KR102631510B1 - Foam composition for shoes midsole having excellent durability - Google Patents
Foam composition for shoes midsole having excellent durability Download PDFInfo
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- KR102631510B1 KR102631510B1 KR1020210070215A KR20210070215A KR102631510B1 KR 102631510 B1 KR102631510 B1 KR 102631510B1 KR 1020210070215 A KR1020210070215 A KR 1020210070215A KR 20210070215 A KR20210070215 A KR 20210070215A KR 102631510 B1 KR102631510 B1 KR 102631510B1
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- South Korea
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- styrene
- weight
- thermoplastic elastomer
- based thermoplastic
- foam
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- 239000006260 foam Substances 0.000 title claims abstract description 47
- 239000000203 mixture Substances 0.000 title claims abstract description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 28
- 230000005484 gravity Effects 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 21
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 21
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims description 20
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 13
- -1 Styrene Ethylene Butylene Styrene Chemical class 0.000 claims description 4
- RLRINNKRRPQIGW-UHFFFAOYSA-N 1-ethenyl-2-[4-(2-ethenylphenyl)butyl]benzene Chemical compound C=CC1=CC=CC=C1CCCCC1=CC=CC=C1C=C RLRINNKRRPQIGW-UHFFFAOYSA-N 0.000 claims description 3
- NGYFVLXDIUCNIG-UHFFFAOYSA-N C=C.C=C.CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 Chemical compound C=C.C=C.CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 NGYFVLXDIUCNIG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002174 Styrene-butadiene Substances 0.000 claims description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 3
- NRJXUPLBIUZXLW-UHFFFAOYSA-N ethene;prop-1-ene;styrene Chemical compound C=C.CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 NRJXUPLBIUZXLW-UHFFFAOYSA-N 0.000 claims description 3
- 239000011115 styrene butadiene Substances 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 18
- 230000006835 compression Effects 0.000 abstract description 16
- 238000007906 compression Methods 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 8
- 239000005977 Ethylene Substances 0.000 abstract description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 8
- 230000035939 shock Effects 0.000 description 8
- 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 description 7
- 239000004156 Azodicarbonamide Substances 0.000 description 7
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 7
- 235000019399 azodicarbonamide Nutrition 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003431 cross linking reagent Substances 0.000 description 7
- 239000004088 foaming agent Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 235000021355 Stearic acid Nutrition 0.000 description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 6
- 239000008117 stearic acid Substances 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000000465 moulding Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 3
- 239000002952 polymeric resin Substances 0.000 description 3
- 229920006124 polyolefin elastomer Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011359 shock absorbing material Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
Classifications
-
- 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
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
Abstract
본 발명은 내구성이 우수한 경량 신발 중창용 발포체 조성물에 관한 것으로, 보다 구체적으로는 EVA, 스티렌계 열가소성 탄성체 및 고분자량 스티렌계 열가소성 탄성체로 이루어진 기재를 사용하여 신발 중창용 발포체를 제조함으로써, 에틸렌계 소재의 발포체와 유사한 경도 및 비중으로 경량성을 가지면서도 영구압축줄음율 및 반발탄성 등의 내구성을 향상시킬 수 있도록 하는, 내구성이 우수한 경량 신발 중창용 발포체 조성물에 관한 것이다.The present invention relates to a foam composition for a lightweight shoe midsole with excellent durability, and more specifically, to manufacture a foam for a shoe midsole using a substrate made of EVA, a styrene-based thermoplastic elastomer, and a high molecular weight styrene-based thermoplastic elastomer, thereby producing an ethylene-based material. It relates to a highly durable lightweight shoe midsole foam composition that has a hardness and specific gravity similar to that of foam and is lightweight while improving durability such as permanent compression set and rebound elasticity.
Description
본 발명은 에틸렌계 소재의 발포체와 유사한 경도 및 비중으로 경량성을 가지면서도 영구압축줄음율 및 반발탄성 등의 내구성을 향상시킬 수 있도록 하는, 내구성이 우수한 경량 신발 중창용 발포체 조성물에 관한 것이다.The present invention relates to a highly durable lightweight shoe midsole foam composition that has a hardness and specific gravity similar to those of foams made of ethylene-based materials, making it lightweight and improving durability such as permanent compression set and rebound elasticity.
