WO2022145967A1 - Ethylene-vinyl acetate composite resin composition having excellent melt elasticity - Google Patents
Ethylene-vinyl acetate composite resin composition having excellent melt elasticity Download PDFInfo
- Publication number
- WO2022145967A1 WO2022145967A1 PCT/KR2021/020041 KR2021020041W WO2022145967A1 WO 2022145967 A1 WO2022145967 A1 WO 2022145967A1 KR 2021020041 W KR2021020041 W KR 2021020041W WO 2022145967 A1 WO2022145967 A1 WO 2022145967A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- vinyl acetate
- ethylene vinyl
- composite resin
- resin composition
- elastomer
- Prior art date
Links
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 title claims abstract description 135
- 239000000805 composite resin Substances 0.000 title claims abstract description 86
- 239000000203 mixture Substances 0.000 title claims abstract description 85
- 239000005038 ethylene vinyl acetate Substances 0.000 title claims abstract description 63
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 title abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 60
- 239000011347 resin Substances 0.000 claims abstract description 60
- 239000006260 foam Substances 0.000 claims description 48
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 25
- 238000004132 cross linking Methods 0.000 claims description 15
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 claims description 15
- 239000003431 cross linking reagent Substances 0.000 claims description 14
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- 239000004088 foaming agent Substances 0.000 claims description 12
- 239000010954 inorganic particle Substances 0.000 claims description 12
- -1 styrene-ethylene-propylene-styrene Chemical class 0.000 claims description 12
- 239000004156 Azodicarbonamide Substances 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 10
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 10
- 229920001971 elastomer Polymers 0.000 claims description 9
- 239000000806 elastomer Substances 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- 229920002943 EPDM rubber Polymers 0.000 claims description 6
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 6
- 239000005062 Polybutadiene Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical group C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 229920003049 isoprene rubber Polymers 0.000 claims description 6
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 6
- 229920002857 polybutadiene Polymers 0.000 claims description 6
- 229920006345 thermoplastic polyamide Polymers 0.000 claims description 6
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 6
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 4
- 229920002397 thermoplastic olefin Polymers 0.000 claims description 4
- YUJXLBCNMLSZFM-UHFFFAOYSA-N (2-azidophenyl)-phenyldiazene Chemical compound [N-]=[N+]=NC1=CC=CC=C1N=NC1=CC=CC=C1 YUJXLBCNMLSZFM-UHFFFAOYSA-N 0.000 claims description 3
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 claims description 3
- OXYKVVLTXXXVRT-UHFFFAOYSA-N (4-chlorobenzoyl) 4-chlorobenzenecarboperoxoate Chemical compound C1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1 OXYKVVLTXXXVRT-UHFFFAOYSA-N 0.000 claims description 3
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 3
- JJRDRFZYKKFYMO-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-ylperoxy)butane Chemical compound CCC(C)(C)OOC(C)(C)CC JJRDRFZYKKFYMO-UHFFFAOYSA-N 0.000 claims description 3
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 claims description 3
- ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical group CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- CEALXSHFPPCRNM-UHFFFAOYSA-L disodium;carboxylato carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OC([O-])=O CEALXSHFPPCRNM-UHFFFAOYSA-L 0.000 claims description 3
- 238000010894 electron beam technology Methods 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- BXIQXYOPGBXIEM-UHFFFAOYSA-N butyl 4,4-bis(tert-butylperoxy)pentanoate Chemical compound CCCCOC(=O)CCC(C)(OOC(C)(C)C)OOC(C)(C)C BXIQXYOPGBXIEM-UHFFFAOYSA-N 0.000 claims description 2
- 239000011342 resin composition Substances 0.000 claims description 2
- JZUFKLXOESDKRF-UHFFFAOYSA-N Chlorothiazide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC2=C1NCNS2(=O)=O JZUFKLXOESDKRF-UHFFFAOYSA-N 0.000 claims 1
- 238000005187 foaming Methods 0.000 description 22
- 230000000704 physical effect Effects 0.000 description 17
- 210000004027 cell Anatomy 0.000 description 16
- 239000002131 composite material Substances 0.000 description 15
- 230000008569 process Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000155 melt Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 210000000497 foam cell Anatomy 0.000 description 6
- 235000010216 calcium carbonate Nutrition 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- UHKPXKGJFOKCGG-UHFFFAOYSA-N 2-methylprop-1-ene;styrene Chemical compound CC(C)=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 UHKPXKGJFOKCGG-UHFFFAOYSA-N 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000004604 Blowing Agent Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920006124 polyolefin elastomer Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 2
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229940070710 valerate Drugs 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
Definitions
- the present invention relates to an ethylene vinyl acetate-elastomer composite resin composition comprising a high expansibility ethylene vinyl acetate copolymer resin. More specifically, it relates to an ethylene vinyl acetate-elastomer composite resin composition having an expansion ratio of 50% or more using ethylene vinyl acetate having an expansion ratio of 80% or more using melt elasticity control.
- ethylene vinyl acetate copolymer the most representative cushion material for sports shoes, which plays a key part in the function of sports shoes, is easy to process at low temperatures, easy to crosslink, and has excellent foam cell formation. , as a functional sneaker material, is being continuously developed.
- thermoplastic elastomer may exhibit improved physical properties by combining the advantages of an ethylene vinyl acetate copolymer and a thermoplastic elastomer, but it is difficult to meet the expected physical properties when the two materials are simply mixed.
- the expansion rate must be high in a certain foam or thermal processing process such as foaming, but conventional ethylene vinyl acetate copolymer resins do not exhibit sufficient expansion properties.
- thermoplastic elastomer used together with the conventional ethylene vinyl acetate copolymer has low melt elasticity, so that the composite material mixed with the two components does not show sufficient foaming properties during the expansion process or during the foaming process, and the foaming properties are poor. Even if it appears, it is difficult to have a uniform cell structure, so there is a limit to its use.
- the expansion ratio of the composite material itself should be 50% or more, preferably 80% or more.
- An object of the present invention is to provide an ethylene vinyl acetate-elastomer composite resin composition having a high expansion ratio and forming a uniform foamed cell structure.
- Another object of the present invention is to provide an ethylene vinyl acetate-elastomer composite resin composition in which processability can be significantly improved when processed with a resin having a high melting point, such as a thermoplastic elastomer.
- an object of the present invention is to provide a high expansion ethylene vinyl acetate copolymer resin that is excellent in foamability and elasticity, and can provide a foam having a smooth surface.
- the present invention can provide an ethylene-vinyl acetate-elastomer composite resin composition with an expansion rate of 50% or more, which is prepared by including a thermoplastic elastomer in a high expansibility ethylene vinyl acetate copolymer resin having an expansion rate of 80% or more.
- the composite resin composition may include 1 to 100 parts by weight of the thermoplastic elastomer based on 100 parts by weight of the high expansibility ethylene vinyl acetate copolymer resin having the expansion coefficient of 80% or more.
- the expansion coefficient of the high expansibility ethylene vinyl acetate copolymer resin may include 100% or more.
- the expansion coefficient of the high expansibility ethylene vinyl acetate copolymer resin may include 130% or more.
- the ethylene vinyl acetate-elastomer composite resin composition may have an expansion rate of 50% or more.
- the ethylene vinyl acetate-elastomer composite resin composition may have an expansion rate of 80% or more.
- the high expansion ethylene vinyl acetate copolymer resin is prepared by modifying the ethylene vinyl acetate copolymer resin by any one method selected from thermal crosslinking, radiation crosslinking, X-ray crosslinking, and electron beam crosslinking.
- thermal crosslinking radiation crosslinking
- X-ray crosslinking X-ray crosslinking
- electron beam crosslinking may include
- thermoplastic elastomer may include radically modifiable ones.
- the thermoplastic elastomer is a styrene-butadiene-styrene resin, a styrene-isobutyrene-styrene resin, a styrene-ethylene-butyrene-styrene resin, a styrene-ethylene-propylene-styrene resin, a styrene- Any one or two selected from isoprene-styrene resin, isoprene rubber, butadiene rubber, chloroprene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, thermoplastic polyolefin elastomer, thermoplastic polyester elastomer, thermoplastic polyamide elastomer and thermoplastic polyurethane It may include more than one.
- the ethylene vinyl acetate-elastomer composite resin foam contains 0.1 to 3 parts by weight of the crosslinking agent, 1 to 20 parts by weight of the foaming agent, and 0.1 to 20 parts by weight of the inorganic particles based on 100 parts by weight of the ethylene vinyl acetate-elastomer composite resin composition can
- the crosslinking agent is di-t-butyl peroxide, di-t-amyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane-3,2,2'-bis(t-butylperoxyisopropyl)benzene, 1, 1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(t-butylperoxy)valerate, benzoyl peroxide, p-chlorobenzoyl peroxide , t-butylperoxybenzoate and 2,5-dimethyl-2,5-di(t-benzoylperoxy)hexane, or a mixture thereof.
- the inorganic particles may include any one or a mixture of two or more selected from calcium carbonate, zinc oxide, calcium oxide, magnesium oxide, silica, alumina and titanium dioxide.
- the ethylene vinyl acetate-elastomer composite resin composition according to the present invention has an advantage in that it has a high expansion ratio and can form a uniform foamed cell structure.
- the ethylene vinyl acetate-elastomer composite resin composition according to the present invention can provide a composition having an expansion rate of 50% or more, more specifically, 80% or more (in a state where the blowing agent is not included) by itself.
- the ethylene vinyl acetate-elastomer composite resin composition according to the present invention exhibits significantly improved processability due to excellent foamability, and has the advantage of being applicable to various facilities.
- the foam according to the present invention has the advantage of having a smooth surface without surface defects while being excellent in flexibility, elasticity and durability.
- expansion ratio means the expansion ratio of only the resin or composite resin composition in a state that does not contain a foaming agent.
- 'modification' refers to crosslinking chemically or physically (eg, ultraviolet rays, radiation, etc.).
- the present invention relates to an ethylene vinyl acetate-elastomer composite resin composition
- the present invention relates to an ethylene vinyl acetate-elastomer composite resin composition comprising ethylene vinyl acetate having an expansion rate of 80% and a thermoplastic elastomer.
- the composite resin composition may include 1 to 100 parts by weight of the thermoplastic elastomer based on 100 parts by weight of the high expansibility ethylene vinyl acetate copolymer resin having an expansion rate of 80% or more.
- the present invention provides an ethylene vinyl acetate copolymer resin and a thermoplastic elastomer having an expansion rate of 50% or more, which are prepared by including 1 to 100 parts by weight of a thermoplastic elastomer, based on 100 parts by weight of a high expansibility ethylene vinyl acetate copolymer resin having an expansion rate of 80% or more.
- the ethylene vinyl acetate-elastomer composite resin composition of the present invention includes a high expansion ethylene vinyl acetate copolymer resin and a thermoplastic elastomer having an expansion ratio of 50% or more under the above conditions. It is more preferred because it can solve the problem of low uniformity of the foamed cell structure and provide an ethylene vinyl acetate-elastomer composite resin composition having remarkably excellent foamability and elasticity.
- the inventors of the present invention studied to have an independent and uniform cell structure in the foaming process, such as functional shoes. It was discovered that the intended physical properties could be secured, and thus the present invention was completed.
- the expansion coefficient of the high expansion ethylene vinyl acetate copolymer resin may be 100% or more, more 130% or more, and more preferably 180% or more.
- the expansion rate of the ethylene vinyl acetate-elastomer composite resin composition may be 50% or more, preferably 80% or more, and more preferably 150% or more.
- the vinyl acetate content in the ethylene vinyl acetate may be 10 to 60%, preferably 15 to 50%, more preferably 20 to 40%, but is not limited thereto.
- the melt index (190 °C 2.16 kg) of the ethylene vinyl acetate may be 0.1 to 8.0 g/10min, preferably 0.2 to 6.0 g/10min, more preferably 0.3 to 4.0 g/10min. may be, but is not limited thereto.
- the high expansion ethylene vinyl acetate copolymer resin of the present invention has a melt index and a vinyl acetate content in the above ranges and an expansion ratio in the above ranges, an ethylene vinyl acetate-elastomer composite resin composition having remarkably excellent foamability and elasticity will be realized.
- the high expansion ethylene vinyl acetate copolymer resin satisfies the above expansion ratio range, and by preparing the ethylene vinyl acetate-elastomer composite resin composition, the mechanical properties and chemical properties between the components are well combined, so that the melt elasticity is further improved.
- the ethylene vinyl acetate-elastomer composite resin composition it is possible to form a foam having a very uniform cell structure.
