KR20200122649A - Composition of environmental-friendly tpu composite material and environmental-friendly tpu film using the same - Google Patents
Composition of environmental-friendly tpu composite material and environmental-friendly tpu film using the same Download PDFInfo
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- 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
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
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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
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
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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
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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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
- C08L2310/00—Masterbatches
Abstract
Description
본 발명은 TPU에 친환경 소재인 피마자유가 30 중량% 이상 함유되어 친환경 복합소재의 기준을 만족시키면서도, 마이그레이션 현상이 없고 일반적인 TPU에 비하여 동등 이상의 물성을 가질 수 있도록 하는, 친환경 TPU 복합소재 조성물 및 이를 이용하여 제조되는 친환경 TPU 필름에 관한 것이다.The present invention contains more than 30% by weight of castor oil, an eco-friendly material in TPU, satisfies the standards of an eco-friendly composite material, does not have a migration phenomenon, and allows it to have physical properties equal to or higher than that of a general TPU, and uses the same. It relates to an eco-friendly TPU film manufactured by doing.
일반적으로 TPU는 기계적 물성 및 탄성력 등이 우수하고 일반적인 탄성체인 가교 고무 등과 같은 열경화성 수지와 달리 사출, 압출 등과 같은 공정을 통해 제품을 생산할 수 있으므로 신발 갑피, 의류용, 자동차 내장재 및 겉창 등 다양한 산업 분야에서 사용되고 있다In general, TPU has excellent mechanical properties and elasticity and can be produced through processes such as injection and extrusion, unlike thermosetting resins such as crosslinked rubber, which is a general elastic material.Therefore, various industrial fields such as shoe uppers, clothing, automobile interior materials and outsoles Is used in
한편, 최근들어 심각해지는 환경오염에 대한 대응책으로 신발 및 의류 등에 친환경 이미지를 주요 마케팅 수단으로 부각시키고 있으며, 이에 완제품 및 부품업체에 친환경 소재를 사용한 부품을 요구하고 있다.Meanwhile, as a countermeasure against serious environmental pollution in recent years, eco-friendly images are being emphasized as a major marketing means for shoes and clothing, and thus finished products and parts manufacturers are demanding parts using eco-friendly materials.
관련 선행기술로써 특허문헌 1 내지 4 등에서는 TPU 중 피마자유 등에서 바이오 폴리올을 추줄하여 제조된 친환경 TPU를 제안하고 있으나 가격이 높고 제품 수급이 어려워 적용에는 어려움이 있다.As a related prior art, Patent Documents 1 to 4, etc., propose eco-friendly TPU manufactured by extracting biopolyol from castor oil among TPU, but it is difficult to apply due to high price and difficulty in product supply.
특히, 친환경 복합소재의 기준은 친환경 소재가 30 중량% 이상 포함되어하는데, 피마자유의 경우 점도가 낮아 TPU 등의 폴리머와 혼합이 어렵고 혼합 후에도 TPU 표면으로 빠져나와 10 중량%이상 도입이 어려운 실정이다.In particular, the standard of eco-friendly composite material contains 30% by weight or more of eco-friendly material.In the case of castor oil, it is difficult to mix with polymers such as TPU due to its low viscosity, and it is difficult to introduce more than 10% by weight as it escapes to the TPU surface even after mixing.
본 발명은 상술한 문제점을 해결하기 위한 것으로, 경도 50D 이상의 TPU 분말 또는, TPU 분말과 NBR 분말의 혼합분말에 피마자유를 혼합하여 피마자유 마스터배치를 먼저 제조하고, 이를 TPU에 적용함으로써 피마자유가 30 중량% 이상 도입되더라도 마이그레이션 현상이 없고 일반적인 TPU에 비하여 동등 이상의 물성을 가질 수 있도록 함을 과제로 한다.The present invention is to solve the above-described problem, by mixing castor oil in a TPU powder having a hardness of 50D or more or a mixture powder of TPU powder and NBR powder to prepare a castor oil masterbatch first, and by applying it to the TPU, castor oil is reduced to 30 Even if more than weight% is introduced, there is no migration phenomenon, and the task is to have physical properties equal to or higher than that of general TPU.
