KR20240025275A - A hydrogenated petroleum resin, adhesive composition including the same, method of preparing the hydrogenated petroleum resin - Google Patents
A hydrogenated petroleum resin, adhesive composition including the same, method of preparing the hydrogenated petroleum resin Download PDFInfo
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- KR20240025275A KR20240025275A KR1020220103302A KR20220103302A KR20240025275A KR 20240025275 A KR20240025275 A KR 20240025275A KR 1020220103302 A KR1020220103302 A KR 1020220103302A KR 20220103302 A KR20220103302 A KR 20220103302A KR 20240025275 A KR20240025275 A KR 20240025275A
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- petroleum resin
- hydrogenated petroleum
- formula
- repeating unit
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- 229920005989 resin Polymers 0.000 title claims abstract description 86
- 239000011347 resin Substances 0.000 title claims abstract description 86
- 239000003208 petroleum Substances 0.000 title claims abstract description 80
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 28
- 239000000853 adhesive Substances 0.000 title claims abstract description 27
- 239000000203 mixture Substances 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims description 10
- -1 n -propyl Chemical group 0.000 claims description 41
- 239000000178 monomer Substances 0.000 claims description 39
- 238000005984 hydrogenation reaction Methods 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 29
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 26
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 22
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 230000003197 catalytic effect Effects 0.000 claims description 12
- 150000001336 alkenes Chemical class 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000004711 α-olefin Substances 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 238000012360 testing method Methods 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- 239000003921 oil Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 8
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000012943 hotmelt Substances 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 239000004831 Hot glue Substances 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000002685 polymerization catalyst Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000007142 ring opening reaction Methods 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229940069096 dodecene Drugs 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 125000003003 spiro group Chemical group 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000000844 transformation Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 1
- BWEKDYGHDCHWEN-UHFFFAOYSA-N 2-methylhex-2-ene Chemical compound CCCC=C(C)C BWEKDYGHDCHWEN-UHFFFAOYSA-N 0.000 description 1
- KNIRLWRQSSLZCZ-UHFFFAOYSA-N 3-ethyloct-3-ene Chemical compound CCCCC=C(CC)CC KNIRLWRQSSLZCZ-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- SUWJESCICIOQHO-UHFFFAOYSA-N 4-methylhex-1-ene Chemical compound CCC(C)CC=C SUWJESCICIOQHO-UHFFFAOYSA-N 0.000 description 1
- JIUFYGIESXPUPL-UHFFFAOYSA-N 5-methylhex-1-ene Chemical compound CC(C)CCC=C JIUFYGIESXPUPL-UHFFFAOYSA-N 0.000 description 1
- 241001550224 Apha Species 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 238000012648 alternating copolymerization Methods 0.000 description 1
- 239000012164 animal wax Substances 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- CKFGINPQOCXMAZ-UHFFFAOYSA-N methanediol Chemical compound OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000012178 vegetable wax Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/02—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings
- C08F232/06—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings having two or more carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/14—Monomers containing five or more carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F240/00—Copolymers of hydrocarbons and mineral oils, e.g. petroleum resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
-
- 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
- C09J145/00—Adhesives based on homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic system; Adhesives based on derivatives of such polymers
Abstract
본 발명은 화학식 1로 표시되는 반복단위, 화학식 2로 표시되는 반복단위 및 화학식 3으로 표시되는 반복단위를 포함하는 수소첨가 석유수지, 및 이를 포함하는 접착용 조성물에 관한 것이다.The present invention relates to a hydrogenated petroleum resin containing a repeating unit represented by Formula 1, a repeating unit represented by Formula 2, and a repeating unit represented by Formula 3, and an adhesive composition containing the same.
Description
본 발명은 디사이클로펜타디엔과 노르보넨 단량체를 특정 비율로 올레핀과 중합한 후 수소화반응을 통하여 얻은 신규의 수소첨가 석유수지, 이를 포함한 접착제 조성물 및 이의 제조방법에 관한 것이다.The present invention relates to a novel hydrogenated petroleum resin obtained by polymerizing dicyclopentadiene and norbornene monomers with olefin at a specific ratio and then hydrogenating it, an adhesive composition containing the same, and a method for producing the same.
석유수지는 점착부여수지로서 접착테이프, 페인트, 잉크, 고무, 타이어 등의 제품에 점착성을 갖게 하는 물질로 주로 사용된다. 통상적으로 석유수지는 디올레핀이나 C5계 또는 C9계 유분을 촉매 또는 열 중합에 의해 중합된다.Petroleum resin is a tackifying resin and is mainly used as a material that provides adhesiveness to products such as adhesive tapes, paints, ink, rubber, and tires. Typically, petroleum resins are polymerized from diolefins or C5-based or C9-based oils using catalysts or thermal polymerization.
C5계 유분으로부터 제조된 석유수지는 핫멜트접착제(이하 "HMA"라고 한다), 핫멜트감압점착제(이하 "HMPSA"라고 한다), 테이프(용제형감압접착제), 도로표지용 페인트 등의 다양한 용도에 널리 사용되고 있으나, 내열성 및 접착성의 개선을 위하여 다양한 방식으로 물성의 개량이 시도되고 있다.Petroleum resin manufactured from C5-based oil is widely used in various applications such as hot melt adhesive (hereinafter referred to as “HMA”), hot melt pressure-sensitive adhesive (hereinafter referred to as “HMPSA”), tape (solvent-type pressure-sensitive adhesive), and paint for road signs. Although it is being used, attempts are being made to improve its physical properties in various ways to improve heat resistance and adhesiveness.
최근까지 석유수지의 원료로서 DCPD를 활용하려는 다양한 연구 결과들이 보고되어 왔으며, 일부 DCPD계열 석유수지를 활용한 접착제가 상용화되어 있다.Until recently, various research results have been reported to utilize DCPD as a raw material for petroleum resins, and some adhesives using DCPD-based petroleum resins have been commercialized.
하지만, 전자기기, 자동차, 타이어 등의 다양한 산업분야의 기술의 고도화에 따라 종래의 접착제에 비해 내열성 및 접착성의 향상을 가져오는 석유수지에 관한 요구가 지속적으로 존재하는 실정이다.However, with the advancement of technology in various industrial fields such as electronic devices, automobiles, and tires, there continues to be a demand for petroleum resins that improve heat resistance and adhesion compared to conventional adhesives.
본 발명의 목적은 신규 구조의 수소첨가 석유수지, 이를 포함하는 내열성 및 접착성이 향상된 접착제 조성물 및 이의 제조방법을 제공하는 것이다.The purpose of the present invention is to provide a hydrogenated petroleum resin of a novel structure, an adhesive composition containing the same with improved heat resistance and adhesion, and a method for manufacturing the same.
일 측면에 따라, 하기 화학식 1로 표시되는 반복단위, 하기 화학식 2로 표시되는 반복단위 및 하기 화학식 3으로 표시되는 반복단위를 포함하는 수소첨가 석유수지가 제공된다.According to one aspect, a hydrogenated petroleum resin is provided including a repeating unit represented by Formula 1 below, a repeating unit represented by Formula 2 below, and a repeating unit represented by Formula 3 below.
<화학식 1> <화학식 2> <화학식 3><Formula 1> <Formula 2> <Formula 3>
상기 화학식 2에서, R21 및 R22는 서로 독립적으로, 수소 또는 C1-C10 직쇄 또는 분지쇄 알킬기이고,In Formula 2, R 21 and R 22 are independently hydrogen or a C 1 -C 10 straight or branched alkyl group,
상기 화학식 3에서, R31은 수소 또는 메틸기이고, R32는 C1-C18 직쇄 또는 분지쇄 알킬기이다.In Formula 3, R 31 is hydrogen or a methyl group, and R 32 is a C 1 -C 18 straight or branched alkyl group.
다른 측면에 따라, 디사이클로펜타디엔 단량체, 노르보넨 단량체 및 C3-C20 올레핀계 단량체를 촉매중합하여 석유수지를 제조하는 단계; 및 상기 석유수지를 수소화 촉매에 의하여 수소첨가 반응을 수행하는 단계를 포함하는, 수소첨가 석유수지의 제조방법이 제공된다.According to another aspect, preparing a petroleum resin by catalytic polymerization of dicyclopentadiene monomer, norbornene monomer, and C 3 -C 20 olefin monomer; and performing a hydrogenation reaction on the petroleum resin using a hydrogenation catalyst. A method for producing a hydrogenated petroleum resin is provided.
