WO2021107664A1 - Thermoplastic elastomer composition, and method for producing injection molded product using same - Google Patents

Thermoplastic elastomer composition, and method for producing injection molded product using same Download PDF

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Publication number
WO2021107664A1
WO2021107664A1 PCT/KR2020/017036 KR2020017036W WO2021107664A1 WO 2021107664 A1 WO2021107664 A1 WO 2021107664A1 KR 2020017036 W KR2020017036 W KR 2020017036W WO 2021107664 A1 WO2021107664 A1 WO 2021107664A1
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weight
parts
block copolymer
copolymer resin
thermoplastic elastomer
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PCT/KR2020/017036
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French (fr)
Korean (ko)
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신나현
박승빈
서석범
이규호
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롯데케미칼 주식회사
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Publication of WO2021107664A1 publication Critical patent/WO2021107664A1/en

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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
    • 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
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • 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
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • 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
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17—Component parts, details or accessories; Auxiliary operations
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • 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
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof

Definitions

  • the present invention relates to a thermoplastic elastomer composition and a method for manufacturing a double injection molded article using the same.
  • thermoplastic elastomer Since a thermoplastic elastomer (TPE) is physically crosslinked unlike solid rubber that is chemically crosslinked, it exhibits elasticity like solid rubber at room temperature and has properties that can be subjected to extrusion and injection molding processes. In a thermoplastic elastomer, long molecules are irregularly twisted like a coil. When a tensile force is applied to a thermoplastic elastomer, the molecules are stretched in the direction of the force. When the applied tensile force is removed, the molecules quickly return to their original disordered arrangement. will do Due to the advantages of such thermoplastic elastomers, such as easy processability and elastic restoring force, various products have been developed as the demand as a substitute material for rubber that cannot be reused is rapidly increasing. For example, the thermoplastic elastomer may be applied to various fields such as automobile parts, construction gaskets, handles, hoses, cushioning materials, and wire insulators.
  • thermoplastic elastomer is used for the handle of various products, and in many cases, it is attached or assembled to a product made of polyamide, also called nylon, to configure the product. Since the thermoplastic elastomer used for the handle is frequently exposed to sweat, oil, etc., oil resistance is required, and furthermore, high adhesion with the polyamide material is required.
  • known thermoplastic elastomers have a problem in that adhesive strength with the polyamide material is very insufficient, so that a separate adhesive must be used or formed into a complex structure and assembled.
  • thermoplastic elastomer having excellent adhesion to the polyamide material member is required. to be.
  • An object of the present invention is to provide a thermoplastic elastomer composition capable of forming a thermoplastic elastomer having excellent oil resistance, double injection property with a polyamide material, and excellent adhesion to a polyamide-based resin-containing polymer member. Further, by using the thermoplastic elastomer composition, it is an object to provide a double injection molded article without a separate adhesive.
  • An exemplary embodiment of the present invention is a first SEBS (styrene-ethylene-butylene-styrene) block copolymer resin; Second SEBS (styrene-ethylene-butylene-styrene) block copolymer resin; SBS (styrene-butylene-styrene) block copolymer resin; maleic anhydride grafted polypropylene resin; and a polyolefin resin; wherein the first SEBS block copolymer resin has a weight average molecular weight of about 250,000 g/mol or more and about 450,000 g/mol or less, and the second SEBS block copolymer resin has a weight average molecular weight of about 100,000 g/mol or more and about 200,000 g/mol or less, the maleic anhydride grafting ratio of the maleic anhydride-grafted polypropylene resin is greater than about 1 part by weight and not more than about 5 parts by weight, and the polyolefin resin is the
  • the polyolefin resin may include at least one of a homo polypropylene resin, a block polypropylene resin, and a random polypropylene resin.
  • thermoplastic elastomer composition may further include a non-aromatic oil.
  • the weight ratio of the first SEBS block copolymer resin and the second SEBS block copolymer resin may be about 5:5 to about 2:8.
  • the content of the SBS block copolymer resin is about 5
  • the content of the maleic anhydride-grafted polypropylene resin may be about 20 parts by weight or more and about 40 parts by weight or less.
  • the content of the non-aromatic oil is about 80 parts by weight or more and about 180 parts by weight or less.
  • Another embodiment of the present invention a polyamide-based resin-containing polymer member; and an elastomer layer prepared using the thermoplastic elastomer composition on the polymer member.
