KR20000058250A - Styrene butadiene block copolymer composition and film - Google Patents

Styrene butadiene block copolymer composition and film Download PDF

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KR20000058250A
KR20000058250A KR1019990068466A KR19990068466A KR20000058250A KR 20000058250 A KR20000058250 A KR 20000058250A KR 1019990068466 A KR1019990068466 A KR 1019990068466A KR 19990068466 A KR19990068466 A KR 19990068466A KR 20000058250 A KR20000058250 A KR 20000058250A
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weight
parts
sbc
block copolymer
hardness
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최형복
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최형복
박정수
한국신발피혁연구소
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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
    • 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
    • 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
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/10—Copolymers of styrene with conjugated dienes
    • 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
    • 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
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/08—Copolymers of styrene
    • C08J2325/10—Copolymers of styrene with conjugated dienes
    • 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
    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
    • 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
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes

Abstract

PURPOSE: A styrene-butadiene block copolymer elastic composition and a film prepared from the composition are provided, to improve the heat resistance and the processibility of the composition into a film or a sheet. CONSTITUTION: The thermoplastic and elastic styrene-butadiene block copolymer composition comprises 10-80 parts by weight of polystyrene-butadiene block copolymer with the hardness of 60-70 (Shore A type); 10-80 parts by weight of polystyrene-butadiene block copolymer with the hardness of 70-90 (Shore A type); 80-90 parts by weight of polystyrene-butadiene block copolymer with the hardness of 60-70 (Shore D type); and optionally 1-100 parts by weight of a processing oil selected form a heavy oil or a light oil consisting of saturated or unsaturated hydrocarbons. Also the thermoplastic and elastic styrene-butadiene block copolymer composition comprises 10-80 parts by weight of polystyrene-butadiene block copolymer with the hardness of 60-70 (Shore A type); 10-80 parts by weight of polystyrene-butadiene block copolymer with the hardness of 70-90 (Shore A type); 10-70 parts by weight of polystyrene-butadiene block copolymer with the hardness of 80-90 (Shore A type); and 1-100 parts by weight of a processing oil selected form a heavy oil or a light oil consisting of saturated or unsaturated hydrocarbons.

Description

스티렌-부타디엔 블록 공중합체 조성물 및 필름 {STYRENE BUTADIENE BLOCK COPOLYMER COMPOSITION AND FILM}Styrene-butadiene block copolymer composition and film {STYRENE BUTADIENE BLOCK COPOLYMER COMPOSITION AND FILM}

본 발명은 폴리스티렌계 열가소성 탄성체 조성물 및 그 가공 방법에 관한 것으로서, 보다 상세하게는 서로 다른 경도를 갖는 스티렌-부타디엔 블록 공중합체 (styrene-butadiene block copolymer, 이하 SBC라고 약칭함)를 혼합한 조성물로서, 가공유를 조성물에 첨가하여 시이트 형상으로 가공하는 방법에 대한 것이다.The present invention relates to a polystyrene-based thermoplastic elastomer composition and a processing method thereof, and more particularly, to a composition in which styrene-butadiene block copolymers (hereinafter, abbreviated as SBC) having different hardness are mixed. A process oil is added to a composition and it processes to the sheet form.

SBC 열가소성 탄성체는 유기 용매하에서 부타디엔과 스티렌으로 중합된 선형 혹은 방사상의 구조를 갖는 블록 공중합체로서, 탄성체로의 가공을 위한 가교 공정을 별도로 필요로 하지 않으며, 우수한 물리적 특성을 갖는 탄성체다. 또한 가교 반응을 통해서 탄성체로 가공되는 일반적인 고무에 비하여 우수한 경도, 인장강도, 신장률 등의 물리적 특성이 우수하며, 다른 수지와의 상용성이 우수하고, 가교 공정이 필요 없으며, 재활용이 가능한 장점을 지니고 있다. 또한 가공유(processing oil)의 첨가로 경도의 조절이 용이하고, 일반 플라스틱 성형법과 같이 압출, 사출성형이 가능하다.SBC thermoplastic elastomer is a block copolymer having a linear or radial structure polymerized with butadiene and styrene in an organic solvent, and does not require a crosslinking process for processing into an elastomer, and is an elastomer having excellent physical properties. In addition, physical properties such as hardness, tensile strength, and elongation are excellent compared to general rubbers processed into elastomers through crosslinking reactions, have excellent compatibility with other resins, do not require a crosslinking process, and are recyclable. have. In addition, it is easy to control the hardness by the addition of processing oil, and extrusion and injection molding are possible as in general plastic molding.

