiene, 1, 3-pentadiene, and combinations thereof.
- Useful component (b) include, e.g., triblock, multi-arm, and radial copolymers including, e.g., styrene-ethylene/butene-styrene (SEBS) , styrene-ethylene/propylene-styrene (SEPS) , styrene-ethylene-ethylene/propylene-styrene (SEEPS) , styrene/isobutylene/styrene (SIBS) , and combination thereof.
- SEBS styrene-ethylene/butene-styrene
- SEPS styrene-ethylene/propylene-styrene
- SEEPS styrene-ethylene-ethylene/propylene-styrene
- SIBS styrene/isobutylene/styrene
- the component (b) comprised in the hot melt adhesive has a styrene content of greater than 15%by weight, preferably from 20%to 35%by weight of the component (b) .
- the styrene content refers to the proportion of styrene blocks included in the component (b) .
- the component (b) proved to greatly contribute to the adhesion property at room temperature and low temperature of the hot melt adhesive composition when cured.
- the melt flow rate of the component (b) may be at least 25 g/10 minutes (190°C, 2.16 kg) , and more preferably at least 30 g/10 minutes (190°C, 2.16 kg) .
- the component (b) contains essentially no, and preferably no unsaturated mid-blocks. Namely, the mid-blocks are saturated, or hydrogenated from diene polymer block.
- the suitable component (b) in the present invention include SEBS, for example KRATON MD 1648 commercially available from Kraton Polymers US LLC.
- the component (b) is present in an amount of 1%to less than 15%by weight, preferably more than 2%to 10%by weight, more preferably 2.5%to 8%, based on the total weight of the hot melt adhesive composition. If the content of the component (b) is present in an amount of 15%or more, the adhesion property of the cured product at high temperature may not be satisfactory.
- the hot melt adhesive composition may optionally comprise at least one styrene block copolymer having a styrene content of less than or equal to 15%. It is preferred to have such styrene block copolymers in the present invention in a small amount which helps boost the adhesion property at high temperature of the hot melt adhesive composition when cured. Suitable example of such styrene block copolymer having a styrene content of less than or equal to 15%include, for example, KRATON MD 1657 commercially available from Kraton Polymers US LLC. If present, the amount of the styrene block copolymer may be 0.5%to 8%, preferably 1%to 5%by weight based on the total weight of the hot melt adhesive composition.
- the hot melt adhesive composition comprises 2%to 20%by weight of an aromatic hydrocarbon resin tackifier (c) , based on the total weight of the hot melt adhesive composition.
- the hydrocarbon resin tackifier described herein refers to resin products manufactured from petroleum-based feedstock.
- the hydrocarbon resin tackifier includes aliphatic, aromatic, mixed aliphatic/aromatic and pure monomer (aromatic) ones.
- the hydrocarbon resin tackifier is a common component in the hot melt adhesive composition to maintain balance between adhesion and cohesion of the formulation.
- the aromatic hydrocarbon resin tackifier can join forces with other components to provide good adhesion property at low temperature to the hot melt adhesive composition when cured.
- Suitable aromatic hydrocarbon resin tackifiers used as component (c) include C8-10 aromatic hydrocarbon resins, preferably C9 aromatic hydrocarbon resins.
- C9 aromatic hydrocarbon resins can be derived from various monomers selected from vinyltoluene, indene, methylindene, styrene, alpha-methyl styrene, and combination thereof.
- the aromatic hydrocarbon resin tackifiers (c) can have a wide range of softening points, such as, from 80° to 150°C as determined by ASTM E 28.
- Examples of commercially aromatic hydrocarbon resin tackifiers include C9 BP-100, C9 BP-120, C9 BP-140 and C9 BP-150 from Bitoner Resin, Kristalex TM 3085 from Eastman, Novares TM 90 from Rütgers Chemicals, and Mkorez MK 85 from Kolon Industries.
- the aromatic hydrocarbon resin tackifier (c) may be present in an amount of 2%to 20%by weight, preferably 2%to 12%by weight, and more preferably from 3%to 10%, based on the total weight of the hot melt adhesive composition.
- the hot melt adhesive composition may optionally comprise an aliphatic hydrocarbon resin tackifier.
- Suitable aliphatic hydrocarbon resin tackifier include branched, unbranched, and cyclic C5-10 aliphatic hydrocarbon resins, preferably C5 aliphatic hydrocarbon resins.
- Examples of C5 aliphatic hydrocarbon resins can be derived from various monomers selected from trans-1, 3-pentadiene, cis-1, 3-pentadiene, 2-methyl-2-butene, dicyclopentadiene (DCPD) , cyclopentadiene, cyclopentene, and combination thereof.
- DCPD dicyclopentadiene
- Examples of commercially available aliphatic hydrocarbon resin tackifiers include C100R, C100W, H130R, and H130W from Eastman; H5-1000 and H5-1001 from Henghe China; SU90, SU100, SU120 and SU130 from Kolon Industries; I-Marv P90, I-Marv P100, and I-Marv P120 from Idemitsu; Regalite R1100, Regalite R1120, and Regalite S1100 from Eastman; JH-6100 and JH-6125 from Jinhai Chenguang.
- the aliphatic hydrocarbon resin tackifier (s) may be present in an amount of 20%to 55%by weight, and preferably 20%to 40%by weight, based on the total weight of the hot melt adhesive composition.
- the hot melt adhesive also comprises 1%to less than 15%by weight of a plasticizer, based on the total weight of the hot melt adhesive composition.
- the plasticizer (d) is added for the purpose of lowering the melt viscosity of hot melt adhesives, to impart flexibility, and to enhance wetting of the subject material, and are not specifically limited as long as they are mutually soluble with the styrene block copolymers according to the purpose of the present invention.
- the plasticizer (d) may be selected from a polybutylene, a paraffinic oil, a naphthenic oil, an aromatic oil, and combination thereof.
- polybutenes, paraffinic oils and/or naphthenic oils are preferable, and polybutenes, being colorless and chemically stable, are particularly preferable.
- the plasticizer (d) may be commercially available from, for example white mineral oil LP 150, LP 350 manufactured by Kukdong Oil and Chemical Co., Diana Fresia S-32, Diana Process Oil PW-90, Daphne Oil KP-68, or manufactured by Idemitsu Kosan Co., Ltd., Enerper M1930 manufactured by BP Chemicals, Ltd., Kaydol manufactured by Crompton Ltd., Primol 352 manufactured by Exxon Inc., or KN 4006, 4008, 4010 from Lubricant Company of PetroChina, Nyflex 222B from Nynas, PS white mineral oil from PetroChina Process Oil NS-100 manufactured by Idemitsu Kosan Co., Ltd., PB 1300 available from Daelim Industrial. These may be used singly or in combination.
- the plasticizer (d) may be present in an amount of 1%to less than 15%by weight, preferably 1%to 10%by weight, based on the total weight of the hot melt adhesive composition. If the plasticizer is added equal to or more than 15%by weight, the setting time would be long, and the adhesion property at room temperature and high temperature of the cured product will be insufficient.
- the hot melt adhesive also comprises 1%to 40%by weight of a wax, based on the total weight of the hot melt adhesive composition.
- the "wax” refers to an organic substance having a weight average molecular weight of less than 10,000, which is solid at normal temperature and becomes liquid when heated, and is commonly considered as a “wax” .
- the waxes are those generally used in hot melt adhesives and are not specifically limited as long as a hot melt adhesive according to the purpose of the present invention is obtained.