일반적으로 신발 중창용 발포체는 EVA(EthyleneVinylAcetate)나 POE(PolyOlefinElastomer) 등의 에틸렌계 고분자 수지를 주기재로 사용하고 있지만, 에틸렌계 고분자 수지의 발현 가능한 성능의 한계로 최근의 소비자 요구를 만족시키지 못하고 있는 실정이다.In general, foam for shoe midsoles uses ethylene-based polymer resins such as EVA (EthyleneVinylAcetate) or POE (PolyOlefinElastomer) as the main material, but due to limitations in the performance that can be achieved with ethylene-based polymer resins, it is not satisfying recent consumer demands. This is the situation.
보다 구체적으로 이러한 에틸렌계 고분자 수지를 기반으로한 발포체는 발포율을 높여 비중을 낮춤으로써 경량화를 가능하게 하지만, 발포율이 높아지면 반발탄성 및 영구압축줄음율 등의 내구성이 취약해지는 단점이 있다.More specifically, foams based on such ethylene-based polymer resins enable lightweighting by lowering specific gravity by increasing the foaming rate, but they have the disadvantage that durability, such as rebound elasticity and permanent compression set, becomes weak as the foaming rate increases.
이를 해결하기 위하여, 특허문헌 1에서는 산업용 발포체 조성물에 있어서, 서로 다른 유리전이온도를 가지는 2종 이상의 스티렌-포화탄화수소계 열가소성 고분자 기재 또는 필요에 따라 폴리에틸렌, 에틸렌 비닐아세테이트 공중합체, 에틸렌-올레핀 공중합체, 고무 등을 블렌드한 블렌드물을 기재로 하고 충전제, 가교제, 발포제 및 기타 첨가제를 투입하여 프레스 성형함으로서 비중이 낮고 영구압축줄음율 등의 내구성이 우수하면서 다양한 온도영역에서 우수한 충격흡수성을 갖는 것을 특징으로 하는 다양한 온도영역에서 우수한 충격흡수성을 갖는 산업용 발포체 조성물에 관한 것으로, 기존의 충격흡수 재료보다 환경적인 측면 혹은 비용적인 측면에서 유리하고 충격흡수성 특성을 갖는 산업용 발포체로서, 특히, 기존 충격흡수 소재가 상온영역에서만 충격흡수 특성이 발현되는데 비해 다양한 온도영역에서도 우수한 충격흡수성 발현되도록 기능성을 부여함으로써 기존에 사용 범위가 제한되어있던 소재의 한계를 극복하는 신규 기능 소재를 제공하여 스포츠용품, 건설용품 등의 산업에 다양한 용도에 적용이 가능하며, 또한, 기존의 충격흡수 재료인 폴리비닐클로라이드와 폴리우레탄을 대체할 수 있어 상기소재 사용으로 인하여 발생되었던 환경오염 문제를 해결할 수 있도록 하는, 산업용 발포체 조성물을 제안하였다.To solve this problem, in Patent Document 1, in the industrial foam composition, two or more types of styrene-saturated hydrocarbon-based thermoplastic polymer bases with different glass transition temperatures or, if necessary, polyethylene, ethylene vinyl acetate copolymer, and ethylene-olefin copolymer. , is based on a blend of rubber, etc., and is press-molded by adding fillers, cross-linking agents, foaming agents, and other additives, so it has a low specific gravity, excellent durability such as permanent compression set, and has excellent shock absorption in various temperature ranges. It relates to an industrial foam composition with excellent shock absorption properties in various temperature ranges. It is an industrial foam composition that is advantageous in terms of environmental or cost over existing shock absorption materials and has shock absorption properties. In particular, existing shock absorption materials are While shock absorption properties are only expressed in the room temperature range, we provide a new functional material that overcomes the limitations of materials that were previously limited in their use by providing functionality that allows excellent shock absorption even in a variety of temperature ranges, and is used in sports goods, construction goods, etc. We propose an industrial foam composition that can be applied to a variety of industrial applications and can replace existing shock-absorbing materials such as polyvinyl chloride and polyurethane, thereby solving the environmental pollution problem caused by the use of these materials. did.
하지만, 상기 특허문헌 1의 경우 영구압축줄음율 등의 내구성은 우수하지만 이는 발포율을 낮추어 비중을 높임에 따라 구현되는 것으로, 높은 비중을 가짐에 따라 경량성이 미비하게 되는 문제점이 있었다.However, in the case of Patent Document 1, durability such as permanent compression set is excellent, but this is achieved by lowering the expansion rate and increasing specific gravity, and there is a problem in that the lightness is insufficient due to the high specific gravity.