이러한 장점들에도 불구하고, SBC는 내열성이 우수하지 못하며, 필름이나 시이트 형상으로의 가공이 어려워서 그 응용 범위가 제한된다는 단점이 있었다.Despite these advantages, SBC has a disadvantage in that heat resistance is not excellent and its application range is limited due to difficulty in processing into a film or sheet shape.

따라서, 본 발명의 목적은 필름이나 시이트 형상으로의 가공이 가능한 SBC 조성물을 제공하여 신발의 외피 소재로 사용할 수 있는 SBC 조성물 및 그 가공방법을 제공함에 있다.Accordingly, it is an object of the present invention to provide an SBC composition that can be processed into a film or sheet shape and to provide an SBC composition and a processing method thereof that can be used as an outer material of a shoe.

발명자들은 다양한 경도를 갖는 SBC를 적당비율로 혼합하여 특정 조성비의 조성물로 제조하면서, 여기에 가공유를 적정 비율로 혼합하여 티-다이(T-die)성형법이나 칼렌더링(calendering)법으로 시이트나 필름을 제조하는 경우, 신발 외피 소재로 사용하기에 적합한 물성을 갖는 SBC 필름이나 시이트를 제조 할 수 있다는 사실을 발견하여 본 발명을 완성하기에 이르렀다.The inventors mix SBCs having various hardness in appropriate ratios to produce a composition with a specific composition ratio, and process oils are mixed in an appropriate ratio to the sheet or film by T-die molding or calendering. In the manufacture of the present invention, the inventors have found that SBC film or sheet having physical properties suitable for use as a shoe jacket material has been completed.

본 발명의 SBC 조성물은 경도가 60∼70(Shore A type, (주)금호에서 생산한 공중합체 KTR 201 제품)인 SBC를 10∼80 중량부, 경도가 70∼90(Shore A type, (주)금호에서 생산한 공중합체 KTR 602 제품)인 SBC를 10∼80 중량부, 경도가 80∼90(Shore D type, 대림에서 생산한 공중합체 K resin 10)인 SBC를 10∼70 중량부 사용하여 kneader에서 온도 100∼140℃에서 5∼10분 혼합하여 제조된다.The SBC composition of the present invention has a hardness of 60 to 70 (Shore A type, copolymer KTR 201 produced by Kumho Co., Ltd.) 10 to 80 parts by weight, hardness of 70 to 90 (Shore A type, ( 10-80 parts by weight of SBC, a copolymer KTR 602 produced by Kumho, and 10-70 parts by weight of SBC, 80-90 (Shore D type, copolymer K resin 10 produced by Daelim) The mixture is prepared by kneader at a temperature of 100 to 140 ° C. for 5 to 10 minutes.

본 발명의 조성물에 배합되는 각 성분에 대하여 이하에서 설명한다.Each component mix | blended with the composition of this invention is demonstrated below.

(1) SBC(1) SBC

부타디엔과 스티렌의 블록 공중합체로서 주로 유화 중합법에 의하여 제조된다. 중합체의 주쇄에 있어서 부타디엔의 구조 트란스 1-4 결합이 약 70%에 달하기 때문에 내부 발열이 크다. 천연고무와 비교하여 내노화성, 내열성, 내유성, 내마모성이 우수하고 항장력, 탄성, 찢김저항등의 물성이 뒤떨어진다.As a block copolymer of butadiene and styrene, it is mainly produced by emulsion polymerization. The internal exotherm is large because the structural trans 1-4 bonds of butadiene amount to about 70% in the main chain of the polymer. Compared with natural rubber, it has excellent aging resistance, heat resistance, oil resistance and abrasion resistance, and is inferior in physical properties such as tensile strength, elasticity and tear resistance.

또한, 내열성이 우수하지 못하여 SBC 단독으로 필름을 제조하였을 때 필름의 보관 안정성이 매우 좋지 못하여 보관 온도가 30∼80℃이상일 때 롤로 감아놓은 SBC 필름들이 서로 달라붙는 현상이 발생하기도 한다.In addition, when the film is produced by SBC alone is not excellent in heat resistance, the storage stability of the film is very poor, the phenomenon that the SBC film wrapped with a roll may stick to each other when the storage temperature is 30 ~ 80 ℃ or more.

