WO2006082478A2 - Hot melt adhesive composition - Google Patents
Hot melt adhesive composition Download PDFInfo
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- WO2006082478A2 WO2006082478A2 PCT/IB2005/004177 IB2005004177W WO2006082478A2 WO 2006082478 A2 WO2006082478 A2 WO 2006082478A2 IB 2005004177 W IB2005004177 W IB 2005004177W WO 2006082478 A2 WO2006082478 A2 WO 2006082478A2
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- 239000000203 mixture Substances 0.000 title claims abstract description 66
- 239000004831 Hot glue Substances 0.000 title claims abstract description 45
- 229920005989 resin Polymers 0.000 claims abstract description 66
- 239000011347 resin Substances 0.000 claims abstract description 66
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000005977 Ethylene Substances 0.000 claims abstract description 44
- 239000004711 α-olefin Substances 0.000 claims abstract description 23
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 16
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 claims abstract description 13
- 229920001038 ethylene copolymer Polymers 0.000 claims abstract description 13
- 239000003208 petroleum Substances 0.000 claims description 24
- 229920001577 copolymer Polymers 0.000 claims description 21
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 10
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 3
- 239000010734 process oil Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- CGPRUXZTHGTMKW-UHFFFAOYSA-N ethene;ethyl prop-2-enoate Chemical compound C=C.CCOC(=O)C=C CGPRUXZTHGTMKW-UHFFFAOYSA-N 0.000 claims 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 239000001993 wax Substances 0.000 description 15
- 239000000853 adhesive Substances 0.000 description 14
- 230000001070 adhesive effect Effects 0.000 description 14
- 125000003118 aryl group Chemical group 0.000 description 8
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical group CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 7
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- -1 polyethylene Polymers 0.000 description 6
- 230000000379 polymerizing effect Effects 0.000 description 6
- 230000032683 aging Effects 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000012943 hotmelt Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 235000019809 paraffin wax Nutrition 0.000 description 2
- 235000019271 petrolatum Nutrition 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012182 japan wax Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000012169 petroleum derived wax Substances 0.000 description 1
- 235000019381 petroleum wax Nutrition 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
-
- 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
-
- 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
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
- C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
- C08L2666/06—Homopolymers or copolymers of unsaturated hydrocarbons; Derivatives thereof
Definitions
- the present invention relates to a hot melt adhesive composition, and more particularly, to a hot melt adhesive composition which has reduced stringing, is clear and is superior in thermal stability.
- Hot melt adhesives are being widely used in various applications, such as packaging, bookbinding and woodworking, due to, for example, their high setting speed, good economical efficiency and freeness from solvents.
- hot melt adhesives string during use, soiling peripheral machineries
- a typical application procedure for hot melt adhesives includes a nozzle coating.
- stringing is generated even after the OFF signal, due to delay in response by the nozzle cavity or mechanical shielding (spring back). This stringing becomes more remarkable when the distance between the nozzle and the article to which the adhesive is applied is long, when the line speed is high or when the melt viscosity of the hot melt adhesive is high. Therefore, when the stringing occurs, the operator must stop the application lines and remove the strings.
- Japanese Patent Application KOKAI Publication No. H07-331221 discloses reducing the stringing by incorporating a specified amount of a specified low molecular weight ethylene/unsaturated carboxylic acid copolymer into a hot melt composition containing specified amounts of a base polymer such as an ethylene/vinyl acetate copolymer or an ethylene/(meth)acrylate copolymer and a tackifying resin.
- a base polymer such as an ethylene/vinyl acetate copolymer or an ethylene/(meth)acrylate copolymer and a tackifying resin.
- Hl 1-61067 discloses blending a specified fumed silica into a hot melt composition containing a specified ethylene/unsaturated ester copolymer, a tackifying resin and a wax, in order to reduce the stringing.
- Japanese Patent Application KOKAI Publication No. 2003-238920 discloses incorporating a specified amount of a polyethylene into a composition two specified ethylene/unsaturated ester.
- Japanese Patent Application KOKAI Publication No. 2004-2634 discloses incorporating, into a base resin such as an ethylene/vinyl acetate copolymer or an ethylene/acrylate ester copolymer, a resin incompatible with the base resin as colloidal particles.
- these hot melt adhesive composition lack clarity, have poor thermal stability, and gel or carbonize during a long period of use, causing clogging of the applicator and bringing about application failure.