본 발명은 상기와 같은 문제점을 해결하기 위한 것으로, EVA, 스티렌계 열가소성 탄성체 및 고분자량 스티렌계 열가소성 탄성체로 이루어진 기재를 사용하여 신발 중창용 발포체를 제조함으로써, 에틸렌계 소재의 발포체와 유사한 경도 및 비중으로 경량성을 가지면서도 영구압축줄음율 및 반발탄성 등의 내구성을 향상시킬 수 있도록 함을 과제로 한다.The present invention is intended to solve the above problems, by manufacturing a foam for a shoe midsole using a substrate made of EVA, a styrene-based thermoplastic elastomer, and a high molecular weight styrene-based thermoplastic elastomer, thereby producing a hardness and specific gravity similar to that of an ethylene-based foam. The goal is to improve durability, such as permanent compression set and rebound elasticity, while being lightweight.
본 발명은 경량 신발 중창용 발포체 조성물에 있어서, EVA(Ethylene Vinyl Acetate), 스티렌계 열가소성 탄성체 및 고분자량 스티렌계 열가소성 탄성체로 이루어진 기재를 사용하는 것을 특징으로 하는, 내구성이 우수한 경량 신발 중창용 발포체 조성물을 과제의 해결 수단으로 한다.The present invention relates to a foam composition for a lightweight shoe midsole with excellent durability, characterized by using a base material made of EVA (Ethylene Vinyl Acetate), a styrene-based thermoplastic elastomer, and a high molecular weight styrene-based thermoplastic elastomer. is used as a means of solving the problem.
보다 구체적으로 상기 기재는, EVA 20 ~ 40 중량%, 스티렌(Styrene) 함량이 1 ~ 20 중량%인 스티렌계 열가소성 탄성체 50 ~ 60 중량% 및, 분자량이 200,000 ~ 500,000g/mol이고 스티렌 함량이 1 ~ 20 중량%인 고분자량 스티렌계 열가소성 탄성체 10 ~ 20 중량%로 이루어지는 것이 바람직하다.More specifically, the substrate contains 20 to 40% by weight of EVA, 50 to 60% by weight of a styrene-based thermoplastic elastomer with a styrene content of 1 to 20% by weight, and a molecular weight of 200,000 to 500,000 g/mol with a styrene content of 1. It is preferably made of 10 to 20% by weight of a high molecular weight styrene-based thermoplastic elastomer.
아울러, 상기 EVA는 VA(vinyl acetate) 함량이 22 ~ 40 중량%이며, MI(melt index)가 3.0 ~ 10g/10min.(190℃, 2.16kg)인 것을 사용하고, 상기 스티렌계 열가소성 탄성체는 SBBS(Styrene Butadiene Butylene Styrene)를 사용하며, 상기 고분자량 스티렌계 열가소성 탄성체는 SEBS(Styrene Ethylene Butylene Styrene), SEPS(Styrene Ethylene Propylene Styrene) 또는 SEEPS(Styrene Ethylene Ethylene Propylene Styrene)를 사용하는 것이 바람직하다.In addition, the EVA has a VA (vinyl acetate) content of 22 to 40% by weight and an MI (melt index) of 3.0 to 10g/10min. (190°C, 2.16kg). The styrene-based thermoplastic elastomer is SBBS. (Styrene Butadiene Butylene Styrene) is used, and the high molecular weight styrene-based thermoplastic elastomer is preferably SEBS (Styrene Ethylene Butylene Styrene), SEPS (Styrene Ethylene Propylene Styrene), or SEEPS (Styrene Ethylene Ethylene Propylene Styrene).
본 발명은 EVA, 스티렌계 열가소성 탄성체 및 고분자량 스티렌계 열가소성 탄성체로 이루어진 기재를 사용하여 신발 중창용 발포체를 제조함으로써, 에틸렌계 소재의 발포체와 유사한 경도 및 비중으로 경량성을 가지면서도 영구압축줄음율 및 반발탄성 등의 내구성을 향상시킬 수 있는 효과가 있다.The present invention manufactures foam for shoe midsoles using a substrate made of EVA, styrene-based thermoplastic elastomer, and high-molecular-weight styrene-based thermoplastic elastomer, thereby providing lightweight properties with hardness and specific gravity similar to foams made of ethylene-based materials, while maintaining permanent compression set. It has the effect of improving durability such as rebound elasticity.