본 발명은 TPU 조성물에 있어서, TPU 30 ~ 60 중량% 및 피마자유 마스터배치 40 ~ 70 중량%로 이루어지는 것을 특징으로 하는, 친환경 TPU 복합소재 조성물 및 이를 이용하여 제조되는 친환경 TPU 필름을 과제의 해결 수단으로 한다.The present invention is a TPU composition, characterized in that consisting of 30 to 60% by weight of TPU and 40 to 70% by weight of the castor oil masterbatch, an eco-friendly TPU composite material composition and an eco-friendly TPU film manufactured using the same. To do.
여기서 상기 피마자유 마스터배치는, TPU 분말 100 중량부에 대하여, 피마자유 300 ~ 400 중량부를 혼합하여 이루어질 수 있다.Here, the castor oil masterbatch may be formed by mixing 300 to 400 parts by weight of castor oil based on 100 parts by weight of the TPU powder.
또한 상기 피마자유 마스터배치는, TPU 분말 80 ~ 95 중량% 및 NBR 분말 5 ~ 20 중량%로 이루어진 기재 100 중량부에 대하여, 피마자유 300 ~ 400 중량부를 혼합하여 이루어질 수도 있다.In addition, the castor oil masterbatch may be formed by mixing 300 to 400 parts by weight of castor oil with respect to 100 parts by weight of the substrate comprising 80 to 95% by weight of TPU powder and 5 to 20% by weight of NBR powder.
본 발명은 경도 50D 이상의 TPU 분말 또는, TPU 분말과 NBR 분말의 혼합분말에 피마자유를 혼합하여 피마자유 마스터배치를 먼저 제조하고, 이를 TPU에 적용함으로써 피마자유가 30 중량% 이상 도입되어 친환경 복합소재의 기준을 만족시키면서도, 마이그레이션 현상이 없고 일반적인 TPU에 비하여 동등 이상의 물성을 가질 수 있는 효과가 있다.In the present invention, castor oil masterbatch is first prepared by mixing castor oil with TPU powder having a hardness of 50D or higher, or a mixture of TPU powder and NBR powder, and by applying it to TPU, castor oil is introduced at least 30% by weight of an eco-friendly composite material. While satisfying the criteria, there is no migration phenomenon and there is an effect of having physical properties equal to or higher than that of general TPU.
본 발명은 친환경 TPU 복합소재 조성물 및 이를 이용하여 제조되는 친환경 TPU 필름에 관한 것으로, 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 relates to an eco-friendly TPU composite material composition and an eco-friendly TPU film manufactured using the same, and only parts necessary to understand the technical configuration of the present invention are described, and descriptions of other parts are omitted so as not to scatter the gist of the present invention. It should be noted that it will be.
본 발명에 따른 친환경 TPU 복합소재 조성물 및 이를 이용하여 제조되는 친환경 TPU 필름을 설명하면 다음과 같다.An eco-friendly TPU composite material composition according to the present invention and an eco-friendly TPU film manufactured using the same will be described as follows.
본 발명에 친환경 TPU 조성물 및 이를 이용하여 제조되는 친환경 TPU 필름은 TPU(thermoplastic polyurethane) 30 ~ 60 중량% 및 피마자유 마스터배치(castor oil master batch) 40 ~ 70 중량%로 이루어지는 것을 특징으로 한다.In the present invention, the eco-friendly TPU composition and the eco-friendly TPU film manufactured using the same are characterized by consisting of 30 to 60% by weight of a thermoplastic polyurethane (TPU) and 40 to 70% by weight of a castor oil master batch.
여기서 상기 피마자유 마스터배치의 함량이 40 중량% 미만이면 친환경 복합소재의 친환경 소재 함량 기준에 미달할 우려가 있으며, 70 중량%를 초과할 경우 TPU와 혼합이 되지 못할 우려가 있다.Here, if the content of the castor oil masterbatch is less than 40% by weight, there is a concern that the content of the eco-friendly material of the eco-friendly composite material may not be met, and if it exceeds 70% by weight, it may not be mixed with the TPU.
