KR101508638B1 - Thermoplastic polyurethane alloy composition for outsole of shoes - Google Patents
Thermoplastic polyurethane alloy composition for outsole of shoes Download PDFInfo
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- KR101508638B1 KR101508638B1 KR20130073122A KR20130073122A KR101508638B1 KR 101508638 B1 KR101508638 B1 KR 101508638B1 KR 20130073122 A KR20130073122 A KR 20130073122A KR 20130073122 A KR20130073122 A KR 20130073122A KR 101508638 B1 KR101508638 B1 KR 101508638B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- 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
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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Abstract
본 발명은 신발 겉창용 열가소성폴리우레탄 복합 조성물에 관한 것으로, 더욱 구체적으로는 열가소성폴리우레탄(thermoplastic polyurethane, TPU)과 폴리염화비닐(polyvinyl chloride, PVC)을 알로이(alloy)하고, 여기에 실란 처리한 탄산칼슘, 실란 처리한 탈크, 실란 처리한 마이카 및 실리카에 담지 시킨 내부 이형제 등으로 복합화하여, 종래의 신발 겉창용 열가소성폴리우레탄 조성물에 비하여 내마모성, 내가수분해성 및 사출성형성을 현저히 개선시킨 신발 겉창용 열가소성폴리우레탄 복합 조성물에 관한 것이다.The present invention relates to a thermoplastic polyurethane composite composition for a shoe outsole. More specifically, the present invention relates to a thermoplastic polyurethane composite composition for a shoe outsole, more specifically a thermoplastic polyurethane (TPU) and a polyvinyl chloride (PVC) alloy, A shoe outsole which is remarkably improved in abrasion resistance, hydrolysis resistance and injection moldability as compared with a conventional thermoplastic polyurethane composition for a shoe outsole can be obtained by composites of calcium carbonate, silane treated talc, silane treated mica, and internal release agent supported on silica, To a thermoplastic polyurethane composite composition.
Description
본 발명은 열가소성폴리우레탄(thermoplastic polyurethane, TPU) 및 상기 열가소성폴리우레탄과 상용성이 우수한 폴리염화비닐(polyvinyl chloride, PVC)을 알로이(alloy)한 기재에, 실란 처리한 탄산칼슘, 실란 처리한 탈크, 실란 처리한 마이카 및 실리카에 담지 시킨 내부 이형제 등을 혼합하여, 종래의 신발 겉창용 열가소성폴리우레탄 조성물에 비하여 사출성형성, 내마모성 및 내가수분해성을 현저히 개선시킨 신발 겉창용 열가소성폴리우레탄 복합 조성물에 관한 것이다.
The present invention relates to a thermoplastic polyurethane (TPU) and a polyvinyl chloride (PVC) having excellent compatibility with the thermoplastic polyurethane, and a method of producing the same, A silane-treated mica, and an internal release agent supported on silica, to provide a thermoplastic polyurethane composite composition for a shoe outsole which is remarkably improved in injection moldability, abrasion resistance and hydrolysis resistance as compared with a conventional thermoplastic polyurethane composition for a shoe outsole .
일반적으로 열가소성폴리우레탄은 내마모성이 다른 열가소성탄성체(Thermoplastic Elastomer, TPE) 중에서도 비교적 우수하며, 또한 기계적강도가 우수하고 저경도를 얻기 쉬우며, 반복 피로 특성이 우수한 특징을 가지고 있을 뿐만 아니라, 내화학성, 내용제성, 내한성 등이 우수하여 자동차, 의류, 신발, 선박 등의 다양한 분야에서 널리 사용되고 있으며, 관련 선행기술로써 특허문헌 1 내지 4 등이 있다.
In general, thermoplastic polyurethanes are relatively excellent among thermoplastic elastomers (TPE) having different abrasion resistance, and have excellent mechanical strength, easy to obtain low hardness, excellent repetitive fatigue characteristics, And is widely used in various fields such as automobiles, clothing, shoes, ships, etc., and Patent Documents 1 to 4 are related prior arts.
하지만, 상기와 같은 열가소성폴리우레탄은 상기와 같은 우수한 특징을 가지는 반면, 내광성이 불충분하고 금형 점착을 일으키기 쉽기 때문에 저경도의 열가소성폴리우레탄의 경우 사출성형성이 떨어지는 문제점이 있다.
However, the above-mentioned thermoplastic polyurethane has excellent characteristics as described above, but has insufficient light resistance and tends to cause mold adhesion, so that the thermoplastic polyurethane having a low hardness has a problem of poor injection moldability.
한편, 일반적으로 신발에 사용되는 열가소성폴리우레탄 조성물은 로고(logo), 갑피(upper), 코싸게(toe cap), 구멍쇠(eyelet), 굽싸게(heel cap), 허리쇠(shank) 등에 적용되고 있다. 이러한 부위는 보행시 바닥면과 마찰이 발생되지 않는 부위라 할 수 있다. 즉, 현재까지 내마모성이 요구되는 신발 겉창용 소재로 열가소성폴리우레탄이 적용되는 사례는 많지 않다고 할 수 있다.
On the other hand, thermoplastic polyurethane compositions generally used in footwear are applied to logos, upper, toe cap, eyelet, heel cap, shank, etc. . These areas can be considered as areas where there is no friction with the floor when walking. In other words, there are not many cases in which thermoplastic polyurethane is applied as a material for shoe outsole which requires abrasion resistance to date.
이러한 요인은 일반적으로 스포츠화나 아웃도어용 신발의 겉창으로 사용되고 있는 소재는 고무소재가 대표적으로 사용되고 있는데, 고무소재의 경우 경도범위가 60 ~ 70(asker A) 범위를 가지며 내마모성이 우수한 특징을 가지는 반면에, 이러한 범위의 저경도 열가소성폴리우레탄 소재의 경우 내마모특성이 떨어지며, 사출시 금속과의 점착성이 발생되고, 제품의 성형성이 떨어지는 문제가 있기 때문에 아직까지 적용에 많은 어려움이 있었다.