상기의 효과를 달성하기 위한 본 발명은 내구성이 우수한 경량 신발 중창용 발포체 조성물에 관한 것으로서, 본 발명의 기술적 구성을 이해하는데 필요한 부분만이 설명되며 그 이외 부분의 설명은 본 발명의 요지를 흩트리지 않도록 생략될 것이라는 것을 유의하여야 한다.The present invention to achieve the above effects relates to a foam composition for a lightweight shoe midsole with excellent durability. Only the parts necessary to understand the technical structure of the present invention are described, and the description of other parts does not distract from the gist of the present invention. Please note that this will be omitted.
이하, 본 발명에 따른 내구성이 우수한 경량 신발 중창용 발포체 조성물을 상세히 설명하면 다음과 같다.Hereinafter, the foam composition for a lightweight shoe midsole with excellent durability according to the present invention will be described in detail as follows.
본 발명에 따른 내구성이 우수한 경량 신발 중창용 발포체 조성물은 EVA(Ethylene Vinyl Acetate), 스티렌계 열가소성 탄성체 및 고분자량 스티렌계 열가소성 탄성체로 이루어진 기재를 사용하는 것을 특징으로 한다.The highly durable lightweight shoe midsole foam composition according to the present invention is characterized by using a base material made of EVA (Ethylene Vinyl Acetate), a styrene-based thermoplastic elastomer, and a high molecular weight styrene-based thermoplastic elastomer.
상기 EVA는 본 발명의 주기재로써 VA(vinyl acetate) 함량이 22 ~ 40 중량%이며, MI(melt index)가 3.0 ~ 10g/10min.(190℃, 2.16kg)인 것을 20 ~ 40 중량% 사용한다.The EVA is the main material of the present invention and has a VA (vinyl acetate) content of 22 to 40% by weight and an MI (melt index) of 3.0 to 10g/10min. (190°C, 2.16kg) at 20 to 40% by weight. do.
여기서 상기 EVA의 함량이 20 중량% 미만에서는 스티렌계 열가소성 탄성체와의 혼합성이 좋지 못해 발포체 제조가 어려워질 우려가 있으며, 40 중량%를 초과하면 물성이 저하될 우려가 있다.Here, if the EVA content is less than 20% by weight, there is a risk of poor mixing with the styrene-based thermoplastic elastomer, making it difficult to manufacture foam, and if it exceeds 40% by weight, there is a risk that physical properties may deteriorate.
그리고, VA 함량이 22 중량% 미만이거나 MI가 3.0g/10min.(190℃, 2.16kg) 미만일 경우 스티렌계 열가소성 탄성체와의 혼합성이 좋지 못해 발포체 제조가 어려워질 우려가 있으며, VA 함량이 40 중량%를 초과하거나 MI가 10g/10min.(190℃, 2.16kg)을 초과할 경우 물성이 저하될 우려가 있다.In addition, if the VA content is less than 22% by weight or the MI is less than 3.0g/10min. (190℃, 2.16kg), there is a risk that foam manufacturing will be difficult due to poor miscibility with the styrene-based thermoplastic elastomer, and the VA content is 40%. If the weight percentage is exceeded or the MI exceeds 10g/10min. (190℃, 2.16kg), there is a risk that the physical properties may deteriorate.
상기 스티렌계 열가소성 탄성체와 고분자량 스티렌계 열가소성 탄성체는 반발탄성 및 영구압축줄음율 등의 물성을 개선하기 위해 첨가되는 것으로, 먼저 스티렌계 열가소성 탄성체는 스티렌(Styrene) 함량이 1 ~ 20 중량%인 SBBS(Styrene Butadiene Butylene Styrene)를 50 ~ 60 중량% 사용한다.The styrene-based thermoplastic elastomer and high molecular weight styrene-based thermoplastic elastomer are added to improve physical properties such as rebound elasticity and permanent compression set. First, the styrene-based thermoplastic elastomer is SBBS with a styrene content of 1 to 20% by weight. (Styrene Butadiene Butylene Styrene) is used in an amount of 50 to 60% by weight.
여기서, 상기 스티렌계 열가소성 탄성체의 스티렌 함량이 상기 범위를 벗어날 경우 발포체 경도가 높고 반발탄성이 낮아 신발용 발포체로 적합하지 않으며, 그 함량이 50 중량% 미만일 경우 영구압축줄음율 등의 특성 개선이 어렵고, 60 중량%를 초과할 경우 발포체 제조가 어려워질 우려가 있다.Here, if the styrene content of the styrene-based thermoplastic elastomer is outside the above range, the foam hardness is high and the rebound elasticity is low, making it unsuitable as a foam for shoes, and if the content is less than 50% by weight, it is difficult to improve properties such as permanent compression set. , if it exceeds 60% by weight, there is a risk that foam production may become difficult.