- Patent Document 1 Jpn. Pat. Appln. KOKAI Publication No. H07-331221
- Patent Document 2 Jpn. Pat. Appln. KOKAI Publication No. Hll-61067
- Patent Document 3 Jpn. Pat. Appln. KOKAI Publication No. 2003-238920
- Patent Document 4 Jpn. Pat. Appln. KOKAI Publication No. 2004-2634 DISCLOSURE OF THE INVENTION
- an object of the present invention is to provide a hot melt adhesive composition which has significantly reduced stringing, and is superior in thermal stability and clarity.
- the present inventors have conducted extensive studies in an attempt to produce a hot melt adhesive composition which is substantially non-stringy, and superior in thermal stability and clarity. During the studies, they have paid attention to ethylene/ ⁇ -olefin copolymers such as those described in U.S. Patent No. 6,107,430. The ethylene/ ⁇ -olefin copolymers can afford hot melt adhesive compositions superior in thermal stability.
- the present inventors have found that the object can be achieved by adding, to the ethylene/ ⁇ -olefin copolymer (first component), a specific polymer, which is incompatible with the copolymer, but can significantly reduce the stringing of the copolymer, i.e., an ethylene/(meth)acrylic acid ester copolymer (second component) and a third component which is compatible with the first and second components, in specified amounts.
- first component ethylene/ ⁇ -olefin copolymer
- second component ethylene/(meth)acrylic acid ester copolymer
- third component which is compatible with the first and second components
- a hot melt adhesive composition comprising: a first component comprising at least one ethylene/C3 - C20 ⁇ -olefin copolymer; a second component comprising at least one ethylene/(meth)acrylic acid ester copolymer in an amount of about 6 to about 12 parts by weight per 100 parts by weight of the first component; and a third component comprising at least one tackifying resin, in an amount of about 50 to about 200 parts by weight per 100 parts by weight of the first component, the third component being compatible with the first and second components.
- a hot melt adhesive composition according to the present invention contains (1) a first component comprising at least one ethylene/C3 - C20 ⁇ -olefin copolymer, (2) a second component comprising at least one ethylene/(meth)acrylic acid ester copolymer, and (3) a third component compatible with the first and second components.
- the ethylene/C ⁇ - C20 ⁇ -olefin copolymer constituting the first component is a copolymer of ethylene with at least one C3 - C20 ⁇ -olefin (for example, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-l-pentine, and 1-octene).
- the ⁇ -olefin is preferably a C4 - C20 ⁇ -olefin, and is more preferably a Cg - Cg ⁇ -olefin, with 1- octene being most preferred.
- the ethylene/ ⁇ -olefin copolymer contains about 20 to about 40 mol% of a C3 - C20 ⁇ -olefin.
- the hot melt adhesive composition of the present invention can be used in various applications, including packaging, bookbinding and woodworking.
- the ethylene/ ⁇ -olefin copolymer preferably has a melt index of about 5 to about 2500 g/10 min., and preferably has a melt index of about 150 to about 2500 g/10 min. for packaging applications.
- the ethylene/ ⁇ -olefin copolymers used in the present invention as well as their preparation method are described in, for example, U.S. Patent No. 6,107,430.
- Ethylene/ 1-octene copolymers are commercially available from Dow Chemical under the trade name, "AFFINITY”. Examples include AFFINITY EG 8185 (melt index: 30.00 g/10 min.), AFFINITY EG 8200G (melt index: 5.00 g/10 min.), AFFINITY GA 1900 (melt index: 1000.00 g/10 min.), AFFINITY GA 1950 (melt index: 500.00 g/10 min.), and AFFINITY PT 1409 (melt index: 6.00 g/10 min.). These ethylene/ 1-octene copolymers have a 1-octene content of 35-37 mol %. The ethylene/ ⁇ -olefin copolymers can be used singly or in combination.
- the second component of the hot melt adhesive composition of the invention is a polymer incompatible with the first component, i.e., the ethylene/ ⁇ -olefin copolymer, and significantly reduces the stringing.
- the second component comprises a copolymer of ethylene with at least one (meth)acrylic acid ester, i.e., an ethylene/(meth)acrylic acid ester copolymer.
- (meth)acrylic acid ester is a generic term for an acrylic acid ester and a methacrylic acid ester.