또 다른 측면에 따라, 상기 수소첨가 석유수지를 포함하는 접착용 조성물이 제공된다.According to another aspect, an adhesive composition containing the hydrogenated petroleum resin is provided.
본 발명의 일 측면에 따른 수소첨가 석유수지는 노르보넨 단량체 유래 반복단위를 포함하는 것에 의하여, 디사이클로펜타디엔 단량체 유래 반복단위로 구성된 수첨석유수지에 비해 개선된 내열성 및 점착성을 가질 수 있다.By containing a repeating unit derived from norbornene monomer, the hydrogenated petroleum resin according to one aspect of the present invention may have improved heat resistance and adhesion compared to a hydrogenated petroleum resin composed of a repeating unit derived from a dicyclopentadiene monomer.
이하에서 설명되는 본 창의적 사상(present inventive concept)은 다양한 변환을 가할 수 있고 여러 가지 실시예를 가질 수 있는 바, 특정 실시예들을 도면에 예시하고, 상세한 설명에 상세하게 설명한다. 그러나, 이는 본 창의적 사상을 특정한 실시 형태에 대해 한정하려는 것이 아니며, 본 창의적 사상의 기술 범위에 포함되는 모든 변환, 균등물 또는 대체물을 포함하는 것으로 이해되어야 한다.The present inventive concept described below can be subjected to various transformations and can have various embodiments, and specific embodiments are illustrated in the drawings and described in detail in the detailed description. However, this is not intended to limit this creative idea to a specific embodiment, and should be understood to include all transformations, equivalents, or substitutes included in the technical scope of this creative idea.
이하에서 사용되는 용어는 단지 특정한 실시예를 설명하기 위해 사용된 것으로, 본 창의적 사상을 한정하려는 의도가 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 이하에서, "포함한다" 또는 "가지다" 등의 용어는 명세서상에 기재된 특징, 숫자, 단계, 동작, 구성 요소, 부품, 성분, 재료 또는 이들을 조합한 것이 존재함을 나타내려는 것이지, 하나 또는 그 이상의 다른 특징들이나, 숫자, 단계, 동작, 구성 요소, 부품, 성분, 재료 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다. 이하에서 사용되는 "/"는 상황에 따라 "및"으로 해석될 수도 있고 "또는"으로 해석될 수도 있다.The terms used below are only used to describe specific embodiments and are not intended to limit the creative idea. Singular expressions include plural expressions unless the context clearly dictates otherwise. Hereinafter, terms such as "comprise" or "have" are intended to indicate the presence of features, numbers, steps, operations, components, parts, ingredients, materials, or combinations thereof described in the specification, but are intended to indicate the presence of one or more of the It should be understood that this does not exclude in advance the presence or addition of other features, numbers, steps, operations, components, parts, components, materials, or combinations thereof. “/” used below may be interpreted as “and” or “or” depending on the situation.
도면에서 여러 층 및 영역을 명확하게 표현하기 위하여 두께를 확대하거나 축소하여 나타내었다. 명세서 전체를 통하여 유사한 부분에 대해서는 동일한 도면 부호를 붙였다. 명세서 전체에서 층, 막, 영역, 판 등의 부분이 다른 부분 "상에" 또는 "위에" 있다고 할 때, 이는 다른 부분의 바로 위에 있는 경우뿐만 아니라 그 중간에 또 다른 부분이 있는 경우도 포함한다. 명세서 전체에서 제1, 제2 등의 용어는 다양한 구성 요소들을 설명하는데 사용될 수 있지만, 구성 요소들은 용어들에 의하여 한정되어서는 안 된다. 용어들은 하나의 구성 요소를 다른 구성 요소로부터 구별하는 목적으로만 사용된다.In order to clearly express various layers and areas in the drawing, the thickness is enlarged or reduced. Throughout the specification, similar parts are given the same reference numerals. Throughout the specification, when a part such as a layer, membrane, region, plate, etc. is said to be “on” or “on” another part, this includes not only the case where it is directly on top of the other part, but also the case where there is another part in between. . Throughout the specification, terms such as first and second may be used to describe various components, but the components should not be limited by the terms. Terms are used only to distinguish one component from another.
본 명세서에서 사용되는 과학 용어는 다르게 정의되지 않는 한 본 발명의 기술분야에 속하는 통상의 기술자가 일반적으로 이해하는 바와 동일하게 이해될 수 있다.Scientific terms used in this specification, unless otherwise defined, may be understood the same as those generally understood by those skilled in the art.
본 명세서에서 '수첨 석유수지'는 전술한 석유수지 중 에틸렌과 같은 불포화 모이어티의 적어도 일부가 수소 첨가 반응에 의하여 포화 탄화수소로 개질된 석유수지를 의미한다.In this specification, 'hydrogenated petroleum resin' refers to a petroleum resin in which at least a portion of the unsaturated moiety such as ethylene in the above-mentioned petroleum resin has been modified into a saturated hydrocarbon through a hydrogenation reaction.
본 명세서에서 '올레핀'은 적어도 하나의 에틸렌성 불포화기(C=C) 결합을 포함하는 불포화 화합물을 포함한다. 예를 들어, 올레핀은 선형 올레핀, 환형 올레핀, α-올레핀 등을 포함할 수 있으나, 이에 한정되는 것은 아니다.As used herein, 'olefin' includes unsaturated compounds containing at least one ethylenically unsaturated group (C=C) bond. For example, olefins may include linear olefins, cyclic olefins, α-olefins, etc., but are not limited thereto.
일 측면에 따른 수소첨가 석유수지는 하기 화학식 1로 표시되는 반복단위, 하기 화학식 2로 표시되는 반복단위 및 하기 화학식 3으로 표시되는 반복단위를 포함할 수 있다.The hydrogenated petroleum resin according to one aspect may include a repeating unit represented by Formula 1 below, a repeating unit represented by Formula 2 below, and a repeating unit represented by Formula 3 below.
<화학식 1> <화학식 2> <화학식 3><Formula 1> <Formula 2> <Formula 3>
일 측면에 따른 수소첨가 석유수지는 상기 화학식 1 내지 3으로 표시되는 반복단위를 포함하고, 분자 구조 내 이중결합이 없는 포화 고리 구조의 반복단위가 공중합된 형태를 갖는다.The hydrogenated petroleum resin according to one aspect includes repeating units represented by the above formulas 1 to 3, and has a form in which repeating units of a saturated ring structure without double bonds in the molecular structure are copolymerized.
여기서, 공중합은 랜덤 공중합, 교대 공중합, 블록 공중합, 그라프트 공중합, 또는 스타 공중합 등 다양한 공중합을 포함할 수 있다.Here, the copolymerization may include various copolymerizations such as random copolymerization, alternating copolymerization, block copolymerization, graft copolymerization, or star copolymerization.
상기 화학식 1 내지 3에 대해서는 아래에서 더 상세히 설명한다.Formulas 1 to 3 will be described in more detail below.
상기 화학식 1로 표시되는 반복단위는 디사이클로펜타디엔 단량체로부터 유래된 반복단위로서, 수소첨가 반응에 의하여 형성될 수 있다. The repeating unit represented by Formula 1 is a repeating unit derived from dicyclopentadiene monomer and can be formed through a hydrogenation reaction.
상기 화학식 2로 표시되는 반복단위는 노르보넨 단량체로부터 유래된 반복단위로서, 비닐형 첨가 촉매 하에서 노르보넨의 고리 풀림(ring opening) 없이 중합이 이루어져서 형성될 수 있다.The repeating unit represented by Formula 2 is a repeating unit derived from norbornene monomer, and can be formed by polymerization without ring opening of norbornene in the presence of a vinyl-type addition catalyst.
상기 화학식 2 중, R21 및 R22는 서로 독립적으로 수소 또는 C1-C10 직쇄 또는 분지쇄 알킬기일 수 있다.In Formula 2, R 21 and R 22 may independently be hydrogen or a C 1 -C 10 straight or branched alkyl group.