  • thermoplastic elastomer composition according to an exemplary embodiment of the present invention has excellent oil resistance and is capable of double injection molding with a polyamide-based resin-containing polymer member, so that a composite structure of the polymer member and the thermoplastic elastomer can be manufactured without a complicated assembly process.
  • the double injection molded article according to an exemplary embodiment of the present invention is attached to the polyamide-based resin-containing polymer member without a separate adhesive, and has very good adhesion to the polymer member.
  • ⁇ a and ⁇ b are defined as ⁇ a and ⁇ b.
  • the unit “parts by weight” may mean a ratio of weight between each component.
  • the weight average molecular weight may be a value converted to polystyrene measured by gel permeation chromatography (GPC).
  • thermoplastic elastomer composition according to the present invention can be manufactured into an integrated molded body through double injection during molding of a polyamide-based member by appropriately controlling fluidity.
  • thermoplastic elastomer when using the thermoplastic elastomer according to the present invention, it is possible to manufacture a thermoplastic elastomer integrally provided with a polyamide-based member without a separate adhesive and assembly process, and the thermoplastic elastomer is suitable for a handle of a product due to its excellent oil resistance. There is an advantage.
  • the SEBS block copolymer resin according to an exemplary embodiment of the present invention may have a saturated olefin structure composed of polyethylene and polybutylene through a process of undergoing a complete catalytic hydrogenation reaction on the polybutadiene block of SBS, which is a precursor.
  • the SEBS block copolymer is a copolymer including an aromatic vinyl compound and a conjugated diene-based compound, and may impart ductility to the thermoplastic elastomer composition.
  • the aromatic vinyl compound may be a hard segment, and may contribute to preventing thermoplastic deformation and imparting physical properties such as a crosslinked product under certain conditions.
  • the conjugated diene-based compound may be a soft segment, and may contribute to imparting ductility properties such as rubber.
  • thermoplastic elastomer composition By applying two different SEBS block copolymer resins to the thermoplastic elastomer composition according to an exemplary embodiment of the present invention, adhesion to a polyamide-based member and double injection properties can be improved.
  • the thermoplastic elastomer composition may include two types of SEBS block copolymer resins having different weight average molecular weights.
  • the thermoplastic elastomer composition has a weight average molecular weight of about 250,000 g/mol or more and about 450,000 g/mol or less (eg, 250,000 g/mol, 260,000 g/mol, 270,000 g/mol) mol, 280,000 g/mol, 290,000 g/mol, 300,000 g/mol, 310,000 g/mol, 320,000 g/mol, 330,000 g/mol, 340,000 g/mol, 350,000 g/mol, 360,000 g/mol, 370,000 g/mol mol, 380,000 g/mol, 390,000 g/mol, 400,000 g/mol, 410,000 g/mol, 420,000 g/mol, 430,000 g/mol, 440,000 g/mol or 450,000 g/
  • the weight ratio of the first SEBS block copolymer resin and the second SEBS block copolymer resin is from about 5:5 to about 2:8 (eg, 5:5, 4:6, 3:7 or 2:8).
  • the weight ratio of the first SEBS block copolymer resin and the second SEBS block copolymer resin satisfies the above range, the oil resistance in the final molded product is better, so that mechanical properties are lowered due to contact with oil products or the human body or appearance quality There may be no problem such as lowering, but is not limited thereto.
  • the SBS block copolymer resin according to an exemplary embodiment of the present invention can ensure uniform adhesion to the polyamide-based member. Specifically, when manufacturing a double injection molded product using the thermoplastic elastomer composition, there may be a deviation in adhesive strength that may occur in a region where heat is not sufficiently supplied away from the gate. can play a role in minimizing it.
  • the content of the SBS copolymer resin is about 5 parts by weight or more and about 30 parts by weight based on 100 parts by weight of the total weight of the first SEBS block copolymer resin and the second SEBS block copolymer resin.
  • the adhesive surface of the final molded article is uniform and thus the adhesive force may be better, and there is no problem such as increase in viscosity and decrease in MI (melt index) of the thermoplastic elastomer composition, so moldability It may be superior to this, but is not limited thereto.
  • the maleic anhydride-grafted polypropylene resin (MAH-g-PP) according to an exemplary embodiment of the present invention may increase adhesion to a polar substrate, specifically, a polyamide-based member.
  • the maleic anhydride-grafted polypropylene resin may serve to improve adhesion to a polar substrate by imparting polarity to the non-polar thermoplastic elastomer composition.