- the wax may be a synthetic wax, and/or a natural wax.
- Natural waxes include those derived from insects, animals, plants, minerals and petroleum. Petroleum waxes are conventionally subdivided into paraffin waxes and microcrystalline waxes, these inherently nonreactive waxes being obtained at different stages in the process of refining crude oil.
- synthetic wax can be derived from ethylene and optionally co-monomers including, for example, propylene.
- synthetic wax include, for example, a polyethylene wax, a Fischer-Tropsh wax, a metallocene catalyzed polyethylene wax, and combination thereof.
- Preferable synthetic wax used in the invention may have a drop melting point (Tm) of from 70 °C to 130 °C, from 70 °C to 120 °C.
- Preferable wax used in the present invention can be selected from a paraffin wax, a microcrystalline wax, a polyethylene wax, a polypropylene wax, a by-product polyethylene wax, a sasol wax, a Fischer-Tropsch synthetic wax, a functionalized wax and combination thereof.
- Fischer-Tropsh wax is Sasolwax H1, C80 from Sasol Wax and SX105 from Shell.
- Useful metallocene catalyzed polyethylene waxes are commercially available under a variety of trade designations including, e.g., LICOWAX from Clariant Int'l Ltd. (Muttenz, Switzerland) , and TRECORA CWP-400 from Trecora Chemical (Pasadena, Texas) .
- the wax (e) may be present in an amount of 1%to 40%, and preferably 1%to 25%by weight, based on the total weight of the hot melt adhesive composition.
- the hot melt adhesive according to the present invention may contain a variety of other additives as necessary.
- additives may include stabilizers, fine particulate fillers, and the like.
- Stabilizers are substances blended in for the purpose of enhancing the stability of hot melt adhesives as well as to prevent reduction of molecular weight of the hot melt adhesive due to heat, or to promote gelling, add color, or prevent odor and the like, and are not specifically limited so long as the purpose of the hot melt adhesive according to the present invention is achieved.
- Stabilizers may also be, for example, anti-oxidants or ultraviolet ray absorbents.
- Anti-oxidants may include, for example, phenolic anti-oxidants, sulfur-related antioxidants, or phosphorus-related anti-oxidants.
- Ultraviolet ray absorbents may include, for example, benzotriazol related ultraviolet ray absorbents, or benzophenone related ultraviolet ray absorbents. Lactone stabilizers may also be added. These may be used either singly or in combinations.
- antioxidants examples include hindered phenol, phosphite, thiodipropionate and the mixtures of above.
- Typical commercial examples of hindered phenol are Evernox 10GF /1726 from Everspring, Irganox 1010 /1726 from BASF, Thanox 1010G /1726 from Rianlon;
- Commercial exampels of phosphite include Everfos 168 from Everspring, Irgafos 168 from BASF, Thanox 168 from Rianlon;
- commercial examples of thiodipropionate include Thanox 412S /DSTP from Rianlon, ADK AO 412S from Adeka, Sumilizer TP-D from Sumitomo.
- the hot melt adhesive according to the present invention may further contain particulate fillers.
- Any fine particulate filler in general use may be used without limitation so long as a hot melt adhesive according to the purpose of the present invention is obtained.
- the fine particulate fillers may include for example, mica, calcium carbonate, kaolin, talc, titanium oxide, diatom earth, urea resins, styrene particles, baked clay, starch, and the like.
- the form thereof is preferably spherical, and the dimensions (diameter if spherical) are not specifically limited.
- the additive may be present in an amount of 0%to 10%by weight, based on the total weight of the hot melt adhesive composition.
- the hot melt adhesive composition according to the present invention may be manufactured by mixing the ethylene alpha-olefin copolymer (a) , styrene block copolymer (b) , the aromatic hydrocarbon resin tackifier (c) , the plasticizer (d) , the wax (e) as well as other additives as necessary, using commonly known methods of manufacture of hot melt adhesives.
- manufacturing may be by blending the aforementioned components in the prescribed quantities, and melting them by heating.
- the order of addition of each component, the method of heating etc. is not specifically limited as long as a hot melt adhesive composition according to the purpose is obtained.
- the hot melt adhesive composition comprises:
- weight ratios of the components are based on the total weight of the hot melt adhesive composition.
- the hot melt composition according to the present invention exhibits a melt viscosity of no greater than 3,000 cP, and preferably no greater than 2,500 cP at 160°C.
- the hot melt composition according to the present invention exhibits a setting time of no more than 3 seconds.
- the hot melt adhesive composition of this invention can be obtained by blending the mixtures of solid components under high temperature, e.g. above 140°C, so that solid can be melted and fully blended and then homogenized with other components. Any feasible blending methods that are known in the art can be adopted to prepare a homogeneous mixture.
- an article comprising a cured product of the hot melt adhesive composition according to the present invention.
- the hot melt adhesive composition in this invention can be applied to or incorporated in a variety of articles including, e.g., fibers, substrates made from fibers (e.g., virgin fibers, recycled fibers, synthetic polymer fibers (e.g., nylon, rayon, polyesters, acrylics, polypropylenes, polyethylene, polyvinyl chloride, polyurethane) , cellulose fibers (e.g., natural cellulose fibers such as wood pulp) , natural fibers (e.g., cotton, silk and wool) , and glass fibers, and combinations thereof) , release liners, porous substrates, cellulose substrates, sheets (e.g., paper, and fiber sheets) , paper products, woven and nonwoven webs (e.g., webs made from fibers (e.g., yarn, thread, filaments, microfibers, blown fibers, and spun
- fibers e.g.,
- the hot melt adhesive composition is useful for bonding a variety of substrates including, e.g., cardboard, coated cardboard, paperboard, fiber board, virgin and recycled kraft, high and low density kraft, chipboard, treated and coated kraft and chipboard, and corrugated versions of the same, clay coated chipboard carton stock, composites, leather, fibers and substrates made from fibers (e.g., virgin fibers, recycled fibers, synthetic polymer fibers, cellulose fibers, and combinations thereof) , release liners, porous substrates (e.g., woven webs, nonwoven webs, and perforated films) , cellulose substrates, sheets (e.g., paper, and fiber sheets) , paper products, tape backings, and combinations thereof.
- Preferred substrates used herein include corrugated cartons or boards laminated with films selected from oriented polypropylene (BOPP) films, polyester (PET) films and the like.
- the hot melt adhesive composition in packaging, bags, boxes, cartons, cases, trays, multi-wall bags, articles that include attachments (e.g., straws attached to drink boxes) , ream wrap, cigarettes (e.g., plug wrap) , filters (e.g., pleated filters and filter frames) , bookbinding, paper products including, e.g., paper towels (e.g., multiple use towels) , toilet paper, facial tissue, wipes, tissues and towels (e.g., paper towels) , preferably corrugated cartons with laminated films.
- attachments e.g., straws attached to drink boxes
- cigarettes e.g., plug wrap
- filters e.g., pleated filters and filter frames
- bookbinding paper products including, e.g., paper towels (e.g., multiple use towels) , toilet paper, facial tissue, wipes, tissues and towels (e.g., paper towels) , preferably corrugated cartons with laminated films.
- the hot melt adhesive composition can be applied to a substrate in any useful form including, e.g., as a coating (e.g., a continuous coatings and discontinuous coatings (e.g., random, pattern, and array) ) , as a bead, as a film (e.g., a continuous films and discontinuous films) , and combinations thereof, using any suitable application method including, e.g., slot coating, spray coating (e.g., spiral spray, random spraying, and random fiberization (e.g., melt blowing) , foaming, extrusion (e.g., applying a bead, fine line extrusion, single screw extrusion, and twin screw extrusion) , wheel application, noncontact coating, contacting coating, gravure, engraved roller, roll coating, transfer coating, screen printing, flexographic, and combinations thereof.
