JP2014051631A - Hot melt resin composition for cardboard - Google Patents
Hot melt resin composition for cardboard Download PDFInfo
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- JP2014051631A JP2014051631A JP2012198404A JP2012198404A JP2014051631A JP 2014051631 A JP2014051631 A JP 2014051631A JP 2012198404 A JP2012198404 A JP 2012198404A JP 2012198404 A JP2012198404 A JP 2012198404A JP 2014051631 A JP2014051631 A JP 2014051631A
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- vinyl acetate
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- 239000011342 resin composition Substances 0.000 title claims abstract description 39
- 239000012943 hotmelt Substances 0.000 title claims abstract description 32
- 229920005989 resin Polymers 0.000 claims abstract description 87
- 239000011347 resin Substances 0.000 claims abstract description 87
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 36
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 36
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 17
- 239000004711 α-olefin Substances 0.000 claims abstract description 17
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000155 melt Substances 0.000 claims abstract description 10
- 239000003208 petroleum Substances 0.000 claims description 25
- 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 14
- 229920001577 copolymer Polymers 0.000 claims description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 12
- 239000005977 Ethylene Substances 0.000 claims description 12
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 7
- 229920006026 co-polymeric resin Polymers 0.000 claims description 7
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- 239000001993 wax Substances 0.000 description 18
- 239000004831 Hot glue Substances 0.000 description 12
- -1 polyethylene Polymers 0.000 description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 3
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-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
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000013032 Hydrocarbon resin Substances 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 229920006271 aliphatic hydrocarbon resin Polymers 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920006270 hydrocarbon resin Polymers 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 230000007257 malfunction Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 150000003097 polyterpenes Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 1
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- OGMSGZZPTQNTIK-UHFFFAOYSA-N 1-methyl-2-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1C OGMSGZZPTQNTIK-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 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
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229930006722 beta-pinene Natural products 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 230000000447 dimerizing effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 229940117927 ethylene oxide Drugs 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- KIOWHOMJXAQSMW-UHFFFAOYSA-N phenol;4,6,6-trimethylbicyclo[3.1.1]hept-3-ene Chemical compound OC1=CC=CC=C1.CC1=CCC2C(C)(C)C1C2 KIOWHOMJXAQSMW-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical compound CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 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
- C08L31/00—Compositions of 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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
- C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C08L31/04—Homopolymers or copolymers of vinyl acetate
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C08L57/02—Copolymers of mineral oil hydrocarbons
-
- 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
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09J123/0853—Vinylacetate
Abstract
Description
本発明は、段ボール用ホットメルト樹脂組成物に関する。 The present invention relates to a hot melt resin composition for corrugated cardboard.
ホットメルト接着剤は、無溶剤であり、瞬間接着、高速接着が可能であるという接着工程および経済面での利点を備えているため、包装、製本、木工等の分野を主体として大量に使用されている。また、ホットメルト接着剤は高温で塗布する必要があるため、塗布時にはホットメルトアプリケーターと言われる専用の塗布装置が用いられる。このホットメルトアプリケーターは、通常、圧縮空気やギヤポンプを用いることにより、１２０〜１９０℃程度まで加熱したホットメルト接着剤を、ノズルの先端から間欠的に吐出（ショット）して、被着体に塗布する。その際、一般的に、ホットメルト接着剤を吐出するノズルの先端から被着体の間で吐出毎にホットメルト接着剤が有する曳糸性に起因する糸状物が発生する。この糸状物が発生すると、様々な使用過程において、周辺装置や被着体を汚染したり、センサーの誤作動や印字ミス等を引き起こすという問題点が発生する。 Hot melt adhesives are solvent-free and have the advantages of bonding process and economics that instant bonding and high-speed bonding are possible, so they are used in large quantities mainly in fields such as packaging, bookbinding and woodworking. ing. Further, since the hot melt adhesive needs to be applied at a high temperature, a dedicated application device called a hot melt applicator is used at the time of application. This hot melt applicator is usually applied to the adherend by intermittently discharging (shot) the hot melt adhesive heated to about 120-190 ° C from the tip of the nozzle by using compressed air or a gear pump. To do. At that time, generally, a thread-like material is generated between the tip of the nozzle that discharges the hot melt adhesive and the adherend between the adherends due to the spinnability of the hot melt adhesive. When this filamentous material is generated, problems such as contamination of peripheral devices and adherends, malfunction of the sensor, printing errors, and the like occur in various usage processes.
そのため、糸曳きを抑制するために、オレフィン系共重合体に非相溶な樹脂としてエチレン−酢酸ビニル共重合体を添加したホットメルト接着剤や、不飽和ポリカルボン酸、その無水物またはそのエステルで変性されてなる糸曳き低減剤を配合したポリオレフィン系ホットメルト接着剤や、エチレン−（メタ）アクリル酸エステル共重合体とポリエチレンとを配合したホットメルト接着剤が開発検討されている（特許文献１〜３参照）。 Therefore, in order to suppress stringing, a hot-melt adhesive in which an ethylene-vinyl acetate copolymer is added as an incompatible resin to an olefin copolymer, an unsaturated polycarboxylic acid, its anhydride or its ester Development studies have been conducted on polyolefin hot-melt adhesives containing a yarn-strengthening agent that has been modified by the above, and hot-melt adhesives containing ethylene- (meth) acrylate copolymer and polyethylene (Patent Literature) 1-3).
また、段ボール用途のホットメルト樹脂組成物としては、前記糸曳きを抑制の他に、接着性として、段ボールに対する剥離接着性や耐クリープ性等、さらには加熱安定性（耐熱性）が求められている。 Moreover, as a hot melt resin composition for corrugated cardboard, in addition to suppressing the above stringing, as adhesiveness, peeling adhesiveness and creep resistance to corrugated cardboard, and further heat stability (heat resistance) are required. Yes.