- the (meth)acrylic acid ester is preferably a Ci - Cg alkyl (for example, methyl, ethyl, propyl and butyl) ester of (meth)acrylic acid, with C ⁇ - C4 alkyl ester of (meth)acrylic acid being more preferred. It is most preferred that the (meth)acrylic acid ester is ethyl acrylate or methyl methacrylate.
- the ethylene/(meth)acrylic acid ester copolymer contains (meth)acrylic acid ester in an amount of, preferably about 5 to about 35 mol %, more preferably about 20 to about 35 mol %.
- the ethylene/(meth)acrylic acid ester copolymer preferably has a melt index of about 20 to about 400 g/10 min.
- Such ethylene/(meth)acrylic acid ester copolymers are commercially available. Examples include an ethylene/ethyl acrylate copolymer sold under the tradename of EVAFLEX-EEA A 704 (melt index: 275g/10 min.; ethyl acrylate content: 25 mol %) and A 709 (melt index: 25g/10 min.; ethyl acrylate content: 34 mol %) by DuPont-Mitsui Polychemicals Co.
- the third component of the hot melt adhesive composition of the present invention is compatible with the first and second components described above, and serves to make the hot melt adhesive composition clear.
- the third component contains at least one kind of tackifying resin.
- the term “compatible with” refers to a "clear” state that a mixture of two or more components molten by heating to an application temperature (usually 160 to 180°, typically 180°) does not exhibit any phase separation of the components, and transmits visible light therethrough, even after allowed to stand for several hours.
- the term "clear state” is defined as a state that when the molten mixture is put in a flat-bottomed glass sample bottle up to a level of 10 cm (height), with the bottle being placed on a news paper sheet, letters on the news paper under the bottle can be read by eye when viewed from right above the molten mixture.
- the third component can be provided by one kind of tackifying resin, or by a combination of a first tackifying resin that is compatible with the first component (ethylene/ ⁇ -olefin copolymer) and a second tackifying resin that is compatible with the second component (ethylene/(meth)acrylic acid ester copolymer).
- the first and second tackifying resins can be provided by petroleum resins. More specifically, the first tackifying resin preferably comprises a fully hydrogenated petroleum resin, more preferably a petroleum resin having a hydrogenation degree of about 95% or higher.
- the second tackifying resin preferably comprises a partially hydrogenated petroleum resin, or more preferably a partially hydrogenated petroleum resin having a hydrogenation degree of about 60 to about 70%.
- Petroleum resins are synthetic resins prepared by polymerizing an unsaturated petroleum fraction.
- Typical examples of the raw materials for these resins include C4 to C5 fractions (such as 1-butene, isobutylene, butadiene, pentene, isoprene, piperidine and 1,3-pentadiene), and C9 to Cio fractions (such as vinyltoluene, indene, ⁇ -methylstyrene and cyclopentadiene), by-produced in naphtha decomposition and having a high saturation degree.
- the petroleum resins include aliphatic petroleum resin, alicyclic petroleum resin, aromatic petroleum resin and a copolymerized petroleum resin of an aliphatic component and aromatic component.
- the aliphatic petroleum resin is a resin obtained by polymerizing the C4 to C5 portions mentioned above.
- the alicyclic petroleum resin is a resin obtained by cyclization dimerization of the acyclic diene component in the C4 to C5 fractions and polymerizing thus obtained dimeric monomers, or polymerizing cyclopentadiene.
- the aromatic petroleum resin is a resin obtained by polymerizing the C9 to C 10 fractions mentioned above.
- the copolymerized petroleum resin of an aliphatic component and aromatic component is a resin obtained by polymerizing the C4 to C5 fractions mentioned above with the C9 to Ci Q fractions mentioned above.
- the partially and fully hydrogenated petroleum resins are commercially available. For example, partially hydrogenated C5 aromatic petroleum resins are available from Idemitsu
- IMARV S-100 softening point: 100°
- IMARV S-110 softening point: 110°
- Fully hydrogenated C5 aromatic petroleum resins are available from Idemitsu Kosan under the tradenames of IMARV P-90 (softening point: 90°), IMARV P-100 (softening point: 100°), IMARV P-125 (softening point: 125°), and EVIARV P-140 (softening point: 140°).