(2) 가공유(processing oil)(2) processing oil

SBC 고무의 가공성(加工性)을 개선하기 위해 첨가되는 오일로서, 석유류 제품에 섞여있는 포화(飽和)또는 불활성(不活性)인 불포화 탄화수소로 이루어진다. 본 발명에 사용 될 수 있는 가공유로는 대황색(帶黃色)의 투명한 경질유(輕質油)로부터 형광(螢光)성을 띠는 중질유(重質油)까지 여러 종류가 있다.An oil added to improve processability of SBC rubber, which is composed of saturated or inert unsaturated hydrocarbons mixed in petroleum products. Processed oils that can be used in the present invention are of various types, from light yellow transparent light oils to fluorescent heavy oils.

이하, 본 발명을 실시 예에 의거 상세히 설명하면 다음과 같다. 이들 실시 예는 오로지 본 발명을 설명하기 위한 것으로, 이들 실시 예에 의하여 본 발명의 범위가 한정되지 않는다는 것은 본 발명이 속하는 분야에서 통상의 지식을 가진 자들에게 자명할 것이다.Hereinafter, the present invention will be described in detail with reference to Examples. These examples are only for illustrating the present invention, it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples.

실시 예 1 : 칼렌더링(calendering)법을 이용한 SBC 필름제조Example 1 SBC film production using a calendering method

본 발명의 SBC 조성들의 각 성분의 조성비율을 하기에 표기한다.The composition ratio of each component of the SBC compositions of the present invention is shown below.

SBC 조성물 (단위:중량부)SBC composition (unit: parts by weight)

경도가 60∼70(Shore A type, (주)금호에서 생산한 공중합체 KTR 201 제품)인 SBC를 10∼80 중량부, 경도가 70∼90(Shore A type, (주)금호에서 생산한 공중합체 KTR 602 제품)인 SBC를 10∼80 중량부, 경도가 80∼90(Shore D type,대림에서 생산한 공중합체 K resin 10)인 SBC를 10∼70 중량부 사용하여 kneader에서 온도 100∼140℃에서 5∼10 min 혼합 후 칼렌더를 이용하여 필름을 제조하였다.10 to 80 parts by weight of SBC having a hardness of 60 to 70 (Shore A type, a copolymer KTR 201 produced by Kumho Co., Ltd.), and a hardness of 70 to 90 (Shore A type, Kumho produced by Kumho Co., Ltd.) 10 to 80 parts by weight of SBC, which is a copolymer KTR 602), and 10 to 70 parts by weight of SBC, which is 80 to 90 (Shore D type, copolymer K resin 10 produced by Daelim), with a temperature of 100 to 140 in a kneader. After mixing for 5 to 10 min at ℃ to prepare a film using a calendar.

각 필름의 두께는 각각 0.1∼1.5 ㎜로 제조하였다.The thickness of each film was produced in 0.1-1.5 mm, respectively.

제조한 필름의 물성은 다음과 같다.Physical properties of the produced film are as follows.

물성Properties 구분division 단위unit 실시예 1Example 1 비고Remarks 두께thickness ㎜Mm 0.1∼1.50.1 to 1.5 인장 강도The tensile strength ㎏/㎠㎏ / ㎠ 187.1187.1 기계방향측정Machine direction measurement 151.4151.4 폭방향측정Width measurement 인열 강도Tear strength ㎏/㎝Kg / cm 53.353.3 기계방향측정Machine direction measurement 45.745.7 폭방향측정Width measurement 신장율Elongation ％% 1,0001,000 기계방향측정Machine direction measurement 677677 폭방향측정Width measurement

실시 예 2. T-die 법을 이용한 SBC 필름제조Example 2 SBC film production using the T-die method

본 발명의 SBC 조성들의 각 성분의 조성비율을 하기에 표기한다.The composition ratio of each component of the SBC compositions of the present invention is shown below.