These factors are generally used for the outsole of shoes for sports shoes and outdoor shoes. Rubber materials have hardness range of 60 ~ 70 (asker A) and excellent wear resistance In the case of a low-hardness thermoplastic polyurethane material having such a range, the abrasion resistance is deteriorated, adhesiveness with the metal occurs at the time of injection, and the moldability of the product is poor.
본 발명은 상기와 같은 연질 열가소성폴리우레탄 소재의 취약한 사출성형성, 내마모성 및 내가수분해성을 해결하기 위한 것으로, 열가소성폴리우레탄 및 상기 열가소성폴리우레탄과 상용성이 우수한 폴리염화비닐을 기재로 하고, 여기에 내마모성능을 향상시키기 위하여 실리카에 담지된 내부 이형제, 사출성형성과 내가수분해성능을 향상시키기 위하여 실란처리한 탄산칼슘과 탈크, 마이카 및 가소제 등을 혼합한 신발 겉창용 열가소성폴리우레탄 복합조성물을 제조함으로써, 내마모성능 및 내가수분해성을 향상시킬 뿐만 아니라 연질 열가소성폴리우레탄의 취약한 사출성형성을 향상시킬 수 있도록 함을 과제로 한다.
The present invention is to solve the weak injection moldability, abrasion resistance and hydrolysis resistance of the flexible thermoplastic polyurethane material as described above, and it relates to a thermoplastic polyurethane and a polyvinyl chloride excellent in compatibility with the thermoplastic polyurethane, An inner mold release agent supported on silica to improve abrasion resistance performance, a thermoplastic polyurethane composite composition for shoe outsole comprising injection molding, silane treated calcium carbonate, talc, mica, plasticizer and the like to improve the water resistance performance Thereby improving the abrasion resistance and hydrolysis resistance as well as improving the poor injection moldability of the soft thermoplastic polyurethane.
또한, 본 발명은 기재룰 조성함에 있어 저가의 폴리염화비닐을 혼용함에 따라, 열가소성폴리우레탄 단독 조성물과 비교하여 원가절감이 가능하도록 함을 다른 과제로 한다.
Another object of the present invention is to reduce costs in comparison with a thermoplastic polyurethane alone composition by mixing low cost polyvinyl chloride in the formation of a substrate.
본 발명은 열가소성폴리우레탄과 폴리염화비닐로 이루어지는 기재를 포함하여 구성되는 것을 특징으로 하는 신발 겉창용 열가소성폴리우레탄 복합 조성물을 과제의 해결 수단으로 한다.
The present invention provides a thermoplastic polyurethane composite composition for a shoe outsole characterized by comprising a substrate composed of a thermoplastic polyurethane and a polyvinyl chloride.
이때, 상기 열가소성폴리우레탄 복합 조성물은,At this time, the thermoplastic polyurethane /
열가소성폴리우레탄 60 ~ 90 중량% 및 폴리염화비닐 10 ~ 40 중량%로 이루어진 기재 100 중량부에 대하여,Based on 100 parts by weight of a substrate composed of 60 to 90% by weight of thermoplastic polyurethane and 10 to 40% by weight of polyvinyl chloride,
가소제 5 ~ 40 중량부, 열안정제 0.1 ~ 2 중량부, 실리카에 담지 시킨 내부 이형제 3 ~ 10 중량부, 실란 처리된 탄산칼슘 2 ~ 10 중량부, 실란 처리된 탈크 2 ~ 10 중량부 및 실란 처리된 마이카 2 ~ 10 중량부로 이루어지는 것이 바람직하다.
5 to 40 parts by weight of a plasticizer, 0.1 to 2 parts by weight of a heat stabilizer, 3 to 10 parts by weight of an internal release agent supported on silica, 2 to 10 parts by weight of silane-treated calcium carbonate, 2 to 10 parts by weight of silane- And 2 to 10 parts by weight of the mica.
아울러, 상기 열가소성폴리우레탄은, 경도가 60 ~ 75(asker A)이며, 인장강도가 15 ~ 35Mpa이고, 녹는점이 150 ~ 200℃ 범위를 가지는 것이 바람직하다.
The thermoplastic polyurethane preferably has a hardness of 60 to 75 (Asker A), a tensile strength of 15 to 35 MPa, and a melting point of 150 to 200 ° C.
또한, 상기 폴리염화비닐은, 중합도가 800 ~ 2500인 것이 바람직하다.
The polyvinyl chloride preferably has a degree of polymerization of 800 to 2,500.
또한, 상기 실리카에 담지 시킨 내부 이형제는, 실리카 100 중량부에 대하여, 내부 이형제 100 ~ 200 중량부가 담지되어 이루어지되, Also, the internal release agent supported on the silica is composed of 100 to 200 parts by weight of the internal release agent supported on 100 parts by weight of silica,
상기 내부 이형제는, 실리콘 오일, 대전방지제, 계면활성제, 폴리에틸렌글리콜, 폴리프로필렌클리콜 또는 폴리에틸렌왁스를 단독 혹은 혼용하여 사용한 것이 바람직하다.
The internal release agent is preferably used alone or in combination of silicone oil, antistatic agent, surfactant, polyethylene glycol, polypropylene glycol or polyethylene wax.
본 발명은 사출성형성과 내마모성, 내가수분해성의 향상을 위하여 연질 열가소성폴리우레탄과 폴리염화비닐을 혼용한 것을 기재로 하고, 또한, 내마모성을 개선시키기 위하여 실리카에 담지 시킨 내부이형제를 사용하였으며, 내가수분해성 및 사출성형성을 향상시키기 위하여 실란처리된 탄산카슘, 탈크, 마이카를 적용함으로써, 종래의 연질 열가소성폴리우레탄 조성물과 비교하여 우수한 마모성능, 사출성형성, 내가수분해 성능을 향상시킬 수 있으며, 저가의 폴리염화비닐의 혼용사용에 따른 원가절감이 가능한 장점이 있다.