  • the maleic anhydride grafting ratio of the maleic anhydride-grafted polypropylene resin is greater than about 1 part by weight and not more than about 5 parts by weight (eg, 1.1 parts by weight, 2 parts by weight, 3 parts by weight). parts by weight, 4 parts by weight, or 5 parts by weight), specifically, about 2 parts by weight or more and about 4 parts by weight or less.
  • the maleic anhydride-grafted polypropylene resin used in a conventional thermoplastic resin composition is mainly prepared by reaction extrusion, and has a low maleic anhydride graft ratio of 0.5 to 1.0 parts by weight.
  • the maleic anhydride-grafted polypropylene resin according to an exemplary embodiment of the present invention may be prepared using a solution method, wherein the maleic anhydride grafting ratio is higher than about 1 part by weight and not more than about 5 parts by weight. .
  • the maleic anhydride-grafted polypropylene resin having a graft ratio of greater than about 1 part by weight and less than or equal to about 5 parts by weight has a high graft ratio, thereby greatly improving adhesion to a polar substrate.
  • the content of the maleic anhydride-grafted polypropylene resin is about 20 parts by weight based on 100 parts by weight of the total weight of the first SEBS block copolymer resin and the second SEBS block copolymer resin.
  • the adhesive force of the final molded article is sufficient, and there may be no problems such as a decrease in grip and a cost increase due to an increase in hardness of the final molded article.
  • the polyolefin resin according to an exemplary embodiment of the present invention improves the processability of the thermoplastic elastomer composition, and may provide suitable mechanical strength to the thermoplastic elastomer produced using the thermoplastic elastomer composition.
  • the polyolefin resin may include at least one of a homo polypropylene resin, a block polypropylene resin, and a random polypropylene resin, but is not limited thereto.
  • the polyolefin resin has a weight average molecular weight of about 100,000 g/mol or more and about 300,000 g/mol or less (eg, 100,000 g/mol, 110,000 g/mol, 120,000 g/mol, 130,000 g/mol).
  • the weight average molecular weight of the polyolefin resin satisfies the above range, there is no problem in that the viscosity of the thermoplastic elastomer composition increases or the miscibility is lowered due to a difference in viscosity between components in the thermoplastic elastomer composition, so that moldability and surface wettability It may be more advantageous in providing a final product having excellent adhesion due to excellent adhesion.
  • the polyolefin resin may be a homo polypropylene resin having a weight average molecular weight of about 100,000 g/mol or more and about 300,000 g/mol or less, but is not limited thereto.
  • the content of the polyolefin resin is about 5 parts by weight or more and about 20 parts by weight or less (for example, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight. parts, 17 parts by weight, 18 parts by weight, 19 parts by weight, or 20 parts by weight), specifically about 10 parts by weight or more and about 20 parts by weight or less.
  • the processability of the thermoplastic elastomer composition may be further improved, and a more suitable mechanical strength may be provided to a thermoplastic elastomer manufactured using the thermoplastic elastomer composition, but is not limited thereto.
  • thermoplastic elastomer composition may further include a non-aromatic oil.
  • the non-aromatic oil according to an exemplary embodiment of the present invention may improve hardness and moldability, which are directly related to the feel of a thermoplastic elastomer, and improve oil resistance.
  • the non-aromatic oil may include paraffin oil.
  • the paraffin oil may have a kinematic viscosity of about 90 cSt or more, specifically about 90 cSt or more and about 180 cSt or less, more specifically about 100 or more and about 150 cSt or less, measured at 40 ° C. in accordance with ASTM D445, in the above range It may be more advantageous to improve hardness, moldability, and oil resistance, but is not limited thereto.
  • the content of the non-aromatic oil is about 80 parts by weight or more and about 180 parts by weight or less.
  • 80 parts by weight, 90 parts by weight, 100 parts by weight, 110 parts by weight, 120 parts by weight, 130 parts by weight, 140 parts by weight, 150 parts by weight, 160 parts by weight, 170 parts by weight or 180 parts by weight Specifically, it may be about 100 parts by weight or more and about 150 parts by weight or less, more specifically about 120 parts by weight or more and about 140 parts by weight or less.
  • the flowability is excellent to improve productivity and processability, and the surface wettability is excellent to have excellent adhesion to dissimilar materials, and the quality of the molded product may also be excellent. It is not limited.
  • the content of the SBS block copolymer resin is about 5 parts by weight or more and about 30 parts by weight. parts, and the content of the maleic anhydride-grafted polypropylene resin may be about 20 parts by weight or more and about 40 parts by weight or less.