しかしながら、従来のホットメルト接着剤においては、糸曳き抑制に関しては各種改善が行われているが、段ボールに対する接着性は十分ではなく、特に高温での耐クリープ性や低温時の接着性等に劣っている。また、糸曳きを改善したポリオレフィン系ホットメルト接着剤も知られているが、コスト低減の観点から、非オレフィン系の材料を主成分とすることが求められている。
すなわち本発明は、段ボールに対する接着性に優れた、糸曳きが少なく、熱安定性良好な、低コストの段ボール用ホットメルト樹脂組成物を提供することを目的とするものである。
However, conventional hot melt adhesives have various improvements in terms of stringing suppression, but the adhesion to corrugated cardboard is not sufficient, and in particular, the creep resistance at high temperature and the adhesion at low temperature are inferior. ing. In addition, polyolefin hot melt adhesives with improved stringing are also known, but from the viewpoint of cost reduction, it is required to use a non-olefin material as a main component.
That is, an object of the present invention is to provide a low-cost hot-melt resin composition for corrugated cardboard that has excellent adhesion to corrugated cardboard, little stringing, and good thermal stability.
本発明は以下の通りである。
（１） エチレン酢酸ビニル共重合樹脂（ＥＶＡ）を２５〜５０質量％、粘着付与剤を１０〜６０質量％、ワックス成分を１０〜３０質量％、α―オレフィン共重体樹脂を０．３〜５質量％含む、段ボール用ホットメルト樹脂組成物。
（２） エチレン酢酸ビニル共重合樹脂（ＥＶＡ）において、酢酸ビニル（ＶＡ）含有量が１０〜５０質量％であり、メルトフローレート（ＭＦＲ）が２００〜３０００ｇ／１０分であり、環球法軟化温度が６０〜１２０℃である、（１）記載の段ボール用ホットメルト樹脂組成物。
（３） α―オレフィン共重体樹脂が、エチレン系樹脂とブテン系樹脂との共重体樹脂、又は、エチレン系樹脂とプロピレン系樹脂との共重体樹脂である、（１）又は（２）に記載の段ボール用ホットメルト樹脂組成物。
（４） 粘着付与剤として、ジシクロペンタジエン（ＤＣＰＤ）・芳香族共重合系の水添石油樹脂を０〜３０質量％、水添Ｃ９石油樹脂を１０〜５０質量％、水添Ｃ５石油樹脂を０〜２０質量％含む、（１）〜（３）いずれかに記載の段ボール用ホットメルト樹脂組成物。
（５）メルトフローレート（ＭＦＲ）が２００〜６００ｇ／１０分のエチレン酢酸ビニル共重合樹脂（ＥＶＡ）の含有量が１〜４０質量％であり、メルトフローレート（ＭＦＲ）が６０１〜２０００ｇ／１０分のエチレン酢酸ビニル共重合樹脂（ＥＶＡ）の含有量が１〜３０質量％である、（２）〜（４）いずれかに記載の段ボール用ホットメルト樹脂組成物。
The present invention is as follows.
(1) 25-50 mass% of ethylene vinyl acetate copolymer resin (EVA), 10-60 mass% of tackifier, 10-30 mass% of wax component, 0.3-5 of α-olefin copolymer resin A hot-melt resin composition for corrugated board containing mass%.
(2) The ethylene vinyl acetate copolymer resin (EVA) has a vinyl acetate (VA) content of 10 to 50% by mass, a melt flow rate (MFR) of 200 to 3000 g / 10 min, and a ring and ball softening temperature. The hot-melt resin composition for corrugated board as described in (1) whose is is 60-120 degreeC.
(3) The α-olefin copolymer resin is a copolymer resin of an ethylene-based resin and a butene-based resin, or a copolymer resin of an ethylene-based resin and a propylene-based resin, according to (1) or (2) Hot-melt resin composition for corrugated board.
(4) 0 to 30% by mass of dicyclopentadiene (DCPD) / aromatic copolymer hydrogenated petroleum resin, 10 to 50% by mass of hydrogenated C9 petroleum resin, and hydrogenated C5 petroleum resin as tackifiers The hot melt resin composition for corrugated board according to any one of (1) to (3), comprising 0 to 20% by mass.
(5) The content of the ethylene vinyl acetate copolymer resin (EVA) having a melt flow rate (MFR) of 200 to 600 g / 10 min is 1 to 40% by mass, and the melt flow rate (MFR) is 601 to 2000 g / 10. The hot melt resin composition for corrugated board according to any one of (2) to (4), wherein the content of ethylene vinyl acetate copolymer resin (EVA) in 1 minute is 1 to 30% by mass.
本発明によって、段ボールに対する接着性に優れた、糸曳きが少なく、熱安定性良好な、低コストの段ボール用ホットメルト樹脂組成物を提供することが可能になる。 According to the present invention, it is possible to provide a low-cost hot-melt resin composition for corrugated cardboard that has excellent adhesion to corrugated cardboard, little stringing, and good thermal stability.
以下、本発明の実施形態について詳細に説明する。
本発明の段ボール用ホットメルト樹脂組成物（以下、樹脂組成物と略す）は、エチレン酢酸ビニル共重合樹脂（ＥＶＡ）を２５〜５０質量％、粘着付与剤を１０〜６０質量％、ワックス成分を１０〜３０質量％、α―オレフィン共重体樹脂を０．３〜５質量％含むものである。
本発明に使用されるエチレン酢酸ビニル共重合樹脂（ＥＶＡ）としては、酢酸ビニル（ＶＡ）含有量が１０〜５０質量％であり、メルトフローレート（ＭＦＲ）が２００〜３０００ｇ／１０分であり、環球法軟化温度が６０〜１２０℃であることが好ましいが、さらに、酢酸ビニル含有率１５〜３５質量％、環球法軟化温度が７５〜９５℃であることがより好ましい。これらのエチレン酢酸ビニル共重合樹脂（ＥＶＡ）は、単独で用いられてもよいし、２種類以上が併用されてもよい。
Hereinafter, embodiments of the present invention will be described in detail.