보다 구체적으로 상기 피마자유 마스터배치는 TPU와 피마자유를 혼합한 것으로, TPU와의 혼합성 및 피마자유의 마이그레이션 발생을 방지하기 위하여 경도 50D(shore D type)이상의 TPU를 고속블랜더에서 분쇄하여 미세 파우더를 제조하고 제조된 TPU 파우더 100 중량부에 대하여 피마자유를 300 ~ 400 중량부를 슈퍼믹스에서 고속으로 혼합하여 마이그레이션이 발생되지 않는 피마자유 마스터배치를 제조 후 이를 적용한다. 여기서 상기 TPU의 경도가 50D 미만일 경우 피마자유의 마이그레이션이 발생할 우려가 있다.More specifically, the castor oil masterbatch is a mixture of TPU and castor oil, and in order to prevent migration of castor oil and blendability with TPU, TPU having a hardness of 50D (shore D type) or more is pulverized in a high-speed blender to produce fine powder. And, based on 100 parts by weight of the prepared TPU powder, 300 to 400 parts by weight of castor oil are mixed at high speed in a supermix to prepare a castor oil masterbatch that does not cause migration, and then apply it. Here, when the hardness of the TPU is less than 50D, there is a concern that the migration of castor oil may occur.
한편, 상기 피마자유 마스터배치는 TPU와 피마자유의 상용성 및 물성을 더욱 개선하기 위하여 NBR(nitrile butadiene rubber) 분말을 적용할 수 있으며, 보다 구체적으로 TPU 분말 80 ~ 95 중량% 및 NBR 분말 5 ~ 20 중량%로 이루어진 기재 100 중량부에 대하여, 피마자유 300 ~ 400 중량부를 혼합하여 이루어지는 것을 사용한다. 여기서 상기 NBR 분말의 함량이 및 피마자유의 함량이 상기 범위를 벗어날 경우 TPU와의 상용성 개선 효율이 미비해질 우려가 있다.Meanwhile, in the castor oil masterbatch, in order to further improve the compatibility and physical properties of TPU and castor oil, nitrile butadiene rubber (NBR) powder may be applied, and more specifically, 80 to 95% by weight of TPU and 5 to 20 of NBR powder. A mixture of 300 to 400 parts by weight of castor oil is used with respect to 100 parts by weight of the base material consisting of weight percent. Here, when the content of the NBR powder and the content of castor oil are out of the above range, there is a concern that the efficiency of improving compatibility with the TPU may become insufficient.
아울러, 본 발명은 상기와 같이 이루어지는 친환경 TPU 복합소재 조성물을 160 ~ 190℃에서 필름형태로 압출함으로써 친환경 TPU 필름을 제조할 수 있다.In addition, the present invention can produce an eco-friendly TPU film by extruding the eco-friendly TPU composite material composition made as described above in a film form at 160 ~ 190 ℃.
이하, 본 발명을 실시예에 의거하여 더욱 구체적으로 설명하겠는 바, 본 발명이 다음 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by the following examples.
1. 피마자유 마스터배치의 제조1. Manufacture of castor oil masterbatch
(제조예 1)(Production Example 1)
고속블랜더에서 분말화된 TPU 분말(55D, Lubrizol, Estane 58133) 100 중량부에 대하여, 피마자유 300 중량부를 혼합하고 슈퍼믹스에서 교반하여 피마자유 마스터배치를 제조하였다.With respect to 100 parts by weight of TPU powder (55D, Lubrizol, Estane 58133) powdered in a high-speed blender, 300 parts by weight of castor oil was mixed and stirred in a supermix to prepare a castor oil masterbatch.