- thermoplastic elastomer itself when manufacturing a composite material using a thermoplastic elastomer based on the conventional ethylene vinyl acetate copolymer.
- the ethylene vinyl acetate-elastomer composite resin composition using the acetate copolymer exhibits excellent foamability even when a high content of the thermoplastic elastomer is used together, and has the advantage of having a smooth and smooth surface without any defect problems.
- thermoplastic elastomer according to an aspect of the present invention is mixed with the high expansion ethylene vinyl acetate resin to improve the elasticity of the ethylene vinyl acetate-elastomer composite resin composition and lower the hardness and compression deformation to produce a high-functional composite material.
- styrene-butadiene-styrene resin styrene-butadiene-styrene, SBS
- styrene-isobutylene-styrene SIBS
- styrene-ethylene-butyrene-styrene resin styrene) -ethylene-butylene-styrene, SEBS
- styrene-ethylene-propylene-styrene SEPS
- SIS isoprene rubber (isoprene) rubber, IR), butadiene rubber (BR), chloroprene rubber (CR), ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM) ), thermoplastic polyolefin elastomers (POE), thermoplastic polyester elastomers (TPEE), thermoplastic polyamide elastomers (TPEE), thermoplastic polyamide elastomers (
- the ethylene vinyl acetate-elastomer composite resin composition contains 1 to 100 parts by weight of the thermoplastic elastomer, preferably 10 to 50 parts by weight, based on 100 parts by weight of the high expansion ethylene vinyl acetate copolymer resin. It may be preferable to obtain a composition having an expansion rate of 50% or more, but is not limited thereto.
- the high expansion ethylene vinyl acetate copolymer resin is prepared by any one method selected from thermal crosslinking of the ethylene vinyl acetate copolymer resin, radiation crosslinking, X-ray crosslinking, electron beam crosslinking, and the like. It may be an ethylene vinyl acetate copolymer resin composition, but is not limited thereto as long as it is a means capable of achieving an expansion rate of 80% or more.
- the high expansion ethylene vinyl acetate copolymer resin adjusted to have an expansion rate of 80% or more through the crosslinking method as described above. If an acetate copolymer resin is used, it can have the same effect as using the cross-linked high expansion ethylene vinyl acetate copolymer resin.
- the expansion rate of the high expansibility ethylene vinyl acetate copolymer resin is 80% or more, more preferably 100% More preferably, it may be 130% or more.
- thermoplastic elastomer In general, when an ethylene-vinyl acetate copolymer is foamed together with another thermoplastic elastomer to form a composite material, the melt elasticity of the thermoplastic elastomer is low, so foaming is not easy and the defect rate is increased.
- the ethylene vinyl acetate-elastomer composite resin composition of the present invention shows improved melt elasticity by essentially including a high expansion ethylene vinyl acetate copolymer resin having an expansion ratio within the above range. Accordingly, as well as having an excellent effect of uniformly foaming, the effect of producing a foam having a smooth surface and excellent appearance is very excellent, and it can be easily applied as a composite material in various fields including high-performance shoes.
- thermoplastic elastomer is styrene-butadiene-styrene resin (styrene-butadiene-styrene, SBS), styrene-isobutylene-styrene (SIBS), styrene-ethylene-butyrene-styrene resin (styrene) -ethylene-butylene-styrene, SEBS), styrene-ethylene-propylene-styrene (SEPS), styrene-isoprene-styrene (SIS), isoprene rubber (isoprene) rubber, IR), butadiene rubber (BR), chloroprene rubber (CR), ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM) ), a radical selected from thermoplastic polyolefin elastomers (POE), thermoplastic polyester elastomers (TPEE), thermoplastic
- the present invention is a high expansion ethylene vinyl acetate copolymer resin and thermoplastic elastomer in which the expansion ratio of the strand that has passed through the orifice having a diameter of 2.096 mm after being melted under the condition of 190 ° C. It relates to an ethylene vinyl acetate-elastomer composite resin foam prepared from a foaming composition comprising a foaming agent and a crosslinking agent in a vinyl acetate-elastomer composite resin composition.
- an ethylene vinyl acetate-elastomer composite resin foam foamed by further including a crosslinking agent, a foaming agent and inorganic particles in the ethylene vinyl acetate-elastomer composite resin composition More specifically, the ethylene vinyl acetate-elastomer composite resin foam contains 0.1 to 3 parts by weight of the crosslinking agent, 1 to 20 parts by weight of the foaming agent, and 0.1 parts by weight of the inorganic particles based on 100 parts by weight of the ethylene vinyl acetate-elastomer composite resin composition. Including to 20 parts by weight, ethylene vinyl acetate-elastomer composite resin foam to be prepared can be provided.
- the ethylene vinyl acetate-elastomer composite resin foam can be easily foamed without problems such as premature foaming, difficulty in forming open cells, and cell collapse during the foaming process. It has an excellent effect of having a smooth luster.
- the ethylene vinyl acetate-elastomer composite resin composition which is entered to prepare the ethylene vinyl acetate-elastomer composite resin foam, may be prepared by further including a foaming agent, a crosslinking agent, and inorganic particles.
- the blowing agent includes azodicarbonamide, azobisisobutyronitrile, diazoaminoazobenzene N,N′-dinitro-sopentamethylenetetramine p-toluenesulfonylhydrazide and p,p′-oxybis(benzene Sulfonyl hydrazide) p-toluene-sulfonyl semicarba, sodium dicarbonate, etc. may be used, but the present invention is not limited thereto.
- any one or a mixture of two or more selected from the blowing agent compound It may be used by mistake, but is not limited thereto.
- the foaming agent achieves uniform dispersion and stably forms a foamed cell structure, and the desired expansion ratio and mechanical properties can be achieved. there is effective
- the crosslinking agent is to further improve the melt elasticity of the ethylene vinyl acetate-elastomer composite resin composition during foaming, and specific examples include di-t-butyl peroxide, di-t-amyl peroxide, t-butylcumyl peroxide.
- Seed dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane,2,5-dimethyl-2,5-di(t-butylperoxy)hexane-3,2 ,2'-bis(t-butylperoxyisopropyl)benzene,1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(t -Butyl peroxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, t-butylperoxybenzoate and any one selected from 2,5-dimethyl-2,5-di (t-benzoylperoxy)hexane
- One or a mixture thereof may be used, but is not limited thereto.
- the content of the crosslinking agent may be 0.1 to 3 parts by weight, specifically 0.2 to 2 parts by weight, more specifically 0.5 to 1 parts by weight, based on 100 parts by weight of the ethylene vinyl acetate-elastomer composite resin composition, but is not limited thereto.
- the ethylene vinyl acetate-elastomer composite resin composition may have sufficient viscoelasticity to withstand the gas pressure generated by the decomposition of the foaming agent during the foaming process.
- the inorganic particles may be, for example, any one or a mixture of two or more selected from calcium carbonate, zinc oxide, calcium oxide, magnesium oxide, silica, alumina and titanium dioxide.
- a mixture of calcium carbonate and titanium dioxide may be used to promote crosslinking and foaming when manufacturing a foam, but is not limited thereto.
- the content of the inorganic particles may be 0.1 to 20 parts by weight, specifically 1 to 18 parts by weight, and more specifically 4 to 15 parts by weight, based on 100 parts by weight of the ethylene vinyl acetate-elastomer composite resin composition, but is not limited thereto.
- the ethylene vinyl acetate-elastomer composite resin composition contains a thermoplastic elastomer having an expansion ratio of less than 50%, as it exhibits a high expansion ratio within the above range, a uniform foamed cell structure can be formed during foaming, and open The effect of stably manufacturing a foam without defects due to cell collapse and the like is excellent.
- the foam composition may further include a dispersant, a viscosity modifier, a colorant, an antioxidant, a UV stabilizer, and an anti-blocking agent, which are commonly used in a range that does not impair the object of the present invention, but is not limited thereto.
- the foam according to an aspect of the present invention may be manufactured through a known foam molding method such as injection foaming.
- a known foam molding method such as injection foaming.
- an ethylene vinyl acetate-elastomer composite resin composition is softened using a known kneader, a roll mill, etc., and then a crosslinking agent, a foaming agent, and inorganic particles are added to the ethylene vinyl acetate-elastomer composite.
- a resin foam composition is prepared and softened using an extruder to prepare pellets.
- This may be put into a foam injection machine, and the ethylene vinyl acetate-elastomer composite resin foam composition is injected into the mold in a mold designed to be reduced in proportion to the foam volume, and then the mold is pressurized, heated, and released to manufacture a foam.
- the mixing and softening are performed at a temperature of 50 to 250 °C, and the injection of the ethylene vinyl acetate-elastomer composite resin foam composition is less than 120 °C, specifically less than 100 °C, more specifically 70 to 100 °C. It can be, and the temperature of the mold may be performed at a temperature of 160 to 180 °C rather than specifically 140 to 200 °C of 100 to 250 °C, but is not limited thereto.
- the expansion ratio may be 120 to 200%, specifically 150 to 180%, but is not limited thereto.
- the foam of the present invention is melted under the condition of 190 ° C. 2.16 kg in the melt index meter, and the expansion ratio of the strand passing through the orifice having a diameter of 2.096 mm is 80% or more High expansion ethylene vinyl acetate copolymer resin is mixed with a thermoplastic elastomer. As it foams, it exhibits excellent physical properties such as light weight, flexibility, elasticity, hardness and compression deformation as a composite material used in sports shoes, and has significantly improved surface properties.
- the surface is not hard and has an excellent effect of having a smooth and smooth luster.
- the hardness of the foam was measured 1 to 2 seconds after pressing the hardness meter on the surface of the foam using an Asker C type hardness meter.
- the rebound elasticity of the foam was calculated as the average value of 4 to 6 measurements after 1 to 3 ball drops using a resilience meter.
- the permanent extrusion shrinkage of the foam was measured by compressing a 10 mm sample to 5 mm, storing it at 50° C., leaving it at room temperature for 30 min, and then measuring the restored height by the calculation method of Equation 1 below.
- A is the diameter of the strand passing through the orifice tube
- B is the diameter of the orifice tube.
- TPEE SK Chemical, G140D
- JTR-TL azodicarbonamide
- TPEE SK Chemical, G140D
- JTR-TL azodicarbonamide
- TPEE SK Chemical, G140D
- JTR-TL azodicarbonamide
- TPEE SK Chemical, G140D
- JTR-TL azodicarbonamide
- TPEE SK Chemical, G140D
- JTR-TL azodicarbonamide
- EVA Expansion Rate (%) EVA content (parts by weight) TPEE Content (parts by weight) Ethylene vinyl acetate Expansion ratio of composite resin composition (%) Example 1 80 100 40 59 Example 2 80 100 60 51 Example 3 80 100 100 43 Example 4 100 100 40 73 Example 5 130 100 40 93 Comparative Example 1 50 100 40 36 Comparative Example 2 30 100 40 21
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Abstract
The present invention relates to an ethylene-vinyl acetate - elastomer composite resin composition comprising highly expandable ethylene-vinyl acetate copolymer resin. More specifically, the present invention relates to an ethylene-vinyl acetate - elastomer composite resin composition having rate of expansion of 50% or higher, the composite resin composition containing ethylene-vinyl acetate having rate of expansion, with melt elasticity controlled, of 80% or higher.
Description
본 발명은 고팽창성 에틸렌비닐아세테이트 공중합체 수지를 포함하는 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물에 관한 것이다. 보다 구체적으로는 용융탄성 제어를 이용한 팽창비율이 80 % 이상인 에틸렌비닐아세테이트를 이용한 팽창률이 50% 이상의 에틸렌비닐아세테이트- 엘라스토머 복합수지 조성물에 관한 것이다.The present invention relates to an ethylene vinyl acetate-elastomer composite resin composition comprising a high expansibility ethylene vinyl acetate copolymer resin. More specifically, it relates to an ethylene vinyl acetate-elastomer composite resin composition having an expansion ratio of 50% or more using ethylene vinyl acetate having an expansion ratio of 80% or more using melt elasticity control.
최근, 가볍고 우수한 탄성을 가지며 낮은 경도 및 압축변형 등 다양한 기능성이 부여된 고기능성 신발에 대한 관심이 높아지면서, 단일 소재가 아닌 복합 소재를 이용한 고기능성 런닝화 등의 개발이 요구되고 있다.Recently, as interest in high-functional shoes that are light and have excellent elasticity and are endowed with various functions such as low hardness and compression deformation, development of high-functional running shoes using a composite material rather than a single material is required.