The present invention is based on a combination of soft thermoplastic polyurethane and polyvinyl chloride for improving injection moldability, abrasion resistance and hydrolysis resistance, and also uses an internal mold release agent supported on silica to improve abrasion resistance, By applying silane treated calcium carbonate, talc and mica in order to improve the decomposability and injection moldability, it is possible to improve the abrasion performance, the injection moldability and the moisture resistance performance compared with the conventional soft thermoplastic polyurethane composition, It is possible to reduce the cost by using a mixture of low-priced polyvinyl chloride.
상기의 효과를 달성하기 위한 본 발명은 신발 겉창용 열가소성폴리우레탄 복합 조성물에 관한 것으로, 본 발명의 기술적 구성을 이해하는데 필요한 부분만이 설명되며 그 이외 부분의 설명은 본 발명의 요지를 흩트리지 않도록 생략될 것이라는 것을 유의하여야 한다.
In order to achieve the above-mentioned effects, the present invention relates to a thermoplastic polyurethane composite composition for a shoe outsole, wherein only the parts necessary for understanding the technical structure of the present invention are explained, and the description of the other parts does not disturb the gist of the present invention It will be omitted.
이하, 본 발명에 따른 신발 겉창용 열가소성폴리우레탄 복합 조성물을 상세히 설명하면 다음과 같다.Hereinafter, the thermoplastic polyurethane composite composition for a shoe outsole according to the present invention will be described in detail.
본 발명에 따른 신발 겉창용 열가소성폴리우레탄 복합 조성물은, 열가소성폴리우레탄과 폴리염화비닐로 이루어지는 기재를 포함하여 구성되는 것을 특징으로 하며, 구체적으로는 열가소성폴리우레탄 60 ~ 90 중량% 및 폴리염화비닐 10 ~ 40 중량%로 이루어진 기재 100 중량부에 대하여, 가소제 5 ~ 40 중량부, 열안정제 0.1 ~ 2 중량부, 실리카에 담지 시킨 내부 이형제 3 ~ 10 중량부, 실란 처리된 탄산칼슘 2 ~ 10 중량부, 실란 처리된 탈크 2 ~ 10 중량부 및 실란 처리된 마이카 2 ~ 10 중량부로 이루어진다.
The thermoplastic polyurethane composite composition for a shoe outsole according to the present invention is characterized in that it comprises a base made of a thermoplastic polyurethane and a polyvinyl chloride. More specifically, it comprises 60 to 90% by weight of a thermoplastic polyurethane and 10 to 10% by weight of a polyvinyl chloride To 40 parts by weight of a plasticizer, 0.1 to 2 parts by weight of a heat stabilizer, 3 to 10 parts by weight of an internal release agent supported on silica, 2 to 10 parts by weight of silane-treated calcium carbonate, 2 to 10 parts by weight of silane-treated talc, and 2 to 10 parts by weight of silane-treated mica.
본 발명에서 사용하는 열가소성폴리우레탄 조성물은 이미 상술한 바와 같이, 내마모성이 다른 열가소성탄성체(Thermoplastic Elastomer, TPE) 중에서도 비교적 우수하며, 또한 기계적강도가 우수하고 저경도를 얻기 쉬우며, 반복 피로 특성이 우수한 특징을 가지고 있을 뿐만 아니라, 내화학성, 내용제성, 내한성 등이 우수하며, 구체적으로 본 발명에서 사용하는 열가소성폴리우레탄 조성물은 폴리에스테계 열가소성폴리우레탄로써 경도가 60 ~ 75(asker A)이며, 인장강도가 15 ~ 35Mpa이고, 녹는점이 150 ~ 200℃ 범위를 가지는 것을 사용하며, 기재를 이루기 위해 60 ~ 90 중량%가 사용된다.As described above, the thermoplastic polyurethane composition used in the present invention is comparatively excellent among thermoplastic elastomers (TPE) having different abrasion resistance, is excellent in mechanical strength, is easy to obtain low hardness, has excellent repetitive fatigue characteristics The thermoplastic polyurethane composition used in the present invention is a polyester thermoplastic polyurethane having a hardness of 60 to 75 (Asker A), a tensile strength A strength of 15 to 35 MPa and a melting point of 150 to 200 DEG C is used, and 60 to 90 wt% is used to form a substrate.
이때, 열가소성폴리우레탄 조성물의 경도, 인장강도 및 녹는점이 상기 범위를 벗어나거나 그 사용량이 90 중량%를 초과할 경우, 사출성형시 치수안정성이 떨어지며, 내가수분해성이 떨어지고, 금형에 점착성이 높아져 작업성이 떨어지는 문제가 있으며, 60 중량% 미만일 경우, 기계적 강도의 저하될 우려가 있다.
When the hardness, tensile strength and melting point of the thermoplastic polyurethane composition are out of the above range or the amount thereof is more than 90% by weight, the dimensional stability during injection molding is poor, the hydrolysis resistance is poor, If the content is less than 60% by weight, the mechanical strength may be lowered.
본 발명에서 사용되는 폴리염화비닐은 본 발명에 따른 신발 겉창용 열가소성폴리우레탄 복합 조성물의 사출성형성 개선, 내마모성개선, 내가수분해성 개선, 원가절감 등을 위해 사용되는 것으로, 중합도가 800 ~ 2500 범위를 가지며, 기재를 이루기 위해 10 ~ 40 중량%가 사용된다.The polyvinyl chloride used in the present invention is used for improvement of injection moldability, wear resistance, improvement of hydrolysis resistance, cost reduction, etc. of the thermoplastic polyurethane composite composition for a shoe outsole according to the present invention. The polyvinyl chloride has a degree of polymerization of 800 to 2500 And 10 to 40% by weight is used for forming the substrate.