- a coating e.g., a continuous coatings and discontinuous coatings (e.g., random, pattern, and array)
- AFFINITY TM GA1900 is ethylene/1-octene copolymer with a melt flow rate of 1000 g/10 min at 190°C, 2.16kg, and melt viscosity of 8195 cP at 177°C, commercially available from DOW.
- AFFINITY TM GA 1000R is maleic anhydride-modified ethylene/1-octene copolymer with a melt flow rate of 660 g/10min at 190°C, 2.16kg, and melt viscosity of 14000 cP at 177°C, commercially available from DOW.
- Kraton MD 1657 is a synthetic SEBS block copolymer with a melt flow rate of 22g/10min at 230°C, 5kg, a styrene content of 13%, commercially available from Kraton.
- Kraton MD 1648 is a synthetic SEBS block copolymer with a melt flow rate of greater than 30g/10min at 190°C, 2.16kg, a styrene content of 20%, commercially available from Kraton.
- Kristalex TM 3085 is alpha-methyl styrene C9 aromatic hydrocarbon resin tackifier, commercially available from Eastman Chemical.
- HD 1120 is dicyclopentadiene (DCPD) resin tackifier, aliphatic hydrocarbon resin tackifiercommercially available from Luhua.
- DCPD dicyclopentadiene
- PB 1300 is a colorless and chemically stable polybutene plasticizer, commercially available from Daelim Industrial.
- SX105 is a Fischer Tropsch wax, with a drop melting point of 115°C, commercially available from Shell.
- Te Cero Wax 30201 H is microcrystalline wax, with a drop melting point of 80°C, commercially available from Th. C. Tromm.
- Irganox 1010 is an anti-oxidant commercially available from BASF.
- the melt viscosity of hot melt adhesive composition in the present invention was measured by using a Brookfield rotational viscometer (digital Brookfield viscometer, DV-II+, available from BROOKFIELD, US) with spindles at 160 °C according to ASTM D1084-1997.
- Brookfield rotational viscometer digital Brookfield viscometer, DV-II+, available from BROOKFIELD, US
- the hot melt adhesive composition exhibiting met viscosity of no greater than 3000cP can be acceptable.
- a bead of adhesive composition measuring 5 cm by 0.2 cm was applied to a first substrate of a 3-layers composite corrugated board made of wastepaper and pulp (product name: K5 x S120X3 x K5, manufactured from Japan Tokan Package) using a MEC ASM-15N Hot Melt Bond Simulator.
- the temperature of the adhesive composition when it was applied to the substrate was referred to the application temperature.
- the application temperature was 160 °C.
- the Bond Simulator timer was started when the substrates were compressed. After a pre- programmed compression time the instrument separates the two substrates by pulling on the second substrate in the Z direction and holding the first substrate in a fixed position and the force required to separate the substrates and the amount of fiber tear present on the adhesive composition was measured. Samples were run in triplicate at each compression time. Initially, the compression time was 0.5 seconds. If the three samples fail to exhibit greater than 75 %Fiber Tear for each sample, the compression time was increased by-0.5 second and the test method was repeated until greater than 75 %fiber tear is noted for all three samples. The setting time was recorded as the compression time at which the three samples achieve greater than 75%fiber tear immediately upon separation. The setting time was recorded in seconds.
- the hot melt adhesive composition exhibiting setting time of no more than 3 seconds can be suitable for industrial application.
- the adhesion property of the hot melt adhesive compositions was determined by Fiber Tear Test (also named as Adhesion Test) .
- the percentage fiber tear was the percentage of fiber that covers the area of the adhesive after two substrates, which had been previously bonded together through the adhesive, were separated by force.
- the percentage of fiber tear exhibited by an adhesive composition was determined as follows. A bead of the adhesive composition measuring 2g/m was applied to a first substrate of corrugated carton with laminated BOPP film manufactured from Tian Di Yi Hao, using a ROCKTENN bond simulator at the specified application temperature.
- the bead of adhesive was contacted with a second substrate of corrugated carton with laminated BOPP film manufactured from Tian Di Yi Hao, which was pressed against the adhesive and the first substrate with a pressure of 0.2 MPa for a period of 3 seconds.
- the resulting constructions were then conditioned at room temperature for at least 24 hours and then conditioned at the specified test temperature for at least 2 hours.
- the substrates of the construction were then separated from one another at the conditioning temperature (e.g., immediately after removing the sample from the conditioning chamber) by pulling the two substrates apart from one another by hand.
- the surface of the adhesive composition was observed and the percent of the surface area of the adhesive composition that was covered by fibers was determined and recorded. A minimum of five samples were prepared and tested for each hot melt adhesive composition. The results were reported in units of %fiber tear.
- the hot melt adhesive composition was considered to be acceptable where more than 75%fiber tear at various ambient temperatures.
- the inventive example 1 showed faster setting time and satisfactory adhesion properties at various ambient temperature through selecting a proper combination of ethylene alpha-olefin copolymer (a) and styrene block copolymer having a styrene content of greater than 15% (b) in a proper amount.
- the comparative compositions containing only aliphatic hydrocarbon resin tackifier without aromatic hydrocarbon resin tackifier (CEx. 4) or higher amount of plasticizer (CEx. 3) could not achieve at least one of the desired properties.
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Abstract
This invention relates to a hot melt adhesive composition. In particular, the present invention relates to a hot melt pressure sensitive adhesive composition exhibiting lower melt viscosity, fast setting time, and good fiber tearing adhesive properties at various ambient temperatures.
Description
This invention relates to a hot melt adhesive composition and use thereof. In particular, the present invention relates to a hot melt adhesive composition exhibiting low melt viscosity, fast setting time, and good fiber tearing adhesive properties at various ambient temperatures.
Hot melt adhesives are often used to bond two substrates together while in a molten state. Such adhesives are widely used for various commercial and industrial applications such as product assembly and packaging. To be commercially viable, most hot melt adhesive compositions must maintain adhesion to the substrate at room temperature and, to be suitable for use in high-speed packaging operations, the adhesive must also exhibit fast setting time. If the setting time is long, the initial strength will be insufficient, and the bonding surface of the object will bounce off.
Much has been written and said about a variety of different types of polymers used in the traditional hot melt adhesive compositions, such as EVA (ethylene vinyl acetate copolymer) or metallocene catalyzed polyolefin. However, these traditional hot melt adhesives are incapable of forming an effective bonding to substrates like corrugated laminated films, especially Biaxially Oriented Polypropylene (BOPP) films or Polyester (PET) films, which surface energy are less than or equal to 32 dynes. Furthermore, in the cases of many uses such as sealing cartons, it is desirable for the hot melt adhesives to exhibit a good fiber tearing bond at various ambient temperatures (from -5℃ to 50℃) where not many traditional hot melt adhesive compositions can endure.
Consequently, there is a need for a hot melt adhesive that exhibits low melt viscosity, fast setting time, and good fiber tearing adhesive properties at various ambient temperatures. Such attributes would make the adhesives particularly well-suited for use in the manufacture of packaging, especially corrugated laminated films.