일 구현예에 따르면, 상기 R21 및 R22는 서로 독립적으로 수소, 메틸기, 에틸기, 프로필기, 이소프로필기, 부틸기, sec-부틸기, 이소부틸기, 또는 tert-부틸기일 수 있다.According to one embodiment, R 21 and R 22 may independently be hydrogen, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, or tert-butyl.
예를 들어, 상기 R21 및 R22 중 적어도 하나는 수소이고 나머지 하나는 메틸기, 에틸기, 프로필기, 이소프로필기, 부틸기, sec-부틸기, 이소부틸기, 또는 tert-부틸기일 수 있다. 예를 들어, 상기 R21 및 R22는 모두 수소일 수 있다.For example, at least one of R 21 and R 22 may be hydrogen and the other may be a methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, isobutyl group, or tert-butyl group. For example, R 21 and R 22 may both be hydrogen.
상기 화학식 3으로 표시되는 반복단위는 디사이클로펜타디엔 단량체와 올레핀 단량체의 고리 형성 반응에 의하여 형성된 반복단위이다.The repeating unit represented by Formula 3 is a repeating unit formed through a ring formation reaction between a dicyclopentadiene monomer and an olefin monomer.
상기 화학식 3에서, R31은 수소 또는 메틸기이고, R32는 C1-C18 직쇄 또는 분지쇄 알킬기이다.In Formula 3, R 31 is hydrogen or a methyl group, and R 32 is a C 1 -C 18 straight or branched alkyl group.
일 구현예에 따르면, 상기 R31은 수소이고, R32는 메틸기, 에틸기, n-프로필기, 이소프로필기, n-부틸기, sec-부틸기, 이소부틸기, tert-부틸기, n-펜틸기, tert-펜틸기, 네오펜틸기, 이소펜틸기, sec-펜틸기, 3-펜틸기, sec-이소펜틸기, n-헥실기, 이소헥실기, sec-헥실기, tert-헥실기, n-헵틸기, 이소헵틸기, sec-헵틸기, tert-헵틸기, n-옥틸기, 이소옥틸기, sec-옥틸기, tert-옥틸기, n-노닐기, 이소노닐기, sec-노닐기, tert-노닐기, n-데실기, 이소데실기, sec-데실기, 또는 tert-데실기일 수 있다.According to one embodiment, R 31 is hydrogen, and R 32 is methyl, ethyl, n -propyl, isopropyl, n -butyl, sec -butyl, isobutyl, tert -butyl, n - Pentyl group, tert -pentyl group, neopentyl group, isopentyl group, sec -pentyl group, 3-pentyl group, sec -isopentyl group, n -hexyl group, isohexyl group, sec -hexyl group, tert -hexyl group , n -heptyl group, isoheptyl group, sec -heptyl group, tert -heptyl group, n -octyl group, isooctyl group, sec -octyl group, tert -octyl group, n -nonyl group, isononyl group, sec -no It may be a nyl group, tert -nonyl group, n -decyl group, isodecyl group, sec -decyl group, or tert -decyl group.
일 구현예에 따르면, 상기 수소첨가 석유수지 내에 상기 화학식 2로 표시되는 반복단위의 몰 비율은 상기 화학식 1로 표시되는 반복단위의 몰 비율보다 낮을 수 있다.According to one embodiment, the molar ratio of the repeating unit represented by Formula 2 in the hydrogenated petroleum resin may be lower than the mole ratio of the repeating unit represented by Formula 1.
예를 들어, 상기 화학식 2로 표시되는 반복단위는 상기 화학식 1로 표시되는 반복단위에 대하여 0.1 내지 0.5 몰비율로 포함될 수 있다. For example, the repeating unit represented by Formula 2 may be included in a molar ratio of 0.1 to 0.5 with respect to the repeating unit represented by Formula 1.
상기 화학식 1로 표시되는 반복단위 및 화학식 2로 표시되는 반복단위의 비율이 상기 범위에 포함되는 경우 석유수지의 접착성의 실질적인 저하 없이 내열성을 향상시킬 수 있다.When the ratio of the repeating unit represented by Formula 1 and the repeating unit represented by Formula 2 is within the above range, heat resistance can be improved without substantially deteriorating the adhesiveness of the petroleum resin.
일 구현예에 따르면, 상기 수소첨가 석유수지는 상기 화학식 1의 반복단위 및 상기 화학식 2의 반복단위를 60 내지 90몰% 포함하고, 상기 화학식 3의 반복단위를 10 내지 40 몰% 포함할 수 있다.According to one embodiment, the hydrogenated petroleum resin may contain 60 to 90 mol% of the repeating unit of Formula 1 and the repeating unit of Formula 2, and 10 to 40 mol% of the repeating unit of Formula 3. .
상기 화학식 1 및 2로 표시되는 반복단위와 상기 화학식 3의 반복단위의 몰 비율이 상기 범위를 만족하는 경우, 연화점의 과도한 상승을 억제할 수 있을 뿐만 아니라, 최종 생성된 석유수지의 악취 저감 효과를 달성할 수 있다.When the molar ratio of the repeating units represented by Chemical Formulas 1 and 2 and the repeating unit of Chemical Formula 3 satisfies the above range, not only can excessive increase in softening point be suppressed, but also the odor reduction effect of the final produced petroleum resin can be achieved. It can be achieved.
본 발명의 일 구현예에 따른 상기 수소첨가 석유수지는 500~2800 g/mol의 중량평균분자량을 가지며, 연화점이 90~130℃이고, 색상은 APHA 색도 기준으로 1~100일 수 있다. 상기와 같은 물성을 만족하는 경우에 접착제 용도로 베이스수지와 배합하여 사용될 수 있다.The hydrogenated petroleum resin according to one embodiment of the present invention has a weight average molecular weight of 500 to 2800 g/mol, a softening point of 90 to 130°C, and a color may be 1 to 100 based on APHA chromaticity. If it satisfies the above physical properties, it can be used in combination with a base resin for adhesive purposes.
일 측면에 따른 전술한 수소첨가 석유수지의 제조방법은 디사이클로펜타디엔 단량체, 노르보넨 단량체 및 C3-C20 올레핀계 단량체를 촉매중합하여 석유수지를 제조하는 단계; 및 상기 석유수지를 수소화 촉매에 의하여 수소첨가 반응을 수행하는 단계를 포함할 수 있다.The method for producing the above-described hydrogenated petroleum resin according to one aspect includes the steps of producing a petroleum resin by catalytic polymerization of dicyclopentadiene monomer, norbornene monomer, and C 3 -C 20 olefinic monomer; And it may include performing a hydrogenation reaction on the petroleum resin using a hydrogenation catalyst.
일 구현예에 따르면, 상기 디사이클로펜타디엔 단량체 및 노르보넨 단량체는 5:5 내지 9:1의 몰비율로 촉매중합될 수 있다.According to one embodiment, the dicyclopentadiene monomer and norbornene monomer may be catalytically polymerized at a molar ratio of 5:5 to 9:1.
예를 들어, 상기 디사이클로펜타디엔 단량체 및 노르보넨 단량체는 6:4 내지 8:2의 몰비율로 촉매중합될 수 있다.For example, the dicyclopentadiene monomer and norbornene monomer may be catalytically polymerized at a molar ratio of 6:4 to 8:2.
여기서, 촉매 중합은 비닐형 첨가 촉매의 존재 하에서 중합이 수행될 수 있다. 비닐형 첨가 촉매 존재하에서 중합 반응이 수행됨에 따라, 디사이클로펜타디엔 단량체 및 노르보넨 단량체의 고리 열림 반응이 최대한 억제될 수 있으며, 디사이클로펜타디엔 및 노르보넨 단량체 각각의 스파이로 고리에 포함된 이중 결합에서 축합반응이 수행될 수 있다. 그 결과, 전술한 수소첨가 석유수지가 상기 화학식 1로 표시되는 반복단위 및 상기 화학식 2로 표시되는 반복단위를 수지 내에 포함할 수 있다.Here, catalytic polymerization may be performed in the presence of a vinyl-type addition catalyst. As the polymerization reaction is carried out in the presence of a vinyl-type addition catalyst, the ring-opening reaction of dicyclopentadiene monomer and norbornene monomer can be suppressed as much as possible, and the double ring-opening reaction contained in the spiro ring of each dicyclopentadiene and norbornene monomer A condensation reaction can be performed on the bond. As a result, the above-described hydrogenated petroleum resin may contain a repeating unit represented by Formula 1 and a repeating unit represented by Formula 2.