- the hot melt adhesive composition of the present invention contains the second component (ethylene/(meth)acrylic acid ester copolymer) in an amount of about 5 to about 12 parts by weight per 100 parts by weight of the first component (ethylene/C ⁇ to C20cr°l e fi n copolymer). If the amount of the second component is less than about 5 parts by weight per 100 parts by weight of the first component, the stringing cannot be sufficiently suppressed. On the other hand, if the amount of the second component exceeds about 12 parts by weight per 100 parts by weight of the first component, the clarity or transparency of the resultant hot melt adhesive composition is insufficient.
- the amount of the second component is preferably about 7 to about 10 parts by weight per 100 parts by weight of the first component.
- the amount of the third component is about 50 to about 250 parts by weight per 100 parts by weight of the first component. If the amount of the third component is less than about 50 parts by weight per 100 parts by weight of the first component, the resultant hot melt adhesive composition becomes elastic and lacks adhesiveness. On the other hand, if the amount of the second component exceeds about 250 parts by weight per 100 parts by weight of the first component, the resultant hot melt adhesive becomes brittle.
- the amount of the first tackifying resin is preferably about 40 to about 150 parts by weight with respect to 100 parts by weight of the first component, and the amount of the second tackifying resin is preferably about 10 to about 50 parts by weight, per 100 parts by weight of the first component.
- the amount of the first tackifying resin is preferably about 70 to about 120 parts by weight per 100 parts by weight of the first component, and the amount of the second tackifying resin is preferably about 20 to about 40 parts by weight per 100 parts by weight of the first component.
- the hot melt adhesive composition of the present invention may contain wax in addition to the first to third components, in order to lower the viscosity of the adhesive composition, thereby suppressing the crystallization of the composition and to adjust service life of the composition.
- wax that are generally used in hot melt adhesives
- examples include synthetic waxes such as Fischer-Tropsch waxes, polyethylene waxes, polypropylene waxes, atactic polypropylene waxes and ethylene/vinyl acetate copolymer; petroleum waxes such as paraffin waxes, purified paraffin waxes and microcrystalline waxes; and natural waxes such as Japan wax, carnauba wax and beeswax.
- the waxes used have a melting point of about 60 to about 120°. These waxes are commercially available.
- the wax is 5 preferably contained in an amount of about 30 to about 85 parts by weight per 100 parts by weight of the first component.
- the hot melt adhesive composition of the present invention can contain an antioxidant.
- an antioxidant Various types of antioxidant that are generally employed for hot melt adhesives can be used. Examples include hindered phenol antioxidants (e.g. o IRGANOX 1010, and 1076 available from Ciba Specialty Chemicals), and phosphite antioxidant (e. g., IRGAFOS 168 available from Ciba Specialty Chemicals).
- the hot melt adhesive composition of the present invention can contain a liquid tackifying resin and/or a process oil.
- a liquid tackifying resin examples include MARUKACLEAR H available from Maruzen Petrochemical, and REGALITE 5 RlOlO available from Eastman Chemical.
- the process oil examples include paraffin oil PW-90 and naphthene oil 371 -N.
- the amount of each component of the hot melt adhesive composition of the present invention is expressed with reference to the weight of the first component.
- the amount of each o component of the hot melt adhesive composition can be specified with reference to the total amount of the hot melt adhesive composition.
- the hot melt adhesive composition of the present invention preferably contains about 20 to about 60% by weight of the first component, about 1 to about 10% by weight of the second component, about 20 to about 60% by weight of the third component, 0 to about 40% 5 by weight of the wax and 0 to about 1 % by weight of the antioxidant.
- the hot melt adhesive composition of the present invention preferably contains about 25 to about 50% by weight of the first component; about 2 to about 4% by weight of the second component; about 20 to about 50% by weight of the first tackifying resin, about 5 to about 20% by weight of the second tackifying resin; about 10 to about 30% by weight of the wax; and 0 to about 1% by weight of the antioxidant.
- a hot melt adhesive composition having the compositions specified in TABLE 1 below was prepared.