이때, 상기 폴리염화비닐의 중합도가 800 미만에서는 내마모성 등의 개선효과가 미비하며, 중합도가 2500을 초과할 경우, 겉창의 과도한 경도상승과 사출성형성이 저하되는 문제가 있다.If the degree of polymerization of the polyvinyl chloride is less than 800, the effect of improving the abrasion resistance is insufficient. If the degree of polymerization is more than 2500, there is a problem that the excessive hardness of the outsole increases and the injection moldability is deteriorated.
아울러, 상기 폴리염화비닐의 사용량이 10 중량% 미만에서는 사출성형성 개선, 내마모성개선, 내가수분해성 개선 효과가 떨어지며, 40 중량%를 초과할 경우, 변형에 대한 회복력이 떨어져 사출 후 제품의 외관이 뒤틀리는 문제가 있다.
If the amount of the polyvinyl chloride is less than 10% by weight, the injection moldability is improved, the abrasion resistance is improved, and the hydrolysis resistance improving effect is deteriorated. If the amount exceeds 40% by weight, There is a problem of twisting.
본 발명에서 사용되는 가소제는 폴리염화비닐이 포함되는 고무 조성물에 널리 사용되는 이미 공지된 조성물로써 특정 가소제에 한정되지 않으나 일 예로 프탈레이트계 가소제 등을 사용할 수 있으며, 상기와 같이 이루어진 기재 100 중량부에 대하여, 5 ~ 40 중량부를 사용한다.The plasticizer used in the present invention is a well-known composition widely used in a rubber composition containing polyvinyl chloride. The plasticizer is not limited to a specific plasticizer. For example, a phthalate plasticizer may be used. 100 parts by weight of the above- 5 to 40 parts by weight are used.
이때, 상기 사용범위는 폴리염화비닐 100 중량부에 대해서 50 ~ 100 중량부를 사용하는 것과 대응되는 범위이다.At this time, the use range is a range corresponding to the use of 50 to 100 parts by weight based on 100 parts by weight of polyvinyl chloride.
한편, 가소제의 사용량이 상기 범위 미만일 경우, 겉창의 경도 상승과 가공성의 현저한 저하가 발생되며, 상기 범위를 초과할 경우, 내마모성 개선효과가 떨어지며, 기계적 강도가 저하될 우려가 있다.
On the other hand, when the amount of the plasticizer used is less than the above range, the hardness of the outsole increases and the workability remarkably decreases. If the amount exceeds the above range, the effect of improving the abrasion resistance is deteriorated and the mechanical strength is lowered.
본 발명에서 사용되는 열안정제는 상기 가소제와 함께 폴리염화비닐이 포함되는 고무 조성물에 널리 사용되는 이미 공지된 조성물로써 특정 열안정제에 한정되지 않으나 일 예로 라울린산바륨 등을 사용할 수 있으며, 상기와 같이 이루어진 기재 100 중량부에 대하여, 0.1 ~ 2 중량부를 사용한다.The heat stabilizer used in the present invention is a known composition widely used in rubber compositions containing polyvinyl chloride together with the above plasticizers. The heat stabilizers are not limited to specific heat stabilizers. For example, barium laurate may be used. 0.1 to 2 parts by weight are used relative to 100 parts by weight of the substrate.
이때, 열안정제의 사용량이 0.1 중량부 미만일 경우, 열안정제에 의한 열화방지효과가 미비할 우려가 있으며, 2 중량부를 초과할 경우, 기계적 강도 및 내마모성 등이 저하될 우려가 있다.
If the amount of the heat stabilizer is less than 0.1 parts by weight, the effect of preventing deterioration by the heat stabilizer may be insufficient. If the amount is more than 2 parts by weight, the mechanical strength and abrasion resistance may be deteriorated.
본 발명에서 사용되는 내부 이형제는 본 발명에 따른 신발 겉창용 열가소성폴리우레탄 복합 조성물의 내마모성능을 개선시키기 위해 사용되는 첨가제로, 실리카에 담지하여 사용하며, 내부 이형제는 실리콘 오일, 대전방지제, 계면활성제, 폴리에틸렌글리콜, 폴리프로필렌클리콜 또는 폴리에틸렌왁스를 단독 혹은 혼용하여 사용할 수 있다.The internal release agent used in the present invention is an additive which is used to improve the abrasion resistance performance of the thermoplastic polyurethane composite composition for shoe outsole according to the present invention and is supported on silica and the internal release agent is selected from the group consisting of silicone oil, , Polyethylene glycol, polypropylene glycol or polyethylene wax may be used singly or in combination.
이때, 상기 내부 이형제의 실리카 담지 비율은 실리카 100 중량부에 대해서 100 ~ 200 중량부를 사용하며, 내부이형제의 실리카 담지 비율이 실리카 100 중량부에 대해서 100 중량부 미만일 경우, 내마모성 개선 효과가 떨어지며, 200 중량부를 초과 하였을 경우에는 제품에 마이그레이션의 발생이 우려되며, 가공성이 저하되는 문제가 있다.In this case, the silica supporting ratio of the internal release agent is 100-200 parts by weight based on 100 parts by weight of silica. When the silica supporting ratio of the internal defoaming agent is less than 100 parts by weight with respect to 100 parts by weight of silica, the effect of improving abrasion resistance is inferior, If the amount is more than the weight part, migration of the product may occur and the processability may be deteriorated.