The hot-melt resin composition for corrugated board of the present invention (hereinafter abbreviated as resin composition) comprises 25 to 50% by mass of an ethylene vinyl acetate copolymer resin (EVA), 10 to 60% by mass of a tackifier, and a wax component. 10 to 30% by mass and 0.3 to 5% by mass of α-olefin copolymer resin.
The ethylene vinyl acetate copolymer resin (EVA) used in the present invention has a vinyl acetate (VA) content of 10 to 50% by mass and a melt flow rate (MFR) of 200 to 3000 g / 10 min. The ring-and-ball method softening temperature is preferably 60 to 120 ° C, and more preferably the vinyl acetate content is 15 to 35% by mass and the ring-and-ball method softening temperature is 75 to 95 ° C. These ethylene vinyl acetate copolymer resins (EVA) may be used alone or in combination of two or more.
さらに、メルトフローレート（ＭＦＲ）が２００〜６００ｇ／１０分のエチレン酢酸ビニル共重合樹脂（ＥＶＡ）の含有量が１〜４０質量％であることがより好ましく、また、メルトフローレート（ＭＦＲ）が６０１〜２０００ｇ／１０分のエチレン酢酸ビニル共重合樹脂（ＥＶＡ）の含有量が１〜３０質量％であることがより好ましい。
例えば、エチレン酢酸ビニル共重合樹脂（ＥＶＡ）としては、ウルトラセン６８４（ＶＡ含有率２０質量％、メルトフローレート（ＭＦＲ）＝２０００、環球法軟化温度８０℃、東ソー株式会社製商品名、「ウルトラセン」は登録商標）、ウルトラセン７２２（ＶＡ含有率２８質量％、メルトフローレート（ＭＦＲ）＝４００、環球法軟化温度８２℃、東ソー株式会社製商品名、「ウルトラセン」は登録商標）、ウルトラセン７３５（ＶＡ含有率２８質量％、メルトフローレート（ＭＦＲ）＝１０００、環球法軟化温度８５℃、東ソー株式会社製商品名、「ウルトラセン」は登録商標）等市販のものが挙げられる。
なお、通常、メルトフローレート（ＭＦＲ）は、ＪＩＳ Ｋ７２１０に準拠して１９０℃、荷重２１．１８Ｎの条件下にて測定されたものを、環球法軟化温度は、ＪＩＳ Ｋ２２０７に準拠して測定されたものをいう。
Furthermore, the content of the ethylene vinyl acetate copolymer resin (EVA) having a melt flow rate (MFR) of 200 to 600 g / 10 min is more preferably 1 to 40% by mass, and the melt flow rate (MFR) is The ethylene vinyl acetate copolymer resin (EVA) content at 601 to 2000 g / 10 min is more preferably 1 to 30% by mass.
For example, as ethylene vinyl acetate copolymer resin (EVA), Ultrasen 684 (VA content 20% by mass, melt flow rate (MFR) = 2000, ring and ball method softening temperature 80 ° C., trade name manufactured by Tosoh Corporation, “Ultra Sen "is a registered trademark), Ultrasen 722 (VA content 28% by mass, melt flow rate (MFR) = 400, ring and ball method softening temperature 82 ° C., trade name manufactured by Tosoh Corporation,“ Ultrasen ”is a registered trademark), Examples include commercially available products such as Ultrasen 735 (VA content 28 mass%, melt flow rate (MFR) = 1000, ring and ball method softening temperature 85 ° C., trade name manufactured by Tosoh Corporation, “Ultrasen” is a registered trademark).
Normally, the melt flow rate (MFR) is measured under the conditions of 190 ° C. and a load of 21.18 N according to JIS K7210, and the ring and ball softening temperature is measured according to JIS K2207. Say something.
樹脂組成物中のエチレン酢酸ビニル共重合樹脂（ＥＶＡ）含有量は、２５〜５０質量％であり、３０〜４５質量％が好ましく、３３〜４０質量％がより好ましい。
含有量が２５質量％未満の場合は、低温での接着性低下が発生するおそれがあり、また、５０質量％を超えると、粘度上昇、耐クリープ性の低下、糸曳き抑制効果の低下などの不具合が発生するおそれがある。
The ethylene vinyl acetate copolymer resin (EVA) content in the resin composition is 25 to 50% by mass, preferably 30 to 45% by mass, and more preferably 33 to 40% by mass.
If the content is less than 25% by mass, the adhesiveness may be lowered at a low temperature. If the content exceeds 50% by mass, the viscosity increases, the creep resistance decreases, the stringing suppression effect decreases, etc. There is a risk of malfunction.