SBC 조성물 (단위:중량부)SBC composition (unit: parts by weight)

경도가 60∼70(Shore A type, (주)금호에서 생산한 공중합체 KTR 201 제품)인 SBC를 10∼80 중량부, 경도가 70∼90(Shore A type,(주)금호에서 생산한 공중합체 KTR 602 제품)인 SBC를 10∼80 중량부, 경도가 80∼90(Shore D type, 대림에서 생산한 공중합체 K resin 10)인 SBC를 10∼70 중량부 사용하여 kneader에서 온도 100∼140℃에서 5∼10 min 혼합 후 T-die를 이용하여 필름을 제조하였다. 각 필름의 두께는 각각 0.1∼1.5 mm로 제조하였다.10 to 80 parts by weight of SBC with a hardness of 60 to 70 (Shore A type, copolymer KTR 201 produced by Kumho Co., Ltd.), and a hardness of 70 to 90 (Shore A type, Kumho Co., Ltd.) 10 to 80 parts by weight of SBC, a blended KTR 602 product, and 10 to 70 parts by weight of SBC, which has a hardness of 80 to 90 (Shore D type, copolymer K resin 10 produced by Daelim), temperature of 100 to 140 in a kneader. After mixing 5 to 10 min at ℃ to prepare a film using T-die. The thickness of each film was produced in 0.1-1.5 mm, respectively.

제조한 필름의 물성은 다음과 같다.Physical properties of the produced film are as follows.

물성Properties 구분division 단위unit 실시예 2Example 2 비고Remarks 두께thickness ㎜Mm 0.1∼1.50.1 to 1.5 인장 강도The tensile strength ㎏/㎠㎏ / ㎠ 140.7140.7 기계방향측정Machine direction measurement 120.1120.1 폭방향측정Width measurement 인열 강도Tear strength ㎏/㎝Kg / cm 53.453.4 기계방향측정Machine direction measurement 49.849.8 폭방향측정Width measurement 신장율Elongation ％% 958958 기계방향측정Machine direction measurement 598598 폭방향측정Width measurement

실시예 3.Example 3.

본 발명의 SBC 조성들의 각 성분의 조성비율을 하기에 표기한다.The composition ratio of each component of the SBC compositions of the present invention is shown below.

SBC 조성물 (단위:중량부)SBC composition (unit: parts by weight)

경도가 60∼70(Shore A type, (주)금호에서 생산한 공중합체 KTR 201 제품)인 SBC를 10∼80 중량부, 경도가 70∼90(Shore A type,(주)금호에서 생산한 공중합체 KTR 602 제품)인 SBC를 10∼80 중량부, 경도가 80∼90(Shore D type, 대림에서 생산한 공중합체 K resin 10)인 SBC를 10∼70 중량부 사용하여 kneader에서 온도 100∼140℃에서 5∼10 min 혼합 후 Processing Oil을 1∼100 중량부 투입하여 3∼10 min 혼합후 칼렌더를 이용하여 필름을 제조하였다. 각 필름의 두께는 각각 0.1∼1.5 mm로 제조하였다.10 to 80 parts by weight of SBC with a hardness of 60 to 70 (Shore A type, copolymer KTR 201 produced by Kumho Co., Ltd.), and a hardness of 70 to 90 (Shore A type, Kumho Co., Ltd.) 10 to 80 parts by weight of SBC, a blended KTR 602 product, and 10 to 70 parts by weight of SBC, which has a hardness of 80 to 90 (Shore D type, copolymer K resin 10 produced by Daelim), temperature of 100 to 140 in a kneader. After mixing 5-10 min at ℃ 1 to 100 parts by weight of Processing Oil was added to mix the film for 3 to 10 min to prepare a film. The thickness of each film was produced in 0.1-1.5 mm, respectively.

제조한 필름의 물성은 다음과 같다.Physical properties of the produced film are as follows.

물성Properties 구분division 단위unit 실시예 3Example 3 비고Remarks 두께thickness ㎜Mm 0.1∼1.50.1 to 1.5 인장 강도The tensile strength ㎏/㎠㎏ / ㎠ 171.3171.3 기계방향측정Machine direction measurement 132.4132.4 폭방향측정Width measurement 인열 강도Tear strength ㎏/㎝Kg / cm 48.648.6 기계방향측정Machine direction measurement 42.742.7 폭방향측정Width measurement 신장율Elongation ％% 1,0001,000 기계방향측정Machine direction measurement 700700 폭방향측정Width measurement

실시예 4.Example 4.