According to the first aspect of the invention, provided herein is a hot melt adhesive composition, based on the total weight of the composition, comprising,
(a) 20%to 60%by weight of an ethylene alpha-olefin copolymer,
(b) 1%to less than 15%by weight of a styrene block copolymer,
(c) 2%to 20%by weight of an aromatic hydrocarbon resin tackifier,
(d) 1%to less than 15%by weight of a plasticizer, and
(e) 1%to 40%by weight of a wax,
wherein the styrene block copolymer (b) has a styrene content of greater than 15%by weight, based on the weight of component (b) .
According to the second aspect of the invention, provided herein is an article comprising a cured product of the hot melt adhesive composition according to the present invention.
According to the third aspect of the invention, provided herein is the use of the hot melt adhesive composition in packaging, bags, boxes, cartons, cases, trays, multi-wall bags, articles with attachments, ream wrap, cigarettes, filters, bookbinding or paper products, preferably corrugated cartons with laminated films.
The invention features a hot melt adhesive composition exhibiting low melt viscosity, fast setting time, and good fiber tearing adhesive properties at various ambient temperatures (from -5℃ to 50℃) .
Other features and aspects of the subject matter are set forth in greater detail below.
In the following passages the present invention is described in more detail. Each aspect so described may be combined with any other aspect or aspects unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.
In the context of the present invention, the terms used are to be construed in accordance with the following definitions, unless a context dictates otherwise.
As used herein, the singular forms “a” , “an” and “the” include both singular and plural referents unless the context clearly dictates otherwise.
The terms “comprising” , “comprises” and “comprised of” as used herein are synonymous with “including” , “includes” or “containing” , “contains” , and are inclusive or open-ended and do not exclude additional, non-recited members, elements or process steps.
The term “setting time” as used herein refers to the positioning time of the hot melt adhesive, and the time required for the adhesive to generate a certain strength within the curing time.
The molecular weights refer to number average molecular weights (Mn) , unless otherwise stipulated. All molecular weight data refer to values obtained by gel permeation chromatography (GPC) , unless otherwise stipulated, e.g., according to DIN 55672.
The recitation of numerical end points includes all numbers and fractions subsumed within the respective ranges, as well as the recited end points.
All references cited in the present specification are hereby incorporated by reference in their entirety.
Unless otherwise defined, all terms used in the disclosing the invention, including technical and scientific terms, have the meaning as commonly understood by one of the ordinary skill in the art to which this invention belongs to. By means of further guidance, term definitions are included to better appreciate the teaching of the present invention.
According to the first aspect of the invention, the hot melt adhesive composition, based on the total weight of the composition, comprising,
(a) 20%to 60%by weight of an ethylene alpha-olefin copolymer,
(b) 1%to less than 15%by weight of a styrene block copolymer,
(c) 2%to 20%by weight of an aromatic hydrocarbon resin tackifier,
(d) 1%to less than 15%by weight of a plasticizer, and
(e) 1%to 40%by weight of a wax,
wherein the styrene block copolymer (b) has a styrene content of greater than 15%by weight, based on the weight of component (b) .
(a) Ethylene alpha-olefin copolymer
According to the present invention, the hot melt adhesive composition comprises 20%to 60%by weight of ethylene alpha-olefin copolymer based on the total weight of the hot melt adhesive composition.
Suitable ethylene alpha-olefin copolymer is derived from at least 60 mole %, at least 65 mole %, or even at least 70 mole %ethylene, and an alpha-olefin monomer. The alpha-olefin monomer has at least three carbon atoms, or even from three to 20 carbon atoms, suitable examples of which include propylene, isobutylene, butene, pentene, hexene, heptene, octene, nonene, decene, dodecene, 4-methyl-1-pentene, 3-methyl pentene-1, 3, 5, 5-trimethyl-hexene-1, 5-ethyl-1-nonene, and combinations thereof.
Examples of the ethylene alpha-olefin copolymers (A) include an ethylene/propylene copolymer, an ethylene/1-octene copolymer, an ethylene/1-butene copolymer, an ethylene/propylene/1-butene copolymer, and a functionalized ethylene alpha-olefin copolymer e.g., a carboxylic acid modified ethylene/propylene copolymer, a carboxylic acid modified ethylene/1-octene copolymer, a carboxylic acid modified ethylene/1-butene copolymer, a carboxylic acid modified ethylene/propylene/1-butene copolymer, a maleic anhydride modified ethylene/propylene copolymer, a maleic anhydride modified ethylene/1-octene copolymer, a maleic anhydride modified ethylene/1-butene copolymer, a maleic anhydride modified ethylene/propylene/1-butene copolymer and combination thereof; and the
ethylene/propylene copolymer, the ethylene/1-octene copolymer, the maleic anhydride modified ethylene/1-octene copolymer, the maleic anhydride modified ethylene/propylene copolymer and the combination thereof are particularly preferable.
The ethylene alpha-olefin copolymer can be prepared using a variety of catalysts including, e.g., a single site catalyst (e.g., metallocene catalysts (e.g., metallocene catalyzed ethylene alpha-olefin copolymers) , constrained geometry catalysts (e.g., homogeneous linear or substantially linear ethylene alpha-olefin interpolymers prepared from ethylene and an alpha-olefin comonomer using a constrained geometry catalyst) ) , multiple single site catalysts, and combinations thereof, preferable ethylene alpha-olefin copolymers are metallocene catalyzed ethylene alpha-olefin copolymers. The polydispersity (Mw/Mn) of the copolymer (A) obtained by polymerizing using a metallocene catalyst is preferably from 1 to 4, more preferably from 1 to 3, and particularly preferably from 1.5 to 3.
In preferred embodiments, the ethylene alpha-olefin copolymers exhibit melt viscosity less than or equal to 20000 cP at 177℃, preferably from 3000 cP to 18000cP at 177℃.
In preferred embodiments, the ethylene alpha-olefin copolymers exhibit a melt index of from about 1 g/10 minutes (min) to 2500 g/10 min, at 190 ℃ using a 2.16 kilogram (kg) weight as measured according to ASTM D1238.
Useful ethylene alpha-olefin copolymers are commercially available under of a variety of trade designations including, e.g., the AFFINITY series of trade designations from Dow, including, e.g., AFFINITY GA 1875, AFFINITY GA 1900, and AFFINITY GA 1950 ethylene-1-octene copolymers, AFFINITY GA 1000R maleic anhydride-modified ethylene-octene copolymer, the INFUSE series of trade designations from DOW including INFUSE 9807 ethylene-ethylene-propylene copolymer, the SABIC POE series of trade designations from Saudi Basic Industries Corp. (Pittsfield, Massachusetts) including SABIC POE C30070D, the LUCENE series of trade designations from LG, the TAFMER series of trade designations from MITSUI, and the EXACT series of trade designations from ExxonMobil Chemical Company (Houston, Texas) including, e.g., EXACT 9061 ethylene butene copolymer.
It is preferred to use at least two different ethylene alpha-olefin copolymers described above in the present hot melt adhesive composition.
According to the present invention, the hot melt adhesive composition comprises 20%to 60%by weight of an ethylene alpha-olefin copolymer based on the total weight of the hot melt adhesive composition. The ethylene alpha-olefin copolymer provides the polymer base to the hot melt adhesive composition; therefore the weight percentage shall be at least 20%, otherwise the adhesion property of the cured product will be deprived, preferably the component (a) is present in an amount of more than 25%to 60%, more preferably 30%to 60%by weight of the hot melt adhesive composition.
(b) Styrene block copolymer
According to the present invention, the hot melt adhesive composition comprises 1%to less than 15%by weight of a styrene block copolymer based on the total weight of the hot melt adhesive composition, wherein the styrene block copolymer has a styrene content of greater than 15%based on the weight of component (b) .