本発明に使用されるワックス成分としては、一般的に、ホットメルト系接着剤に使用されるものであれば、特に限定されないが、例えば、精製パラフィンワックス、パラフィンワックス、マイクロクリスタリンワックスなどの石油系ワックス、ポリエチレンワックス、フィッシャートロフィックワックス、結晶性ポリエチレンワックス、結晶性ポリプロピレンワックス、アタクチックポリプロピレンワックス、エチレン・一酸化炭素共重合体ワックスなどの合成ワックスなどが挙げられる。これらの中でも特に、ポリエチレンワックス、フィッシャートロフィックワックスなどが好適である。これらワックス成分は、１種のみであってもよいし、２種以上であってもよい。
樹脂組成物中のワックス成分含有量は、１０〜３０質量％であり、１５〜２０質量％が好ましい。
含有量が１０質量％未満の場合は、粘度上昇や固化性能の低下などが発生するおそれがあり、また、３０質量％を超えると接着性の低下などが発生するおそれがある。
例えば、サゾールＨ１（サゾール社製、フィッシャートロフィックワックス、「ＳａＳＯＬ（サゾール）」は登録商標）、ＣＰＷ９０Ｆ（千葉ファインケミカル株式会社製、ポリエチレンワックス）等市販のものが挙げられる。
The wax component used in the present invention is not particularly limited as long as it is generally used for hot melt adhesives. For example, petroleum-based oils such as refined paraffin wax, paraffin wax, and microcrystalline wax are used. Examples thereof include synthetic waxes such as wax, polyethylene wax, Fischer tropic wax, crystalline polyethylene wax, crystalline polypropylene wax, atactic polypropylene wax, and ethylene / carbon monoxide copolymer wax. Among these, polyethylene wax, Fischer tropic wax and the like are particularly suitable. These wax components may be used alone or in combination of two or more.
The wax component content in the resin composition is 10 to 30% by mass, and preferably 15 to 20% by mass.
If the content is less than 10% by mass, the viscosity may increase or the solidification performance may decrease, and if it exceeds 30% by mass, the adhesiveness may decrease.
For example, commercially available products such as Sasol H1 (manufactured by Sasol, Fischer Trophy wax, “SaSOL (Sasol)” is a registered trademark), CPW90F (manufactured by Chiba Fine Chemical Co., Ltd., polyethylene wax) can be used.
本発明に使用されるα―オレフィン共重体樹脂とは、一般的に、エチレン系樹脂と炭素数３〜２０のα−オレフィン系樹脂とが共重合した少なくとも１種のオレフィン系共重合体である。炭素数３〜２０のα−オレフィン系樹脂としては、たとえば、プロピレン系樹脂、イソブチレン系樹脂、ブテン系樹脂、１−ペンテン系樹脂、１−ヘキセン系樹脂、４−メチル−１−ペンテン系樹脂、１−オクテン系樹脂等が挙げられる。上記オレフィン系共重合体のなかでも、エチレン系樹脂と炭素数４〜８のα−オレフィンとの共重合体が好ましい。
さらに、エチレン系樹脂とブテン系樹脂との共重体樹脂、又は、エチレン系樹脂とプロピレン系樹脂との共重体樹脂がより好ましい。これらのα―オレフィン共重体樹脂は、単独で用いられてもよいし、２種類以上が併用されてもよい。
樹脂組成物中のα―オレフィン共重体樹脂含有量は、０．３〜５質量％であり、０．５〜４質量％が好ましく、１〜３質量％がより好ましい。
含有量が０．３質量％未満の場合は、糸曳き抑制効果の低下などが発生するおそれがあり、また、５質量％を超えると低温接着性の低下や熱安定性の低下などが発生するおそれがある。
例えば、タフマーＰ０４８０（三井化学株式会社製、エチレン・プロピレン共重合体、「タフマー」は登録商標）、タフマーＡ４０７０Ｓ（エチレン・ブテン共重合体、三井化学株式会社製、α―オレフィン共重体樹脂、「タフマー」は登録商標）等市販のものが挙げられる。
The α-olefin copolymer resin used in the present invention is generally at least one olefin copolymer obtained by copolymerizing an ethylene resin and an α-olefin resin having 3 to 20 carbon atoms. . Examples of the α-olefin resin having 3 to 20 carbon atoms include propylene resin, isobutylene resin, butene resin, 1-pentene resin, 1-hexene resin, 4-methyl-1-pentene resin, Examples thereof include 1-octene resins. Among the olefin copolymers, a copolymer of an ethylene resin and an α-olefin having 4 to 8 carbon atoms is preferable.
Furthermore, a copolymer resin of ethylene resin and butene resin or a copolymer resin of ethylene resin and propylene resin is more preferable. These α-olefin copolymer resins may be used alone or in combination of two or more.
The α-olefin copolymer resin content in the resin composition is 0.3 to 5% by mass, preferably 0.5 to 4% by mass, and more preferably 1 to 3% by mass.
When the content is less than 0.3% by mass, there is a possibility that the effect of suppressing the stringing may be reduced. When the content exceeds 5% by mass, the low-temperature adhesiveness and the thermal stability are reduced. There is a fear.
For example, Tafmer P0480 (manufactured by Mitsui Chemicals, ethylene / propylene copolymer, “Tafmer” is a registered trademark), Tafmer A4070S (ethylene / butene copolymer, manufactured by Mitsui Chemicals, Inc., α-olefin copolymer resin, “ Commercially available products such as “Tuffmer” are registered trademarks).