본 발명의 SBC 조성들의 각 성분의 조성비율을 하기에 표기한다.The composition ratio of each component of the SBC compositions of the present invention is shown below.

SBC 조성물 (단위:중량부)SBC composition (unit: parts by weight)

경도가 60∼70(Shore A type, (주)금호에서 생산한 공중합체 KTR 201 제품)인 SBC를 10∼80 중량부, 경도가 70∼90(Shore A type, (주)금호에서 생산한 공중합체 KTR 602 제품)인 SBC를 10∼80 중량부, 경도가 80∼90(Shore D type, 대림에서 생산한 공중합체 K resin 10)인 SBC를 10∼70 중량부 사용하여 kneader에서 온도 100∼140℃에서 5∼10 min 혼합 후 Processing Oil을 1∼100 중량부 투입하여 3∼10 min 혼합 후 T-die 를 이용하여 필름을 제조하였다. 각 필름의 두께는 각각 0.1∼1.5 mm로 제조하였다.10 to 80 parts by weight of SBC having a hardness of 60 to 70 (Shore A type, a copolymer KTR 201 produced by Kumho Co., Ltd.), and a hardness of 70 to 90 (Shore A type, Kumho produced by Kumho Co., Ltd.) 10 to 80 parts by weight of SBC, a blended KTR 602 product, and 10 to 70 parts by weight of SBC, which has a hardness of 80 to 90 (Shore D type, copolymer K resin 10 produced by Daelim), temperature of 100 to 140 in a kneader. After mixing 5-10 min at ℃ 1 to 100 parts by weight of Processing Oil was added to mix the film 3 to 10 min to prepare a film using T-die. The thickness of each film was produced in 0.1-1.5 mm, respectively.

제조한 필름의 물성은 다음과 같다.Physical properties of the produced film are as follows.

물성Properties 구분division 단위unit 실시예 4Example 4 비고Remarks 두께thickness ㎜Mm 0.1∼1.50.1 to 1.5 인장 강도The tensile strength ㎏/㎠㎏ / ㎠ 135.3135.3 기계방향측정Machine direction measurement 112.1112.1 폭방향측정Width measurement 인열 강도Tear strength ㎏/㎝Kg / cm 50.150.1 기계방향측정Machine direction measurement 45.345.3 폭방향측정Width measurement 신장율Elongation ％% 1,0001,000 기계방향측정Machine direction measurement 640640 폭방향측정Width measurement

실시예 5.Example 5.

본 발명의 SBC 조성들의 각 성분의 조성비율을 하기에 표기한다.The composition ratio of each component of the SBC compositions of the present invention is shown below.

SBC 조성물 (단위:중량부)SBC composition (unit: parts by weight)

경도가 60∼70(Shore A type, (주)금호에서 생산한 공중합체 KTR 201 제품)인 SBC를 10∼80 중량부, 경도가 70∼90(Shore A type, (주)금호에서 생산한 공중합체 KTR 602 제품)인 SBC를 10∼80 중량부, 경도가 80∼90(Shore D type, 대림에서 생산한 공중합체 K resin 10)인 SBC를 10∼70 중량부 사용하여 kneader에서 온도 100∼140℃에서 5∼10 min 혼합 후, 유색 안료를 0.1∼20 중량부 첨가하여 3∼10 min 혼합 후 칼렌더를 이용하여 필름을 제조하였다. 각 필름의 두께는 각각 0.1∼1.5 mm로 제조하였다.10 to 80 parts by weight of SBC having a hardness of 60 to 70 (Shore A type, KTR 201 produced by Kumho Co., Ltd.), 10 to 80 parts by weight of SBC, a blended KTR 602 product, and 10 to 70 parts by weight of SBC, which has a hardness of 80 to 90 (Shore D type, copolymer K resin 10 produced by Daelim), temperature of 100 to 140 in a kneader. After 5 to 10 min of mixing at 0.1 ° C., 0.1-20 parts by weight of the colored pigment was added, and then a film was prepared using a calender after 3 to 10 min of mixing. The thickness of each film was produced in 0.1-1.5 mm, respectively.

제조한 필름의 물성은 다음과 같다.Physical properties of the produced film are as follows.