특히, 운동화 기능에 있어 핵심적인 부분을 담당하는 운동화의 쿠션 소재로 가장 대표적인 에틸렌비닐아세테이트 공중합체(Ethylene vinyl acetate copolymer, EVA)는, 저온 가공이 쉽고 가교가 용이할 뿐만 아니라 발포 셀 형성이 우수하여, 기능성 운동화 소재로 꾸준히 개발이 이루어지고 있다.In particular, ethylene vinyl acetate copolymer (EVA), the most representative cushion material for sports shoes, which plays a key part in the function of sports shoes, is easy to process at low temperatures, easy to crosslink, and has excellent foam cell formation. , as a functional sneaker material, is being continuously developed.
또한, 상기 에틸렌비닐아세테이트 공중합체와 열가소성 엘라스토머를 혼합한 복합소재의 사용이 점점 증가하고 있으며, 또한 최근에 저비중 물성을 요구하는 트렌드에 따라 여러 가지 고융점의 열가소성 엘라스토머를 사용하여 복합 소재를 개발하고 있다.In addition, the use of composite materials in which the ethylene vinyl acetate copolymer and thermoplastic elastomer are mixed is increasing, and in accordance with the recent trend requiring low specific gravity properties, various high melting point thermoplastic elastomers are used to develop composite materials. are doing
이러한 열가소성 엘라스토머를 이용한 복합 소재는 에틸렌비닐아세테이트 공중합체와 열가소성 엘라스토머의 장점이 접목되어 보다 향상된 물성을 나타낼 수 있으나, 실제 두 물질을 단순 혼합하는 경우 기대하는 물성을 충족하기 어렵다.A composite material using such a thermoplastic elastomer may exhibit improved physical properties by combining the advantages of an ethylene vinyl acetate copolymer and a thermoplastic elastomer, but it is difficult to meet the expected physical properties when the two materials are simply mixed.
열가소성 엘라스토머 복합 소재가 충분한 물성 향상 효과를 얻기 위해서는 일정한 발포체 또는 발포와 같은 열가공 과정에서 팽창률이 높아야 하는데, 통상의 에틸렌비닐아세테이트 공중합체 수지는 팽창특성이 충분히 나타나지 않는다.In order for the thermoplastic elastomer composite material to obtain a sufficient effect of improving properties, the expansion rate must be high in a certain foam or thermal processing process such as foaming, but conventional ethylene vinyl acetate copolymer resins do not exhibit sufficient expansion properties.
또한, 이러한 종래의 에틸렌비닐아세테이트 공중합체와 함께 사용되는 상기의 열가소성 엘라스토머는 용융탄성이 낮아, 두 성분을 혼합한 복합 소재는 팽창과정 중 또는 발포과정에서 충분한 발포 특성이 나타나지도 않고, 발포특성이 나타난다 하더라도 균일한 셀 구조를 갖기 어려워서 사용에 한계가 있다. In addition, the thermoplastic elastomer used together with the conventional ethylene vinyl acetate copolymer has low melt elasticity, so that the composite material mixed with the two components does not show sufficient foaming properties during the expansion process or during the foaming process, and the foaming properties are poor. Even if it appears, it is difficult to have a uniform cell structure, so there is a limit to its use.
뿐만 아니라, 종래의 에틸렌비닐아세테이트 공중합체를 열가소성 엘라스토머와 같은 융점이 높은 수지와 가공하는 경우, 가공성이 현저히 낮고, 제조된 발포체가 충분한 탄성, 기계적 강도 등의 물성을 충족하기 어려운 문제점이 있음을 또한 발견하게 되었다.In addition, when processing the conventional ethylene vinyl acetate copolymer with a resin with a high melting point such as a thermoplastic elastomer, the processability is remarkably low, and it is difficult to satisfy the physical properties such as sufficient elasticity and mechanical strength of the manufactured foam. found it
상기 문제를 해결하기 위하여 많은 연구를 한 결과 발포 과정에서 독립되고 균일한 셀 구조를 갖기 위해서는 복합소재 자체(발포체를 넣지 않은 복합소재 자체)의 팽창비가 50%이상, 좋게는 80% 이상이 되어야 발포과정에서 균일한 셀 구조를 갖고 의도된 물성을 확보할 수 있음을 발견하여, 본 발명을 완성하였다.As a result of many studies to solve the above problem, in order to have an independent and uniform cell structure in the foaming process, the expansion ratio of the composite material itself (composite material itself without foam) should be 50% or more, preferably 80% or more. In the process, it was discovered that it was possible to have a uniform cell structure and secure intended physical properties, thereby completing the present invention.
즉, 종래의 에틸렌비닐아세테이트 공중합체를 열가소성 엘라스토머와 같은 융점이 높은 수지와 가공하는 경우, 가공성이 현저히 낮아짐에 따라 신발 제조 설비에서의 가공이 어렵고 불량률이 높아지는 문제가 있으며, 제조한 발포체가 충분한 탄성, 기계적 강도 등의 물성을 충족하기 어려운 문제점이 또한 있음을 발견하게 되었다.That is, when the conventional ethylene vinyl acetate copolymer is processed with a resin with a high melting point, such as a thermoplastic elastomer, as the processability is significantly lowered, there is a problem in that processing in the shoe manufacturing facility is difficult and the defect rate is high, and the manufactured foam has sufficient elasticity It has been found that there is also a problem in that it is difficult to satisfy physical properties such as , mechanical strength, and the like.
본 발명의 목적은 에틸렌비닐아세테이트의 용융탄성 및 팽창률을 개선하여, 높은 팽창비율을 가지며 고 기능성 런닝화 소재로서 적합한 물성을 구현하는 고 팽창성 에틸렌비닐아세테이트 복합수지 조성물을 제공하는 것이다.It is an object of the present invention to provide a high expansion ethylene vinyl acetate composite resin composition that improves the melt elasticity and expansion rate of ethylene vinyl acetate, has a high expansion ratio, and realizes physical properties suitable as a high functional running shoe material.
본 발명의 목적은 높은 팽창비율을 가지며 균일한 발포 셀 구조를 형성하는 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물을 제공하는 것이다.An object of the present invention is to provide an ethylene vinyl acetate-elastomer composite resin composition having a high expansion ratio and forming a uniform foamed cell structure.
또한, 본 발명의 목적은 열가소성 엘라스토머와 같은 융점이 높은 수지와 가공하는 경우, 가공성이 현저히 개선될 수 있는 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물을 제공하는 것이다.Another object of the present invention is to provide an ethylene vinyl acetate-elastomer composite resin composition in which processability can be significantly improved when processed with a resin having a high melting point, such as a thermoplastic elastomer.
또한, 본 발명의 목적은 발포성 및 탄성이 우수하며, 매끄러운 표면을 가지는 발포체를 제공할 수 있는 고팽창성 에틸렌비닐아세테이트 공중합체 수지를 제공하는 것이다.In addition, an object of the present invention is to provide a high expansion ethylene vinyl acetate copolymer resin that is excellent in foamability and elasticity, and can provide a foam having a smooth surface.
본 발명은 팽창률이 80%이상의 고팽창성 에틸렌비닐아세테이트 공중합체 수지에 열가소성 엘라스토머 포함하여 제조되는 팽창률 50 %이상의 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물을 제공할 수 있다.The present invention can provide an ethylene-vinyl acetate-elastomer composite resin composition with an expansion rate of 50% or more, which is prepared by including a thermoplastic elastomer in a high expansibility ethylene vinyl acetate copolymer resin having an expansion rate of 80% or more.
본 발명의 일 양태에 따른, 복합수지 조성물은 상기 팽창률이 80%이상의 고팽창성 에틸렌비닐아세테이트 공중합체 수지 100 중량부에 대하여, 상기 열가소성 엘라스토머 1 내지 100 중량부를 포함하는 것일 수 있다.According to an aspect of the present invention, the composite resin composition may include 1 to 100 parts by weight of the thermoplastic elastomer based on 100 parts by weight of the high expansibility ethylene vinyl acetate copolymer resin having the expansion coefficient of 80% or more.
본 발명의 일 양태에 따른, 상기 고팽창성 에틸렌비닐아세테이트 공중합체수지의 팽창률은 100 %이상인 것을 포함할 수 있다.According to an aspect of the present invention, the expansion coefficient of the high expansibility ethylene vinyl acetate copolymer resin may include 100% or more.
본 발명의 일 양태에 따른, 상기 고팽창성 에틸렌비닐아세테이트 공중합체수지의 팽창률은 130 %이상의 것을 포함할 수 있다.According to an aspect of the present invention, the expansion coefficient of the high expansibility ethylene vinyl acetate copolymer resin may include 130% or more.
본 발명의 일 양태에 따른, 상기 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물의 팽창률이 50 %이상인 것을 포함할 수 있다.According to an aspect of the present invention, the ethylene vinyl acetate-elastomer composite resin composition may have an expansion rate of 50% or more.
본 발명의 일 양태에 따른, 상기 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물의 팽창률이 80 %이상인 것을 포함할 수 있다.According to an aspect of the present invention, the ethylene vinyl acetate-elastomer composite resin composition may have an expansion rate of 80% or more.
본 발명의 일 양태에 따른, 상기 고팽창성 에틸렌비닐아세테이트 공중합체 수지는 에틸렌비닐아세테이트 공중합체 수지를 열가교, 방사선가교, X-레이가교, 전자선가교에서 선택되는 어느 하나의 방법으로 개질하여 제조되는 것을 포함할 수 있다.According to an aspect of the present invention, the high expansion ethylene vinyl acetate copolymer resin is prepared by modifying the ethylene vinyl acetate copolymer resin by any one method selected from thermal crosslinking, radiation crosslinking, X-ray crosslinking, and electron beam crosslinking. may include
본 발명의 일 양태에 따른, 상기 열가소성 엘라스토머는 라디칼 개질 가능한 것을 포함할 수 있다.According to an aspect of the present invention, the thermoplastic elastomer may include radically modifiable ones.
본 발명의 일 양태에 따른, 상기 열 가소성 엘라스토머는 스티렌-부타디엔-스티렌 수지, 스티렌-이소부티렌-스티렌 수지, 스티렌-에틸렌-부티렌-스티렌 수지, 스티렌-에틸렌-프로필렌-스티렌 수지, 스티렌-이소프렌-스티렌 수지, 이소프렌 고무, 부타디엔 고무, 클로로프렌 고무, 에틸렌-프로필렌 고무, 에틸렌-프로필렌-디엔 고무, 열가소성 폴리올레핀 엘라스토머, 열가소성 폴리에스테르 엘라스토머, 열가소성 폴리아미드 엘라스토머 및 열가소성 폴리우레탄에서 선택되는 어느 하나 또는 둘 이상의 인 것을 포함할 수 있다.According to an aspect of the present invention, the thermoplastic elastomer is a styrene-butadiene-styrene resin, a styrene-isobutyrene-styrene resin, a styrene-ethylene-butyrene-styrene resin, a styrene-ethylene-propylene-styrene resin, a styrene- Any one or two selected from isoprene-styrene resin, isoprene rubber, butadiene rubber, chloroprene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, thermoplastic polyolefin elastomer, thermoplastic polyester elastomer, thermoplastic polyamide elastomer and thermoplastic polyurethane It may include more than one.
본 발명의 일 양태에 따라, 상기 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물에 가교제, 발포제 및 무기입자를 더 포함하여 발포한 에틸렌 비닐아세테이트-엘라스토머 복합수지 발포체를 제공할 수 있다.According to one aspect of the present invention, it is possible to provide an ethylene vinyl acetate-elastomer composite resin foam foamed by further including a crosslinking agent, a foaming agent and inorganic particles in the ethylene vinyl acetate-elastomer composite resin composition.