本発明に使用される粘着付与剤としては、特に限定されないが、例えば、脂肪族系炭化水素樹脂、脂環族系炭化水素樹脂、芳香族系炭化水素樹脂、スチレン系樹脂、ポリテルペン系樹脂、ロジン系樹脂などの石油樹脂や、これらの変生物が挙げられ、これらを１種または２種以上組み合わせて使用することができる。変性物としては、特に限定しないが、例えば、水素添加、不均化、２量化、エステル化などの変性手段を施したものが挙げられ、水添（水素添加）石油樹脂が特に好ましい。
前記脂肪族系炭化水素樹脂としては、特に限定されず、例えば、１−ブテン、イソブチレン、ブタジエン、ペンテン、イソプレン、ピペリジン、１，３−ペンタジエンなどのＣ４〜Ｃ５のモノまたはジオレフィンを主成分とする重合体などが挙げられる。
前記脂環族系炭化水素樹脂としては、特に限定されず、例えば、Ｃ４〜Ｃ５留分中の非環式ジエン成分を環化２量体化させ、この２量体モノマーを重合させた樹脂や、シクロペンタジエンなどの環化モノマーを重合させた樹脂、芳香族炭化水素樹脂を核内水添させた樹脂などが挙げられる。
前記芳香族系炭化水素樹脂としては、特に限定されず、例えば、ビニルトルエン、インデン、α−メチルスチレン、シクロペンタジエンなどのＣ９〜Ｃ１０のビニル芳香族炭化水素を主成分とした樹脂などが挙げられる。
前記スチレン系樹脂としては、特に限定されず、例えば、スチレン、ビニルトルエン、α−メチルスチレン、イソプロペニルトルエンなどの重合体が挙げられる。
前記ポリテルペン系樹脂としては、特に限定されず、例えば、α−ピネン重合体、β−ピネン重合体、ジペンテン重合体、テルペン−フェノール重合体、α−ピネン−フェノール重合体などが挙げられる。
前記ロジン系樹脂としては、特に限定されず、例えば、ガムロジン、ウッドロジン、トール油などのロジンが挙げられる。
The tackifier used in the present invention is not particularly limited, and examples thereof include aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, aromatic hydrocarbon resins, styrene resins, polyterpene resins, and rosins. Petroleum resins such as resin and their metamorphs can be mentioned, and these can be used alone or in combination of two or more. Although it does not specifically limit as a modified | denatured thing, For example, what gave modification | denaturation means, such as hydrogenation, disproportionation, dimerization, esterification, is mentioned, A hydrogenated (hydrogenated) petroleum resin is especially preferable.
The aliphatic hydrocarbon resin is not particularly limited, and for example, C4 to C5 mono- or diolefin such as 1-butene, isobutylene, butadiene, pentene, isoprene, piperidine, 1,3-pentadiene and the like as a main component. And the like.
The alicyclic hydrocarbon resin is not particularly limited. For example, a resin obtained by cyclizing and dimerizing an acyclic diene component in a C4 to C5 fraction and polymerizing the dimer monomer may be used. And a resin obtained by polymerizing a cyclized monomer such as cyclopentadiene, a resin obtained by hydrogenating an aromatic hydrocarbon resin, and the like.
The aromatic hydrocarbon resin is not particularly limited, and examples thereof include resins mainly composed of C9 to C10 vinyl aromatic hydrocarbons such as vinyltoluene, indene, α-methylstyrene, and cyclopentadiene. .
The styrene resin is not particularly limited, and examples thereof include polymers such as styrene, vinyl toluene, α-methyl styrene, and isopropenyl toluene.
The polyterpene resin is not particularly limited, and examples thereof include an α-pinene polymer, a β-pinene polymer, a dipentene polymer, a terpene-phenol polymer, and an α-pinene-phenol polymer.
The rosin resin is not particularly limited, and examples thereof include rosins such as gum rosin, wood rosin and tall oil.
また、粘着付与剤としては、前記したように、水添石油樹脂が好ましく、特に、ジシクロペンタジエン（ＤＣＰＤ）・芳香族共重合系の水添石油樹脂、水添Ｃ９石油樹脂、水添Ｃ５石油樹脂がより好ましい。なお、ジシクロペンタジエン（ＤＣＰＤ）・芳香族共重合系の水添石油樹脂とは、一般的に、シクロペンタジエン系化合物と芳香族化合物を共重合し、得られる共重合体に水素添加した、水素添加石油樹脂である。
例えば、イーストタックＣ１１５Ｗ（水添Ｃ５石油樹脂、イーストマンケミカル社製商品名）、アルコンＭ１００、アルコンＰ１１５、アルコンＳＭ−１０（水添Ｃ９石油樹脂、荒川化学工業株式会社製商品名、「アルコン」は登録商標）、アイマーブＰ１００、アイマーブＰ１２５、アイマーブＰ１４０、アイマーブＳ１００、アイマーブＳ１１０（ジシクロペンタジエン（ＤＣＰＤ）・芳香族共重合系の水添石油樹脂、出光興産株式会社製商品名、「アイマーブ」は登録商標）等市販のものが使用できる。
また、樹脂組成物中の粘着付与剤含有量は、１０〜６０質量％であり、２５〜５０質量％が好ましく、４０〜５０質量％がより好ましい。含有量が１０質量％未満の場合は、糸曳き抑制効果の低下や接着性の低下などが発生するおそれがあり、また、５０質量％を超えると低温接着性の低下などが発生するおそれがある。
さらに、粘着付与剤として、樹脂組成物中、ジシクロペンタジエン（ＤＣＰＤ）・芳香族共重合系の水添石油樹脂を０〜３０質量％、水添Ｃ９石油樹脂を１０〜５０質量％、水添Ｃ５石油樹脂を０〜２０質量％の割合で含むことが特に好ましい。
As described above, hydrogenated petroleum resins are preferable as the tackifier, and in particular, dicyclopentadiene (DCPD) / aromatic copolymer hydrogenated petroleum resins, hydrogenated C9 petroleum resins, and hydrogenated C5 petroleum. A resin is more preferable. The dicyclopentadiene (DCPD) / aromatic copolymer-based hydrogenated petroleum resin is generally a hydrogenated petroleum resin obtained by copolymerizing a cyclopentadiene compound and an aromatic compound and hydrogenating the resulting copolymer. It is an added petroleum resin.
For example, East tack C115W (hydrogenated C5 petroleum resin, trade name manufactured by Eastman Chemical Co., Ltd.), Alcon M100, Alcon P115, Alcon SM-10 (hydrogenated C9 petroleum resin, trade name manufactured by Arakawa Chemical Industries, Ltd., “ALCON” Is a registered trademark), Imabe P100, Imabe P125, Imabe P140, Imabe S100, Imabe S110 (dicyclopentadiene (DCPD) / aromatic copolymer hydrogenated petroleum resin, trade name of Idemitsu Kosan Co., Ltd., “Imabe” is A commercially available product such as a registered trademark can be used.