일 구현예에 따르면, 상기 촉매 중합은 비닐형 첨가 촉매, 예를 들어 Pd, Ti, Co 및 Ni 중에서 선택된 1종 이상의 전이금속을 포함하는 전이금속촉매의 존재하에서 20 내지 50℃에서 중합반응이 수행될 수 있다.According to one embodiment, the catalytic polymerization is carried out at 20 to 50° C. in the presence of a vinyl-type addition catalyst, for example, a transition metal catalyst containing at least one transition metal selected from Pd, Ti, Co, and Ni. It can be.
노르보넨 단량체는 열에 의하여 고리 열림 반응이 쉽게 진행될 수 있으나, 비닐형 첨가 촉매를 사용함에 따라, 노르보넨의 스파이로 고리를 포함하는 포화 탄화수소 고리의 반복단위를 석유수지 내에 도입할 수 있으며, 이를 통해 석유수지의 내열성이 향상되고, 비극성 기재와의 접착성이 향상되는 효과를 얻을 수 있다.Norbornene monomer can easily undergo a ring opening reaction by heat, but by using a vinyl-type addition catalyst, a repeating unit of a saturated hydrocarbon ring including the spiro ring of norbornene can be introduced into the petroleum resin, through which The heat resistance of the petroleum resin is improved and the adhesion to non-polar substrates is improved.
일 구현예에 따르면, 상기 촉매 중합은 벌크 중합 또는 용액 중합 방법에 의해 수행될 수 있다. 예를 들어, 상기 촉매 중합은 용액 중합법에 의해 수행될 수 있다.According to one embodiment, the catalytic polymerization may be performed by bulk polymerization or solution polymerization. For example, the catalytic polymerization may be performed by solution polymerization.
용액 중합을 위해 상기 단량체를 용해시킬 수 있는 용매를 사용할 수 있으며, 예를 들어, 톨루엔, 메틸렌 클로라이드, 헥산, 자일렌, 트리클로로 벤젠, 알킬벤젠, 아세토니트릴, 디메틸포름아마이드, N-메틸피롤리돈, 메틸아세트아마이드, 디메틸설폭사이드, 감마-부티로락톤, 푸르프랄, 아세톤 및 이들의 혼합 용매로 이루어진 군에서 선택된 1종 이상의 용매를 사용할 수 있다.For solution polymerization, a solvent capable of dissolving the monomer can be used, for example, toluene, methylene chloride, hexane, xylene, trichlorobenzene, alkylbenzene, acetonitrile, dimethylformamide, N-methylpyrroli One or more solvents selected from the group consisting of ethanol, methylacetamide, dimethyl sulfoxide, gamma-butyrolactone, furfural, acetone, and mixed solvents thereof can be used.
상기 용매의 함량은 중합을 위한 단량체 성분을 모두 용해시킬 수 있는 수준이면 충분하고, 예를 들어 디사이클로펜타디엔 및 노르보넨 단량체 총 몰수 대비 2 내지 10몰의 범위로 사용할 수 있다.The content of the solvent is sufficient as long as it can dissolve all monomer components for polymerization. For example, it can be used in the range of 2 to 10 moles compared to the total number of moles of dicyclopentadiene and norbornene monomers.
일 구현예에 따르면, 상기 C3-C20 올레핀계 단량체는 직쇄 또는 분지쇄 알파 올레핀계 단량체일 수 있다. 예를 들어, 상기 C3-C20 올레핀계 단량체는 직쇄 알파 올레핀계 단량체, 분지쇄 알파 올레핀계 단량체, 또는 이들의 조합을 포함할 수 있다.According to one embodiment, the C 3 -C 20 olefin monomer may be a straight chain or branched alpha olefin monomer. For example, the C 3 -C 20 olefinic monomer may include a straight-chain alpha-olefinic monomer, a branched-chain alpha-olefinic monomer, or a combination thereof.
일 구현예에 따르면, 상기 C3-C20 직쇄 알파 올레핀계 단량체로는 에틸렌(또는 에텐), 프로필렌(또는 프로펜), 1-부텐, 1-펜텐, 1-헥센, 1-헵텐, 1-옥텐, 1-데센, 1-운데센, 1-도데센, 1-테트라데센, 1-헥사데센, 1-아이토센, 또는 이들의 조합을 포함할 수 있으나, 이에 한정되는 것은 아니며, 1개의 탄소-탄소 이중결합을 포함하고 탄소수 3 내지 20으로 이루어진 직쇄의 알켄 화합물을 모두 포함할 수 있다.According to one embodiment, the C 3 -C 20 straight chain alpha olefin monomers include ethylene (or ethene), propylene (or propene), 1-butene, 1-pentene, 1-hexene, 1-heptene, 1- It may include, but is not limited to, octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-itocene, or a combination thereof, and has one carbon -It may include all straight-chain alkene compounds containing a carbon double bond and having 3 to 20 carbon atoms.
예를 들어, 상기 C3-C20 분지쇄 알파 올레핀계 단량체는 이소부틸렌, 3-메틸-1부텐, 2-메틸-1-부텐, 3-메틸-1-부텐, 4-메틸-1-부텐, 3-메틸-1-펜텐, 4-메틸-1-펜텐, 4-메틸-1-헥센, 5-메틸-1-헥센, 디메틸 펜텐, 디에틸 헥센, 또는 이들의 조합을 포함할 수 있으나, 이에 한정되는 것은 아니며, 1개의 탄소-탄소 이중결합을 포함하고 탄소수 3 내지 20으로 이루어진 분지쇄의 알켄 화합물을 모두 포함할 수 있다.For example, the C 3 -C 20 branched chain alpha olefin monomer is isobutylene, 3-methyl-1butene, 2-methyl-1-butene, 3-methyl-1-butene, 4-methyl-1- It may include butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 5-methyl-1-hexene, dimethyl pentene, diethyl hexene, or combinations thereof. , but is not limited thereto, and may include all branched-chain alkene compounds containing one carbon-carbon double bond and having 3 to 20 carbon atoms.
예를 들어, 상기 C3-C20 직쇄 또는 분지쇄 알파 올레핀계 단량체는 1-헥센, 1-헵텐, 1-옥텐, 1-데센, 또는 도데센일 수 있다.For example, the C 3 -C 20 straight chain or branched alpha olefin monomer may be 1-hexene, 1-heptene, 1-octene, 1-decene, or dodecene.
상기 수소첨가 석유수지의 제조방법은 상기 촉매 중합 이후에 용매를 제거하는 단계를 더 포함할 수 있다. 용매의 제거는 증류, 오븐에서의 건조 등 당업계에서 일반적으로 사용하는 방법을 통하여 수행될 수 있다.The method for producing the hydrogenated petroleum resin may further include the step of removing the solvent after the catalyst polymerization. Removal of the solvent can be performed through methods commonly used in the art, such as distillation and drying in an oven.
촉매 중합에 의해 얻은 석유수지는 이후 수소화 반응 단계를 거친다.Petroleum resin obtained through catalytic polymerization then undergoes a hydrogenation reaction step.
수소첨가 반응은 불포화 상태인 탄소-탄소 이중결합에 수소가 첨가되어 단일 결합을 형성하는 반응으로서, 촉매 중합에 의해 얻은 석유수지에 이중 결합이 모두 사라질때까지 수행될 수 있다.The hydrogenation reaction is a reaction in which hydrogen is added to an unsaturated carbon-carbon double bond to form a single bond, and can be performed until all double bonds disappear in the petroleum resin obtained through catalytic polymerization.
수소첨가 반응은 수소화 촉매의 첨가에 의해 진행되며 고도의 발열 과정을 수반하기 때문에 온도 제어 요건이 까다로우며 높은 압력을 유지해야 한다. 바람직하기로, 상기 수소첨가 반응은 50 내지 150bar의 압력 하에 150 내지 300℃에서 수행한다. 만약 그 온도 및 압력이 상기 범위 미만이면 충분히 수소첨가 반응이 수행되지 못하고, 이와 반대로 상기 범위를 초과하면 가혹한 반응조건에 의해 분자구조가 파괴될 수 있으므로, 상기 범위 내에서 적절히 조절한다.The hydrogenation reaction is carried out by the addition of a hydrogenation catalyst and involves a highly exothermic process, so temperature control requirements are stringent and high pressure must be maintained. Preferably, the hydrogenation reaction is performed at 150 to 300° C. under a pressure of 50 to 150 bar. If the temperature and pressure are below the above range, the hydrogenation reaction cannot be sufficiently performed. Conversely, if the temperature and pressure exceed the above range, the molecular structure may be destroyed due to the harsh reaction conditions, so adjust appropriately within the above range.