본 발명의 일 양태에 따른. 상기 에틸렌 비닐아세테이트-엘라스토머 복합수지 발포체는, 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물 100 중량부에 대하여 상기 가교제 0.1 내지 3 중량부, 상기 발포제 1 내지 20 중량부 및 상기 무기입자 0.1 내지 20 중량부를 포함할 수 있다.According to one aspect of the present invention. The ethylene vinyl acetate-elastomer composite resin foam contains 0.1 to 3 parts by weight of the crosslinking agent, 1 to 20 parts by weight of the foaming agent, and 0.1 to 20 parts by weight of the inorganic particles based on 100 parts by weight of the ethylene vinyl acetate-elastomer composite resin composition can
본 발명의 일 양태에 따른, 상기 가교제는 디-t-부틸퍼옥시드, 디-t-아밀퍼옥시드, t-부틸큐밀퍼옥시드, 디큐밀퍼옥시드, 2,5-디메틸-2,5-디(t-부틸퍼옥시)헥산, 2,5-디메틸-2,5-디(t-부틸퍼옥시)헥산-3,2,2'-비스(t-부틸퍼옥시이소프로필)벤젠, 1,1-비스(t-부틸퍼옥시)-3,3,5-트리메틸시클로헥산, n-부틸-4,4-비스(t-부틸퍼옥시)발러레이트, 벤조일퍼옥시드, p-클로로벤조일퍼옥시드, t-부틸퍼옥시벤조에이트 및 2,5-디메틸-2,5-디 (t-벤조일퍼옥시)헥산에서 선택되는 어느 하나 또는 이들의 혼합물을 포함할 수 있다.According to an aspect of the present invention, the crosslinking agent is di-t-butyl peroxide, di-t-amyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane-3,2,2'-bis(t-butylperoxyisopropyl)benzene, 1, 1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(t-butylperoxy)valerate, benzoyl peroxide, p-chlorobenzoyl peroxide , t-butylperoxybenzoate and 2,5-dimethyl-2,5-di(t-benzoylperoxy)hexane, or a mixture thereof.
본 발명의 일 양태에 따라, 상기 아조디카본아미드, 아조비스이소부티로니트릴, 디아조아미노아조벤젠 N,N'-디니트로- 소펜타메틸렌테트라민 p-톨루엔술포닐히드라지드 및 p,p'-옥시비스 (벤젠술포닐히드라지드) p-톨루엔-술포닐세미카바, 소디움디카보네이트에서 선택되는 어느 하나 또는 이들의 혼합물을 포함할 수 있다.According to an aspect of the present invention, the azodicarbonamide, azobisisobutyronitrile, diazoaminoazobenzene N,N'-dinitro- sopentamethylenetetramine p-toluenesulfonylhydrazide and p,p' -Oxybis (benzenesulfonyl hydrazide) p-toluene-sulfonyl semicarba, sodium dicarbonate, any one selected from, or a mixture thereof may be included.
본 발명의 일 양태에 따라, 상기 무기입자로는 탄산칼슘, 산화아연, 산화칼슘, 산화마그네슘, 실리카, 알루미나 및 이산화티탄에서 선택되는 어느 하나 또는 둘 이상의 혼합물인 것을 포함할 수 있다.According to an aspect of the present invention, the inorganic particles may include any one or a mixture of two or more selected from calcium carbonate, zinc oxide, calcium oxide, magnesium oxide, silica, alumina and titanium dioxide.
본 발명에 따른 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물은 높은 팽창비율을 가지며 균일한 발포 셀 구조를 형성할 수 있는 장점이 있다.The ethylene vinyl acetate-elastomer composite resin composition according to the present invention has an advantage in that it has a high expansion ratio and can form a uniform foamed cell structure.
즉, 본 발명에 따른 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물은 그 자체로 (발포제가 포함되지 않은 상태) 50 % 이상 더욱 구체적으로 80 % 이상의 팽창률을 갖는 조성물을 제공할 수 있다.That is, the ethylene vinyl acetate-elastomer composite resin composition according to the present invention can provide a composition having an expansion rate of 50% or more, more specifically, 80% or more (in a state where the blowing agent is not included) by itself.
또한, 본 발명에 따른 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물은 발포성이 우수하여 현저히 향상되는 가공성을 나타내어, 다양한 설비에 적용 가능한 장점이 있다.In addition, the ethylene vinyl acetate-elastomer composite resin composition according to the present invention exhibits significantly improved processability due to excellent foamability, and has the advantage of being applicable to various facilities.
또한, 본 발명에 따른 발포체는 유연성, 탄성 및 내구성이 우수한 동시에 표면 불량 없이 매끄러운 표면을 가지는 장점이 있다.In addition, the foam according to the present invention has the advantage of having a smooth surface without surface defects while being excellent in flexibility, elasticity and durability.
이하 첨부된 도면들을 포함한 구체예 또는 실시예를 통해 본 발명을 더욱 상세히 설명한다. 다만 하기 구체예 또는 실시예는 본 발명을 상세히 설명하기 위한 하나의 참조일 뿐 본 발명이 이에 한정되는 것은 아니며, 여러 형태로 구현될 수 있다. Hereinafter, the present invention will be described in more detail through embodiments or examples including the accompanying drawings. However, the following specific examples or examples are only a reference for describing the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms.
또한 달리 정의되지 않는 한, 모든 기술적 용어 및 과학적 용어는 본 발명이 속하는 당업자 중 하나에 의해 일반적으로 이해되는 의미와 동일한 의미를 갖는다. 본 발명에서 설명에 사용되는 용어는 단지 특정 구체예를 효과적으로 기술하기 위함이고 본 발명을 제한하는 것으로 의도되지 않는다.Also, unless defined otherwise, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description herein is for the purpose of effectively describing particular embodiments only and is not intended to limit the invention.
또한 명세서 및 첨부된 특허청구범위에서 사용되는 단수 형태는 문맥에서 특별한 지시가 없는 한 복수 형태도 포함하는 것으로 의도할 수 있다.Also, the singular forms used in the specification and appended claims may also be intended to include the plural forms unless the context specifically dictates otherwise.
또한 어떤 부분이 어떤 구성요소를 "포함"한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성요소를 더 포함할 수 있는 것을 의미한다.Also, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.
본 발명에서"팽창비율"의 의미는 발포제를 포함하지 않는 상태의 수지 또는 복합수지 조성물 만의 팽창비율을 의미한다.In the present invention, "expansion ratio" means the expansion ratio of only the resin or composite resin composition in a state that does not contain a foaming agent.
본 명세서에서 '개질'이라는 것은 화학적 또는 물리적(예: 자외선, 방사선 등)으로 가교를 수행한 것을 의미한다.As used herein, 'modification' refers to crosslinking chemically or physically (eg, ultraviolet rays, radiation, etc.).
본 발명은 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물에 관한 것으로, 본 발명은 80% 팽창율을 가지는 에틸렌비닐아세테이트와 열가소성 엘라스토머를 포함하는 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물에 관한 것이다.The present invention relates to an ethylene vinyl acetate-elastomer composite resin composition, and the present invention relates to an ethylene vinyl acetate-elastomer composite resin composition comprising ethylene vinyl acetate having an expansion rate of 80% and a thermoplastic elastomer.
일 구현예로는, 상기 복합 수지 조성물은 팽창률이 80%이상의 고팽창성 에틸렌비닐아세테이트 공중합체 수지 100 중량부에 대하여, 상기 열가소성 엘라스토머 1 내지 100 중량부를 포함할 수 있다.In one embodiment, the composite resin composition may include 1 to 100 parts by weight of the thermoplastic elastomer based on 100 parts by weight of the high expansibility ethylene vinyl acetate copolymer resin having an expansion rate of 80% or more.
일 예로, 본 발명은 팽창률이 80 %이상의 고팽창성 에틸렌비닐아세테이트 공중합체 수지 100 중량부에 대하여, 열가소성 엘라스토머 1 내지 100 중량부를 포함하여 제조되는 팽창률 50 %이상인 에틸렌비닐아세테이트 공중합체 수지 및 열가소성 엘라스토머를 포함한다.As an example, the present invention provides an ethylene vinyl acetate copolymer resin and a thermoplastic elastomer having an expansion rate of 50% or more, which are prepared by including 1 to 100 parts by weight of a thermoplastic elastomer, based on 100 parts by weight of a high expansibility ethylene vinyl acetate copolymer resin having an expansion rate of 80% or more. include
일 구현예로서 본 발명의 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물은 상기 조건 하에서 50 % 이상의 팽창비율을 가지는 고팽창성 에틸렌비닐아세테이트 공중합체수지 및 열가소성 엘라스토머를 포함함에 따라, 종래 두 수지를 함께 사용할 때 발생되는 발포 셀 구조의 낮은 균일성 문제를 해결하고, 발포성 및 탄성이 현저히 우수한 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물을 제공할 수 있어서 더 선호된다.As an embodiment, the ethylene vinyl acetate-elastomer composite resin composition of the present invention includes a high expansion ethylene vinyl acetate copolymer resin and a thermoplastic elastomer having an expansion ratio of 50% or more under the above conditions. It is more preferred because it can solve the problem of low uniformity of the foamed cell structure and provide an ethylene vinyl acetate-elastomer composite resin composition having remarkably excellent foamability and elasticity.
또한 본 발명의 발명자들은 기능성 신발과 같이, 발포 과정에서 독립되고 균일한 셀 구조를 갖도록 하기 위하여 연구한 결과, 팽창비가 80 % 이상인 고팽창성 에틸렌비닐아세테이트 공중합체 수지를 사용함으로써 균일한 셀 구조를 갖고 의도된 물성을 확보할 수 있음을 발견하게 되어 본 발명을 완성하였다.In addition, the inventors of the present invention studied to have an independent and uniform cell structure in the foaming process, such as functional shoes. It was discovered that the intended physical properties could be secured, and thus the present invention was completed.
본 발명의 일 양태에서, 상기 고팽창성 에틸렌비닐아세테이트 공중합체 수지의 팽창률이 100% 이상, 더욱 130 %이상 인 것일 수 있고 더욱 좋게는 180% 이상일 수 있다.In one aspect of the present invention, the expansion coefficient of the high expansion ethylene vinyl acetate copolymer resin may be 100% or more, more 130% or more, and more preferably 180% or more.
본 발명의 일 양태에서, 상기 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물의 팽창률이 50 %이상, 좋게는 80 %이상, 더욱 좋게는 150% 이상인 것일 수 있다.In one aspect of the present invention, the expansion rate of the ethylene vinyl acetate-elastomer composite resin composition may be 50% or more, preferably 80% or more, and more preferably 150% or more.
상기 에틸렌비닐아세테이트에서 비닐아세테이트 함량이 10 내지 60 % 일 수 있으며, 바람직하게는 15 내지 50 % 일 수 있으며, 더욱 바람직하게는 20 내지 40% 일 수 있으나 이에 제한되는 것은 아니다. 또한 본 발명에서는 상기 에틸렌 비닐 아세테이트의 용융 지수 (190℃2.16 kg)는 0.1 내지 8.0 g/10min 일 수 있으며 바람직하게는 0.2 내지 6.0 g/10min 일 수 있으며, 더욱 바람직하게는 0.3 내지 4.0 g/ 10min 일수 있으나 이에 제한되는 것은 아니다.The vinyl acetate content in the ethylene vinyl acetate may be 10 to 60%, preferably 15 to 50%, more preferably 20 to 40%, but is not limited thereto. In addition, in the present invention, the melt index (190 ℃ 2.16 kg) of the ethylene vinyl acetate may be 0.1 to 8.0 g/10min, preferably 0.2 to 6.0 g/10min, more preferably 0.3 to 4.0 g/10min. may be, but is not limited thereto.
본 발명의 고팽창성 에틸렌비닐아세테이트 공중합체 수지가 상기 범위의 용융지수 및 비닐아세테이트 함량을 가지며 상술한 범위의 팽창비율을 가지는 경우, 현저히 우수한 발포성 및 탄성을 갖는 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물을 구현할 수 있다.When the high expansion ethylene vinyl acetate copolymer resin of the present invention has a melt index and a vinyl acetate content in the above ranges and an expansion ratio in the above ranges, an ethylene vinyl acetate-elastomer composite resin composition having remarkably excellent foamability and elasticity will be realized. can
구체적으로, 고팽창성 에틸렌비닐아세테이트 공중합체 수지가 상기 팽창비율 범위를 만족하며, 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물을 제조함으로써 성분들 간의 기계적 특성 및 화학 특성이 잘 결합되어 용융탄성이 보다 향상된다. 또한 상기 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물을 사용함으로써 매우 균일한 셀 구조를 갖는 발포체를 형성할 수 있다.Specifically, the high expansion ethylene vinyl acetate copolymer resin satisfies the above expansion ratio range, and by preparing the ethylene vinyl acetate-elastomer composite resin composition, the mechanical properties and chemical properties between the components are well combined, so that the melt elasticity is further improved. In addition, by using the ethylene vinyl acetate-elastomer composite resin composition, it is possible to form a foam having a very uniform cell structure.