The component (b) may include an aromatic vinyl polymer block and a saturated midblock, preferably a hydrogenated conjugated diene polymer block. The blocks can be arranged in a variety of configurations including, e.g., linear, branched, radial, star and combinations thereof. The aromatic vinyl polymer block can be derived from a variety of aromatic vinyl compounds including, e.g., styrene, alpha-methylstyrene, beta-methylstyrene, o-, m-, p-methylstyrene, t-butylstyrene-2, 4, 6-trimethylstyrene, monofluorostyrene, difluorostyrene, monochlorostyrene, dichlorostyrene, methoxystyrene, 1, 3-vinylnaphthalene, vinylanthracene, indene, acenaphthylene, and combinations thereof. The hydrogenated diene polymer block can be derived from a variety of diene-containing compounds including, e.g., isoprene, butadiene, hexadiene, 2, 3-dimethyl-1, 3-butadiene, 1, 3-pentadiene, and combinations thereof. Useful component (b) include, e.g., triblock, multi-arm, and radial copolymers including, e.g., styrene-ethylene/butene-styrene (SEBS) , styrene-ethylene/propylene-styrene (SEPS) , styrene-ethylene-ethylene/propylene-styrene (SEEPS) , styrene/isobutylene/styrene (SIBS) , and combination thereof.
According to the present invention, the component (b) comprised in the hot melt adhesive has a styrene content of greater than 15%by weight, preferably from 20%to 35%by weight of the component (b) . The styrene content refers to the proportion of styrene blocks included in the component (b) . The component (b) proved to greatly contribute to the adhesion property at room temperature and low temperature of the hot melt adhesive composition when cured.
Preferably, the melt flow rate of the component (b) may be at least 25 g/10 minutes (190℃, 2.16 kg) , and more preferably at least 30 g/10 minutes (190℃, 2.16 kg) .
Preferably, the component (b) contains essentially no, and preferably no unsaturated mid-blocks. Namely, the mid-blocks are saturated, or hydrogenated from diene polymer block. The suitable component (b) in the present invention include SEBS, for example KRATON MD 1648 commercially available from Kraton Polymers US LLC.
According to the present invention, the component (b) is present in an amount of 1%to less than 15%by weight, preferably more than 2%to 10%by weight, more preferably 2.5%to 8%, based on the total weight of the hot melt adhesive composition. If the content of the component (b) is present in an amount of 15%or more, the adhesion property of the cured product at high temperature may not be satisfactory.
The hot melt adhesive composition may optionally comprise at least one styrene block copolymer having a styrene content of less than or equal to 15%. It is preferred to have such styrene block copolymers in the present invention in a small amount which helps boost the adhesion property at high temperature of the hot melt adhesive composition when cured. Suitable example of such styrene block copolymer having a styrene content of less than or equal to 15%include, for example, KRATON MD 1657 commercially available from Kraton Polymers US LLC. If present, the amount of the styrene block copolymer may be 0.5%to 8%, preferably 1%to 5%by weight based on the total weight of the hot melt adhesive composition.
(c) Tackifier
According to the present invention, the hot melt adhesive composition comprises 2%to 20%by weight of an aromatic hydrocarbon resin tackifier (c) , based on the total weight of the hot melt adhesive composition.
The hydrocarbon resin tackifier described herein refers to resin products manufactured from petroleum-based feedstock. Generally, the hydrocarbon resin tackifier includes aliphatic, aromatic, mixed aliphatic/aromatic and pure monomer (aromatic) ones. The hydrocarbon resin tackifier is a common component in the hot melt adhesive composition to maintain balance between adhesion and cohesion of the formulation. In addition to this effect, the inventor surprisingly found that the aromatic hydrocarbon resin tackifier can join forces with other components to provide good adhesion property at low temperature to the hot melt adhesive composition when cured.
Suitable aromatic hydrocarbon resin tackifiers used as component (c) include C8-10 aromatic hydrocarbon resins, preferably C9 aromatic hydrocarbon resins. Examples of C9 aromatic hydrocarbon resins can be derived from various monomers selected from vinyltoluene, indene, methylindene, styrene, alpha-methyl styrene, and combination thereof.
The aromatic hydrocarbon resin tackifiers (c) can have a wide range of softening points, such as, from 80° to 150℃ as determined by ASTM E 28.
Examples of commercially aromatic hydrocarbon resin tackifiers include C9 BP-100, C9 BP-120, C9 BP-140 and C9 BP-150 from Bitoner Resin, KristalexTM 3085 from Eastman, Novares TM 90 from Rütgers Chemicals, and Mkorez MK 85 from Kolon Industries.
According to the present invention, the aromatic hydrocarbon resin tackifier (c) may be present in an amount of 2%to 20%by weight, preferably 2%to 12%by weight, and more preferably from 3%to 10%, based on the total weight of the hot melt adhesive composition.
The hot melt adhesive composition may optionally comprise an aliphatic hydrocarbon resin tackifier. Suitable aliphatic hydrocarbon resin tackifier include branched, unbranched, and cyclic C5-10 aliphatic
hydrocarbon resins, preferably C5 aliphatic hydrocarbon resins. Examples of C5 aliphatic hydrocarbon resins can be derived from various monomers selected from trans-1, 3-pentadiene, cis-1, 3-pentadiene, 2-methyl-2-butene, dicyclopentadiene (DCPD) , cyclopentadiene, cyclopentene, and combination thereof.
Examples of commercially available aliphatic hydrocarbon resin tackifiers include C100R, C100W, H130R, and H130W from Eastman; H5-1000 and H5-1001 from Henghe China; SU90, SU100, SU120 and SU130 from Kolon Industries; I-Marv P90, I-Marv P100, and I-Marv P120 from Idemitsu; Regalite R1100, Regalite R1120, and Regalite S1100 from Eastman; JH-6100 and JH-6125 from Jinhai Chenguang.
It is preferred to use a combination of an aromatic hydrocarbon resin tackifier and an aliphatic hydrocarbon resin tackifier in the present hot melt adhesive composition.
If present, the aliphatic hydrocarbon resin tackifier (s) may be present in an amount of 20%to 55%by weight, and preferably 20%to 40%by weight, based on the total weight of the hot melt adhesive composition.
(d) Plasticizer
According to the present invention, the hot melt adhesive according also comprises 1%to less than 15%by weight of a plasticizer, based on the total weight of the hot melt adhesive composition. The plasticizer (d) is added for the purpose of lowering the melt viscosity of hot melt adhesives, to impart flexibility, and to enhance wetting of the subject material, and are not specifically limited as long as they are mutually soluble with the styrene block copolymers according to the purpose of the present invention.
The plasticizer (d) may be selected from a polybutylene, a paraffinic oil, a naphthenic oil, an aromatic oil, and combination thereof. In particular, polybutenes, paraffinic oils and/or naphthenic oils are preferable, and polybutenes, being colorless and chemically stable, are particularly preferable.
The plasticizer (d) may be commercially available from, for example white mineral oil LP 150, LP 350 manufactured by Kukdong Oil and Chemical Co., Diana Fresia S-32, Diana Process Oil PW-90, Daphne Oil KP-68, or manufactured by Idemitsu Kosan Co., Ltd., Enerper M1930 manufactured by BP Chemicals, Ltd., Kaydol manufactured by Crompton Ltd., Primol 352 manufactured by Exxon Inc., or KN 4006, 4008, 4010 from Lubricant Company of PetroChina, Nyflex 222B from Nynas, PS white mineral oil from PetroChina Process Oil NS-100 manufactured by Idemitsu Kosan Co., Ltd., PB 1300 available from Daelim Industrial. These may be used singly or in combination.