일 구현예에 따르면, 수소화 촉매는 본 발명에서 특별히 한정하지 않으며, 공지된 수소화 촉매면 어느 것이든 사용 가능하다. 예를 들면, 상기 수소화 촉매로는 Ni, Pd, Co, Pt 및 Rh 중에서 선택된 1종 이상의 촉매를 포함할 수 있다.According to one embodiment, the hydrogenation catalyst is not particularly limited in the present invention, and any known hydrogenation catalyst can be used. For example, the hydrogenation catalyst may include one or more catalysts selected from Ni, Pd, Co, Pt, and Rh.
상기 수소화 촉매는 디사이클로펜타디엔 및 노르보넨 총 1몰에 대하여 0.001 내지 0.5, 바람직하기로 0.05 내지 0.2 몰비로 사용한다. 상기 범위를 만족하는 경우에 석유수지 내 이중결합이 모두 단일결합으로 수소화될 수 있다.The hydrogenation catalyst is used in a molar ratio of 0.001 to 0.5, preferably 0.05 to 0.2, based on a total of 1 mole of dicyclopentadiene and norbornene. When the above range is satisfied, all double bonds in the petroleum resin can be hydrogenated into single bonds.
일 구현예에 따르면, 상기 촉매 중합에서 사용된 중합 촉매 및 상기 수소화 반응에서 사용된 수소화 촉매는 서로 동일하거나 상이할 수 있다.According to one embodiment, the polymerization catalyst used in the catalytic polymerization and the hydrogenation catalyst used in the hydrogenation reaction may be the same or different from each other.
일 구현예에 따르면, 상기 중합 촉매 및 수소화 촉매는 동일할 수 있다. According to one embodiment, the polymerization catalyst and the hydrogenation catalyst may be the same.
예를 들어, 일 구현예에 따르면, 상기 중합 촉매 및 수소화 촉매는 각각 Ni 또는 Pd계 촉매일 수 있다.For example, according to one embodiment, the polymerization catalyst and the hydrogenation catalyst may each be a Ni- or Pd-based catalyst.
상기 중합 촉매와 수소화 촉매를 동일하게 사용함으로써, 촉매 중합 후 촉매 제거 공정을 생략할 수 있으며, 공정을 단순화하여 효율의 향상을 가져올 수 있다.By using the same polymerization catalyst and hydrogenation catalyst, the catalyst removal process after catalyst polymerization can be omitted, and the process can be simplified to improve efficiency.
일 측면에 따른 접착용 조성물은 전술한 수소첨가 석유수지를 포함할 수 있다.The adhesive composition according to one aspect may include the hydrogenated petroleum resin described above.
일 구현예에 따르면, 상기 수소첨가 석유수지는 핫멜트 접착제, 감압형 접착제, 잉크, 페인트, 로드마킹용 페인트 등에 점·접착 성능을 부여할 수 있으며, 또한, 천연고무, 합성고무 등과 같은 다양한 수지에 배합되어 접착제로 유용하게 사용될 수 있다.According to one embodiment, the hydrogenated petroleum resin can provide adhesive and adhesive properties to hot melt adhesives, pressure-sensitive adhesives, inks, paints, road marking paints, etc., and can also be applied to various resins such as natural rubber and synthetic rubber. It can be mixed and usefully used as an adhesive.
아울러, 본 발명의 일 구현예에 따른 수소첨가 석유수지는 베이스 수지와 배합되어 접착제 조성물로 제공될 수 있다.In addition, the hydrogenated petroleum resin according to one embodiment of the present invention may be mixed with a base resin and provided as an adhesive composition.
일 구현예에 따르면, 상기 베이스 수지는 스티렌-아이소프렌 블록코폴리머, 스티렌-아이소프렌-스티렌 블록코폴리머, 스티렌-부타디엔 블록코폴리머, 스티렌-부타디엔-스티렌 블록코폴리머과 같은 스티렌계 블록코폴리머(styrenic block copolymers), 폴리에틸렌, 폴리프로필렌, 에틸렌비닐아세테이트 및 프로필렌-에틸렌코폴리머와 같은 에틸렌계 폴리올레핀블록코폴리머(ethylene based poly olefin block copolymer)로부터 1종 이상 선택될 수 있다.According to one embodiment, the base resin is a styrene-based block copolymer (such as styrene-isoprene block copolymer, styrene-isoprene-styrene block copolymer, styrene-butadiene block copolymer, and styrene-butadiene-styrene block copolymer). One or more types may be selected from ethylene based poly olefin block copolymers such as styrenic block copolymers, polyethylene, polypropylene, ethylene vinyl acetate, and propylene-ethylene copolymer.
일 구현예에 따르면, 상기 접착제 조성물은 베이스 수지와 석유수지의 상용성을 향상시키기 위하여 파라핀 왁스, 마이크로스탈린 왁스 같은 합성왁스나 동물성 천연왁스, 식물성 천연왁스, 방향족계 오일, 나프텐계 오일 및 파라핀계 오일로 이루어지는 군으로부터 1종 이상 선택되는 첨가제를 더 포함할 수 있다.According to one embodiment, the adhesive composition includes synthetic wax such as paraffin wax, microstalin wax, natural animal wax, natural vegetable wax, aromatic oil, naphthenic oil, and paraffin-based oil to improve compatibility between the base resin and the petroleum resin. It may further include one or more additives selected from the group consisting of oils.
상기 접착제 조성물로 제조된 접착제는 핫멜트형 접착제(HMA, Hot melt adhesive) 또는 감압형 접착제(HMPSA, Hot melt sensitive adhesive)로 사용될 수 있다.Adhesives made from the adhesive composition can be used as a hot melt adhesive (HMA) or a hot melt sensitive adhesive (HMPSA).
전술한 바의 본 발명의 일 구현예에 따른 접착제는 수소첨가 석유수지가 수소첨가 반응에 의해 이중 결합이 없고, 저분자량의 올리고머가 발생하지 않아 이들로 인해 발생하는 불쾌한 냄새 (취기)가 개선된다. 이러한 접착제는 접착제의 사용이 요구되는 모든 분야, 그 중에서도 기저귀, 생리대, 성인용 기저귀 등 인체에 접촉하는 위생용품용 핫멜트 감압 접착제 또는 접착제에 바람직하게 사용이 가능하다In the adhesive according to one embodiment of the present invention as described above, the hydrogenated petroleum resin has no double bonds due to the hydrogenation reaction and does not generate low molecular weight oligomers, thereby improving the unpleasant odor caused by these. . These adhesives can be preferably used in all fields that require the use of adhesives, especially hot-melt pressure-sensitive adhesives or adhesives for sanitary products that come in contact with the human body, such as diapers, sanitary napkins, and adult diapers.
이하, 실시예를 통하여 본 발명을 더욱 구체적으로 설명하기로 하지만, 하기 실시예가 본 발명의 범위를 제한하는 것은 아니며, 이는 본 발명의 이해를 돕기 위한 것으로 해석되어야 할 것이다.Hereinafter, the present invention will be described in more detail through examples. However, the following examples do not limit the scope of the present invention, and should be interpreted to aid understanding of the present invention.