(제조예 2)(Production Example 2)
고속블랜더에서 분말화된 TPU 분말(55D, Lubrizol, Estane 58133) 80 중량% 및 NBR 분말(Zeon, Nipol 1411) 20 중량%로 이루어진 기재 100 중량부에 대하여, 피마자유 300 중량부를 혼합하고 슈퍼믹스에서 교반하여 피마자유 마스터배치를 제조하였다.Based on 100 parts by weight of the base material consisting of 80% by weight of TPU powder (55D, Lubrizol, Estane 58133) and 20% by weight of NBR powder (Zeon, Nipol 1411) powdered in a high-speed blender, 300 parts by weight of castor oil was mixed and in a supermix Stirring to prepare a castor oil masterbatch.
(제조예 3)(Production Example 3)
고속블랜더에서 분말화된 TPU 분말(55D, Lubrizol, Estane 58133) 95 중량% 및 NBR 분말(Zeon, Nipol 1411) 5 중량%로 이루어진 기재 100 중량부에 대하여, 피마자유 400 중량부를 혼합하고 슈퍼믹스에서 교반하여 피마자유 마스터배치를 제조하였다.Based on 100 parts by weight of the base material consisting of 95% by weight of TPU powder (55D, Lubrizol, Estane 58133) powdered in a high-speed blender and 5% by weight of NBR powder (Zeon, Nipol 1411), 400 parts by weight of castor oil was mixed and in a supermix Stirring to prepare a castor oil masterbatch.
2. 친환경 TPU 복합소재의 제조2. Manufacture of eco-friendly TPU composite material
(실시예 1)(Example 1)
TPU 60 중량% 및 제조예 1에 따른 피마자유 마스터배치 40 중량%를 혼합하여 친환경 TPU 복합소재를 제조하였다.An eco-friendly TPU composite material was prepared by mixing 60% by weight of TPU and 40% by weight of the castor oil masterbatch according to Preparation Example 1.
(실시예 2)(Example 2)
TPU 50 중량% 및 제조예 1에 따른 피마자유 마스터배치 50 중량%를 혼합하여 친환경 TPU 복합소재를 제조하였다.An eco-friendly TPU composite material was prepared by mixing 50% by weight of TPU and 50% by weight of the castor oil masterbatch according to Preparation Example 1.
(실시예 3)(Example 3)
TPU 60 중량% 및 제조예 2에 따른 피마자유 마스터배치 40 중량%를 혼합하여 친환경 TPU 복합소재를 제조하였다.An eco-friendly TPU composite material was prepared by mixing 60% by weight of TPU and 40% by weight of the castor oil masterbatch according to Preparation Example 2.
(실시예 4)(Example 4)
TPU 60 중량% 및 제조예 2에 따른 피마자유 마스터배치 40 중량%를 혼합하여 친환경 TPU 복합소재를 제조하였다.An eco-friendly TPU composite material was prepared by mixing 60% by weight of TPU and 40% by weight of the castor oil masterbatch according to Preparation Example 2.
(실시예 5)(Example 5)
TPU 50 중량% 및 제조예 3에 따른 피마자유 마스터배치 50 중량%를 혼합하여 친환경 TPU 복합소재를 제조하였다.An eco-friendly TPU composite material was prepared by mixing 50% by weight of TPU and 50% by weight of the castor oil masterbatch according to Preparation Example 3.
(실시예 6)(Example 6)
TPU 30 중량% 및 제조예 3에 따른 피마자유 마스터배치 70 중량%를 혼합하여 친환경 TPU 복합소재를 제조하였다.An eco-friendly TPU composite material was prepared by mixing 30% by weight of TPU and 70% by weight of the castor oil masterbatch according to Preparation Example 3.
(비교예 1)(Comparative Example 1)
TPU 100 중량부를 사용하였다.100 parts by weight of TPU was used.
2. 친환경 TPU 복합소재의 평가2. Evaluation of eco-friendly TPU composite materials
상기 실시예 및 비교예에 따른 소재에 대한 경도, 인장강도, 신장율 및 인열강도를 평가하였으며, 그 결과는 아래 [표 1]과 같다.The hardness, tensile strength, elongation and tear strength of the materials according to the Examples and Comparative Examples were evaluated, and the results are shown in [Table 1] below.