그리고 고분자량 스티렌계 열가소성 탄성체는 분자량이 200,000 ~ 500,000g/mol이고 스티렌 함량이 1 ~ 20 중량%인 SEBS(Styrene Ethylene Butylene Styrene), SEPS(Styrene Ethylene Propylene Styrene) 또는 SEEPS(Styrene Ethylene Ethylene Propylene Styrene)를 10 ~ 20 중량% 사용한다.And high molecular weight styrene-based thermoplastic elastomers include SEBS (Styrene Ethylene Butylene Styrene), SEPS (Styrene Ethylene Propylene Styrene), or SEEPS (Styrene Ethylene Ethylene Propylene Styrene) with a molecular weight of 200,000 to 500,000 g/mol and a styrene content of 1 to 20% by weight. Use 10 to 20% by weight.
여기서, 상기 고분자량 스티렌계 열가소성 탄성체의 분자량 및 스티렌 함량이 상기 범위를 벗어날 경우 영구압축줄음율 등의 특성 개선이 어려워질 우려가 있다. 그리고 그 함량이 10 중량% 미만일 경우 영구압축줄음율 등의 특성 개선이 어렵고, 20 중량%를 초과할 경우 발포체 제조가 어려워질 우려가 있다.Here, if the molecular weight and styrene content of the high molecular weight styrene-based thermoplastic elastomer are outside the above range, there is a risk that it will be difficult to improve properties such as compression set. In addition, if the content is less than 10% by weight, it is difficult to improve characteristics such as permanent compression set, and if it exceeds 20% by weight, there is a risk that foam production may become difficult.
아울러, 본 발명은 상기와 같은 기재에 대하여 통상의 발포체용 첨가제를 사용할 수 있으며, 발포체용 첨가제는 발포체를 제조하기 위해 첨가되는 이미 공지된 통상의 첨가제로써 예를 들면, 산화아연, 스테아린산, 가교제(DCP(Dicumyl peroxide) 등), 발포제(ADCA(azodicarbonamide) 등) 등을 적용할 수 있으나, 여기에 한정되는 것은 아니고 해당 발포체의 사용환경이나 대상 등을 고려하여 이미 공지된 다양한 발포체용 첨가제의 사용이 가능하다.In addition, the present invention can use conventional foam additives for the above-mentioned substrate, and the foam additives include known conventional additives added to produce foam, such as zinc oxide, stearic acid, and crosslinking agent ( DCP (Dicumyl peroxide), etc.), foaming agents (ADCA (azodicarbonamide), etc.) can be applied, but it is not limited to this, and considering the use environment or target of the foam, the use of various already known foam additives is possible. possible.
이하, 본 발명을 아래 실시예에 의거하여 더욱 상세히 설명하겠는바 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail based on the examples below, but the present invention is not limited by the examples.
1. 신발 중창용 발포체의 기재 제조1. Manufacturing of base material for shoe midsole foam
(제조예 1)(Production Example 1)
VA 함량이 28 중량%이며 MI가 3.0g/10min.(190℃, 2.16kg)인 EVA 30 중량%, 스티렌(Styrene) 함량이 18 중량%인 SBBS 50 중량% 및, 분자량이 220,000g/mol이고 스티렌 함량이 18 중량%인 SEEPS 20 중량%를 다이(Die) 온도 160 ~ 200℃로 설정된 이축압출기에서 혼합하여 제조하였다.30% by weight of EVA with a VA content of 28% by weight and an MI of 3.0g/10min. (190°C, 2.16kg), 50% by weight of SBBS with a styrene content of 18% by weight, and a molecular weight of 220,000g/mol. 20% by weight of SEEPS with a styrene content of 18% by weight was prepared by mixing in a twin-screw extruder set at a die temperature of 160 to 200°C.