[제조예 1][Production Example 1]
1L 오토클레이브에 디사이클로펜타디엔(DCPD) 및 노르보넨 1.5 mol(7:3 비율)을 용매인 톨루엔 4 mol에 용해시킨 혼합물을 만들고, 여기에 1-헥센 0.5 mol 및 Pd계 촉매를 첨가하고, 반응기 체결 후, 반응 온도를 40℃로 유지하며 2시간 동안 촉매중합시킨 후 반응을 종결하였다. 반응 완료 후, 생성된 석유수지에서 미반응 유분을 제거하여 석유수지를 수득하였다. 상기 수득된 석유수지 중량에 대하여 수소첨가용매로 톨루엔을 1.5배로 투입하여 완전히 용해시키고, 1L 오토클레이브 투입하였다.A mixture of dicyclopentadiene (DCPD) and 1.5 mol of norbornene (7:3 ratio) dissolved in 4 mol of toluene as a solvent was prepared in a 1L autoclave, and 0.5 mol of 1-hexene and a Pd-based catalyst were added thereto. After connecting the reactor, the reaction temperature was maintained at 40°C and catalytic polymerization was performed for 2 hours, and then the reaction was terminated. After completion of the reaction, unreacted oil was removed from the produced petroleum resin to obtain a petroleum resin. Toluene was added as a hydrogenation solvent in 1.5 times the weight of the obtained petroleum resin to completely dissolve it, and then placed in a 1L autoclave.
반응기 체결한 후에 수소압력 80 bar 및 온도 230℃에서 90분 동안 수소첨가 반응을 수행하였다. 반응이 종료된 후, 반응 생성액을 10 torr의 진공상태에서 260℃로 10분간 증류시켜 수소첨가 석유수지 50g을 제조하였다.After connecting the reactor, a hydrogenation reaction was performed for 90 minutes at a hydrogen pressure of 80 bar and a temperature of 230°C. After the reaction was completed, the reaction product was distilled at 260°C for 10 minutes under a vacuum of 10 torr to prepare 50 g of hydrogenated petroleum resin.
제조된 수소첨가 석유수지의 중량평균분자량(Mw)은 880이고, 연화점은 99℃이었다.The weight average molecular weight (Mw) of the produced hydrogenated petroleum resin was 880, and the softening point was 99°C.
[제조예 2][Production Example 2]
디사이클로펜타디엔과 노르보넨을 9:1로 배합한 것을 제외하고는 실시예 1과 동일한 방법으로 수소첨가 석유수지를 제조하였다. 제조된 수소첨가 석유수지의 중량평균분자량(Mw)은 970이고, 연화점은 106℃이었다.Hydrogenated petroleum resin was prepared in the same manner as in Example 1, except that dicyclopentadiene and norbornene were mixed in a ratio of 9:1. The weight average molecular weight (Mw) of the produced hydrogenated petroleum resin was 970, and the softening point was 106°C.
[제조예 3][Production Example 3]
디사이클로펜타디엔과 노르보넨을 5:5로 배합한 것을 제외하고는 실시예 1과 동일한 방법으로 수소첨가 석유수지를 제조하였다. 제조된 수소첨가 석유수지의 중량평균분자량(Mw)은 710이고, 연화점은 86℃이었다.Hydrogenated petroleum resin was prepared in the same manner as in Example 1, except that dicyclopentadiene and norbornene were mixed in a ratio of 5:5. The weight average molecular weight (Mw) of the produced hydrogenated petroleum resin was 710, and the softening point was 86°C.
[제조예 4][Production Example 4]
노르보넨을 첨가하지 않은 점을 제외하고는 실시예 1과 동일한 방법으로 수소첨가 석유수지를 제조하였다. 제조된 수소첨가 석유수지의 중량평균분자량(Mw)은 1050이고, 연화점은 111℃이었다.Hydrogenated petroleum resin was prepared in the same manner as in Example 1, except that norbornene was not added. The weight average molecular weight (Mw) of the produced hydrogenated petroleum resin was 1050, and the softening point was 111°C.
[제조예 5][Production Example 5]
디사이클로펜타디엔과 노르보넨을 4:6으로 배합한 것을 제외하고는 실시예 1과 동일한 방법으로 수소첨가 석유수지를 제조하였다. 제조된 수소첨가 석유수지의 중량평균분자량(Mw)은 650이고, 연화점은 79℃이었다.Hydrogenated petroleum resin was prepared in the same manner as in Example 1, except that dicyclopentadiene and norbornene were mixed in a ratio of 4:6. The weight average molecular weight (Mw) of the produced hydrogenated petroleum resin was 650, and the softening point was 79°C.
[제조예 6][Production Example 6]
1L 오토클레이브에 디사이클로펜타디엔(DCPD) 1.5 mol을 용매인 톨루엔 4 mol에 용해시킨 혼합물을 만들고, 여기에 1-헥센 0.5 mol을 첨가하고, 반응기 체결 후, 반응 온도를 270℃로 유지하며 2시간 동안 열중합 반응시킨 후 반응을 종결하였다. 반응 완료 후, 생성된 석유수지를 240℃에서 5분 동안 증류하여 미반응 유분을 회수하고 남은 석유수지를 수득하였다. 상기 수득된 석유수지에 대하여 수소첨가용매로 톨루엔을 1.5배로 투입하여 완전히 용해시키고, 1L 오토클레이브 투입하였다.A mixture of 1.5 mol of dicyclopentadiene (DCPD) dissolved in 4 mol of toluene as a solvent was prepared in a 1L autoclave, 0.5 mol of 1-hexene was added thereto, and after connecting the reactor, the reaction temperature was maintained at 270°C and 2 After thermal polymerization was performed for a period of time, the reaction was terminated. After completion of the reaction, the produced petroleum resin was distilled at 240°C for 5 minutes to recover the unreacted fraction and obtain the remaining petroleum resin. Toluene was added 1.5 times as a hydrogenation solvent to the obtained petroleum resin to completely dissolve it, and then placed in a 1L autoclave.
여기에 팔라듐 촉매 0.2 mol을 투입하고, 반응기 체결한 후에 수소압력 80 bar 및 온도 230℃에서 90분 동안 수소첨가 반응을 수행하였다. 반응이 종료된 후, 반응 생성액을 10 torr의 진공상태에서 260℃로 10분간 증류시켜 수소첨가 석유수지를 제조하였다. 제조된 수소첨가 석유수지의 중량평균분자량(Mw)은 850이고, 연화점은 85℃이었다.0.2 mol of palladium catalyst was added here, and after the reactor was connected, a hydrogenation reaction was performed for 90 minutes at a hydrogen pressure of 80 bar and a temperature of 230°C. After the reaction was completed, the reaction product was distilled at 260°C for 10 minutes under a vacuum of 10 torr to prepare a hydrogenated petroleum resin. The weight average molecular weight (Mw) of the produced hydrogenated petroleum resin was 850, and the softening point was 85°C.
평가예 1: 내열성 평가Evaluation Example 1: Heat resistance evaluation
시험관에 샘플 10g 계량 후 180℃ 오븐에서 Aging 진행하였다. 24시간 후 가드너 비색계(Gardner color scale)로 평가하였다. Gardner color는 총 18단계의 색상이 있으며 육안으로 가장 가까운 색상의 단계 색상을 기록하였다. 내열성이 낮은 수지는 고온 노화 실험에서 색상이 변화되어 높은 값의 가드너 색 점수를 보인다.After weighing 10g of sample in a test tube, aging was performed in an oven at 180°C. After 24 hours, it was evaluated using the Gardner color scale. There are a total of 18 levels of Gardner color, and the color level of the color closest to the naked eye was recorded. Resins with low heat resistance change color in high-temperature aging experiments and show high Gardner color scores.
평가예 2: 점착력 평가 - Ball TackEvaluation Example 2: Adhesion Evaluation - Ball Tack
점착력을 ASTM D3121 방법으로 평가하였다.Adhesion was evaluated using the ASTM D3121 method.
접착제가 20∼30 마이크로미터로 발려진 시험편 테이프를 가로 10cm, 세로 50cm로 잘라주었다. 한 쪽 끝에 Ball tack tester(JIS Z0237)를 놓고 그 각도를 표준경사각 30도로 하여 설치하고 그 위에 Steel ball No.9를 굴려 굴러간 거리를 측정하였다. 볼이 적게 굴러 갈수록 Tack의 성능은 우수한 것이다.The test piece tape with 20 to 30 micrometers of adhesive was cut into 10 cm wide and 50 cm long. A ball tack tester (JIS Z0237) was placed at one end and its angle was set to a standard inclination angle of 30 degrees. Steel ball No. 9 was rolled on it and the rolled distance was measured. The less the ball rolls, the better the tack performance.