아울러, 상기와 같이 실리카에 담지 시킨 내부 이형제는 기재 100 중량부에 대하여 3 ~ 10 중량부를 사용하는데, 그 사용량이 3 중량부 미만일 경우, 열가소성 조성물의 내마모성 개선효과가 떨어지며, 10 중량부를 초과할 경우, 경우 경도의 상승과 사출성형성의 저하가 우려된다.
If the amount of the internal release agent is less than 3 parts by weight, the effect of improving the abrasion resistance of the thermoplastic composition may deteriorate. When the amount of the internal release agent is more than 10 parts by weight, , There is a fear of an increase in hardness and a decrease in injection moldability.
본 발명에서 사용되는 실란처리된 탄산칼슘은 본 발명에 따른 신발 겉창용 열가소성폴리우레탄 복합 조성물의 사출성형성과 내가수분해성능을 향상시키기 위하여 첨가되는 것으로, 기재 100 중량부에 대해서 2 ~ 10중량부를 사용하는데, 상기 실란 처리된 탄산칼슘이 2 중량부 미만일 경우, 열가소성 소폴리우레탄 복합 조성물의 내가수분해성 개선효과가 미비하고, 10 중량부를 초과하였을 경우 기계적 강도 및 내마모성능의 저하가 우려된다.
The silane-treated calcium carbonate used in the present invention is added to improve the injection molding performance and the moisture resistance of the thermoplastic polyurethane composite composition for a shoe outsole according to the present invention, and is 2 to 10 parts by weight per 100 parts by weight of the base material When the silane-treated calcium carbonate is less than 2 parts by weight, the hydrolysis resistance improving effect of the thermoplastic small-polyurethane composite composition is insufficient. When the amount of the silane-treated calcium carbonate exceeds 10 parts by weight, mechanical strength and abrasion resistance are deteriorated.
본 발명에서 사용되는 실란 처리된 탈크는 본 발명에 따른 신발 겉창용 열가소성폴리우레탄 복합 조성물의 사출성형성과 내가수분해성능을 향상시키기 위하여 첨가되는 것으로, 기재 100 중량부에 대해서 2 ~ 10 중량부를 사용하는데, 상기 실란 처리된 탈크를 2 중량부 미만일 경우, 열가소성 소폴리우레탄 복합 조성물의 사출성형시 치수안정성 개선효과가 떨어지며, 10 중량부를 초과하였을 경우 기계적 강도 및 내마모성능의 저하가 우려된다.
The silane-treated talc used in the present invention is added to improve the injection molding property and moisture resistance of the thermoplastic polyurethane composite composition for a shoe outsole according to the present invention, and is used in an amount of 2 to 10 parts by weight based on 100 parts by weight of the base material If the amount of the silane-treated talc is less than 2 parts by weight, the effect of improving the dimensional stability of the thermoplastic small-polyurethane composite composition during injection molding is poor. If the amount is more than 10 parts by weight, mechanical strength and abrasion resistance may be deteriorated.
본 발명에서 사용되는 실란 처리된 마이카는 본 발명에 따른 신발 겉창용 열가소성폴리우레탄 복합 조성물의 사출성형성과 내가수분해성능을 향상시키기 위하여 첨가되는 것으로, 기재 100 중량부에 대해서 2 ~ 10중량부를 사용하는데, 상기 실란처리된 마이카를 2 중량부 미만일 경우, 열가소성 소폴리우레탄 복합 조성물의 사출성형시 치수안정성 개선효과가 떨어지며, 10 중량부를 초과하였을 경우 기계적 강도 및 내마모성능의 저하가 우려된다.
The silane-treated mica used in the present invention is added to improve the injection molding property and the moisture resistance of the thermoplastic polyurethane composite composition for a shoe outsole according to the present invention, and is used in an amount of 2 to 10 parts by weight based on 100 parts by weight of the substrate If the amount of the silane-treated mica is less than 2 parts by weight, the dimensional stability of the thermoplastic small-polyurethane composite composition may not be improved. When the amount of the mica exceeds 10 parts by weight, mechanical strength and abrasion resistance may be deteriorated.
여기서, '실란 처리'란, 실란 커플링제로 표면이 코팅된 것을 의미하며, 탄산칼슘, 탈크 또는 마이카가 100 중량부에 대하여 실란 커플링제 3 ~ 7 중량부가 코팅되며, 실란커플링제로는 비닐트리에톡시실란, 비닐트리(2-메톡시에톡시)실란 등의 비닐실란이나, 3-메타크릴록시프로필트리메톡시실란, N-페닐-3-아미노프로필트리메톡시실란, 3-메트랍토프필트리메톡시실란, 비스(트리에톡시실리프로필)테트라설페인, 티오시아나토프로필트리에톡시실란 등을 적용할 수 있다.Here, 'silane treatment' means that the surface is coated with a silane coupling agent, and 3 to 7 parts by weight of a silane coupling agent is coated on 100 parts by weight of calcium carbonate, talc or mica. As the silane coupling agent, Methacryloxypropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, Phytrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfane, thiocyanatopropyltriethoxysilane, and the like can be applied.
한편, 상기 실란커플링제의 코팅량이 3 중량부 미만일 경우에는 분산성이 저하될 우려가 있으며, 7 중량부를 초과할 경우, 기계적 강도가 저하될 우려가 있다.On the other hand, if the coating amount of the silane coupling agent is less than 3 parts by weight, the dispersibility may be lowered. If the amount is more than 7 parts by weight, the mechanical strength may be lowered.
이상과 같은 조성 성분들로 이루어진 신발 겉창용 열가소성폴리우레탄 복합 조성물의 제조공정을 설명하면 다음과 같다.
A process for producing a thermoplastic polyurethane composite composition for a shoe outsole comprising the above-mentioned composition components will be described below.