  • the content of the SBS block copolymer resin is about 5 parts by weight or more and about 30 parts by weight. parts, and the content of the maleic anhydride-grafted polypropylene resin is about 20 parts by weight or more and about 40 parts by weight or less, the content of the polyolefin resin is about 5 parts by weight or more and about 20 parts by weight or less, and the non-aromatic The content of the oil may be about 80 parts by weight or more and about 180 parts by weight or less.
  • the thermoplastic elastomer composition may further include additives commonly used in the art.
  • the thermoplastic elastomer composition may further include an additive selected from the group consisting of inorganic fillers, heat stabilizers, antioxidants and slip agents.
  • the thermoplastic elastomer composition may further include an inorganic filler as an additive to improve physical properties and molding processability of the thermoplastic elastomer composition.
  • the inorganic filler may include at least one selected from the group consisting of talc, calcium carbonate, clay, nanoclay, and kaolin, but is not limited thereto.
  • the content of the inorganic filler is about 50 parts by weight or more and about 150 parts by weight or less, specifically about 75 parts by weight or more and about 125 parts by weight based on 100 parts by weight of the total weight of the first SEBS block copolymer resin and the second SEBS block copolymer resin. may be less than or equal to parts by weight.
  • the improvement effect such as physical properties and molding processability of the thermoplastic elastomer composition may be excellent, but the present invention is not limited thereto.
  • thermoplastic elastomer composition according to the present invention enables double injection with a polyamide-based member through the blending of the composition as described above, and furthermore, the thermoplastic elastomer manufactured using double injection can be combined with a polyamide-based member without a separate adhesive. It can be attached with high adhesion and have excellent oil resistance.
  • Another embodiment of the present invention a polyamide-based resin-containing polymer member; and an elastomer layer prepared using the thermoplastic elastomer composition on the polymer member.
  • thermoplastic elastomer composition according to the present invention has excellent double injection property and adhesion with the polyamide-based member, a thermoplastic elastomer can be manufactured without a separate adhesive on the polyamide-based member through the double injection method.
  • the double injection method in the present specification may be applied without limitation to the double injection method generally known in the art.
  • the polyamide-based resin-containing polymer member is a polyolefin-based resin (eg, a polyethylene-based resin, a polypropylene-based resin, etc.), a polycarbonate-based resin, in addition to the polyamide-based resin, It may further include a coalescence, a combination thereof.
  • a polyolefin-based resin eg, a polyethylene-based resin, a polypropylene-based resin, etc.
  • a polycarbonate-based resin in addition to the polyamide-based resin
  • the type of resin that can be added is not limited thereto, and various resins generally used in the art may be further included.
  • the polyamide-based resin-containing polymer member may further include glass fibers.
  • the polyamide-based resin-containing polymer member further includes glass fibers, rigidity may be further improved.
  • the content of the glass fiber may be appropriately adjusted according to the physical properties required for the final product.
  • the double injection molded article may be one in which a thermoplastic elastomer is bonded to a polyamide-based resin-containing polymer member.
  • the thermoplastic elastomer of the double injection-molded article may be applied to a portion with a lot of human contact, such as a handle, and the thermoplastic elastomer has excellent oil resistance, so that deterioration of physical properties can be minimized even with frequent use.
  • the double injection molded article as described above may be an automobile interior material or a tool such as an electric drill or driver, and the handle portion thereof may be composed of a thermoplastic elastomer.
  • the prepared pellets were dried at about 80 ° C. for about 2 hours and then injected at an injection temperature of about 260 ° C. in a 150 ton injection machine to prepare a specimen for evaluation of physical properties, and the physical properties thereof were measured and shown in Table 1 below.
  • First SEBS block copolymer resin (first SEBS): Kraton G1651 (weight average molecular weight: 350,000 g/mol)
  • Second SEBS block copolymer resin (second SEBS): Kraton G1650 (weight average molecular weight: 130,000 g/mol)
  • SBS block copolymer resin (SBS): LCY GP7533 (weight average molecular weight: 130,000 g/mol)
  • Homo polypropylene resin Lotte Chemical SJ-170 (weight average molecular weight: 190,000 g/mol)
  • Paraffin oil Shell Catenex T145
  • Inorganic filler Calcium carbonate, KOCH CMS-8000
  • MFI Melt flow index
  • Adhesion For the evaluation of adhesion between different materials, a specimen of Lanxess' AKV30 with a size of 10 ⁇ 15 ⁇ 2 mm was prepared and double inserts were placed on a polyamide-based member (70 wt% nylon 6 and 30 wt% glass fiber). injection, and 100 mm/min in the 90° direction. Adhesion was measured according to VDI2019 with speed.