According to the present invention, the plasticizer (d) may be present in an amount of 1%to less than 15%by weight, preferably 1%to 10%by weight, based on the total weight of the hot melt adhesive
composition. If the plasticizer is added equal to or more than 15%by weight, the setting time would be long, and the adhesion property at room temperature and high temperature of the cured product will be insufficient.
(e) Wax
According to the present invention, the hot melt adhesive according also comprises 1%to 40%by weight of a wax, based on the total weight of the hot melt adhesive composition.
As used herein, the "wax" refers to an organic substance having a weight average molecular weight of less than 10,000, which is solid at normal temperature and becomes liquid when heated, and is commonly considered as a "wax" . The waxes are those generally used in hot melt adhesives and are not specifically limited as long as a hot melt adhesive according to the purpose of the present invention is obtained.
Specifically, the wax may be a synthetic wax, and/or a natural wax. Natural waxes include those derived from insects, animals, plants, minerals and petroleum. Petroleum waxes are conventionally subdivided into paraffin waxes and microcrystalline waxes, these inherently nonreactive waxes being obtained at different stages in the process of refining crude oil.
Further, synthetic wax can be derived from ethylene and optionally co-monomers including, for example, propylene. Examples of synthetic wax include, for example, a polyethylene wax, a Fischer-Tropsh wax, a metallocene catalyzed polyethylene wax, and combination thereof. Preferable synthetic wax used in the invention may have a drop melting point (Tm) of from 70 ℃ to 130 ℃, from 70 ℃ to 120 ℃.
Preferable wax used in the present invention can be selected from a paraffin wax, a microcrystalline wax, a polyethylene wax, a polypropylene wax, a by-product polyethylene wax, a sasol wax, a Fischer-Tropsch synthetic wax, a functionalized wax and combination thereof.
Typical commercial example of Fischer-Tropsh wax is Sasolwax H1, C80 from Sasol Wax and SX105 from Shell. Useful metallocene catalyzed polyethylene waxes are commercially available under a variety of trade designations including, e.g., LICOWAX from Clariant Int'l Ltd. (Muttenz, Switzerland) , and TRECORA CWP-400 from Trecora Chemical (Pasadena, Texas) .
According to the present invention, the wax (e) may be present in an amount of 1%to 40%, and preferably 1%to 25%by weight, based on the total weight of the hot melt adhesive composition.
Additive
The hot melt adhesive according to the present invention may contain a variety of other additives as necessary. Examples of such additives may include stabilizers, fine particulate fillers, and the like.
Stabilizers are substances blended in for the purpose of enhancing the stability of hot melt adhesives as well as to prevent reduction of molecular weight of the hot melt adhesive due to heat, or to promote gelling, add color, or prevent odor and the like, and are not specifically limited so long as the purpose of the hot melt adhesive according to the present invention is achieved. Stabilizers may also be, for example, anti-oxidants or ultraviolet ray absorbents.
Anti-oxidants may include, for example, phenolic anti-oxidants, sulfur-related antioxidants, or phosphorus-related anti-oxidants. Ultraviolet ray absorbents may include, for example, benzotriazol related ultraviolet ray absorbents, or benzophenone related ultraviolet ray absorbents. Lactone stabilizers may also be added. These may be used either singly or in combinations.
Examples of commercially available anti-oxidants include hindered phenol, phosphite, thiodipropionate and the mixtures of above. Typical commercial examples of hindered phenol are Evernox 10GF /1726 from Everspring, Irganox 1010 /1726 from BASF, Thanox 1010G /1726 from Rianlon; Commercial exampels of phosphite include Everfos 168 from Everspring, Irgafos 168 from BASF, Thanox 168 from Rianlon; Commercial examples of thiodipropionate include Thanox 412S /DSTP from Rianlon, ADK AO 412S from Adeka, Sumilizer TP-D from Sumitomo.
The hot melt adhesive according to the present invention may further contain particulate fillers. Any fine particulate filler in general use may be used without limitation so long as a hot melt adhesive according to the purpose of the present invention is obtained. The fine particulate fillers may include for example, mica, calcium carbonate, kaolin, talc, titanium oxide, diatom earth, urea resins, styrene particles, baked clay, starch, and the like. The form thereof is preferably spherical, and the dimensions (diameter if spherical) are not specifically limited.
In particular preferred embodiments, the additive may be present in an amount of 0%to 10%by weight, based on the total weight of the hot melt adhesive composition.
Adhesive composition
The hot melt adhesive composition according to the present invention may be manufactured by mixing the ethylene alpha-olefin copolymer (a) , styrene block copolymer (b) , the aromatic hydrocarbon resin tackifier (c) , the plasticizer (d) , the wax (e) as well as other additives as necessary, using commonly known methods of manufacture of hot melt adhesives. For example, manufacturing may be by blending the aforementioned components in the prescribed quantities, and melting them by heating. The order of addition of each component, the method of heating etc. is not specifically limited as long as a hot melt adhesive composition according to the purpose is obtained.
In a preferred embodiment, the hot melt adhesive composition comprises:
20%to 60%, preferably 25%to 60%, and preferably 30%to 60%by weight of an ethylene alpha-olefin copolymer,
1%to less than 15%, preferably 2%to 10%by weight, and more preferably 2.5%to 8%by weight of a styrene block copolymer having a styrene content of greater than 15%;
0.5%to 8%, preferably 1%to 5%by weight of a styrene block copolymer having a styrene content of less than or equal to 15%;
2%to 20%, preferably 2%to 12%by weight of an aromatic hydrocarbon resin tackifier,
20%to 55%, preferably 20%to 40%by weight of an aliphatic hydrocarbon resin tackifier,
1%to less than 15%, preferably 1%to 10%by weight of a plasticizer,
1%to 40%, preferably 1%to 25%by weight of a wax, and
0%to 10%by weight of by weight of an additive,
wherein the weight ratios of the components are based on the total weight of the hot melt adhesive composition.
In one embodiment, the hot melt composition according to the present invention exhibits a melt viscosity of no greater than 3,000 cP, and preferably no greater than 2,500 cP at 160℃.
In another embodiment, the hot melt composition according to the present invention exhibits a setting time of no more than 3 seconds.
The hot melt adhesive composition of this invention can be obtained by blending the mixtures of solid components under high temperature, e.g. above 140℃, so that solid can be melted and fully blended and then homogenized with other components. Any feasible blending methods that are known in the art can be adopted to prepare a homogeneous mixture.
Article and Uses
According to the second aspect of the invention, provided herein is an article comprising a cured product of the hot melt adhesive composition according to the present invention. The hot melt adhesive composition in this invention can be applied to or incorporated in a variety of articles including, e.g., fibers, substrates made from fibers (e.g., virgin fibers, recycled fibers, synthetic polymer fibers (e.g., nylon, rayon, polyesters, acrylics, polypropylenes, polyethylene, polyvinyl chloride, polyurethane) , cellulose fibers (e.g., natural cellulose fibers such as wood pulp) , natural fibers (e.g., cotton, silk and wool) , and glass fibers, and combinations thereof) , release liners, porous substrates, cellulose substrates, sheets (e.g., paper, and fiber sheets) , paper products, woven and nonwoven webs (e.g., webs made from fibers (e.g., yarn, thread, filaments, microfibers, blown fibers, and spun fibers) perforated films, and combinations thereof) , tape backings, and combinations thereof.