먼저, 폴리염화비닐 10 ~ 40 중량%에, (기재 100중량부를 기준으로)가소제 5 ~ 40 중량부, 열안정제 0.2 ~ 2 중량부를 90 ~ 100℃의 슈퍼믹서를 이용하여 20 ~ 40분간 선 믹싱한 후, 열가소성폴리우레탄 60 ~ 90중량부%, (기재 100중량부를 기준으로)실리카에 담지된 내부이형제 3 ~ 10 중량부, 실란 처리된 탄산칼슘 2 ~ 10 중량부, 실란 처리된 탈크 2 ~ 10 중량부, 실란 처리된 마이카 2 ~ 10 중량부를 170 ~ 200℃의 이축압출기에서 펠렛을 제조한다. 상기 제조된 펠렛은 180 ~ 200℃의 사출기를 통해서 신발 겉창용 열가소성폴리우레탄 복합물을 제조한다.
First, 5 to 40 parts by weight of a plasticizer (based on 100 parts by weight of the substrate) and 0.2 to 2 parts by weight of a heat stabilizer are preliminarily mixed with 10 to 40% by weight of polyvinyl chloride using a super mixer at 90 to 100 DEG C for 20 to 40 minutes 60 to 90 parts by weight of thermoplastic polyurethane, 3 to 10 parts by weight of an internal release agent supported on silica (based on 100 parts by weight of the substrate), 2 to 10 parts by weight of silane-treated calcium carbonate, 2 to 10 parts by weight of silane- And 2 to 10 parts by weight of silane-treated mica were prepared in a twin-screw extruder at 170 to 200 占 폚. The prepared pellets are manufactured through an extruder at 180 to 200 ° C to produce a thermoplastic polyurethane composite for a shoe outsole.
이하, 본 발명을 실시예에 의거하여 더욱 구체적으로 설명하겠는바, 본 발명이 다음 실시예에 의해 한정되는 것은 아니다.
Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited by the following examples.
1. 신발 겉창용 열가소성폴리우레탄 복합조성물 제조
1. Production of Thermoplastic Polyurethane Composite Composition for Shoe Outsole
(실시예 1)(Example 1)
중합도가 800인 폴리염화비닐 10 중량%에, (기재 100중량부를 기준으로)프탈레이트계 가소제 5 중량부, 열안정제인 라울린산바륨 0.1중량부를 100℃의 슈퍼믹서를 이용하여 30분간 선 믹싱한 후, 경도 60A(asker A), 인장강도 15Mpa, 녹는점 150℃ 열가소성폴리우레탄 90 중량%, (기재 100중량부를 기준으로)실리카에 담지된 내부이형제(실리카/내부이형제 담지비율, 1:1)를 10 중량부, 실란 처리된 탄산칼슘 2중량부, 실란 처리된 탈크 2중량부, 실란 처리된 마이카 10 중량부를 180℃의 이축압축기에서 펠렛을 제조하고, 제조된 펠렛을 180℃의 사출기에서 열가소성폴리우레탄 복합 조성물을 제조하였다.
5 parts by weight of a phthalate plasticizer (based on 100 parts by weight of the base material) and 0.1 part by weight of barium laurethate as a heat stabilizer were preliminarily mixed for 30 minutes by using a super mixer at 100 캜 in 10% by weight of polyvinyl chloride having a degree of polymerization of 800 (Silica / internal crosslinking agent loading ratio: 1: 1) supported on silica (based on 100 parts by weight of the substrate), 90% by weight of a thermoplastic polyurethane having a melting point of 150 占 폚, a hardness of 60 A (asker A) , 2 parts by weight of silane-treated calcium carbonate, 2 parts by weight of silane-treated talc and 10 parts by weight of silane-treated mica were prepared in a twin-screw compressor at 180 DEG C, and the resulting pellets were thermoplastic To prepare a polyurethane composite composition.
(실시예 2)(Example 2)
중합도가 1700인 폴리염화비닐 20중량부%에, (기재 100중량부를 기준으로)프탈레이트계 가소제 20 중량부, 열안정제인 라울린산바륨 0.5중량부를 100℃의 슈퍼믹서를 이용하여 30분간 선 믹싱한 후, 경도 66A(asker A), 인장강도 20Mpa, 녹는점 150℃ 열가소성폴리우레탄 80 중량%, (기재 100 중량부를 기준으로)실리카에 담지된 내부이형제(실리카/내부이형제 담지비율, 1:1.5)를 5 중량부, 실란 처리된 탄산칼슘 5중량부, 실란 처리된 탈크 5 중량부, 실란 처리된 마이카 5 중량부를 180℃의 이축압축기에서 펠렛을 제조하고, 제조된 펠렛을 180℃의 사출기에서 열가소성폴리우레탄 복합 조성물을 제조하였다.
20 parts by weight of a phthalate plasticizer (based on 100 parts by weight of the base material) and 0.5 part by weight of barium laurethate as a heat stabilizer were added to 20 parts by weight of polyvinyl chloride having a degree of polymerization of 1,700 by pre-mixing for 30 minutes using a super mixer at 100 캜 (Silica / internal defibrillator loading ratio, 1: 1.5) supported on silica (based on 100 parts by weight of the base material), a hardness of 66 A, a tensile strength of 20 MPa, a melting point of 150 캜, a thermoplastic polyurethane content of 80% ), 5 parts by weight of silane-treated calcium carbonate, 5 parts by weight of silane-treated talc and 5 parts by weight of silane-treated mica were prepared in a twin-screw compressor at 180 DEG C, To prepare a thermoplastic polyurethane composite composition.