- AFFINITY GA 1950 is an ethylene/ 1-octene copolymer available from Dow Chemical (melt index: 500.00 g/10 min.; 1-octene content: 35-37 mol %), and is a first component of the invention:
- ACRYFT CM5021 is an ethylene/methyl methacrylate copolymer available from Sumitomo Chemical (melt index: 450 g/10 min.; methyl methacrylate content: 28 mol %), and is a second component of the invention;
- EEA A704 is an ethylene/ethyl acrylate copolymer available from Mitsui DuPont Polychemical 1 (melt index: 275 g/10 min.; ethyl acrylate content: 25 mol %), and is a second component of the invention;
- IMARV P125 is a fully hydrogenated C5 aromatic petroleum resins available from Idemitsu Kosan (softening point: 125°; average molecular weight by VPO: 880), and is a first tackifying resin of the invention;
- IMARV S-100 is a partially hydrogenated C5 aromatic petroleum resins available from Idemitsu Kosan (softening point: 100°; average molecular weight by VPO: 700), and is a second tackifying resin of the invention;
- BARECO PX-100 is a Fischer-Tropsch wax (melting point: 98°) available from Baker Petrol ite;
- IRGANOX 1010 is a hindered phenol antioxidant available from Ci ba Specialty Chemicals.
- the initial viscosity of the composition is measured at 180° with No. 21 spindle.
- 100 g of the hot melt adhesive is placed in a 225-cc glass jar and the jar is covered with aluminum and capped. Then, the jar is placed in an oven and heated at 180° for one week, at which the viscosity is measured in the same manner as in the initial viscosity described above.
- the viscosity change rate is calculated according to the following equation: ⁇ [(viscosity after heat aging) - (initial viscosity)] / (initial viscosity) ⁇ x 100 5 Initial Clarity (Compatibility Test
- a flat-bottomed glass sample bottle having a volume of 110 cc is placed on a news paper sheet (not particularly limited, but usually the font is in Mincho-tai having a size of 3 mm), and the hot melt adhesive sample molten at an application temperature of 180°is put in the bottle up to a level of 1 cm. Then, letters on the o news paper under the bottle are read by eye from above the adhesive sample. When the letters are readable, the adhesive sample is added to a level of another 1 cm, and the letters are read similarly. This operation is repeated to an adhesive level of 10 cm or more. When the letters are readable even at a level of 10 cm, the sample is judged as clear.
- the adhered corrugated cardboard pieces is put in a 5 thermostat held at -20°, -10°, 5°, 23°, 50° or 60° for 12 hours or more, and under these atmospheres, the two pieces are forcibly peeled by hand.
- the ratio (%) of the broken cardboard piece portion area to the entire adhered area is measured. If the ratio is 80% or more, the adhesive composition is judged as passing the test at that temperature.
- the stringing property of the hot melt adhesive is evaluated basically by the method disclosed in Jpn. Pat. Appln. KOKAI Publication No. 2004-2634, except that the number of shots is set at 100, the temperature of the tank, hose and nozzle is set at 180° or 170°, the nozzle diameter is set at 20/1000 inches and the pump pressure is set to 0.3 or 0.2 MPa.
- the amount of the adhesive composition fallen on the pan is measured and the form of the fallen adhesive composition is observed.
- "D” means drops only
- S means strings only
- DS means almost drops with slight strings
- “SD” means almost strings with slight drops.
- the hot melt adhesive composition of the present invention is superior in adhesivity, exhibits good thermal stability (low in viscosity change before and after heat aging), is superior in clarity and is substantially free from stringing.
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- Chemical & Material Sciences (AREA)
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
- Adhesives Or Adhesive Processes (AREA)
Priority Applications (2)
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JP2007548921A JP5236950B2 (ja) | 2005-01-05 | 2005-12-29 | ホットメルト接着剤組成物 |