The hot melt adhesive composition is useful for bonding a variety of substrates including, e.g., cardboard, coated cardboard, paperboard, fiber board, virgin and recycled kraft, high and low density
kraft, chipboard, treated and coated kraft and chipboard, and corrugated versions of the same, clay coated chipboard carton stock, composites, leather, fibers and substrates made from fibers (e.g., virgin fibers, recycled fibers, synthetic polymer fibers, cellulose fibers, and combinations thereof) , release liners, porous substrates (e.g., woven webs, nonwoven webs, and perforated films) , cellulose substrates, sheets (e.g., paper, and fiber sheets) , paper products, tape backings, and combinations thereof. Preferred substrates used herein include corrugated cartons or boards laminated with films selected from oriented polypropylene (BOPP) films, polyester (PET) films and the like.
According to the third aspect of the invention, provided herein is the use of the hot melt adhesive composition in packaging, bags, boxes, cartons, cases, trays, multi-wall bags, articles that include attachments (e.g., straws attached to drink boxes) , ream wrap, cigarettes (e.g., plug wrap) , filters (e.g., pleated filters and filter frames) , bookbinding, paper products including, e.g., paper towels (e.g., multiple use towels) , toilet paper, facial tissue, wipes, tissues and towels (e.g., paper towels) , preferably corrugated cartons with laminated films.
The hot melt adhesive composition can be applied to a substrate in any useful form including, e.g., as a coating (e.g., a continuous coatings and discontinuous coatings (e.g., random, pattern, and array) ) , as a bead, as a film (e.g., a continuous films and discontinuous films) , and combinations thereof, using any suitable application method including, e.g., slot coating, spray coating (e.g., spiral spray, random spraying, and random fiberization (e.g., melt blowing) , foaming, extrusion (e.g., applying a bead, fine line extrusion, single screw extrusion, and twin screw extrusion) , wheel application, noncontact coating, contacting coating, gravure, engraved roller, roll coating, transfer coating, screen printing, flexographic, and combinations thereof.
The following examples are intended to assist one skilled in the art to better understand and practice the present invention. The scope of the invention is not limited by the examples but is defined in the appended claims. All parts and percentages are based on weight unless otherwise stated.
Examples
The following materials were used in the examples.
AFFINITYTM GA1900 is ethylene/1-octene copolymer with a melt flow rate of 1000 g/10 min at 190℃, 2.16kg, and melt viscosity of 8195 cP at 177℃, commercially available from DOW.
AFFINITYTMGA 1000R is maleic anhydride-modified ethylene/1-octene copolymer with a melt flow rate of 660 g/10min at 190℃, 2.16kg, and melt viscosity of 14000 cP at 177℃, commercially available from DOW.
Kraton MD 1657 is a synthetic SEBS block copolymer with a melt flow rate of 22g/10min at 230℃, 5kg, a styrene content of 13%, commercially available from Kraton.
Kraton MD 1648 is a synthetic SEBS block copolymer with a melt flow rate of greater than 30g/10min at 190℃, 2.16kg, a styrene content of 20%, commercially available from Kraton.
KristalexTM 3085 is alpha-methyl styrene C9 aromatic hydrocarbon resin tackifier, commercially available from Eastman Chemical.
HD 1120 is dicyclopentadiene (DCPD) resin tackifier, aliphatic hydrocarbon resin tackifiercommercially available from Luhua.
PB 1300 is a colorless and chemically stable polybutene plasticizer, commercially available from Daelim Industrial.
SX105 is a Fischer Tropsch wax, with a drop melting point of 115℃, commercially available from Shell.
Te Cero Wax 30201 H is microcrystalline wax, with a drop melting point of 80℃, commercially available from Th. C. Tromm.
Irganox 1010 is an anti-oxidant commercially available from BASF.
Test Methods:
Melt viscosity
The melt viscosity of hot melt adhesive composition in the present invention was measured by using a Brookfield rotational viscometer (digital Brookfield viscometer, DV-II+, available from BROOKFIELD, US) with spindles at 160 ℃ according to ASTM D1084-1997.
The hot melt adhesive composition exhibiting met viscosity of no greater than 3000cP can be acceptable.
Setting time
A bead of adhesive composition measuring 5 cm by 0.2 cm was applied to a first substrate of a 3-layers composite corrugated board made of wastepaper and pulp (product name: K5 x S120X3 x K5, manufactured from Japan Tokan Package) using a MEC ASM-15N Hot Melt Bond Simulator. The temperature of the adhesive composition when it was applied to the substrate was referred to the application temperature. The application temperature was 160 ℃. Two seconds after the bead of adhesive was applied to the first substrate, the bead of adhesive was contacted with the second substrate of the same material as the first substrate, which was then pressed against the first substrate with a pressure of 0.2 MPa and for a period of time (referred to herein as the compression time) . The Bond Simulator timer was started when the substrates were compressed. After a pre-
programmed compression time the instrument separates the two substrates by pulling on the second substrate in the Z direction and holding the first substrate in a fixed position and the force required to separate the substrates and the amount of fiber tear present on the adhesive composition was measured. Samples were run in triplicate at each compression time. Initially, the compression time was 0.5 seconds. If the three samples fail to exhibit greater than 75 %Fiber Tear for each sample, the compression time was increased by-0.5 second and the test method was repeated until greater than 75 %fiber tear is noted for all three samples. The setting time was recorded as the compression time at which the three samples achieve greater than 75%fiber tear immediately upon separation. The setting time was recorded in seconds.
The hot melt adhesive composition exhibiting setting time of no more than 3 seconds can be suitable for industrial application.
Fiber Tear Test (Adhesion Test)
The adhesion property of the hot melt adhesive compositions was determined by Fiber Tear Test (also named as Adhesion Test) . The percentage fiber tear was the percentage of fiber that covers the area of the adhesive after two substrates, which had been previously bonded together through the adhesive, were separated by force. The percentage of fiber tear exhibited by an adhesive composition was determined as follows. A bead of the adhesive composition measuring 2g/m was applied to a first substrate of corrugated carton with laminated BOPP film manufactured from Tian Di Yi Hao, using a ROCKTENN bond simulator at the specified application temperature. One second after the bead of adhesive was applied to the first substrate, the bead of adhesive was contacted with a second substrate of corrugated carton with laminated BOPP film manufactured from Tian Di Yi Hao, which was pressed against the adhesive and the first substrate with a pressure of 0.2 MPa for a period of 3 seconds. The resulting constructions were then conditioned at room temperature for at least 24 hours and then conditioned at the specified test temperature for at least 2 hours. The substrates of the construction were then separated from one another at the conditioning temperature (e.g., immediately after removing the sample from the conditioning chamber) by pulling the two substrates apart from one another by hand. The surface of the adhesive composition was observed and the percent of the surface area of the adhesive composition that was covered by fibers was determined and recorded. A minimum of five samples were prepared and tested for each hot melt adhesive composition. The results were reported in units of %fiber tear.
The hot melt adhesive composition was considered to be acceptable where more than 75%fiber tear at various ambient temperatures.
Inventive Examples 1 to 7 (Ex. 1 to Ex. 7) and Comparative Examples 1 to 5 (CEx. 1 to CEx. 4)
All Inventive Examples and Comparative Examples were prepared by combining the components in the amounts (parts by weight) specified in Table 1 and heating the same to from 140℃ to 150 ℃ with
mixing, and the properties were tested using the methods stated above, and the results of evaluations are shown in Tables 1 and 2.