(실시예 3)(Example 3)
중합도가 2500인 폴리염화비닐 40중량부%에, (기재 100중량부를 기준으로)프탈레이트계 가소제 40 중량부, 열안정제인 라울린산바륨 2 중량부를 100℃의 슈퍼믹서를 이용하여 30분간 선 믹싱한 후, 경도 75(asker A), 인장강도 35Mpa, 녹는점 200℃ 열가소성폴리우레탄 60중량%, (기재 100 중량부를 기준으로)실리카에 담지된 내부이형제(실리카/내부이형제 담지비율, 1:2)를 3 중량부, 실란처리된 탄산칼슘 10중량부, 실란처리된 탈크 10 중량부, 실란처리된 마이카 2 중량부를 180℃의 이축압축기에서 펠렛을 제조하고, 제조된 펠렛을 180℃의 사출기에서 열가소성폴리우레탄 복합 조성물을 제조하였다.
40 parts by weight of a phthalate plasticizer (based on 100 parts by weight of the base material) and 2 parts by weight of barium laurethate as a heat stabilizer were mixed by 40% by weight of polyvinyl chloride having a degree of polymerization of 2,500 by 30 minutes by using a super mixer at 100 캜 (Silica / internal mold supporting ratio, 1: 2) supported on silica (based on 100 parts by weight of the base material), hardness of 75 (Asker A), tensile strength of 35 Mpa, melting point of 200 占 폚, 60 weight% of thermoplastic polyurethane ), 10 parts by weight of silane-treated calcium carbonate, 10 parts by weight of silane-treated talc, and 2 parts by weight of silane-treated mica were prepared in a twin-screw compressor at 180 DEG C, To prepare a thermoplastic polyurethane composite composition.
(비교예 1)(Comparative Example 1)
경도 66A(asker A), 인장강도 20Mpa, 녹는점 150℃ 열가소성폴리우레탄 100중량부에 대하여, 실리카에 담지된 내부이형제(실리카/내부이형제 담지비율, 1:1.5)를 5 중량부를 180℃의 이축압축기에서 펠렛을 제조하고, 제조된 펠렛을 180℃의 사출기에서 열가소성폴리우레탄 복합 조성물을 제조하였다.
5 parts by weight of an internal mold release agent (silica / internal mold release agent loading ratio, 1: 1.5) supported on silica was added to 100 parts by weight of a thermoplastic polyurethane having a hardness of 66 A (Asker A), a tensile strength of 20 MPa, The pellets were produced in a compressor, and the thermoplastic polyurethane composite composition was prepared by injection molding the pellets at 180 ° C.
(비교예 2)(Comparative Example 2)
경도 66A(asker A), 인장강도 20Mpa, 녹는점 150℃ 열가소성폴리우레탄 100 중량부에 대하여, 실란처리된 탄산칼슘 5중량부, 실란처리된 탈크 2.5 중량부, 실란처리된 마이카 2.5 중량부를 180℃의 이축압축기에서 펠렛을 제조하고, 제조된 펠렛을 180℃의 사출기에서 열가소성폴리우레탄 복합 조성물을 제조하였다.
5 parts by weight of silane-treated calcium carbonate, 2.5 parts by weight of silane-treated talc and 2.5 parts by weight of silane-treated mica were added to 180 parts by weight of a thermoplastic polyurethane at a temperature of 180 占 폚 To prepare a pellet. The pellets thus prepared were molded into a thermoplastic polyurethane composite composition at an extruder at 180 ° C.
(비교예 3)(Comparative Example 3)
중합도가 1000인 폴리염화비닐 20중량%에, (기재 100중량부를 기준으로)프탈레이트계 가소제 20 중량부, 열안정제인 라울린산바륨 1중량부를 100℃의 슈퍼믹서를 이용하여 30분간 선 믹싱한 후, 경도 66A(asker A), 인장강도 20Mpa, 녹는점 150℃ 열가소성폴리우레탄 80중량%, (기재 100중량부를 기준으로)실란 처리된 탄산칼슘 5중량부, 실란 처리된 탈크 2.5 중량부, 실란 처리된 마이카 2.5 중량부를 180℃의 이축압축기에서 펠렛을 제조하고, 제조된 펠렛을 180℃의 사출기에서 열가소성폴리우레탄 복합 조성물을 제조하였다.
20 parts by weight of a phthalate plasticizer (based on 100 parts by weight of the substrate) and 1 part by weight of barium laurethate as a heat stabilizer were preliminarily mixed for 30 minutes by using a super mixer at 100 캜 in 20% by weight of polyvinyl chloride having a degree of polymerization of 1000 5 parts by weight of silane-treated calcium carbonate (based on 100 parts by weight of the substrate), 2.5 parts by weight of silane-treated talc, 2.5 parts by weight of silane (based on 100 parts by weight of the base), a hardness of 66 A and a tensile strength of 20 MPa, 2.5 parts by weight of the treated mica was prepared in a twin-screw compressor at 180 DEG C, and the thermoplastic polyurethane composite composition was prepared by injection molding the pellet at 180 DEG C.
(비교예 4)(Comparative Example 4)
경도 66A(asker A), 인장강도 20Mpa, 녹는점 150℃ 열가소성폴리우레탄 100중량부에 대하여, 실리카에 담지된 내부이형제(실리카/내부이형제 담지비율, 1:1.5)를 5중량부, 실란 처리된 탄산칼슘 5중량부, 실란 처리된 탈크 2.5 중량부, 실란 처리된 마이카 2.5 중량부를 180℃의 이축압축기에서 펠렛을 제조하고, 제조된 펠렛을 180℃의 사출기에서 열가소성폴리우레탄 복합 조성물을 제조하였다.
5 parts by weight of an inner mold release agent (silica / inner mold release agent loading ratio, 1: 1.5) supported on silica was added to 100 parts by weight of a thermoplastic polyurethane having a hardness of 66 A (Asker A), a tensile strength of 20 MPa, 5 parts by weight of calcium carbonate, 2.5 parts by weight of silane-treated talc and 2.5 parts by weight of silane-treated mica were prepared in a twin-screw extruder at 180 DEG C, and the resulting pellets were molded at 180 DEG C in an extruder to prepare a thermoplastic polyurethane composite composition.