  • Example 1 and Comparative Example 1 when the maleic anhydride graft ratio of the maleic anhydride-grafted polypropylene resin is 1 part by weight, it can be confirmed that the adhesive strength is too low, and when the maleic anhydride grafting ratio is 3 parts by weight, excellent It can be seen that adhesion can be implemented. Accordingly, it can be seen that when prescribing for actual use, it is advantageous in terms of adhesion improvement to prescribe maleic anhydride-grafted polypropylene having a maleic anhydride graft ratio of more than 1 part by weight.
  • Comparative Example 2 which does not contain the second SEBS block copolymer resin, it can be confirmed that it exhibits poor moldability according to a very low melt flow index compared to Example 1, and has significantly lower adhesion compared to Example 1 can be seen to indicate.
  • Comparative Example 2 containing only the first SEBS block copolymer resin without the second SEBS block copolymer resin has very poor oil resistance.
  • Comparative Example 5 containing only the second SEBS block copolymer resin without the first SEBS block copolymer resin has improved oil resistance, but it can be confirmed that physical properties such as elongation, tensile strength and adhesion are very poor. Therefore, it can be confirmed that when the first SEBS block copolymer resin and the second SEBS block copolymer resin are properly mixed as in the example, the adhesive strength and mechanical properties of the thermoplastic elastomer can be simultaneously satisfied.
  • Comparative Example 3 which did not contain the SBS block copolymer resin, there was a problem in that there was a slight deviation in the adhesion form at the injection location far from the gate except for the central portion that was continuously heated close to the gate.
  • the hardness was slightly increased, and it was confirmed that the quality characteristics such as cushioning feeling were slightly decreased. Therefore, it can be confirmed that it is necessary to prescribe the SBS block copolymer resin as in Example 1 in order to express the overall uniform adhesion to the thermoplastic elastomer and to improve the quality such as grip.

Abstract

The present invention relates to a thermoplastic elastomer composition, and a method for producing an injection molded product using said thermoplastic elastomer composition. The thermoplastic elastomer comprises: a predetermined first styrene-ethylene-butylene-styrene (SEBS) block copolymer resin; a second styrene-ethylene-butylene-styrene (SEBS) block copolymer resin; a styrene-butylene-styrene (SBS) block copolymer resin; a maleic anhydride grafted polypropylene resin; and a polyolefin resin.

Description

열가소성 탄성체 조성물 및 이를 이용한 이중 사출 성형품의 제조방법Thermoplastic elastomer composition and method for manufacturing double injection molded article using same
본 발명은 열가소성 탄성체 조성물 및 이를 이용한 이중 사출 성형품의 제조방법에 관한 것이다.The present invention relates to a thermoplastic elastomer composition and a method for manufacturing a double injection molded article using the same.
열가소성 탄성체(Thermoplastic elastomer, TPE)는 화학적 가교결합을 하는 고형 고무와는 달리 물리적 가교결합을 하고 있기 때문에, 상온에서는 고형 고무와 같은 탄성을 나타내며, 압출 및 사출 성형 가공을 할 수 있는 성질을 가진다. 열가소성 탄성체는 평상시에는 긴 분자가 불규칙하게 코일처럼 뒤틀린 상태에 있으며, 열가소성 탄성체에 인장력을 가하면 분자들은 힘의 방향으로 늘어나게 되고, 가하여진 인장력이 제거되면 분자들은 다시 신속하게 원래의 모습인 무질서한 배열을 하게 된다. 이와 같은 열가소성 탄성체의 용이한 가공성과 탄성 복원력 등의 장점으로 인하여, 재사용이 안되는 고무의 대체 소재로써 빠르게 수요가 증가하면서 다양한 제품이 개발되어 왔다. 예를 들어, 열가소성 탄성체는 자동차용 부품, 건축용 가스켓, 손잡이, 호스, 완충재, 전선 절연체 등의 다양한 분야에 적용될 수 있다. Since a thermoplastic elastomer (TPE) is physically crosslinked unlike solid rubber that is chemically crosslinked, it exhibits elasticity like solid rubber at room temperature and has properties that can be subjected to extrusion and injection molding processes. In a thermoplastic elastomer, long molecules are irregularly twisted like a coil. When a tensile force is applied to a thermoplastic elastomer, the molecules are stretched in the direction of the force. When the applied tensile force is removed, the molecules quickly return to their original disordered arrangement. will do Due to the advantages of such thermoplastic elastomers, such as easy processability and elastic restoring force, various products have been developed as the demand as a substitute material for rubber that cannot be reused is rapidly increasing. For example, the thermoplastic elastomer may be applied to various fields such as automobile parts, construction gaskets, handles, hoses, cushioning materials, and wire insulators.