(asker A)Hardness
(asker A)
(kgf/cm2)The tensile strength
(kgf/cm 2 )
(%)Elongation
(%)
(kgf/cm)Tear strength
(kgf/cm)
상기 [표 1]에서와 같이, 본 발명의 실시예에 따른 친환경 TPU 복합소재는 친환경 소재인 피마자유가 30 중량% 이상 함유되어 친환경 복합소재의 기준을 만족시키면서도 마이그레이션 현상이 없고 일반적인 TPU에 비하여 동등 이상의 물성을 가짐을 알 수 있다.As shown in [Table 1], the eco-friendly TPU composite material according to the embodiment of the present invention contains 30% by weight or more of castor oil, an eco-friendly material, and satisfies the criteria of an eco-friendly composite material, but does not have a migration phenomenon, and is equal to or higher than that of general TPU. It can be seen that it has physical properties.
상술한 바와 같이, 본 발명에 따른 친환경 TPU 복합소재 조성물 및 이를 이용하여 제조되는 친환경 TPU 필름을 상기의 바람직한 실시 예를 통해 설명하고, 그 우수성을 확인하였지만 해당 기술 분야의 당업자라면 하기의 특허청구범위에 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 eco-friendly TPU composite material composition according to the present invention and the eco-friendly TPU film manufactured using the same have been described through the above preferred embodiments, and the excellence thereof has been confirmed. It will be understood that various modifications and changes can be made to the present invention without departing from the spirit and scope of the present invention described in FIG.
Claims (4)
TPU 30 ~ 60 중량% 및 피마자유 마스터배치 40 ~ 70 중량%로 이루어지는 것을 특징으로 하는, 친환경 TPU 복합소재 조성물.
In the TPU composition,
An eco-friendly TPU composite composition, characterized in that consisting of 30 to 60% by weight of TPU and 40 to 70% by weight of the castor oil masterbatch.
상기 피마자유 마스터배치는,
TPU 분말 100 중량부에 대하여, 피마자유 300 ~ 400 중량부를 혼합하여 이루어지는 것을 특징으로 하는, 친환경 TPU 복합소재 조성물.
The method of claim 1,
The castor oil masterbatch,
An eco-friendly TPU composite material composition, characterized in that made by mixing 300 to 400 parts by weight of castor oil based on 100 parts by weight of TPU powder.
상기 피마자유 마스터배치는,
TPU 분말 80 ~ 95 중량% 및 NBR 분말 5 ~ 20 중량%로 이루어진 기재 100 중량부에 대하여, 피마자유 300 ~ 400 중량부를 혼합하여 이루어지는 것을 특징으로 하는, 친환경 TPU 복합소재 조성물.
The method of claim 1,
The castor oil masterbatch,
TPU powder 80 to 95% by weight and NBR powder 5 to 20% by weight based on 100 parts by weight of the substrate, characterized in that formed by mixing 300 to 400 parts by weight of castor oil, eco-friendly TPU composite composition.
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| KR100932422B1 (en) | 2007-11-15 | 2009-12-17 | (주)지케이 | Eco-friendly bio flooring |
| KR20100113611A (en) | 2008-02-01 | 2010-10-21 | 로께뜨프레르 | Thermoplastic compositions based on soluble starch and method for preparing such compositions |
| KR101387887B1 (en) | 2011-07-14 | 2014-04-22 | (주)엘지하우시스 | Bio interior sheet and and manufacturing method thereof |
| KR20170065850A (en) | 2015-12-04 | 2017-06-14 | 삼성전자주식회사 | Polymer composition, electronic device and method for producing of the same |
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| KR100932422B1 (en) | 2007-11-15 | 2009-12-17 | (주)지케이 | Eco-friendly bio flooring |
| KR20100113611A (en) | 2008-02-01 | 2010-10-21 | 로께뜨프레르 | Thermoplastic compositions based on soluble starch and method for preparing such compositions |
| KR101387887B1 (en) | 2011-07-14 | 2014-04-22 | (주)엘지하우시스 | Bio interior sheet and and manufacturing method thereof |
| KR20170065850A (en) | 2015-12-04 | 2017-06-14 | 삼성전자주식회사 | Polymer composition, electronic device and method for producing of the same |
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