2. 신발 겉창용 열가소성폴리우레탄 복합조성물 평가
2. Evaluation of Thermoplastic Polyurethane Composite Composition for Shoe Outsole
상기 실시예 1 내지 3 및 비교예 1 내지 4에 의해 제조된 신발 겉창용 열가소성폴리우레탄 복합조성물에 대해서 아래의 시험방법에 준하여 평가하여 그 결과를 아래 [표 1]에 나타내었다.
The thermoplastic polyurethane composite compositions for shoe outsole prepared according to Examples 1 to 3 and Comparative Examples 1 to 4 were evaluated in accordance with the following test methods and the results are shown in Table 1 below.
1) 인장강도 : KSM 6518 방법을 사용하여 측정하였다.1) Tensile strength: Measured using the KSM 6518 method.
2) 내마모성 : KSM 6625 방법을 사용하여 측정하였다.2) Abrasion resistance: Measured using the KSM 6625 method.
3) 사출성형성 : 사출 후 제품의 수축 및 변형을 평가하였다.
3) Injection moldability: The shrinkage and deformation of the product after injection were evaluated.
상기 [표 1]에 나타난 바와 같이, 실시예 1 내지 3은 전반적으로 인장강도가 150kg/cm2 이상, 내마모성 200% 이상, 사출성형성도 우수한 결과를 보였다.As shown in Table 1, Examples 1 to 3 showed excellent tensile strengths of not less than 150 kg / cm 2 , abrasion resistance of not less than 200%, and excellent injection moldability.
반면에 비교예 1은 열가소성폴리우레탄를 단독 기재로 사용한 것으로 내마모성능은 양호하나 사출성형성이 떨어지는 문제가 발생하였다. 또한 비교예 2의 경우 사출성형성은 양호하나, 내마모성 개선을 위한 실리카에 담지된 내부이형제의 미 사용에 따른 내마모성능이 취약한 결과를 보였다. 비교예 3은 열가소성폴리우레탄에 폴리염화비닐의 혼용과 실란처리된 탈크, 탄산칼슘, 마이카를 적용하여 사출성형성은 개선되었으나, 내마모성이 현저히 떨어지는 문제 발생하였다. 비교예 4의 경우 열가소성폴리우레탄을 단독 기재로 사용에 따른 사출성형성에 문제가 발생하는 것으로 나타났다.
On the other hand, in Comparative Example 1, thermoplastic polyurethane was used as a sole substrate and the abrasion resistance performance was good but the injection moldability was poor. In Comparative Example 2, the injection moldability was good, but the abrasion resistance performance of the inner mold agent supported on the silica for improving the abrasion resistance was poor. In Comparative Example 3, injection moldability was improved by applying mixed polyvinyl chloride to the thermoplastic polyurethane and silk treated talc, calcium carbonate and mica, but the wear resistance was significantly lowered. In the case of Comparative Example 4, it was found that there was a problem in injection moldability by using thermoplastic polyurethane as a single substrate.
상술한 바와 같은, 본 발명의 바람직한 실시예에 따른 신발 겉창용 열가소성폴리우레탄 복합 조성물을 상기한 설명 및 도면에 따라 설명하였지만 이는 예를 들어 설명한 것에 불과하며 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 다양한 변화 및 변경이 가능하다는 것을 이 분야의 통상적인 기술자들은 잘 이해할 수 있을 것이다.As described above, the thermoplastic polyurethane composite composition for a shoe outsole according to the preferred embodiment of the present invention has been described with reference to the above description and drawings. However, the present invention is merely illustrative and not restrictive within the scope of the present invention. It will be understood by those of ordinary skill in the art that various changes and modifications may be made.
Claims (5)
상기 열가소성폴리우레탄 복합 조성물은,
열가소성폴리우레탄 60 ~ 90 중량% 및 폴리염화비닐 10 ~ 40 중량%로 이루어진 기재 100 중량부에 대하여,
가소제 5 ~ 40 중량부, 열안정제 0.1 ~ 2 중량부, 실리카에 담지 시킨 내부 이형제 3 ~ 10 중량부, 실란 처리된 탄산칼슘 2 ~ 10 중량부, 실란 처리된 탈크 2 ~ 10 중량부 및 실란 처리된 마이카 2 ~ 10 중량부로 이루어지는 것을 특징으로 하는 신발 겉창용 열가소성폴리우레탄 복합 조성물.
A thermoplastic polyurethane composite composition for a shoe outsole comprising a base made of thermoplastic polyurethane and polyvinyl chloride,
In the thermoplastic polyurethane composite composition,
Based on 100 parts by weight of a substrate composed of 60 to 90% by weight of thermoplastic polyurethane and 10 to 40% by weight of polyvinyl chloride,
5 to 40 parts by weight of a plasticizer, 0.1 to 2 parts by weight of a heat stabilizer, 3 to 10 parts by weight of an internal release agent supported on silica, 2 to 10 parts by weight of silane-treated calcium carbonate, 2 to 10 parts by weight of silane- And 2 to 10 parts by weight of a mica.
상기 열가소성폴리우레탄은,
경도가 60 ~ 75(asker A)이며, 인장강도가 15 ~ 35Mpa이고, 녹는점이 150 ~ 200℃ 범위를 가지는 것을 특징으로 하는 신발 겉창용 열가소성폴리우레탄 복합 조성물.
The method according to claim 1,
In the thermoplastic polyurethane,
A hardness of 60 to 75 (Asker A), a tensile strength of 15 to 35 MPa, and a melting point of 150 to 200 占 폚.
상기 폴리염화비닐은,
중합도가 800 ~ 2500인 것을 특징으로 하는 신발 겉창용 열가소성폴리우레탄 복합 조성물.The method according to claim 1,
The above-
And a degree of polymerization of 800 to 2500. The thermoplastic polyurethane composite composition of claim 1,
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