이는 종래 에틸렌비닐아세테이트 공중합체를 기반으로 열가소성 엘라스토머를 사용하여 복합소재를 제조하는 경우, 상기 열가소성 엘라스토머 자체의 낮은 발포성으로 인하여 고품질의 발포체를 제조하는 것이 어려운 것과 비교하여, 본 발명의 고팽창성 에틸렌비닐아세테이트 공중합체를 이용한 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물은 고함량의 열가소성 엘라스토머를 함께 사용하여도 우수한 발포성을 나타내며, 제조되는 발포체가 불량 문제없이 부드럽고 매끄러운 표면을 갖는 장점이 있다.This is compared to the fact that it is difficult to prepare a high-quality foam due to the low foamability of the thermoplastic elastomer itself when manufacturing a composite material using a thermoplastic elastomer based on the conventional ethylene vinyl acetate copolymer. The ethylene vinyl acetate-elastomer composite resin composition using the acetate copolymer exhibits excellent foamability even when a high content of the thermoplastic elastomer is used together, and has the advantage of having a smooth and smooth surface without any defect problems.
본 발명의 일 양태에 따른 열가소성 엘라스토머는 상기 고팽창성 에틸렌비닐아세테이트 수지와 혼합되어 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물의 탄성을 향상시키고 경도와 압축변형을 낮춰 고기능성의 복합 소재로 제조하기 위한 것이다. 구체적으로 예를 들면 스티렌-부타디엔-스티렌 수지(styrene-butadiene-styrene, SBS), 스티렌-이소부티렌-스티렌 수지(styrene-isobutylene-styrene, SIBS), 스티렌-에틸렌-부티렌-스티렌수지(styrene-ethylene-butylene-styrene, SEBS), 스티렌-에틸렌-프로필렌-스티렌 수지(styrene-ethylene-propylene-styrene, SEPS), 스티렌-이소프렌-스티렌 수지(styrene-isoprene-styrene, SIS), 이소프렌 고무(isoprene rubber, IR), 부타디엔 고무(butadiene rubber, BR), 클로로프렌 고무(chloroprene rubber, CR), 에틸렌-프로필렌 고무(ethylene propylene rubber, EPM), 에틸렌-프로필렌-디엔 고무(ethylene-propylene-diene rubber, EPDM), 열가소성 폴리올레핀엘라스토머(thermoplastic polyolefin elastomers, POE), 열가소성 폴리에스테르 엘라스토머(thermoplastic polyester elastomers, TPEE), 열가소성 폴리아미드엘라스토머(thermoplastic polyamide elastomers, TPA) 및 열가소성 폴리우레탄(thermoplastic polyurethane, TPU) 등에서 선택되는 어느 하나 또는 둘 이상의 혼합물일 수 있다.The thermoplastic elastomer according to an aspect of the present invention is mixed with the high expansion ethylene vinyl acetate resin to improve the elasticity of the ethylene vinyl acetate-elastomer composite resin composition and lower the hardness and compression deformation to produce a high-functional composite material. Specifically, for example, styrene-butadiene-styrene resin (styrene-butadiene-styrene, SBS), styrene-isobutylene-styrene (SIBS), styrene-ethylene-butyrene-styrene resin (styrene) -ethylene-butylene-styrene, SEBS), styrene-ethylene-propylene-styrene (SEPS), styrene-isoprene-styrene (SIS), isoprene rubber (isoprene) rubber, IR), butadiene rubber (BR), chloroprene rubber (CR), ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM) ), thermoplastic polyolefin elastomers (POE), thermoplastic polyester elastomers (TPEE), thermoplastic polyamide elastomers (TPA) and thermoplastic polyurethane (TPU), etc. It may be one or a mixture of two or more.
일 구현예로서, 상기 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물은 상기 고팽창성 에틸렌비닐아세테이트 공중합체 수지 100 중량부에 대하여, 상기 열가소성 엘라스토머를 1 내지 100 중량부, 좋게는 10 내지 50 중량부를 포함하는 것이 팽창률이 50% 이상인 조성물을 수득하는데 바람직한 것일 수 있으나 이에 제한되는 것은 아니다.In one embodiment, the ethylene vinyl acetate-elastomer composite resin composition contains 1 to 100 parts by weight of the thermoplastic elastomer, preferably 10 to 50 parts by weight, based on 100 parts by weight of the high expansion ethylene vinyl acetate copolymer resin. It may be preferable to obtain a composition having an expansion rate of 50% or more, but is not limited thereto.
본 발명의 일 양태에서, 상기 고팽창성 에틸렌비닐아세테이트 공중합체 수지는 에틸렌비닐아세테이트 공중합체 수지를 열가교, 방사선가교, X-레이가교 전자선 가교 등에서 선택되는 어느 하나의 방법으로 제조되는 것인 고팽창성 에틸렌비닐아세테이트 공중합체 수지 조성물 일 수 있으나, 80% 이상의 팽창율을 달성할 수 있는 수단이라면 이에 제한되는 것은 아니다.In one aspect of the present invention, the high expansion ethylene vinyl acetate copolymer resin is prepared by any one method selected from thermal crosslinking of the ethylene vinyl acetate copolymer resin, radiation crosslinking, X-ray crosslinking, electron beam crosslinking, and the like. It may be an ethylene vinyl acetate copolymer resin composition, but is not limited thereto as long as it is a means capable of achieving an expansion rate of 80% or more.
구체적으로 상기와 같은 가교방법을 통하여 팽창률이 80% 이상이 되도록 조절된 상기 고팽창성 에틸렌비닐아세테이트 공중합체 수지를 사용하는데 특징이 있으나, 상기 가교방법을 통하지 않더라도 상기 팽창률이 80% 이상인 고팽창성 에틸렌비닐아세테이트 공중합체 수지를 사용한다면, 상기 가교된 고팽창성 에틸렌비닐아세테이트 공중합체 수지를 사용한 것과 동일한 효과를 가질 수 있다.Specifically, it is characterized by using the high expansion ethylene vinyl acetate copolymer resin adjusted to have an expansion rate of 80% or more through the crosslinking method as described above. If an acetate copolymer resin is used, it can have the same effect as using the cross-linked high expansion ethylene vinyl acetate copolymer resin.
상기 고팽창성 에틸렌비닐아세테이트 공중합체 수지의 팽창률은 용융지수 측정기에서 190℃2.16 kg 조건 하에 용융되어 지름이 2.096mm인 오리피스(orifice)를 통과한 스트랜드의 팽창비율이 80% 이상, 더욱 좋게는 100%이상, 더욱 좋게는 130 %이상인 것일 수 있다.The expansion rate of the high expansibility ethylene vinyl acetate copolymer resin is 80% or more, more preferably 100% More preferably, it may be 130% or more.
일반적으로, 에틸렌비닐아세테이트 공중합체를 다른 열가소성 엘라스토머와 함께 발포하여 복합소재로 제조하는 경우, 상기 열가소성 엘라스토머의 용융탄성이 낮아 발포가 용이하지 않고 불량률이 증가한다.In general, when an ethylene-vinyl acetate copolymer is foamed together with another thermoplastic elastomer to form a composite material, the melt elasticity of the thermoplastic elastomer is low, so foaming is not easy and the defect rate is increased.
그러나, 본 발명의 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물은 상기 범위의 팽창비율을 가지는 고팽창성 에틸렌비닐아세테이트 공중합체 수지를 필수적으로 포함함에 따라 향상된 용융탄성을 나타낸다. 이에 따라, 균일하게 발포되는 효과가 우수할 뿐만 아니라, 표면이 매끄럽고 외관이 우수한 발포체를 제조할 수 있는 효과가 매우 뛰어나, 고기능성 신발을 포함한 다양한 분야의 복합소재로 용이하게 적용할 수 있다.However, the ethylene vinyl acetate-elastomer composite resin composition of the present invention shows improved melt elasticity by essentially including a high expansion ethylene vinyl acetate copolymer resin having an expansion ratio within the above range. Accordingly, as well as having an excellent effect of uniformly foaming, the effect of producing a foam having a smooth surface and excellent appearance is very excellent, and it can be easily applied as a composite material in various fields including high-performance shoes.
상기 열 가소성 엘라스토머는 스티렌-부타디엔-스티렌 수지(styrene-butadiene-styrene, SBS), 스티렌-이소부티렌-스티렌 수지(styrene-isobutylene-styrene, SIBS), 스티렌-에틸렌-부티렌-스티렌 수지(styrene-ethylene-butylene-styrene, SEBS), 스티렌-에틸렌-프로필렌-스티렌 수지(styrene-ethylene-propylene-styrene, SEPS), 스티렌-이소프렌-스티렌 수지(styrene-isoprene-styrene, SIS), 이소프렌 고무(isoprene rubber, IR), 부타디엔 고무(butadiene rubber, BR), 클로로프렌 고무(chloroprene rubber, CR), 에틸렌-프로필렌 고무(ethylene propylene rubber, EPM), 에틸렌-프로필렌-디엔 고무(ethylene-propylene-diene rubber, EPDM), 열가소성 폴리올레핀 엘라스토머(thermoplastic polyolefin elastomers, POE), 열가소성 폴리에스테르 엘라스토머(thermoplastic polyester elastomers, TPEE), 열가소성 폴리아미드 엘라스토머(thermoplastic polyamide elastomers, TPA) 및 열가소성 폴리우레탄(thermoplastic polyurethane, TPU) 등에서 선택되는 라디칼 가교 가능한 것일 수 있다.The thermoplastic elastomer is styrene-butadiene-styrene resin (styrene-butadiene-styrene, SBS), styrene-isobutylene-styrene (SIBS), styrene-ethylene-butyrene-styrene resin (styrene) -ethylene-butylene-styrene, SEBS), styrene-ethylene-propylene-styrene (SEPS), styrene-isoprene-styrene (SIS), isoprene rubber (isoprene) rubber, IR), butadiene rubber (BR), chloroprene rubber (CR), ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM) ), a radical selected from thermoplastic polyolefin elastomers (POE), thermoplastic polyester elastomers (TPEE), thermoplastic polyamide elastomers (TPA) and thermoplastic polyurethane (TPU), etc. It may be cross-linkable.
또한 본 발명은 용융지수 측정기에서 190℃2.16 kg 조건 하에 용융되어 지름이 2.096mm인 오리피스를 통과한 스트랜드의 팽창비율이 80 % 이상인 고팽창성 에틸렌비닐아세테이트 공중합체 수지, 열가소성 엘라스토머를 포함하여 제조한 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물에 발포제 및 가교제를 포함하는 발포 조성물로 제조되는 에틸렌비닐아세테이트-엘라스토머 복합수지 발포체에 관한 것이다.In addition, the present invention is a high expansion ethylene vinyl acetate copolymer resin and thermoplastic elastomer in which the expansion ratio of the strand that has passed through the orifice having a diameter of 2.096 mm after being melted under the condition of 190 ° C. It relates to an ethylene vinyl acetate-elastomer composite resin foam prepared from a foaming composition comprising a foaming agent and a crosslinking agent in a vinyl acetate-elastomer composite resin composition.
또한, 상기 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물에 가교제, 발포제 및 무기입자를 더 포함하여 발포한 에틸렌 비닐아세테이트-엘라스토머 복합수지 발포체를 제공 할 수 있다. 더욱 구체적으로 설명하면, 상기 에틸렌 비닐아세테이트-엘라스토머 복합수지 발포체는, 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물 100 중량부에 대하여 상기 가교제 0.1 내지 3 중량부, 상기 발포제 1 내지 20 중량부 및 상기 무기입자 0.1 내지 20 중량부를 포함하여, 제조되는 에틸렌 비닐아세테이트-엘라스토머 복합수지 발포체를 제공 할 수 있다.In addition, it is possible to provide an ethylene vinyl acetate-elastomer composite resin foam foamed by further including a crosslinking agent, a foaming agent and inorganic particles in the ethylene vinyl acetate-elastomer composite resin composition. More specifically, the ethylene vinyl acetate-elastomer composite resin foam contains 0.1 to 3 parts by weight of the crosslinking agent, 1 to 20 parts by weight of the foaming agent, and 0.1 parts by weight of the inorganic particles based on 100 parts by weight of the ethylene vinyl acetate-elastomer composite resin composition. Including to 20 parts by weight, ethylene vinyl acetate-elastomer composite resin foam to be prepared can be provided.
상기 에틸렌 비닐아세테이트-엘라스토머 복합수지 발포체는 발포 과정에서, 조기 발포, 오픈 셀 형성의 어려움 및 셀 붕괴와 같은 문제없이 용이하게 발포 가능하며, 제조된 발포체 또한 우수한 물성과 동시에 표면이 단단하지 않고 부드러우며 매끄러운 광택을 갖는 우수한 효과를 갖는다.The ethylene vinyl acetate-elastomer composite resin foam can be easily foamed without problems such as premature foaming, difficulty in forming open cells, and cell collapse during the foaming process. It has an excellent effect of having a smooth luster.