(제조예 2)(Production Example 2)
VA 함량이 28 중량%이며 MI가 3.0g/10min.(190℃, 2.16kg)인 EVA 20 중량%, 스티렌(Styrene) 함량이 18 중량%인 SBBS 60 중량% 및, 분자량이 220,000g/mol이고 스티렌 함량이 18 중량%인 SEEPS 20 중량%를 다이(Die) 온도 160 ~ 200℃로 설정된 이축압출기에서 혼합하여 제조하였다.20% by weight of EVA with a VA content of 28% by weight and an MI of 3.0g/10min. (190°C, 2.16kg), 60% by weight of SBBS with a styrene content of 18% by weight, and a molecular weight of 220,000g/mol. 20% by weight of SEEPS with a styrene content of 18% by weight was prepared by mixing in a twin-screw extruder set at a die temperature of 160 to 200°C.
(제조예 3)(Production Example 3)
VA 함량이 28 중량%이며 MI가 3.0g/10min.(190℃, 2.16kg)인 EVA 40 중량%, 스티렌(Styrene) 함량이 18 중량%인 SBBS 50 중량% 및, 분자량이 220,000g/mol이고 스티렌 함량이 18 중량%인 SEEPS 10 중량%를 다이(Die) 온도 160 ~ 200℃로 설정된 이축압출기에서 혼합하여 제조하였다.40% by weight of EVA with a VA content of 28% by weight and an MI of 3.0g/10min. (190°C, 2.16kg), 50% by weight of SBBS with a styrene content of 18% by weight, and a molecular weight of 220,000g/mol. SEEPS 10 wt% with a styrene content of 18 wt% was prepared by mixing in a twin-screw extruder set at a die temperature of 160 to 200°C.
2. 신발 중창용 발포체의 제조2. Manufacturing of foam for shoe midsoles
(실시예 1)(Example 1)
상기 제조예 1에 따른 기재 100 중량부에 대하여, 산화아연 5 중량부, 스테아린산 1 중량부, 가교제(DCP) 0.8 중량부 및 발포제(ADCA) 3.0 중량부를 혼합하여 컴파운드를 제조한 후, 이를 금형에 투입하여 온도 155℃, 압력 150kgf/cm2에서 40분간 성형하여 발포체를 제조하였다.With respect to 100 parts by weight of the base material according to Preparation Example 1, a compound was prepared by mixing 5 parts by weight of zinc oxide, 1 part by weight of stearic acid, 0.8 parts by weight of a cross-linking agent (DCP), and 3.0 parts by weight of a foaming agent (ADCA), and then placed in a mold. The foam was manufactured by molding for 40 minutes at a temperature of 155°C and a pressure of 150kgf/cm 2 .
(실시예 2)(Example 2)
상기 제조예 2에 따른 기재 100 중량부에 대하여, 산화아연 5 중량부, 스테아린산 1 중량부, 가교제(DCP) 0.8 중량부 및 발포제(ADCA) 3.0 중량부를 혼합하여 컴파운드를 제조한 후, 이를 금형에 투입하여 온도 155℃, 압력 150kgf/cm2에서 40분간 성형하여 발포체를 제조하였다.With respect to 100 parts by weight of the base material according to Preparation Example 2, a compound was prepared by mixing 5 parts by weight of zinc oxide, 1 part by weight of stearic acid, 0.8 parts by weight of a cross-linking agent (DCP), and 3.0 parts by weight of a foaming agent (ADCA), and then placed in a mold. The foam was manufactured by molding for 40 minutes at a temperature of 155°C and a pressure of 150kgf/cm 2 .
(실시예 3)(Example 3)
상기 제조예 3에 따른 기재 100 중량부에 대하여, 산화아연 5 중량부, 스테아린산 1 중량부, 가교제(DCP) 0.8 중량부 및 발포제(ADCA) 3.0 중량부를 혼합하여 컴파운드를 제조한 후, 이를 금형에 투입하여 온도 155℃, 압력 150kgf/cm2에서 40분간 성형하여 발포체를 제조하였다.A compound was prepared by mixing 5 parts by weight of zinc oxide, 1 part by weight of stearic acid, 0.8 parts by weight of a cross-linking agent (DCP), and 3.0 parts by weight of a foaming agent (ADCA) with respect to 100 parts by weight of the base material according to Preparation Example 3, and then placed in a mold. The foam was manufactured by molding for 40 minutes at a temperature of 155°C and a pressure of 150kgf/cm 2 .