물성Properties 구분division 단위unit 실시예 5Example 5 비고Remarks 두께thickness ㎜Mm 0.1∼1.50.1 to 1.5 인장 강도The tensile strength ㎏/㎠㎏ / ㎠ 185.2185.2 기계방향측정Machine direction measurement 153.2153.2 폭방향측정Width measurement 인열 강도Tear strength ㎏/㎝Kg / cm 52.452.4 기계방향측정Machine direction measurement 45.845.8 폭방향측정Width measurement 신장율Elongation ％% 1,0001,000 기계방향측정Machine direction measurement 700700 폭방향측정Width measurement

실시 예 6.Example 6.

본 발명의 SBC 조성들의 각 성분의 조성비율을 하기에 표기한다.The composition ratio of each component of the SBC compositions of the present invention is shown below.

SBC 조성물 (단위:중량부)SBC composition (unit: parts by weight)

경도가 60∼70(Shore A type, (주)금호에서 생산한 공중합체 KTR 201 제품)인 SBC를 10∼80 중량부, 경도가 70∼90(Shore A type, (주)금호에서 생산한 공중합체 KTR 602 제품)인 SBC를 10∼80 중량부, 경도가 80∼90(Shore D type, 대림에서 생산한 공중합체 K resin 10)인 SBC를 10∼70 중량부 사용하여 kneader에서 온도 100∼140℃에서 5∼10 min 혼합 후, 유색 안료를 0.1∼20 중량부 첨가하여 3∼10 min 혼합 후 T-die 를 이용하여 필름을 제조하였다. 각 필름의 두께는 각각 0.1∼1.5 mm로 제조하였다.10 to 80 parts by weight of SBC having a hardness of 60 to 70 (Shore A type, KTR 201 produced by Kumho Co., Ltd.), 10 to 80 parts by weight of SBC, a blended KTR 602 product, and 10 to 70 parts by weight of SBC, which has a hardness of 80 to 90 (Shore D type, copolymer K resin 10 produced by Daelim), temperature of 100 to 140 in a kneader. After 5-10 min of mixing at 0.1 ° C., 0.1-20 parts by weight of the colored pigment was added, followed by 3-10 min of mixing to prepare a film using T-die. The thickness of each film was produced in 0.1-1.5 mm, respectively.

제조한 필름의 물성은 다음과 같다.Physical properties of the produced film are as follows.

물성Properties 구분division 단위unit 실시예 6Example 6 비고Remarks 두께thickness ㎜Mm 0.1∼1.50.1 to 1.5 인장 강도The tensile strength ㎏/㎠㎏ / ㎠ 142.5142.5 기계방향측정Machine direction measurement 121.8121.8 폭방향측정Width measurement 인열 강도Tear strength ㎏/㎝Kg / cm 52.452.4 기계방향측정Machine direction measurement 51.351.3 폭방향측정Width measurement 신장율Elongation ％% 970970 기계방향측정Machine direction measurement 650650 폭방향측정Width measurement

실시예 7.Example 7.

실시예 1∼실시예 6 으로부터 제조된 SBC 필름 위에 수용성 폴리우레탄을 코팅하여 고주파 융착성이 우수한 투명, 유색의 SBC 필름을 제조 할 수 있었다.A water-soluble polyurethane was coated on the SBC films prepared in Examples 1 to 6 to prepare a transparent and colored SBC film excellent in high frequency fusion.

본 발명의 조성비를 갖는 SBC 조성물을 사용하여 제조된 SBC 필름이나 시이트는 신발용 외피 소재로 사용되는 데 적합한 물성을 갖는다. 종래의 SBC 열가소성 탄성체는 시이트나 필름 형상으로의 가공이 어려웠으나 본 발명의 특정 조성비를 갖는 SBC 조성물은 시이트나 필름 형상으로의 가공이 용이하여 SBC 수지를 이용하여 신발 외피용 소재로 사용될 수 있는 시이트나 필름을 제조할 수 있다는 효과가 있다.The SBC film or sheet produced using the SBC composition having the composition ratio of the present invention has suitable physical properties for use as a shoe outer material. Conventional SBC thermoplastic elastomer was difficult to process into sheet or film shape, but the SBC composition having a specific composition ratio of the present invention can be easily processed into a sheet or film shape and thus can be used as a material for shoe skin using SBC resin. The effect is that the film can be produced.