상기 에틸렌비닐아세테이트-엘라스토머 복합수지 발포체를 제조하기 위하여 들어가는 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물에 발포제, 가교제 및 무기입자등이 더 포함되어 제조될 수 있다.The ethylene vinyl acetate-elastomer composite resin composition, which is entered to prepare the ethylene vinyl acetate-elastomer composite resin foam, may be prepared by further including a foaming agent, a crosslinking agent, and inorganic particles.
상기 발포제로는 아조디카본아미드, 아조비스이소부티로니트릴, 디아조아미노아조벤젠 N,N'-디니트로-소펜타메틸렌테트라민 p-톨루엔술포닐히드라지드 및 p,p'-옥시비스 (벤젠술포닐히드라지드) p-톨루엔-술포닐세미카바, 소디움디카보네이트 등이 사용될 수 있으나 이에 제한되는 것은 아니다.The blowing agent includes azodicarbonamide, azobisisobutyronitrile, diazoaminoazobenzene N,N′-dinitro-sopentamethylenetetramine p-toluenesulfonylhydrazide and p,p′-oxybis(benzene Sulfonyl hydrazide) p-toluene-sulfonyl semicarba, sodium dicarbonate, etc. may be used, but the present invention is not limited thereto.
바람직하게는, 발포제 화합물에서 선택되는 어느 하나 또는 둘 이상의 혼합물을 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물 100 중량부에 대하여 1 내지 20 중량부, 구체적으로 2 내지 16 중량부, 보다 구체적으로 3 내지 10 중량부 사용하는 것일 수 있으나, 이에 제한되는 것은 아니다. 상기 함량 범위의 아조계 화합물을 사용하여 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물을 발포하는 경우, 발포제가 균일한 분산을 이루며 안정적으로 발포 셀 구조를 형성하고, 목적하는 발포배율 및 기계적 물성을 달성할 수 있어 효과적이다.Preferably, 1 to 20 parts by weight, specifically 2 to 16 parts by weight, more specifically 3 to 10 parts by weight, based on 100 parts by weight of the ethylene vinyl acetate-elastomer composite resin composition, any one or a mixture of two or more selected from the blowing agent compound It may be used by mistake, but is not limited thereto. In the case of foaming the ethylene vinyl acetate-elastomer composite resin composition using the azo compound in the above content range, the foaming agent achieves uniform dispersion and stably forms a foamed cell structure, and the desired expansion ratio and mechanical properties can be achieved. there is effective
또한, 상기 가교제는 발포 시 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물에 용융탄성을 더욱 향상시키기 위한 것으로, 구체적인 예를 들면 디-t-부틸퍼옥시드, 디-t-아밀퍼옥시드, t-부틸큐밀퍼옥시드, 디큐밀퍼옥시드, 2,5-디메틸-2,5-디(t-부틸퍼옥시)헥산,2,5-디메틸-2,5-디(t-부틸퍼옥시)헥산-3,2,2'-비스(t-부틸퍼옥시이소프로필)벤젠,1,1-비스(t-부틸퍼옥시)-3,3,5-트리메틸시클로헥산, n-부틸-4,4-비스(t-부틸퍼옥시)발러레이트, 벤조일퍼옥시드, p-클로로벤조일퍼옥시드, t-부틸퍼옥시벤조에이트 및 2,5-디메틸-2,5-디 (t-벤조일퍼옥시)헥산에서 선택되는 어느 하나 또는 이들의 혼합물을 사용하는 것일 수 있으나, 이에 제한되는 것은 아니다. 상기 가교제의 함량은 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물 100 중량부에 대하여 0.1 내지 3 중량부, 구체적으로 0.2 내지 2 중량부, 보다 구체적으로 0.5 내지 1 중량부일 수 있으나, 이에 제한되는 것은 아니다. 상기 범위의 가교제를 사용하는 경우, 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물이 발포 과정에서 발포제의 분해로 발생되는 가스압을 견딜 수 있는 충분한 점탄성을 가질 수 있다.In addition, the crosslinking agent is to further improve the melt elasticity of the ethylene vinyl acetate-elastomer composite resin composition during foaming, and specific examples include di-t-butyl peroxide, di-t-amyl peroxide, t-butylcumyl peroxide. Seed, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane,2,5-dimethyl-2,5-di(t-butylperoxy)hexane-3,2 ,2'-bis(t-butylperoxyisopropyl)benzene,1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(t -Butyl peroxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, t-butylperoxybenzoate and any one selected from 2,5-dimethyl-2,5-di (t-benzoylperoxy)hexane One or a mixture thereof may be used, but is not limited thereto. The content of the crosslinking agent may be 0.1 to 3 parts by weight, specifically 0.2 to 2 parts by weight, more specifically 0.5 to 1 parts by weight, based on 100 parts by weight of the ethylene vinyl acetate-elastomer composite resin composition, but is not limited thereto. When the crosslinking agent in the above range is used, the ethylene vinyl acetate-elastomer composite resin composition may have sufficient viscoelasticity to withstand the gas pressure generated by the decomposition of the foaming agent during the foaming process.
또한, 상기 무기입자로는 구체적인 예를 들면, 탄산칼슘, 산화아연, 산화칼슘, 산화마그네슘, 실리카, 알루미나 및 이산화 티탄에서 선택되는 어느 하나 또는 둘 이상의 혼합물인 것일 수 있다. 바람직하게는 탄산칼슘 및 이산화 티탄의 혼합물을 사용하여 발포체 제조 시 가교 및 발포를 촉진시키는 것일 수 있으나, 이에 제한되는 것은 아니다. 상기 무기입자의 함량은 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물 100 중량부에 대하여 0.1 내지 20 중량부, 구체적으로 1 내지 18 중량부, 보다 구체적으로 4 내지 15 중량부일 수 있으나, 이에 제한되는 것은 아니다.In addition, the inorganic particles may be, for example, any one or a mixture of two or more selected from calcium carbonate, zinc oxide, calcium oxide, magnesium oxide, silica, alumina and titanium dioxide. Preferably, a mixture of calcium carbonate and titanium dioxide may be used to promote crosslinking and foaming when manufacturing a foam, but is not limited thereto. The content of the inorganic particles may be 0.1 to 20 parts by weight, specifically 1 to 18 parts by weight, and more specifically 4 to 15 parts by weight, based on 100 parts by weight of the ethylene vinyl acetate-elastomer composite resin composition, but is not limited thereto.
상기 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물은 50 % 미만의 팽창비율을 가지는 열가소성 엘라스토머를 포함함에도 불구하고 상기 범위의 높은 팽창비율을 나타냄에 따라, 발포 시 균일한 발포 셀 구조를 형성할 수 있으며, 오픈 셀 및 셀 붕괴 등으로 인한 불량 없이 안정적으로 발포체를 제조할 수 있는 효과가 뛰어나다.Although the ethylene vinyl acetate-elastomer composite resin composition contains a thermoplastic elastomer having an expansion ratio of less than 50%, as it exhibits a high expansion ratio within the above range, a uniform foamed cell structure can be formed during foaming, and open The effect of stably manufacturing a foam without defects due to cell collapse and the like is excellent.
또한, 상기 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물을 이용하여 발포체를 제조하는 경우, 목적하는 탄성, 유연성, 경도, 내구성 등의 물성을 용이하게 구현할 수 있으며, 제조되는 발포체가 보다 매끄러운 표면과 우수한 광택을 나타내는 장점이 있다.In addition, when a foam is manufactured using the ethylene vinyl acetate-elastomer composite resin composition, desired physical properties such as elasticity, flexibility, hardness, and durability can be easily realized, and the manufactured foam has a smoother surface and excellent gloss. There are advantages to indicate.
또한, 상기 발포 조성물은 본 발명의 목적을 저해하지 않는 범위에서 통상 사용되는 분산제, 점도 조절제, 착색제, 산화 방지제, 자외선 안정제 및 블러킹 방지제 등을 더 포함할 수 있으나, 이에 제한되는 것은 아니다.In addition, the foam composition may further include a dispersant, a viscosity modifier, a colorant, an antioxidant, a UV stabilizer, and an anti-blocking agent, which are commonly used in a range that does not impair the object of the present invention, but is not limited thereto.
본 발명의 일 양태에 따른 발포체는 사출 발포 등 공지의 발포 성형 방법을 통해 제조되는 것일 수 있다. 구체적으로 예를 들어, 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물을 공지의 니더(kneader), 롤 밀(roll mill) 등을 이용하여 연화시킨 후 가교제, 발포제, 무기입자를 첨가한 에틸렌비닐아세테이트-엘라스토머 복합수지 발포체 조성물을 제작, 압출기(extruder)를 이용하여 연화시켜 펠렛 형태로 제조한다.The foam according to an aspect of the present invention may be manufactured through a known foam molding method such as injection foaming. Specifically, for example, an ethylene vinyl acetate-elastomer composite resin composition is softened using a known kneader, a roll mill, etc., and then a crosslinking agent, a foaming agent, and inorganic particles are added to the ethylene vinyl acetate-elastomer composite. A resin foam composition is prepared and softened using an extruder to prepare pellets.
이를 폼 사출기에 투입하여 발포체 체적 대비 일정 비율로 축소 설계된 금형 내에 에틸렌비닐아세테이트-엘라스토머 복합수지 발포체 조성물을 금형에 사출한 후 금형을 가압, 가열 후 해제하여 발포체를 제조하는 것일 수 있다.This may be put into a foam injection machine, and the ethylene vinyl acetate-elastomer composite resin foam composition is injected into the mold in a mold designed to be reduced in proportion to the foam volume, and then the mold is pressurized, heated, and released to manufacture a foam.
이 때, 상기 혼합 및 연화는 50 내지 250℃의 온도에서, 에틸렌비닐아세테이트-엘라스토머 복합수지 발포체 조성물 사출은 120℃미만, 구체적으로 100℃미만, 보다 구체적으로 70 내지 100℃의 온도에서 수행되는 것일 수 있으며, 금형의 온도는 100 내지 250℃구체적으로 140 내지 200℃보다 구체적으로 160 내지 180℃의 온도에서 수행될 수 있으나 이에 제한되는 것은 아니다.At this time, the mixing and softening are performed at a temperature of 50 to 250 °C, and the injection of the ethylene vinyl acetate-elastomer composite resin foam composition is less than 120 °C, specifically less than 100 °C, more specifically 70 to 100 °C. It can be, and the temperature of the mold may be performed at a temperature of 160 to 180 °C rather than specifically 140 to 200 °C of 100 to 250 °C, but is not limited thereto.
발포배율은 120 내지 200 %, 구체적으로 150 내지 180 %일 수 있으나, 이에 제한되는 것은 아니다.The expansion ratio may be 120 to 200%, specifically 150 to 180%, but is not limited thereto.
본 발명의 발포체는 상기 용융지수 측정기에서 190℃2.16 kg 조건 하에 용융되어 지름이 2.096mm인 오리피스를 통과한 스트랜드의 팽창비율이 80 % 이상인 고팽창성 에틸렌비닐아세테이트 공중합체 수지를 열가소성 엘라스토머와 함께 혼합하여 발포함에 따라, 운동화에 사용되는 복합소재로서의 경량화, 유연성, 탄성, 경도 및 압축변형 등의 우수한 물성을 발현할 뿐만 아니라, 현저히 향상된 표면특성을 가진다.The foam of the present invention is melted under the condition of 190 ° C. 2.16 kg in the melt index meter, and the expansion ratio of the strand passing through the orifice having a diameter of 2.096 mm is 80% or more High expansion ethylene vinyl acetate copolymer resin is mixed with a thermoplastic elastomer. As it foams, it exhibits excellent physical properties such as light weight, flexibility, elasticity, hardness and compression deformation as a composite material used in sports shoes, and has significantly improved surface properties.
특히, 종래 에틸렌비닐아세테이트 공중합체와 열가소성 엘라스토머를 포함하는 복합소재의 발포 공정상의 문제, 구체적으로 조기 발포, 오픈 셀 형성의 어려움 및 셀 붕괴와 같은 문제없이 용이하게 발포 가능하며, 제조된 발포체 또한 우수한 물성과 동시에 표면이 단단하지 않고 부드러우며 매끄러운 광택을 갖는 효과가 우수하다.In particular, it can be easily foamed without problems such as problems in the foaming process of a conventional composite material containing an ethylene vinyl acetate copolymer and a thermoplastic elastomer, specifically, early foaming, difficulty in forming open cells, and cell collapse. At the same time as physical properties, the surface is not hard and has an excellent effect of having a smooth and smooth luster.