평가예 3: Peel StrengthEvaluation Example 3: Peel Strength
UTM기기를 활용하여 측정하였다. 먼저 PET 필름에 샘플(접착제)를 25 마이크로미터 두께로 도포해서 테이프를 제조했다. 이를 SUS-304 강판에 부착하였다. PET 필름이 부착된 부분을 UTM 그립에 장착한 후 30mm/min 의 속도로 측정했다. 이때 UTM 장비에 입력되는 수치가 접착력(kgf/in)을 의미하는 것이다.It was measured using a UTM device. First, a tape was manufactured by applying a sample (adhesive) to a PET film to a thickness of 25 micrometers. This was attached to a SUS-304 steel plate. The part where the PET film was attached was mounted on a UTM grip and measured at a speed of 30 mm/min. At this time, the value entered into the UTM equipment represents the adhesive force (kgf/in).
평가예 4: 접착력 평가 - Holding PowerEvaluation Example 4: Adhesion Evaluation - Holding Power
접착력을 ASTM D3330 방법으로 평가하였다.Adhesion was evaluated using the ASTM D3330 method.
접착제가 20∼30 마이크로미터로 발려진 시험편 테이프를 가로 2인치, 세로 6인치 만큼 잘라 주었다. 시험편을 이형지에 붙이고, 가로 1인치, 세로 2인치로 만든 후, 세척한 SUS 304 강판에 붙였다(이때 붙지 않는 시험편이 약 2cm 이상이 되도록 붙이고, 측정에 필요한 부분을 Cheminstruments社 Roll down기기를 활용하여 Roll을 1회 왕복하여 압착시켰다). SUS 304 강판에 붙지 않은 시험편이 약 2cm가 되도록 가위로 잘랐다. SUS 304 강판에 붙지 않은 시험편을 Cohesion 측정용 고리에 끼우고 통과하는 시험편과 접착시켰다. 고정용 스카치 테이프로 시험편이 접착된 SUS 304 강판의 가로 끝부분을 기준으로 평행하게 앞 뒤 각각 2개씩 붙이고, 스템플러로 Cohesion 측정용 고리와 SUS304 강판 사이에 평행하게 2개를 찍어 고정시켜주었다. SUS 304 강판에 시험편이 가로 1인치, 세로 1인치 붙어 있도록 나머지 붙어 있는 시험편을 잘랐다.A test piece of tape coated with 20 to 30 micrometers of adhesive was cut to 2 inches wide and 6 inches long. The test piece was attached to the release paper, made into a width of 1 inch and length of 2 inches, and then attached to a cleaned SUS 304 steel plate (at this time, the test piece that did not stick was attached so that it was about 2 cm or more, and the part needed for measurement was cut using a Cheminstruments roll down device). The roll was compressed by reciprocating once). The test piece that did not stick to the SUS 304 steel plate was cut with scissors to about 2 cm. The test piece that was not attached to the SUS 304 steel plate was inserted into the ring for measuring cohesion and adhered to the test piece that passed. Two specimens were attached at the front and back in parallel based on the horizontal end of the SUS 304 steel plate to which the test piece was attached using Scotch tape for fixation, and two were stamped and fixed in parallel between the ring for cohesion measurement and the SUS 304 steel plate using a stamper. The remaining test piece was cut so that the test piece was 1 inch wide and 1 inch long on the SUS 304 steel plate.
Shear test oven안의 SUS 강판 거치대에 걸어두었다. 시험편에 붙여 진 holding power 측정용 고리에 1kg 추를 걸어두었다. 타이머에 추가 떨어진 시간을 기록했다.It was hung on a SUS steel plate holder in a shear test oven. A 1kg weight was hung on the ring for measuring holding power attached to the test specimen. The timer recorded the time the pendulum fell.
평가예 5: 접착력 평가 - SAFTEvaluation Example 5: Adhesion Evaluation - SAFT
접착력을 ASTM D3654 방법으로 평가하였다.Adhesion was evaluated using the ASTM D3654 method.
접착제가 20∼30 마이크로미터로 발려진 시험편 테이프를 2인치*6인치 만큼 잘랐다. 시험편을 이형지에 붙이고, 가로 1인치, 세로 2인치로 만든 후, 세척한 SUS 304 강판에 붙였다(이때 붙지 않는 시험편이 약 2cm 이상이 되도록 붙이고, 측정에 필요한 부분을 Cheminstruments社 Roll down기기를 활용하여 Roll을 1회 왕복하여 압착시켰다). SUS 304 강판에 붙지 않은 시험편이 약 2cm가 되도록 가위로 잘라주었다. SUS 304 강판에 붙지 않은 시험편을 Cohesion 측정용 고리에 끼우고 통과하는 시험편과 접착시켰다. 고정용 스카치 테이프로 시험편이 접착된 SUS 304 강판의 가로 끝부분을 기준으로 평행하게 앞뒤 각각 2개씩 붙이고, 스템플러로 Cohesion 측정용 고리와 SUS304 강판 사이에 평행하게 2개를 찍어 고정시켜 주었다. SUS 304 강판에 시험편이 가로 1인치, 세로 1인치 붙어 있도록 나머지 붙어 있는 시험편을 잘랐다.The test piece tape coated with 20 to 30 micrometers of adhesive was cut to 2 inches by 6 inches. The test piece was attached to the release paper, made into a width of 1 inch and length of 2 inches, and then attached to a cleaned SUS 304 steel plate (at this time, the test piece that did not stick was attached so that it was about 2 cm or more, and the part needed for measurement was cut using a Cheminstruments roll down device). The roll was compressed by reciprocating once). The test piece that was not attached to the SUS 304 steel plate was cut with scissors so that it was about 2 cm. The test piece that was not attached to the SUS 304 steel plate was inserted into the ring for measuring cohesion and adhered to the test piece that passed. Two specimens were attached at the front and back in parallel based on the horizontal end of the SUS 304 steel plate to which the test piece was attached using Scotch tape for fixation, and two were stamped and fixed in parallel between the cohesion measurement ring and the SUS 304 steel plate using a stapler. The remaining test piece was cut so that the test piece was 1 inch wide and 1 inch long on the SUS 304 steel plate.
Shear test oven안의 SUS 강판 거치대에 걸어두었다. 시험편에 붙여진 holding power [0186] 측정용 고리에 1kg 추를 걸어두었다. 그리고, 오븐 온도를 0.4도/분으로 승온시켜 추가 떨어질 때의 온도를 기록하였다.It was hung on a SUS steel plate holder in a shear test oven. A 1 kg weight was hung on the holding power measurement ring attached to the test specimen. Then, the oven temperature was raised at 0.4 degrees/min and the temperature when the weight fell was recorded.
실시예 1 내지 3 및 비교예 1 내지 3Examples 1 to 3 and Comparative Examples 1 to 3
폴리머로 Exxonmobil chemical社 Vistamaxx 6202(metallocene catalyzed poly propylene) 20wt% 및 Evonik社 Vestoplast 703(Amorphous propylene-ethylene copolymer) 20wt%, 오일로 KL-240 미창석유화학社) 22.5wt%와 제조예 1 내지 3에서 제조한 수소첨가 석유수지와 제조예 4 내지 6에서 제조한 수소첨가 석유수지 50wt%를 각각 포함하는 혼합물 100 중량부에 대하여, 항산화제(송원산업社 社 Songnox 1010) 0.75 중량부를 섞어 HMPSA 접착제(me-PP based HMPSA)인 실시예 1 내지 3 및 비교예 1 내지 3의 핫멜트 감압 접착제(HMPSA)를 제조하였다.As a polymer, Exxonmobil Chemical's Vistamaxx 6202 (metallocene catalyzed poly propylene) 20wt% and Evonik's Vestoplast 703 (Amorphous propylene-ethylene copolymer) 20wt%, as an oil, KL-240 Michang Petrochemical Co.) 22.5wt% and Preparation Examples 1 to 3 With respect to 100 parts by weight of the mixture containing the hydrogenated petroleum resin prepared and 50 wt% of the hydrogenated petroleum resin prepared in Preparation Examples 4 to 6, 0.75 parts by weight of antioxidant (Songnox 1010, Songwon Industrial Co., Ltd.) was mixed and HMPSA adhesive (me -PP based HMPSA) hot melt pressure sensitive adhesive (HMPSA) of Examples 1 to 3 and Comparative Examples 1 to 3 were prepared.