Table 1.
Table 2.
As shown in Tables 1 and 2, comparing to the comparative example 1 and 2, the inventive example 1 showed faster setting time and satisfactory adhesion properties at various ambient temperature through selecting a proper combination of ethylene alpha-olefin copolymer (a) and styrene block copolymer having a styrene content of greater than 15% (b) in a proper amount. In addition, the comparative compositions containing only aliphatic hydrocarbon resin tackifier without aromatic hydrocarbon resin tackifier (CEx. 4) or higher amount of plasticizer (CEx. 3) , could not achieve at least one of the desired properties.
Although some preferred embodiments have been described, many modifications and variations may be made thereto in light of the above teachings. It is therefore to be understood that the invention may be practiced otherwise than as specifically described without departing from the scope of the appended claims.
Claims (15)
- A hot melt adhesive composition, based on the total weight of the composition, comprising,(a) 20%to 60%by weight of an ethylene alpha-olefin copolymer,(b) 1%to less than 15%by weight of a styrene block copolymer,(c) 2%to 20%by weight of an aromatic hydrocarbon resin tackifier,(d) 1%to less than 15%by weight of a plasticizer, and(e) 1%to 40%by weight of a wax,wherein the styrene block copolymer (b) has a styrene content of greater than 15%by weight, based on the weight of component (b) .
- The hot melt adhesive composition according to claim 1, wherein the ethylene alpha-olefin copolymer (a) is selected from an ethylene/propylene copolymer, an ethylene/1-octene copolymer, an ethylene/1-butene copolymer, an ethylene/propylene/1-butene copolymer, a carboxylic acid modified ethylene/propylene copolymer, a carboxylic acid modified ethylene/1-octene copolymer, a carboxylic acid modified ethylene/1-butene copolymer, a carboxylic acid modified ethylene/propylene/1-butene copolymer, a maleic anhydride modified ethylene/propylene copolymer, a maleic anhydride modified ethylene/1-octene copolymer, a maleic anhydride modified ethylene/1-butene copolymer, a maleic anhydride modified ethylene/propylene/1-butene copolymer, and combination thereof; preferably an ethylene/propylene copolymer, an ethylene/1-octene copolymer, a maleic anhydride modified ethylene/1-octene copolymer, a maleic anhydride modified ethylene/propylene copolymer and the combination thereof.
- The hot melt adhesive composition according to claim 1 or 2, wherein the styrene block copolymer (b) has a styrene content of from 20%to 35%by weight.
- The hot melt adhesive composition according to any of the preceding claims, wherein the styrene block copolymer (b) has a melt flow rate of at least 25 g/10 minutes (190℃, 2.16 kg) , and preferably at least 30 g/10 minutes (190℃, 2.16 kg) .
- The hot melt adhesive composition according to any of the preceding claims, wherein the composition further comprises at least one styrene block copolymer having a styrene content of less than or equal to 15%.
- The hot melt adhesive composition according to any of the preceding claims, wherein the aromatic hydrocarbon resin tackifier (c) is C8-10 aromatic hydrocarbon resins, preferably C9 aromatic hydrocarbon resins, more preferably C9 aromatic hydrocarbon resins derived from monomers selected from vinyltoluene, indene, methylindene, styrene, alpha-methyl styrene, and combination thereof.
- The hot melt adhesive composition according to any of the preceding claims, wherein the hot melt adhesive composition further comprises 20%to 55%by weight, and preferably 20%to 40%by weight of an aliphatic hydrocarbon resin tackifier, based on the total weight of the hot melt adhesive composition.
- The hot melt adhesive composition according to claim 7, wherein the aliphatic hydrocarbon resin tackifier is selected from branched, unbranched, and cyclic C5-10 aliphatic hydrocarbon resins, preferably C5 aliphatic hydrocarbon resins derived from monomers selected from trans-1, 3-pentadiene, cis-1, 3-pentadiene, 2-methyl-2-butene, dicyclopentadiene (DCPD) , cyclopentadiene, cyclopentene, and combination thereof.
- The hot melt adhesive composition according to any of the preceding claims, wherein the plasticizer (d) is selected from a polybutylene, a paraffinic oil, a naphthenic oil, an aromatic oil and combination thereof.
- The hot melt adhesive composition according to any of the preceding claims, wherein the wax (e) is a synthetic wax, and/or a natural wax, preferably selected from a paraffin wax, a microcrystalline wax, a polyethylene wax, a polypropylene wax, a by-product polyethylene wax, a sasol wax, a Fischer-Tropsch synthetic wax, a functionalized wax and combination thereof.
- The hot melt adhesive composition according to any of the preceding claims, wherein the composition further comprises at least one additive selected from an anti-oxidant, a ultraviolet ray absorbent, a fine particulate filler and combination thereof.
- The hot melt adhesive composition according to any of the preceding claims, wherein the melt viscosity of the hot melt adhesive composition is no greater than 3,000 cP, and preferably no greater than 2, 500 cP at 160℃.
- The hot melt adhesive composition according to any of the preceding claims, wherein the setting time of the hot melt adhesive composition is no more than 3 seconds.
- An article comprising a cured product of the hot melt adhesive composition according to any of the preceding claims.
- Use of the hot melt adhesive composition according to any of claims 1 to 13 in packaging, bags, boxes, cartons, cases, trays, multi-wall bags, articles that include attachments, ream wrap, cigarettes, filters, bookbinding or paper products, preferably corrugated cartons with laminated films.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2023/074722 WO2024164133A1 (en) | 2023-02-07 | 2023-02-07 | Hot melt adhesive composition and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2023/074722 WO2024164133A1 (en) | 2023-02-07 | 2023-02-07 | Hot melt adhesive composition and use thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2024164133A1 true WO2024164133A1 (en) | 2024-08-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2023/074722 WO2024164133A1 (en) | 2023-02-07 | 2023-02-07 | Hot melt adhesive composition and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2024164133A1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001034719A1 (en) * | 1999-11-05 | 2001-05-17 | H.B. Fuller Licensing & Financing, Inc. | Hot melt adhesives and method of use thereof in bookbinding at low application temperature |
| US20060135694A1 (en) * | 2004-12-17 | 2006-06-22 | Vaughan Steven R | Hot melt adhesive composition |
| US20160002508A1 (en) * | 2014-07-03 | 2016-01-07 | Bostik, Inc. | Cohesively Failing, Non-Staining Hot Melt Adhesives |
| US20210139752A1 (en) * | 2018-07-24 | 2021-05-13 | Henkel Ag & Co. Kgaa | Hot melt adhesive composition having lower melt viscosity |
-
2023
- 2023-02-07 WO PCT/CN2023/074722 patent/WO2024164133A1/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001034719A1 (en) * | 1999-11-05 | 2001-05-17 | H.B. Fuller Licensing & Financing, Inc. | Hot melt adhesives and method of use thereof in bookbinding at low application temperature |
| US20060135694A1 (en) * | 2004-12-17 | 2006-06-22 | Vaughan Steven R | Hot melt adhesive composition |
| US20160002508A1 (en) * | 2014-07-03 | 2016-01-07 | Bostik, Inc. | Cohesively Failing, Non-Staining Hot Melt Adhesives |
| US20210139752A1 (en) * | 2018-07-24 | 2021-05-13 | Henkel Ag & Co. Kgaa | Hot melt adhesive composition having lower melt viscosity |
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