이하 실시예 및 비교예를 바탕으로 본 발명을 더욱 상세히 설명한다. 다만 하기 실시예 및 비교예는 본 발명을 더욱 상세히 설명하기 위한 하나의 예시일 뿐, 본 발명이 하기 실시예 및 비교예에 의해 제한되는 것은 아니다. Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples. However, the following examples and comparative examples are merely examples for explaining the present invention in more detail, and the present invention is not limited by the following examples and comparative examples.
(평가)(evaluation)
1. 발포 성형성1. Foam moldability
발포체의 발포셀을 육안으로 관찰하여, 발포셀의 크기 및 균일성이 우수한 경우 ◎양호한 경우 ○발포셀의 크기가 크고 균일성이 낮은 경우 △조기발포가 발생하거나 셀 형성이 어려운 경우 X로 표기하였다.Observe the foam cells of the foam with the naked eye, and when the size and uniformity of the foam cells are excellent ◎ When the size of the foam cells is large and the uniformity is low △ When early foaming occurs or it is difficult to form the cells, X was marked .
2. 외관2. Appearance
발포체의 외관을 육안으로 확인하여, 표면이 거칠거나 주름진 현상이 관찰될 경우 '불량', 외관 불량은 없고 표면 광택이 떨어지는 경우 '양호', 외관 불량 없이 표면 광택이 매우 우수한 경우 '우수'로 표기하였다.Check the appearance of the foam with the naked eye, and if the surface is rough or wrinkled, it is marked as 'bad', if there is no appearance defect and the surface gloss is low, it is marked as 'good', if the surface gloss is very good without bad appearance, it is marked as 'excellent' did
3. 경도3. Hardness
발포체의 경도는 Asker C Type 경도계를 이용, 발포체 표면에 경도계 눌러준 뒤 1~2초 후 측정하였다.The hardness of the foam was measured 1 to 2 seconds after pressing the hardness meter on the surface of the foam using an Asker C type hardness meter.
4. 반발 탄성4. Rebound elasticity
발포체의 반발 탄성은 Resilience 측정계를 이용, 1~3회 Ball Drop 후 4~6회 측정 치 평균값으로 계산하였다.The rebound elasticity of the foam was calculated as the average value of 4 to 6 measurements after 1 to 3 ball drops using a resilience meter.
5. 영구압출 줄음률5. Permanent extrusion reduction rate
발포체의 영구압출 줄음률은 10mm 시료를 5mm로 압축 하여 50℃조건에서 보관 후, 상온에서 30min 방치 후 복원된 높이를 하기 식 1의 계산법으로 측정하였다.The permanent extrusion shrinkage of the foam was measured by compressing a 10 mm sample to 5 mm, storing it at 50° C., leaving it at room temperature for 30 min, and then measuring the restored height by the calculation method of Equation 1 below.
[식 1][Equation 1]
6. 팽창비율6. Expansion rate
용융지수 측정기에서 190 ℃2.16 kg 조건 하에 용융되어 지름이 2.096mm 인 오리피스(orifice)를 통과한 스트랜드의 팽창비율을 아래 수학식 1과 같이 계산하였다.The expansion ratio of the strand that was melted under the condition of 190 ° C. 2.16 kg in a melt index meter and passed through an orifice having a diameter of 2.096 mm was calculated as in Equation 1 below.
[수학식 1][Equation 1]
(수학식 1에서 A는 오리피스 관을 통과한 스트랜드의 직경이고, 상기 B는 오리피스 관의 직경이다.) (In Equation 1, A is the diameter of the strand passing through the orifice tube, and B is the diameter of the orifice tube.)
[실시예 1][Example 1]
팽창비율이 80%인 고팽창성 에틸렌비닐아세테이트 공중합체 수지 100 중량부에 대하여, TPEE(Thermoplastic Polyester Elastomer, SK케미칼, G140D) 40 중량부를 180℃의 직경 27mm 이축 압출기에 투입하여 스크류 속도 300rpm으로 혼합하여 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물을 제조하였다. 제조된 복합수지 조성물의 팽팡비율은 표 1에 표기하였다. With respect to 100 parts by weight of the high expansion ethylene vinyl acetate copolymer resin having an expansion ratio of 80%, 40 parts by weight of TPEE (Thermoplastic Polyester Elastomer, SK Chemicals, G140D) was put into a twin-screw extruder with a diameter of 27 mm at 180° C. and mixed at a screw speed of 300 rpm. An ethylene vinyl acetate-elastomer composite resin composition was prepared. The inflation ratio of the prepared composite resin composition is shown in Table 1.
이를 이용하여 제조된 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물 100 중량부에 대하여, 디큐밀퍼옥시드(Perkadox BC-FF, Akzonobel) 0.8 중량부, 아조디카본아미드(JTR-TL, 금양) 7 중량부, 탄산칼슘(B50 CaCO3, 부원) 4 중량부, 이산화티탄(B50 TiO2, 부원) 8 중량부를 롤 밀(roll mill)에 투입하여 혼합한 후, 단축 압출기에서 압출 후 컷팅하여 펠렛 형태의 발포체 조성물을 제조하였다. 제조된 발포체 조성물을 발포 후 발포 셀을 관찰하였을 때 발포셀 균일 성, 외관 및 발포체 물성을 확인하여 표 2에 나타내었다.Based on 100 parts by weight of the ethylene vinyl acetate-elastomer composite resin composition prepared using this, 0.8 parts by weight of dicumyl peroxide (Perkadox BC-FF, Akzonobel), 7 parts by weight of azodicarbonamide (JTR-TL, Geumyang), 4 parts by weight of calcium carbonate (B50 CaCO3, Buwon) and 8 parts by weight of titanium dioxide (B50 TiO 2 , Buwon) were put into a roll mill and mixed, and then extruded in a single screw extruder and cut to obtain a foam composition in the form of pellets prepared. When the foam cell was observed after foaming the prepared foam composition, the foam cell uniformity, appearance, and foam physical properties were confirmed and shown in Table 2.
[실시예 2][Example 2]
팽창비율이 80%인 고팽창성 에틸렌비닐아세테이트 공중합체 수지 100 중량부에 대하여, TPEE를(SK케미칼, G140D) 60 중량부로 사용하여 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물을 제조하고, 상기 에틸렌비닐아세테이트-엘라스토머 복합수지 100 중량부에 아조디카본아미드(JTR-TL, 금양) 6.5 중량부 사용한 것을 제외하고는 실시 예 1과 동일하게 실시 하였다. 하기 표 2에 물성을 나타내었다. Based on 100 parts by weight of the high expansion ratio ethylene vinyl acetate copolymer resin having an expansion ratio of 80%, TPEE (SK Chemical, G140D) was used in 60 parts by weight to prepare an ethylene vinyl acetate-elastomer composite resin composition, and the ethylene vinyl acetate- It was carried out in the same manner as in Example 1, except that 6.5 parts by weight of azodicarbonamide (JTR-TL, Geumyang) was used in 100 parts by weight of the elastomer composite resin. The physical properties are shown in Table 2 below.
[실시예 3][Example 3]
팽창비율이 80 %인 고팽창성 에틸렌비닐아세테이트 공중합체 수지 100 중량부에 대하여, TPEE를 (SK케미칼, G140D) 100중량부로 사용하여 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물을 제조하고, 상기 에틸렌비닐아세테이트-엘라스토머 복합수지 100 중량부에 아조디카본아미드(JTR-TL, 금양) 6 중량부 사용한 것을 제외하고는 실시 예 1과 동일하게 실시 하였다. 하기 표 2에 물성을 나타내었다. With respect to 100 parts by weight of a high expansion ethylene vinyl acetate copolymer resin having an expansion ratio of 80%, 100 parts by weight of TPEE (SK Chemical, G140D) was used to prepare an ethylene vinyl acetate-elastomer composite resin composition, and the ethylene vinyl acetate- It was carried out in the same manner as in Example 1, except that 6 parts by weight of azodicarbonamide (JTR-TL, Geumyang) was used in 100 parts by weight of the elastomer composite resin. The physical properties are shown in Table 2 below.
[실시예 4][Example 4]
팽창비율이 100 %인 고팽창성 에틸렌비닐아세테이트 공중합체 수지 100 중량부에 대하여, TPEE를 (SK케미칼, G140D) 40중량부로 사용하여 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물을 제조하고, 상기 에틸렌비닐아세테이트-엘라스토모 복합수지 100 중량부에 아조디카본아미드(JTR-TL, 금양)7.5중량부 사용한 것을 제외하고는 실시 예 1과 동일하게 실시 하였다. 하기 표 2에 물성을 나타내었다. Based on 100 parts by weight of the high expansion ethylene vinyl acetate copolymer resin having an expansion ratio of 100%, TPEE (SK Chemical, G140D) was used in 40 parts by weight to prepare an ethylene vinyl acetate-elastomer composite resin composition, and the ethylene vinyl acetate- It was carried out in the same manner as in Example 1, except that 7.5 parts by weight of azodicarbonamide (JTR-TL, Geumyang) was used in 100 parts by weight of the elastomo composite resin. The physical properties are shown in Table 2 below.
[실시예 5][Example 5]
팽창비율이 130 %인 고팽창성 에틸렌비닐아세테이트 공중합체 수지 100 중량부에 대하여, TPEE를 (SK케미칼, G140D) 40중량부로 사용하여 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물을 제조하고, 상기 에틸렌비닐아세테이트-엘라스토모 복합수지 100 중량부에 아조디카본아미드(JTR-TL, 금양)8중량부 사용한 것을 제외하고는 실시 예 1과 동일하게 실시 하였다. 하기 표 2에 물성을 나타내었다. Based on 100 parts by weight of the high expansion ethylene vinyl acetate copolymer resin having an expansion ratio of 130%, TPEE (SK Chemical, G140D) was used in 40 parts by weight to prepare an ethylene vinyl acetate-elastomer composite resin composition, and the ethylene vinyl acetate- It was carried out in the same manner as in Example 1, except that 8 parts by weight of azodicarbonamide (JTR-TL, Geumyang) was used in 100 parts by weight of the elastomo composite resin. The physical properties are shown in Table 2 below.
[비교예 1][Comparative Example 1]
팽창비율이 50 %인 고팽창성 에틸렌비닐아세테이트 공중합체 수지 100 중량부에 대하여, TPEE를 (SK케미칼, G140D) 40 중량부로 사용하여 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물을 제조하고, 상기 에틸렌비닐아세테이트-엘라스토머 복합수지 100 중량부에 아조디카본아미드(JTR-TL, 금양) 5 중량부 사용한 것을 제외하고는 실시 예 1과 동일하게 실시 하였다. 하기 표 2에 물성을 나타내었다. With respect to 100 parts by weight of the high expansion ethylene vinyl acetate copolymer resin having an expansion ratio of 50%, TPEE (SK Chemical, G140D) was used in 40 parts by weight to prepare an ethylene vinyl acetate-elastomer composite resin composition, and the ethylene vinyl acetate- It was carried out in the same manner as in Example 1, except that 5 parts by weight of azodicarbonamide (JTR-TL, Geumyang) was used in 100 parts by weight of the elastomer composite resin. The physical properties are shown in Table 2 below.