Moreover, tackifier content in a resin composition is 10-60 mass%, 25-50 mass% is preferable and 40-50 mass% is more preferable. When the content is less than 10% by mass, there is a possibility that the effect of suppressing stringing or a decrease in adhesiveness may occur, and when the content exceeds 50% by mass, there may be a decrease in low-temperature adhesiveness. .
Further, as a tackifier, in the resin composition, 0-30% by mass of dicyclopentadiene (DCPD) / aromatic copolymer-based hydrogenated petroleum resin, 10-50% by mass of hydrogenated C9 petroleum resin, hydrogenated. It is particularly preferable to contain C5 petroleum resin in a proportion of 0 to 20% by mass.
本発明の樹脂組成物は、さらに酸化防止剤を含んでいてもよい。使用される酸化防止剤としては、特に限定しないが、フェノール系、有機イオウ系、ヒンダードフェノール系、ヒンダードアミン系、有機リン系ヒンダートフェノール系、アミン系等が挙げられる。例えば、フェノール系酸化防止剤としてペンタエリトリイルテトラキス−３−（３，５−ジ−ターシャリーブチル−４−ヒドロキシフェニル）プロピオネート（ＳＯＮＧＮＯＸ１０１０、ＳＯＮＧＷＯＮ ＩＮＤ．製商品名）及びｎ−オクタデシル−３−（３，５−ジ−ターシャリーブチル−４−ヒドロキシフェニル）プロピオネート（ＳＯＮＧＮＯＸ１０７６、ＳＯＮＧＷＯＮ ＩＮＤ．製商品名）と、リン系酸化防止剤としてトリス（２，４−ジ−ターシャリーブチルフェニル）ホスファイト（ＳＯＮＧＮＯＸ１６８０、ＳＯＮＧＷＯＮ ＩＮＤ．製商品名）等が挙げられる。また、これらを１種または２種以上組み合わせて使用することができる。
また、樹脂組成物中の酸化防止剤の含有量は、０．１〜２質量％が好ましく、０．２〜１質量％がより好ましい。含有量が、０．１〜２質量％の範囲内にあることにより、熱安定性等がより一層向上する。
The resin composition of the present invention may further contain an antioxidant. Although it does not specifically limit as antioxidant used, A phenol type, an organic sulfur type, a hindered phenol type, a hindered amine type, an organic phosphorus type hindered phenol type, an amine type etc. are mentioned. For example, pentaerythriyltetrakis-3- (3,5-di-tertiarybutyl-4-hydroxyphenyl) propionate (trade name of SONGNOX1010, manufactured by SONGWON IND.) And n-octadecyl-3- (3,5-di-tertiarybutyl-4-hydroxyphenyl) propionate (SONGNOX1076, a product name made by SONGWON IND.) And tris (2,4-di-tertiarybutylphenyl) phosphite as a phosphorus-based antioxidant (SONGNOX1680, SONGWON IND. Trade name) and the like. Moreover, these can be used 1 type or in combination of 2 or more types.
Moreover, 0.1-2 mass% is preferable and, as for content of antioxidant in a resin composition, 0.2-1 mass% is more preferable. When the content is in the range of 0.1 to 2% by mass, the thermal stability and the like are further improved.
さらに、樹脂組成物には、必要に応じて、高級脂肪酸、高級脂肪酸金属塩等の離型剤、カップリング剤、シリコーンオイルやシリコーンゴム粉末等の応力緩和剤、カーボンブラック等の顔料または染料、紫外線吸収剤、界面活性剤、ノンハロゲン、ノンアンチモンの難燃剤等を適量配合しても良い。 Further, the resin composition may include a release agent such as higher fatty acid and higher fatty acid metal salt, a coupling agent, a stress relaxation agent such as silicone oil or silicone rubber powder, a pigment or dye such as carbon black, if necessary, An appropriate amount of an ultraviolet absorber, a surfactant, a non-halogen, a non-antimony flame retardant, or the like may be blended.
本発明の樹脂組成物は、各種原材料を均一に分散混合できるのであれば、いかなる手法を用いても調製できるが、一般的な手法として、所定の配合量の原材料をミキサー等によって十分混合した後、ミキシングロール、押出機、らいかい機、プラネタリミキサ等によって混合又は溶融混練し、必要に応じて脱泡する方法等を挙げることができる。 The resin composition of the present invention can be prepared by any method as long as various raw materials can be uniformly dispersed and mixed. As a general method, however, after a predetermined amount of raw materials are sufficiently mixed by a mixer or the like And a method of mixing or melt-kneading with a mixing roll, an extruder, a raking machine, a planetary mixer, etc., and defoaming if necessary.
以下、本発明の好適な実施例について説明するが、本発明はこれらの実施例に限定されるものではない。
（実施例１〜５、比較例１〜３）
表１に示した配合に従って、ホットメルト樹脂組成物を調整した。なお、表１中の配合単位は、質量部である。
この調合には内容量が１Ｌの加熱ニーダーを使用した。各成分の全配合量が５００ｇになるように１８０℃に設定した加熱ニーダーに投入し、十分に溶融させた。その後、樹脂組成物が均一になるまで混練りした。混練りの回転数は、最大６０ｒｐｍに至るまで除々に上げた。十分に混練り後、溶融した樹脂組成物を取り出し、室温（２５℃）にて冷却固化させた。
得られたホットメルト樹脂組成物について、粘度、糸曳き性、低温接着性、耐クリープ性、熱安定性を下記に示す方法により評価した。結果を表２に示した。
EXAMPLES Hereinafter, although the suitable Example of this invention is described, this invention is not limited to these Examples.