Claims (4)

폴리스티렌-부타디엔 열가소성 블록 공중합체 탄성체(SBC) 조성물에 있어서, 경도가 60∼70(Shore A type)인 SBC 10∼80 중량부, 경도가 70∼90(Shore A type)인 SBC 10∼80 중량부, 및 경도가 80∼90(Shore D type)인 SBC 10∼70 중량부로 이루어지는 것을 특징으로 하는 폴리스티렌-부타디엔 열가소성 블록 공중합체 탄성체 조성물In the polystyrene-butadiene thermoplastic block copolymer elastomer (SBC) composition, 10 to 80 parts by weight of SBC having a hardness of 60 to 70 (Shore A type) and 10 to 80 parts by weight of SBC having a hardness of 70 to 90 (Shore A type) And a polystyrene-butadiene thermoplastic block copolymer elastomer composition comprising 10 to 70 parts by weight of SBC having a hardness of 80 to 90 (Shore D type). 제1항의 폴리스티렌-부타디엔 열가소성 블록 공중합체 조성물에 있어서, 포화 또는 불포화 탄화수소로 이루어진 중질유 또는 경질유에서 선택되는 가공유를 1∼100 중량부 추가로 더 함유하는 것을 특징으로 하는 폴리스티렌-부타디엔 열가소성 블록 공중합체 조성물.The polystyrene-butadiene thermoplastic block copolymer composition of claim 1, further comprising 1 to 100 parts by weight of a processing oil selected from heavy or light oils consisting of saturated or unsaturated hydrocarbons. . 폴리스티렌-부타디엔 열가소성 블록 공중합체(SBC)조성물에 있어서, 경도가 60∼70(Shore A type)인 SBC 10∼80 중량부, 경도가 70∼90(Shore A type)인 SBC 10∼80 중량부,경도가 80∼90(Shore A type)인 SBC 10∼70 중량부 및 포화 또는 불포화 탄화수소로 이루어진 중질유 또는 경질유에서 선택되는 가공유 1∼100 중량부로 이루어지는 것을 특징으로하는 폴리스티렌-부타디엔 열가소성 블록 공중합체 조성물로 제조되는 필름.In the polystyrene-butadiene thermoplastic block copolymer (SBC) composition, 10 to 80 parts by weight of SBC having a hardness of 60 to 70 (Shore A type), 10 to 80 parts by weight of SBC having a hardness of 70 to 90 (Shore A type), A polystyrene-butadiene thermoplastic block copolymer composition comprising 10 to 70 parts by weight of SBC having a hardness of 80 to 90 (Shore A type) and 1 to 100 parts by weight of a processing oil selected from heavy or light oils composed of saturated or unsaturated hydrocarbons. Film manufactured. 제3항의 폴리스티렌-부타디엔 열가소성 블록 공중합체 조성물로 제조되는 필름에 있어서, 상기 필름이 수용성 폴리우레탄 코팅층을 추가로 더 포함하는 것을 특징으로 하는 폴리스티렌-부타디엔 열가소성 블록 공중합체 조성물 필름.The film made of the polystyrene-butadiene thermoplastic block copolymer composition of claim 3, wherein the film further comprises a water-soluble polyurethane coating layer.
KR1019990068466A 1999-12-31 1999-12-31 Styrene butadiene block copolymer composition and film KR20000058250A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20020030859A (en) * 2000-10-18 2002-04-26 박연차 Composite for footwear out-sole
KR20180062541A (en) * 2016-11-30 2018-06-11 (주)퓨쳐테크 A Elastic Sheet for Outsole and A Manufacturing Method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06107744A (en) * 1992-09-30 1994-04-19 Nippon Zeon Co Ltd Impact resistant polystyrene-based resin and its production
KR100300360B1 (en) * 1999-03-09 2001-09-13 김명곤 THERMOPLASTIC Rubber ELASTOMER

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06107744A (en) * 1992-09-30 1994-04-19 Nippon Zeon Co Ltd Impact resistant polystyrene-based resin and its production
KR100300360B1 (en) * 1999-03-09 2001-09-13 김명곤 THERMOPLASTIC Rubber ELASTOMER

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20020030859A (en) * 2000-10-18 2002-04-26 박연차 Composite for footwear out-sole
KR20180062541A (en) * 2016-11-30 2018-06-11 (주)퓨쳐테크 A Elastic Sheet for Outsole and A Manufacturing Method thereof

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