KR1020077015397A KR101184492B1 (ko) | 2005-01-05 | 2005-12-29 | 고온 용융 접착 조성물 |
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JP2005000604A JP2006188580A (ja) | 2005-01-05 | 2005-01-05 | ホットメルト接着剤組成物 |
JP2005-000604 | 2005-01-05 |
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WO2006082478A2 true WO2006082478A2 (en) | 2006-08-10 |
WO2006082478A3 WO2006082478A3 (en) | 2006-09-28 |
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PCT/IB2005/004177 WO2006082478A2 (en) | 2005-01-05 | 2005-12-29 | Hot melt adhesive composition |
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KR (1) | KR101184492B1 (ru) |
WO (1) | WO2006082478A2 (ru) |
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WO2012115279A1 (en) * | 2011-02-25 | 2012-08-30 | Henkel Ag & Co. Kgaa | Hot melt adhesive |
WO2014011744A3 (en) * | 2012-07-10 | 2014-04-17 | Adhesive T Echnologies, Inc. | Method and apparatus for modifying polymer compositions |
JP2015527437A (ja) * | 2012-09-19 | 2015-09-17 | エクソンモービル ケミカル パテンツ インコーポレイテッド | プロピレンベースのポリマーおよびエチレンベースのポリマーの接着剤組成物 |
EP3074478A4 (en) * | 2013-11-29 | 2017-07-19 | Henkel AG & Co. KGaA | Hot melt adhesive |
US10625915B2 (en) | 2008-01-21 | 2020-04-21 | Cpi Card Group—Minnesota, Inc. | Ultrasecure card package |
WO2020122008A1 (en) * | 2018-12-13 | 2020-06-18 | Henkel Ag & Co. Kgaa | Hot-melt adhesive |
EP3839002A1 (en) | 2019-12-20 | 2021-06-23 | Bostik Sa | Hot-melt adhesive composition |
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JP2006188580A (ja) * | 2005-01-05 | 2006-07-20 | Nippon Fuller Kk | ホットメルト接着剤組成物 |
JP5584851B2 (ja) * | 2008-08-06 | 2014-09-10 | 東亞合成株式会社 | 縁貼り用ホットメルト接着剤組成物、及び、縁貼り方法 |
JP6023399B2 (ja) * | 2010-12-27 | 2016-11-09 | ヘンケルジャパン株式会社 | ホットメルト接着剤 |
JP5875850B2 (ja) * | 2011-12-16 | 2016-03-02 | 東京応化工業株式会社 | 積層体及び分離方法 |
JP2014009255A (ja) | 2012-06-28 | 2014-01-20 | Henkel Japan Ltd | ホットメルト接着剤 |
JP2014009256A (ja) | 2012-06-28 | 2014-01-20 | Henkel Japan Ltd | ホットメルト接着剤 |
JP6028998B2 (ja) * | 2012-09-10 | 2016-11-24 | 日立化成株式会社 | 段ボール用ホットメルト樹脂組成物 |
US20140079897A1 (en) * | 2012-09-14 | 2014-03-20 | Henkel Corporation | Adhesive Compositions and Use Thereof |
JP6159118B2 (ja) * | 2013-03-28 | 2017-07-05 | 日東電工株式会社 | フィルタ濾材の製造装置 |
JP2014234399A (ja) | 2013-05-30 | 2014-12-15 | ヘンケルジャパン株式会社 | ホットメルト接着剤 |
JP6438222B2 (ja) | 2014-06-30 | 2018-12-12 | ヘンケルジャパン株式会社 | ホットメルト接着剤 |
JP6104974B2 (ja) * | 2015-04-03 | 2017-03-29 | ヘンケルジャパン株式会社 | ホットメルト接着剤 |
JP6914522B2 (ja) * | 2017-08-10 | 2021-08-04 | 積水フーラー株式会社 | ホットメルト接着剤 |
JP7039004B2 (ja) * | 2017-12-27 | 2022-03-22 | 積水フーラー株式会社 | ホットメルト接着剤 |
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- 2005-12-29 JP JP2007548921A patent/JP5236950B2/ja active Active
- 2005-12-29 WO PCT/IB2005/004177 patent/WO2006082478A2/en not_active Application Discontinuation
- 2005-12-29 KR KR1020077015397A patent/KR101184492B1/ko active IP Right Grant
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US11267628B2 (en) | 2008-01-21 | 2022-03-08 | Cpi Card Group—Minnesota, Inc. | Ultrasecure card package |
US10625915B2 (en) | 2008-01-21 | 2020-04-21 | Cpi Card Group—Minnesota, Inc. | Ultrasecure card package |
US11905089B2 (en) | 2008-01-21 | 2024-02-20 | Cpi Card Group—Minnesota, Inc. | Ultrasecure card package |
US11034497B2 (en) | 2008-01-21 | 2021-06-15 | CPI Card Group—Colorado, Inc. | Ultrasecure card package |
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EP3839002A1 (en) | 2019-12-20 | 2021-06-23 | Bostik Sa | Hot-melt adhesive composition |
US12098310B2 (en) | 2019-12-20 | 2024-09-24 | Bostik Sa | Hot-melt adhesive composition |
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Also Published As
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JP5236950B2 (ja) | 2013-07-17 |
JP2008527067A (ja) | 2008-07-24 |
KR20070104546A (ko) | 2007-10-26 |
KR101184492B1 (ko) | 2012-09-19 |
JP2006188580A (ja) | 2006-07-20 |
WO2006082478A3 (en) | 2006-09-28 |
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