(Examples 1-5, Comparative Examples 1-3)
A hot melt resin composition was prepared according to the formulation shown in Table 1. In addition, the compounding unit in Table 1 is a mass part.
A heating kneader having an internal volume of 1 L was used for this preparation. It put into the heating kneader set to 180 degreeC so that the total compounding quantity of each component might be 500 g, and it was fully fuse | melted. Then, it knead | mixed until the resin composition became uniform. The kneading speed was gradually increased up to a maximum of 60 rpm. After sufficiently kneading, the molten resin composition was taken out and cooled and solidified at room temperature (25 ° C.).
The obtained hot melt resin composition was evaluated for viscosity, stringiness, low temperature adhesion, creep resistance, and thermal stability by the following methods. The results are shown in Table 2.
ウルトラセン（ＵＥ）７３５；ＶＡ含有率２８質量％、メルトフローレート（ＭＦＲ）＝１０００、環球法軟化点８５、東ソー株式会社製商品名
ウルトラセン（ＵＥ）６８４；ＶＡ含有率２０質量％、メルトフローレート（ＭＦＲ）＝２０００、環球法軟化点８０東ソー株式会社製商品名
タフマーＰ０４８０；三井化学株式会社製商品名、エチレン・プロピレン系α−オレフィン共重体樹脂
タフマーＡ４０７０Ｓ；三井化学株式会社製商品名、エチレン・ブテン系α−オレフィン共重体樹脂
イーストタックＣ１１５Ｗ；イーストマンケミカル社製商品名、水添Ｃ５石油樹脂
アルコンＰ１００；荒川化学工業株式会社製商品名、水添Ｃ９石油樹脂、
アイマーブＰ１００；出光興産株式会社製商品名、ジシクロペンタジエン（ＤＣＰＤ）・芳香族共重合系の水添石油樹脂
サゾールＨ１；サゾール社製商品名、フィッシャートロピックスワックス
Imabu P100; trade name, manufactured by Idemitsu Kosan Co., Ltd., dicyclopentadiene (DCPD) / aromatic copolymer-based hydrogenated petroleum resin Sazole H1; trade name, manufactured by Sazol, Fischer Tropics wax
（粘度）
日本接着剤工業会規格ＪＡＩ７（ホットメルト接着剤試験方法）に準じて各ホットメルト樹脂組成物の粘度（溶融粘度）をＢ法、測定温度１８０℃で測定した。
(viscosity)
Viscosity (melt viscosity) of each hot-melt resin composition was measured at Method B at a measurement temperature of 180 ° C. in accordance with Japan Adhesive Industry Association Standard JAI7 (Test Method for Hot Melt Adhesive).
（糸曳き性）
糸曳き性については、ホットメルトガンの先端から距離３０ｃｍの所に被着体（段ボール）を垂直に配置し、その間に落下物を捕獲するための板状の受け皿を敷いておく。２０℃の無風雰囲気下、下記条件で、交流電源シーケンサーを用いて、ホットメルト樹脂組成物を６００ショット／５分の条件で間欠塗布し、受け皿上に溜まった落下物の質量を測定した。すなわち、落下物の質量が重く、落下物が糸状であれば塗布時の糸曳き性が大きく、落下物の質量が軽く、落下物が瞬時に粒状になれば塗布時の糸曳き性が小さいと判定した。
ホットメルトアプリケーター：商品名「ノードソンプロブルー４」（ノードソン社製）
ホットメルトガン：Ｈ−２００ガン（ノズル径：１６／１０００インチ、ノズル：１オリフィスノズル）
吐出エアー圧力：２．５ｋｇ
タンク、ホースおよびガンの温度：１７０℃
(Threading property)
For stringing properties, an adherend (corrugated cardboard) is vertically arranged at a distance of 30 cm from the tip of the hot melt gun, and a plate-shaped receiving tray for catching falling objects is placed between them. The hot melt resin composition was intermittently applied under the conditions of 600 shots / 5 minutes using an AC power supply sequencer under a 20 ° C. no wind atmosphere under the following conditions, and the mass of the fallen matter accumulated on the tray was measured. That is, if the fallen object is heavy and the fallen object is thread-like, the stringing property during application is large.If the fallen object is light and the fallen object becomes granulated instantaneously, the stringing property during application is small. Judged.
Hot melt applicator: Trade name “Nordson Pro Blue 4” (manufactured by Nordson)
Hot melt gun: H-200 gun (nozzle diameter: 16/1000 inch, nozzle: 1 orifice nozzle)
Discharge air pressure: 2.5kg
Tank, hose and gun temperature: 170 ° C
（低温接着性）
ホットメルト樹脂組成物を段ボールに３±０．３ｇ／ｍ塗付し（塗布温度１８０±２℃）、オープンタイム２秒をとったのち、同種の段ボールと貼り合わせて荷重１９．６Ｎで圧締する。セットタイム２秒をとったのち、圧締を開放した。接着試験片を５℃環境下で１２時間以上放置し、接着試験片の接着部を剥離形式で、負荷荷重９．８Ｎで破壊させたとき、８０％以上の接着試験片で、段ボールが８０〜１００％材質破壊した場合を「◎」とし、段ボールが６０〜７９％材質破壊した場合を「○」とし、段ボールが３０〜５９％材質破壊の場合を「△」とし、それ以外は接着性不良「×」とする。
(Low temperature adhesion)
Apply 3 ± 0.3g / m of hot melt resin composition to corrugated cardboard (application temperature 180 ± 2 ° C), take 2 seconds of open time, and then bond with the same kind of corrugated cardboard and press with a load of 19.6N To do. After a set time of 2 seconds, the clamping was released. When the adhesion test piece is left in a 5 ° C. environment for 12 hours or more, and the bonded portion of the adhesion test piece is peeled off at a load of 9.8 N, the adhesion test piece is 80% or more and the cardboard is 80 to 80%. 100% material failure is indicated as “◎”, corrugated cardboard is 60-79% material failure is indicated as “◯”, and corrugated cardboard is 30-59% material failure is indicated as “△”. “×”.