(비교예 1)(Comparative Example 1)
VA 함량이 28 중량%이며 MI가 3.0g/10min.(190℃, 2.16kg)인 EVA 100 중량부에 대하여, 산화아연 5 중량부, 스테아린산 1 중량부, 가교제(DCP) 0.8 중량부 및 발포제(ADCA) 3.0 중량부를 혼합하여 컴파운드를 제조한 후, 이를 금형에 투입하여 온도 155℃, 압력 150kgf/cm2에서 40분간 성형하여 발포체를 제조하였다.For 100 parts by weight of EVA with a VA content of 28% by weight and an MI of 3.0g/10min. (190°C, 2.16kg), 5 parts by weight of zinc oxide, 1 part by weight of stearic acid, 0.8 parts by weight of crosslinking agent (DCP), and foaming agent ( After mixing 3.0 parts by weight of ADCA) to prepare a compound, it was put into a mold and molded for 40 minutes at a temperature of 155°C and a pressure of 150kgf/cm 2 to produce a foam.
(비교예 2)(Comparative Example 2)
VA 함량이 28 중량%이며 MI가 3.0g/10min.(190℃, 2.16kg)인 EVA 50 중량% 및 경도가 80A이고 MI가 3.0g/10min.(190℃, 2.16kg)인 POE 50 중량%로 이루어진 기재 100 중량부에 대하여, 산화아연 5 중량부, 스테아린산 1 중량부, 가교제(DCP) 0.8 중량부 및 발포제(ADCA) 3.0 중량부를 혼합하여 컴파운드를 제조한 후, 이를 금형에 투입하여 온도 155℃, 압력 150kgf/cm2에서 40분간 성형하여 발포체를 제조하였다.50% by weight of EVA with a VA content of 28% by weight and an MI of 3.0g/10min. (190°C, 2.16kg) and 50% by weight of POE with a hardness of 80A and an MI of 3.0g/10min. (190°C, 2.16kg) A compound was prepared by mixing 5 parts by weight of zinc oxide, 1 part by weight of stearic acid, 0.8 parts by weight of a cross-linking agent (DCP), and 3.0 parts by weight of a foaming agent (ADCA) with respect to 100 parts by weight of a base material, and then put into a mold and heated to a temperature of 155°C. The foam was manufactured by molding for 40 minutes at ℃ and pressure of 150 kgf/cm 2 .
3. 신발 중창용 발포체의 평가3. Evaluation of foam for shoe midsoles
상기 실시예 및 비교예에 따른 발포체에 대해 아래와 같은 시험항목 및 방법으로 시험하였으며, 그 결과는 아래 [표 1]에 나타내었다.The foams according to the above examples and comparative examples were tested using the test items and methods below, and the results are shown in [Table 1] below.
(1) 경도(1) Hardness
KS M6660에 준하여 쇼어(shore) C형 경도계를 사용하여 측정하였다.It was measured using a shore C-type hardness tester in accordance with KS M6660.
(2) 비중(2) Specific gravity
KS M6519에 준하여 우에시마(Ueshima)사의 자동비중 측정 장치인 모델DMA-3을 이용하여 측정하였다.It was measured using Model DMA-3, an automatic specific gravity measuring device from Ueshima, in accordance with KS M6519.
(3) 반발탄성(3) Rebound elasticity
ASTM D2632에 준하여 측정하였다.Measurements were made according to ASTM D2632.
(4) 영구압축줄음율(4) Permanent compression reduction rate
시편을 두께가 10mm가 되도록 절단한 후, 지름이 30±0.05mm인 원기둥 형태로 제조한 시험편을 KS M6660에 준하여 측정하였다. 2장의 평행금속판 사이에 시험편을 넣고, 시험편 두께의 50%에 해당하는 스페이서를 끼운 후 압축시켜 50±0.1℃로 유지되는 오픈에서 6시간 열처리한 후 압축상태를 해제하고 실온에서 30분간 방치한 후 시험편의 두께를 측정하였으며, 영구압축줄음율은 다음 수학식 1에 의하여 계산하였다.After cutting the specimen to a thickness of 10 mm, the test specimen manufactured in the form of a cylinder with a diameter of 30 ± 0.05 mm was measured according to KS M6660. Place the test piece between two parallel metal plates, insert a spacer equivalent to 50% of the thickness of the test piece, compress it, heat treat it in an open environment maintained at 50 ± 0.1°C for 6 hours, release the compression, and leave it at room temperature for 30 minutes. The thickness of the test piece was measured, and the permanent compression set was calculated using Equation 1 below.