[비교예 2][Comparative Example 2]
팽창비율이 30 %인 팽창성 에틸렌비닐아세테이트 공중합체 수지 100 중량부에 대하여, TPEE를 (SK케미칼, G140D) 40중량부로 사용하여 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물을 제조하고, 상기 에틸렌비닐아세테이트-엘라스토모 복합수지 100 중량부에 아조디카본아미드(JTR-TL, 금양)4.5 중량부 사용한 것을 제외하고는 실시 예 1과 동일하게 실시 하였다. 하기 표 2에 물성을 나타내었다. Based on 100 parts by weight of the expandable ethylene vinyl acetate copolymer resin having an expansion ratio of 30%, TPEE (SK Chemical, G140D) was used in 40 parts by weight to prepare an ethylene vinyl acetate-elastomer composite resin composition, and the ethylene vinyl acetate-ela It was carried out in the same manner as in Example 1, except that 4.5 parts by weight of azodicarbonamide (JTR-TL, Geumyang) was used in 100 parts by weight of Stomo composite resin. The physical properties are shown in Table 2 below.
| EVA의 팽창비율(%)EVA Expansion Rate (%) | EVA 함량(중량부) EVA content (parts by weight) |
TPEE 함량(중량부) TPEE Content (parts by weight) |
에틸렌비닐아세테이트 복합수지 조성물의 의 팽창비율(%)Ethylene vinyl acetate Expansion ratio of composite resin composition (%) |
|
| 실시예 1Example 1 | 8080 | 100100 | 4040 | 5959 |
| 실시예 2Example 2 | 8080 | 100100 | 6060 | 5151 |
| 실시예 3Example 3 | 8080 | 100100 | 100100 | 4343 |
| 실시예 4Example 4 | 100100 | 100100 | 4040 | 7373 |
| 실시예 5Example 5 | 130130 | 100100 | 4040 | 9393 |
| 비교예 1Comparative Example 1 | 5050 | 100100 | 4040 | 3636 |
| 비교예 2Comparative Example 2 | 3030 | 100100 | 4040 | 2121 |
| 발포 성형성foam moldability | 외관Exterior |
발포 배율 (%)Foaming magnification (%) |
경도 (Asker C)Hardness (Asker C) |
반발 탄성 (%)rebound elasticity (%) |
영구압축 줄음률(%)Permanent compression reduction rate (%) | |
| 실시예 1Example 1 | ◎◎ | 우수Great | 160160 | 4747 | 6060 | 5353 |
| 실시예 2Example 2 | ◎◎ | 우수Great | 160160 | 5050 | 5757 | 5555 |
| 실시예 3Example 3 | ○○ | 양호Good | 160160 | 5151 | 5454 | 5454 |
| 실시예 4Example 4 | ◎◎ | 우수Great | 160160 | 4848 | 6060 | 5151 |
| 실시예 5Example 5 | ◎◎ | 우수Great | 160160 | 4848 | 6262 | 4747 |
| 비교예1Comparative Example 1 | △△ | 불량error | 160160 | 4242 | 4848 | 6666 |
| 비교예 2Comparative Example 2 | XX | 불량error | 160160 | 4141 | 4646 | 6868 |
Claims (13)
- 팽창률이 80%이상의 고팽창성 에틸렌비닐아세테이트 공중합체 수지에 열가소성 엘라스토머 포함하여 제조되는 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물.An ethylene vinyl acetate-elastomer composite resin composition prepared by including a thermoplastic elastomer in a high expansibility ethylene vinyl acetate copolymer resin having an expansion rate of 80% or more.
- 제 1항에 있어서,The method of claim 1,상기 팽창률이 80%이상의 고팽창성 에틸렌비닐아세테이트 공중합체 수지 100 중량부에 대하여, 상기 열가소성 엘라스토머 1 내지 100 중량부를 포함하여 제조되는 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물.An ethylene vinyl acetate-elastomer composite resin composition prepared by including 1 to 100 parts by weight of the thermoplastic elastomer with respect to 100 parts by weight of the high expansion rate ethylene vinyl acetate copolymer resin having the expansion rate of 80% or more.
- 제 1항에 있어서,The method of claim 1,상기 고팽창성 에틸렌비닐아세테이트 공중합체수지의 팽창률이 100 %이상인 것인 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물.The high expansibility ethylene vinyl acetate-elastomer composite resin composition wherein the expansion rate of the ethylene vinyl acetate copolymer resin is 100% or more.
- 제 1항에 있어서2. The method of claim 1상기 고팽창성 에틸렌비닐아세테이트 공중합체수지의 팽창률이 130 %이상의 것인 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물.The high expansibility ethylene vinyl acetate copolymer resin has an expansion rate of 130% or more of the ethylene vinyl acetate-elastomer composite resin composition.
- 제 1항에 있어서,The method of claim 1,상기 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물의 팽창률이 80 %이상인 것인 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물.The ethylene vinyl acetate-elastomer composite resin composition has an expansion rate of 80% or more.
- 제 1항에 있어서,The method of claim 1,상기 고팽창성 에틸렌비닐아세테이트 공중합체 수지는 에틸렌비닐아세테이트 공중합체 수지를 열가교, 방사선가교, X-레이가교, 전자선가교에서 선택되는 어느 하나의 방법으로 개질하여 제조되는 것인 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물.The high expansion ethylene vinyl acetate copolymer resin is an ethylene vinyl acetate copolymer resin prepared by modifying an ethylene vinyl acetate copolymer resin by any one method selected from thermal crosslinking, radiation crosslinking, X-ray crosslinking, and electron beam crosslinking. resin composition.
- 제 1항에 있어서,The method of claim 1,상기 반응성 엘라스토머는 라디칼 개질 가능한 것인 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물.The reactive elastomer is an ethylene vinyl acetate-elastomer composite resin composition that can be radically modified.
- 제 7항에 있어서,8. The method of claim 7,상기 열 가소성 엘라스토머는 스티렌-부타디엔-스티렌 수지, 스티렌-이소부티렌-스티렌 수지, 스티렌-에틸렌-부티렌-스티렌 수지, 스티렌-에틸렌-프로필렌-스티렌 수지, 스티렌-이소프렌-스티렌 수지, 이소프렌 고무, 부타디엔 고무, 클로로프렌 고무, 에틸렌-프로필렌 고무, 에틸렌-프로필렌-디엔 고무, 열가소성 폴리올레핀 엘라스토머, 열가소성 폴리에스테르 엘라스토머, 열가소성 폴리아미드 엘라스토머 및 열가소성 폴리우레탄에서 선택되는 어느 하나 또는 둘 이상의 혼합물인 것인 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물.The thermoplastic elastomer is styrene-butadiene-styrene resin, styrene-isobutyrene-styrene resin, styrene-ethylene-butyrene-styrene resin, styrene-ethylene-propylene-styrene resin, styrene-isoprene-styrene resin, isoprene rubber, Butadiene rubber, chloroprene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, thermoplastic polyolefin elastomer, thermoplastic polyester elastomer, thermoplastic polyamide elastomer and thermoplastic polyurethane, which is any one or a mixture of two or more ethylene vinyl acetate - Elastomer composite resin composition.
- 제 1항 내지 8항에서 선택되는 어느 한 항의 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물에 가교제, 발포제 및 무기입자를 더 포함하여 발포한 에틸렌 비닐아세테이트-엘라스토머 복합수지 발포체.An ethylene vinyl acetate-elastomer composite resin foam formed by further including a crosslinking agent, a foaming agent and inorganic particles in the ethylene vinyl acetate-elastomer composite resin composition of any one of claims 1 to 8.
- 제 9항에 있어서,10. The method of claim 9,상기 에틸렌 비닐아세테이트-엘라스토머 복합수지 발포체는, 에틸렌비닐아세테이트-엘라스토머 복합수지 조성물 100 중량부에 대하여 상기 가교제 0.1 내지 3 중량부, 상기 발포제 1 내지 20 중량부 및 상기 무기입자 0.1 내지 20 중량부를 포함하여 제조되는 에틸렌 비닐아세테이트-엘라스토머 복합수지 발포체.The ethylene vinyl acetate-elastomer composite resin foam contains 0.1 to 3 parts by weight of the crosslinking agent, 1 to 20 parts by weight of the foaming agent, and 0.1 to 20 parts by weight of the inorganic particles based on 100 parts by weight of the ethylene vinyl acetate-elastomer composite resin composition. The manufactured ethylene vinyl acetate-elastomer composite resin foam.
- 제 9항에 있어서,10. The method of claim 9,상기 가교제는 디-t-부틸퍼옥시드, 디-t-아밀퍼옥시드, t-부틸큐밀퍼옥시드, 디큐밀퍼옥시드, 2,5-디메틸-2,5-디(t-부틸퍼옥시)헥산, 2,5-디메틸-2,5-디(t-부틸퍼옥시)헥산-3,2,2'-비스(t-부틸퍼옥시이소프로필)벤젠, 1,1-비스(t-부틸퍼옥시)-3,3,5-트리메틸시클로헥산, n-부틸-4,4-비스(t-부틸퍼옥시)발러레이트, 벤조일퍼옥시드, p-클로로벤조일퍼옥시드, t-부틸퍼옥시벤조에이트, 및 2,5-디메틸-2,5-디 (t-벤조일퍼옥시)헥산 에서 선택되는 어느 하나 또는 이들의 혼합물인 에틸렌 비닐아세테이트-엘라스토머 복합수지 발포체.The crosslinking agent is di-t-butyl peroxide, di-t-amyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane , 2,5-Dimethyl-2,5-di(t-butylperoxy)hexane-3,2,2'-bis(t-butylperoxyisopropyl)benzene, 1,1-bis(t-butylperoxy) Oxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(t-butylperoxy)valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, t-butylperoxybenzoate , and 2,5-dimethyl-2,5-di (t-benzoyl peroxy) hexane, or a mixture thereof, an ethylene vinyl acetate-elastomer composite resin foam.
- 제 9항에 있어서,10. The method of claim 9,상기 아조디카본아미드, 아조비스이소부티로니트릴, 디아조아미노아조벤젠 N,N'-디니트로- 소펜타메틸렌테트라민 p-톨루엔술포닐히드라지드 및 p,p'-옥시비스 (벤젠술포닐히드라지드) p-톨루엔-술포닐세미카바, 소디움디카보네이트 에서 선택되는 어느 하나 또는 이들의 혼합물인 것인 에틸렌 비닐아세테이트-엘라스토머 복합수지 발포체.Azodicarbonamide, azobisisobutyronitrile, diazoaminoazobenzene N,N'-dinitro- sopentamethylenetetramine p-toluenesulfonylhydrazide and p,p'-oxybis (benzenesulfonylhydra) Zide) p-toluene-sulfonyl semicarba, sodium dicarbonate, any one selected from, or a mixture thereof, ethylene vinyl acetate-elastomer composite resin foam.
- 제 9항에 있어서,10. The method of claim 9,상기 무기입자로는 탄산칼슘, 산화아연, 산화칼슘, 산화마그네슘, 실리카, 알루미나 및 이산화티탄에서 선택되는 어느 하나 또는 둘 이상의 혼합물인 것인 에틸렌 비닐아세테이트-엘라스토머 복합수지 발포체.The inorganic particles include any one or a mixture of two or more selected from calcium carbonate, zinc oxide, calcium oxide, magnesium oxide, silica, alumina and titanium dioxide, ethylene vinyl acetate-elastomer composite resin foam.
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| CN117050419A (en) * | 2023-09-22 | 2023-11-14 | 饭田（佛山）橡塑有限公司 | Resin foaming sound-proof material, preparation method and application |
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| JPH06228355A (en) * | 1993-02-02 | 1994-08-16 | Fujikura Ltd | Polyolefin foam with flame retardancy and heat resistance |
| JPH0859754A (en) * | 1994-08-18 | 1996-03-05 | Sekisui Plastics Co Ltd | Production of impact-resistant foamable resin particle |
| KR20040082122A (en) * | 2003-03-18 | 2004-09-24 | 주식회사 엘지화학 | Industrial Bead Using Styrene-Butadiene-Styrene Copolymer |
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| KR101879316B1 (en) | 2016-10-26 | 2018-07-17 | 한국신발피혁연구원 | Low specific gravity foam compositions and low specific gravity foam using the same |
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- 2021-12-28 WO PCT/KR2021/020041 patent/WO2022145967A1/en active Application Filing
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Patent Citations (5)
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| JPH0680811A (en) * | 1992-09-04 | 1994-03-22 | Hitachi Chem Co Ltd | Highly expanded crosslinked polyolefin |
| JPH06228355A (en) * | 1993-02-02 | 1994-08-16 | Fujikura Ltd | Polyolefin foam with flame retardancy and heat resistance |
| JPH0859754A (en) * | 1994-08-18 | 1996-03-05 | Sekisui Plastics Co Ltd | Production of impact-resistant foamable resin particle |
| KR20040082122A (en) * | 2003-03-18 | 2004-09-24 | 주식회사 엘지화학 | Industrial Bead Using Styrene-Butadiene-Styrene Copolymer |
| KR20110124836A (en) * | 2010-05-12 | 2011-11-18 | 동서대학교산학협력단 | Ethylene vinyl acetate resin composition for masai sensor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117050419A (en) * | 2023-09-22 | 2023-11-14 | 饭田（佛山）橡塑有限公司 | Resin foaming sound-proof material, preparation method and application |
| CN117050419B (en) * | 2023-09-22 | 2024-02-20 | 饭田（佛山）橡塑有限公司 | Resin foaming sound-proof material, preparation method and application |
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| TW202229433A (en) | 2022-08-01 |
| CN116710523A (en) | 2023-09-05 |
| KR20220095729A (en) | 2022-07-07 |
| TWI805153B (en) | 2023-06-11 |
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