（耐クリープ性）
段ボール（２×２５×１００ｍｍ）に１８０℃に加熱溶融したホットメルト樹脂組成物を直径４ｍｍのビード状で２５ｍｍ幅方向に塗布し２秒間放置したのちに、もう一方の段ボールを重ね合わせて、９．８×１０４Ｐａで５秒の条件で圧締した。貼り合わせ後、室温（２５℃）に１日放置したのち、５０℃雰囲気中０．９８Ｎ／２５ｍｍの荷重を加え、落下時間（ｈｒ）を測定した。
(Creep resistance)
A hot melt resin composition heated and melted at 180 ° C. on cardboard (2 × 25 × 100 mm) was applied in a 25 mm width direction in the form of a bead with a diameter of 4 mm and left to stand for 2 seconds. Compressed at 8 × 10 4 Pa for 5 seconds. After bonding, the substrate was allowed to stand at room temperature (25 ° C.) for 1 day, then a load of 0.98 N / 25 mm was applied in a 50 ° C. atmosphere, and the drop time (hr) was measured.
（熱安定性）
ホットメルト樹脂組成物を２５０ｍｌ容のサンプル瓶に１５０ｇ取り、加熱して１８０℃で３３６時間維持した。このときの状態の変化を観察して、下記基準に従って、ホットメルト樹脂組成物の熱安定性を評価した。
「◎」：状態の変化なし
「○」：わずかに分離がみられるが、実用上許容される範囲である
「×」：ゲル化物、炭化物などの発生あり
(Thermal stability)
150 g of the hot-melt resin composition was placed in a 250 ml sample bottle, heated and maintained at 180 ° C. for 336 hours. The change in the state at this time was observed, and the thermal stability of the hot melt resin composition was evaluated according to the following criteria.
“◎”: No change in state “○”: Slight separation, but in a practically acceptable range “×”: Generation of gelled products, carbides, etc.
表２に示したように、α―オレフィン共重体樹脂を含まない比較例１は、糸曳き性に劣り（糸曳き量が多い）、α―オレフィン共重体樹脂の含有量が５質量％を超える比較例２は、低温接着性や熱安定性に劣り、エチレン酢酸ビニル共重合樹脂（ＥＶＡ）の含有量が５０質量％を超える比較例３は、糸曳き性や耐クリープ性に劣ることがわかる。それに対し、本発明の実施例１〜５は、粘度が比較的小さく、また、糸曳き性、低温接着性、耐クリープ性、熱安定性いずれも優れていることがわかる。
本発明によって、段ボールに対する接着性に優れた、糸曳きが少なく、熱安定性良好な、段ボール用ホットメルト樹脂組成物を提供することができた。
As shown in Table 2, Comparative Example 1 containing no α-olefin copolymer resin is inferior in stringiness (a large amount of stringing), and the content of α-olefin copolymer resin exceeds 5% by mass. Comparative Example 2 is inferior in low-temperature adhesiveness and thermal stability, and Comparative Example 3 in which the content of ethylene vinyl acetate copolymer resin (EVA) exceeds 50% by mass is inferior in stringiness and creep resistance. . On the other hand, Examples 1-5 of this invention have a comparatively small viscosity, and it turns out that all are excellent in stringing property, low temperature adhesiveness, creep resistance, and heat stability.
According to the present invention, it was possible to provide a hot melt resin composition for corrugated cardboard having excellent adhesion to corrugated cardboard, little stringing, and good thermal stability.
Claims (5)
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| JP2012198404A JP6028998B2 (en) | 2012-09-10 | 2012-09-10 | Corrugated hot melt resin composition |
| CN201380043067.7A CN104704075B (en) | 2012-09-10 | 2013-09-06 | Corrugated board thermoplastic resin compositions |
| PCT/JP2013/074131 WO2014038671A1 (en) | 2012-09-10 | 2013-09-06 | Hot-melt resin composition for corrugated cardboard |
| TW102132626A TW201420707A (en) | 2012-09-10 | 2013-09-10 | Hot-melt resin composition for corrugated cardboard |
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| JP2016138222A (en) * | 2015-01-29 | 2016-08-04 | 日立化成株式会社 | Hot-melt adhesive composition |
| JP2017128687A (en) * | 2016-01-22 | 2017-07-27 | 東洋インキＳｃホールディングス株式会社 | Hot-melt composition, and cap material and food container formed by using the same |
| JP2021004327A (en) * | 2019-06-27 | 2021-01-14 | 東洋インキＳｃホールディングス株式会社 | Adhesive resin composition, sheet, lid material, member set for hermetic vessel and vessel |
| US11613675B2 (en) * | 2019-01-31 | 2023-03-28 | Synthomer Adhesive Technologies Llc | Packaging adhesives comprising low volatile tackifier compositions |
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| MY175621A (en) * | 2017-10-13 | 2020-07-02 | Kong Wai Ming Bryan | Composition of polymeric bonding material |
| KR102120589B1 (en) * | 2019-06-17 | 2020-06-08 | 이흥수 | Adhesive composition for furniture molding having excellent adhesion and antioxidant property and material for furniture molding |
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| CN104704075B (en) | 2016-08-24 |
| CN104704075A (en) | 2015-06-10 |
| JP6028998B2 (en) | 2016-11-24 |
| TW201420707A (en) | 2014-06-01 |
| WO2014038671A1 (en) | 2014-03-13 |
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