제조 조건은 100ml 비커에 4종(석유수지, 폴리머, 오일, 항산화제)의 원료를 넣고 180℃에서 4시간 교반하여 제조하였고, 상세한 중량부 및 특성평가 결과는 하기 표 1에 나타내었다.The manufacturing conditions were prepared by putting four types of raw materials (petroleum resin, polymer, oil, and antioxidant) in a 100ml beaker and stirring at 180°C for 4 hours. The detailed weight portion and property evaluation results are shown in Table 1 below.
석유수지
(wt%)Hydrogenation
petroleum balance
(wt%)
(wt%)Oil
(wt%)
(gf/in,at SUS)Peel strength
(gf/in,at SUS)
(min, 30℃)Holding power
(min, 30℃)
(℃ at
SUS, Ramp
0.4℃/minSAFT
(℃ at
SUS, Ramp
0.4℃/min
*Aged는 각 시료를 70℃에서 3일 동안 방치한 후, 측정한 결과를 나타낸 것이다*Aged indicates the results measured after each sample was left at 70℃ for 3 days.
상기 표에서 보는 바와 같이, 디사이클로펜타디엔 및 노르보넨의 비율이 5:5~9:1로서 디사이클로펜타디엔 유래 반복단위의 일부가 노르보넨 유래 반복단위로 치환된 제조예 1 내지 3의 수소첨가 석유수지를 적용한 실시예 1 내지 3의 핫멜트 감압 접착제는 노르보넨 유래 반복단위를 포함하지 않는 비교예 1 및 3에 비해 유사하거나 개선된 접착력을 보이면서, 이와 동시에 개선된 내열성을 가지며, 노르보넨의 함량이 디사이클로펜타디엔의 함량보다 높은 제조예 5의 수소첨가 석유수지를 적용한 비교예 2의 핫멜트 감압 접착제에 비해 내열성 및 접착력이 현저히 향상되었다. As shown in the table above, the ratio of dicyclopentadiene and norbornene is 5:5 to 9:1, and the hydrogen of Preparation Examples 1 to 3 in which some of the dicyclopentadiene-derived repeating units are replaced with norbornene-derived repeating units. The hot melt pressure-sensitive adhesives of Examples 1 to 3 using added petroleum resins show similar or improved adhesion compared to Comparative Examples 1 and 3 that do not contain norbornene-derived repeating units, and at the same time have improved heat resistance, and have improved heat resistance and Heat resistance and adhesion were significantly improved compared to the hot melt pressure-sensitive adhesive of Comparative Example 2 using the hydrogenated petroleum resin of Preparation Example 5, which had a higher dicyclopentadiene content.
본 발명의 단순한 변형 또는 변경은 모두 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다.Any simple modification or change of the present invention can be easily implemented by those skilled in the art, and all such modifications or changes can be considered to be included in the scope of the present invention.
Claims (11)
<화학식 1> <화학식 2> <화학식 3>
상기 화학식 2에서, R21 및 R22는 서로 독립적으로, 수소 또는 C1-C10 직쇄 또는 분지쇄 알킬기이고,
상기 화학식 3에서, R31은 수소 또는 메틸기이고, R32는 C1-C18 직쇄 또는 분지쇄 알킬기이다.Hydrogenated petroleum resin comprising a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and a repeating unit represented by the following formula (3):
<Formula 1><Formula2><Formula3>
In Formula 2, R 21 and R 22 are independently hydrogen or a C 1 -C 10 straight or branched alkyl group,
In Formula 3, R 31 is hydrogen or a methyl group, and R 32 is a C 1 -C 18 straight or branched alkyl group.
상기 화학식 2로 표시되는 반복단위는 상기 화학식 1로 표시되는 반복단위에 대하여 0.1 내지 0.5 몰비율로 포함된, 수소첨가 석유수지.According to paragraph 1,
A hydrogenated petroleum resin in which the repeating unit represented by Formula 2 is contained in a molar ratio of 0.1 to 0.5 with respect to the repeating unit represented by Formula 1.
상기 수소첨가 석유수지는 상기 화학식 1의 반복단위 및 상기 화학식 2의 반복단위를 60 내지 90몰% 포함하고, 상기 화학식 3의 반복단위를 10 내지 40 몰% 포함하는, 수소첨가 석유수지.According to paragraph 1,
The hydrogenated petroleum resin contains 60 to 90 mol% of the repeating unit of the formula (1) and the repeating unit of the formula (2), and 10 to 40 mol% of the repeating unit of the formula (3).
상기 R21은 수소이고, R22는 수소, 메틸기, 에틸기, 프로필기, 이소프로필기, 부틸기, sec-부틸기, 이소부틸기, 또는 tert-부틸기인, 수소첨가 석유수지.According to paragraph 1,
Wherein R 21 is hydrogen, and R 22 is hydrogen, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, or tert-butyl, hydrogenated petroleum resin.
상기 R31은 수소이고, R32는 메틸기, 에틸기, n-프로필기, 이소프로필기, n-부틸기, sec-부틸기, 이소부틸기, tert-부틸기, n-펜틸기, tert-펜틸기, 네오펜틸기, 이소펜틸기, sec-펜틸기, 3-펜틸기, sec-이소펜틸기, n-헥실기, 이소헥실기, sec-헥실기, tert-헥실기, n-헵틸기, 이소헵틸기, sec-헵틸기, tert-헵틸기, n-옥틸기, 이소옥틸기, sec-옥틸기, tert-옥틸기, n-노닐기, 이소노닐기, sec-노닐기, tert-노닐기, n-데실기, 이소데실기, sec-데실기, 또는 tert-데실기인, 수소첨가 석유수지.According to paragraph 1,
R 31 is hydrogen, and R 32 is methyl, ethyl, n -propyl, isopropyl, n -butyl, sec -butyl, isobutyl, tert -butyl, n -pentyl, tert -phene. Tyl group, neopentyl group, isopentyl group, sec -pentyl group, 3-pentyl group, sec -isopentyl group, n -hexyl group, isohexyl group, sec -hexyl group, tert -hexyl group, n -heptyl group, Isoheptyl group, sec -heptyl group, tert -heptyl group, n -octyl group, isooctyl group, sec -octyl group, tert -octyl group, n -nonyl group, isononyl group, sec -nonyl group, tert -nonyl group , n -decyl group, isodecyl group, sec -decyl group, or tert -decyl group, hydrogenated petroleum resin.
상기 석유수지를 수소화 촉매에 의하여 수소첨가 반응을 수행하는 단계를 포함하는, 수소첨가 석유수지의 제조방법.Preparing a petroleum resin by catalytic polymerization of dicyclopentadiene monomer, norbornene monomer, and C 3 -C 20 olefin monomer; and
A method for producing hydrogenated petroleum resin, comprising the step of performing a hydrogenation reaction on the petroleum resin using a hydrogenation catalyst.
상기 디사이클로펜타디엔 단량체 및 노르보넨 단량체는 5:5 내지 9:1의 몰비율로 촉매중합되는, 수소첨가 석유수지의 제조방법.According to clause 6,
A method for producing hydrogenated petroleum resin, wherein the dicyclopentadiene monomer and norbornene monomer are catalytically polymerized at a molar ratio of 5:5 to 9:1.
상기 C3-C20 올레핀계 단량체는 직쇄 또는 분지쇄 알파 올레핀계 단량체인, 수소첨가 석유수지의 제조방법.According to clause 6,
The C 3 -C 20 olefin monomer is a straight-chain or branched alpha-olefin monomer. A method for producing hydrogenated petroleum resin.
상기 촉매 중합은 Pd, Ti, Co 및 Ni 중에서 선택된 1종 이상의 전이금속을 포함하는 전이금속촉매의 존재하에서 20 내지 50℃에서 중합반응을 수행하는, 수소첨가 석유수지의 제조방법.According to clause 6,
The catalytic polymerization is a method of producing hydrogenated petroleum resin, in which the polymerization reaction is performed at 20 to 50 ° C. in the presence of a transition metal catalyst containing one or more transition metals selected from Pd, Ti, Co, and Ni.
상기 수소화 촉매는 Ni, Pd, Co, Pt 및 Rh 중에서 선택된 1종 이상의 촉매인, 수소첨가 석유수지의 제조방법.According to clause 6,
A method for producing a hydrogenated petroleum resin, wherein the hydrogenation catalyst is one or more catalysts selected from Ni, Pd, Co, Pt and Rh.
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