(수학식 1)(Equation 1)
t0 : 시험편의 초기 두께t 0 : initial thickness of the test piece
tf : 열처리 후 냉각되었을 때 시험편의 두께t f : Thickness of the test piece when cooled after heat treatment
tx : 스페이서의 두께t x : Thickness of spacer
(50℃×6시간, %)Permanent compression reduction rate
(50℃×6 hours, %)
상기 [표 1]에서와 같이, 본 발명의 실시예에 따른 신발 중창용 발포체는 비교예와 같은 에틸렌계 소재의 발포체와 유사한 경도 및 비중으로 경량성을 가지면서도 비교예에 비하여 반발탄성 및 영구압축줄음율 등의 내구성이 우수함을 알 수 있다.As shown in [Table 1], the foam for a shoe midsole according to an embodiment of the present invention has a hardness and specific gravity similar to the foam of an ethylene-based material such as the comparative example, and is lightweight, but has rebound elasticity and permanent compression compared to the comparative example. It can be seen that durability, such as shrinkage rate, is excellent.
상술한 바와 같이, 본 발명에 따른 내구성이 우수한 경량 신발 중창용 발포체 조성물은 상기의 바람직한 실시 예를 통해 설명하고, 그 우수성을 확인하였지만 해당 기술 분야의 당업자라면 하기의 특허 청구 범위에 기재된 본 발명의 사상 및 영역으로부터 벗어나지 않는 범위 내에서 본 발명을 다양하게 수정 및 변경시킬 수 있음을 이해할 수 있을 것이다.As described above, the foam composition for a lightweight shoe midsole with excellent durability according to the present invention has been explained through the above preferred embodiments and its excellence has been confirmed, but those skilled in the art will recognize the present invention as described in the following patent claims. It will be understood that various modifications and changes can be made to the present invention without departing from its spirit and scope.
Claims (3)
EVA(Ethylene Vinyl Acetate), 스티렌계 열가소성 탄성체 및 고분자량 스티렌계 열가소성 탄성체로 이루어진 기재를 사용하며,
상기 기재는,
EVA 20 ~ 40 중량%, 스티렌(Styrene) 함량이 1 ~ 20 중량%인 스티렌계 열가소성 탄성체 50 ~ 60 중량% 및, 분자량이 200,000 ~ 500,000g/mol이고 스티렌 함량이 1 ~ 20 중량%인 고분자량 스티렌계 열가소성 탄성체 10 ~ 20 중량%로 이루어지며,
상기 EVA는 VA(vinyl acetate) 함량이 22 ~ 40 중량%이며, MI(melt index)가 3.0 ~ 10g/10min.(190℃, 2.16kg)인 것을 사용하고,
상기 스티렌계 열가소성 탄성체는 SBBS(Styrene Butadiene Butylene Styrene)를 사용하며,
상기 고분자량 스티렌계 열가소성 탄성체는 SEBS(Styrene Ethylene Butylene Styrene), SEPS(Styrene Ethylene Propylene Styrene) 또는 SEEPS(Styrene Ethylene Ethylene Propylene Styrene)를 사용하며,
경도 48 내지 50, 비중 0.199 내지 2.00 및 반발탄성 65 내지 70%로 이루어진 것을 특징으로 하는, 내구성이 우수한 경량 신발 중창용 발포체 조성물.In the foam composition for lightweight shoe midsoles,
It uses a substrate made of EVA (Ethylene Vinyl Acetate), styrene-based thermoplastic elastomer, and high molecular weight styrene-based thermoplastic elastomer.
The above description,
20 to 40% by weight of EVA, 50 to 60% by weight of styrene-based thermoplastic elastomer with a styrene content of 1 to 20% by weight, and high molecular weight with a molecular weight of 200,000 to 500,000 g/mol and a styrene content of 1 to 20% by weight. It consists of 10 to 20% by weight of styrene-based thermoplastic elastomer,
The EVA has a VA (vinyl acetate) content of 22 to 40% by weight and an MI (melt index) of 3.0 to 10g/10min. (190°C, 2.16kg).
The styrene-based thermoplastic elastomer uses SBBS (Styrene Butadiene Butylene Styrene),
The high molecular weight styrene-based thermoplastic elastomer uses SEBS (Styrene Ethylene Butylene Styrene), SEPS (Styrene Ethylene Propylene Styrene), or SEEPS (Styrene Ethylene Ethylene Propylene Styrene).
A foam composition for a lightweight shoe midsole with excellent durability, characterized in that it consists of a hardness of 48 to 50, a specific gravity of 0.199 to 2.00, and a rebound elasticity of 65 to 70%.
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