일 예로, 열가소성 탄성체는 다양한 제품의 손잡이 용도로 사용되며, 많은 경우 나일론으로도 불리는 폴리아미드 소재의 제품에 부착 또는 조립되어 제품을 구성한다. 손잡이 용도로 사용되는 열가소성 탄성체는 땀, 기름 등에 노출이 잦게 되므로 오일 저항성이 요구되며, 나아가 폴리아미드 소재와의 높은 접착력이 요구된다. 다만, 알려져 있는 열가소성 탄성체는 폴리아미드 소재와의 접착력이 매우 부족하여 별도의 접착제를 사용하거나, 복잡한 구조로 성형하여 조립하여야 하는 문제점이 있다. 그러므로, 이중 사출 성형을 통하여 별도의 접착제 또는 복잡한 조립 공정 없이 폴리아미드 소재의 부재와 열가소성 탄성체의 복합체를 형성할 수 있고, 나아가 폴리아미드 소재의 부재와의 접착력이 우수한 열가소성 탄성체에 대한 연구가 필요한 실정이다.For example, the thermoplastic elastomer is used for the handle of various products, and in many cases, it is attached or assembled to a product made of polyamide, also called nylon, to configure the product. Since the thermoplastic elastomer used for the handle is frequently exposed to sweat, oil, etc., oil resistance is required, and furthermore, high adhesion with the polyamide material is required. However, known thermoplastic elastomers have a problem in that adhesive strength with the polyamide material is very insufficient, so that a separate adhesive must be used or formed into a complex structure and assembled. Therefore, through double injection molding, a composite of a polyamide material member and a thermoplastic elastomer can be formed without a separate adhesive or a complicated assembly process, and further research on a thermoplastic elastomer having excellent adhesion to the polyamide material member is required. to be.
본 발명의 배경기술은 대한민국 공개특허 제10-2016-0114994호 등에 개시되어 있다.Background art of the present invention is disclosed in Republic of Korea Patent Publication No. 10-2016-0114994 and the like.
본 발명은 내유성이 우수하고, 폴리아미드 소재와의 이중 사출성을 가지며, 나아가 폴리아미드계 수지 함유 고분자 부재와의 접착력이 우수한 열가소성 탄성체를 형성할 수 있는 열가소성 탄성체 조성물을 제공하고자 한다. 나아가, 상기 열가소성 탄성체 조성물을 이용하여, 별도의 접착제가 구비되지 않은 이중 사출 성형품을 제공하고자 한다. An object of the present invention is to provide a thermoplastic elastomer composition capable of forming a thermoplastic elastomer having excellent oil resistance, double injection property with a polyamide material, and excellent adhesion to a polyamide-based resin-containing polymer member. Further, by using the thermoplastic elastomer composition, it is an object to provide a double injection molded article without a separate adhesive.
1. 본 발명의 일 실시상태는, 제1 SEBS(styrene-ethylene-butylene-styrene) 블록 공중합체 수지; 제2 SEBS(styrene-ethylene-butylene-styrene) 블록 공중합체 수지; SBS(styrene-butylene-styrene) 블록 공중합체 수지; 무수말레산 그라프트된 폴리프로필렌 수지; 및 폴리올레핀 수지;를 포함하고, 상기 제1 SEBS 블록 공중합체 수지는 중량평균분자량이 약 250,000 g/mol 이상 약 450,000 g/mol 이하이고, 상기 제2 SEBS 블록 공중합체 수지는 중량평균분자량이 약 100,000 g/mol 이상 약 200,000 g/mol 이하이고, 상기 무수말레산 그라프트된 폴리프로필렌 수지의 무수말레산 그라프트율은 약 1 중량부 초과 약 5 중량부 이하이고, 상기 폴리올레핀 수지는 상기 제1 SEBS 블록 공중합체 수지 및 제2 SEBS 블록 공중합체 수지의 총중량 100 중량부에 대하여 약 5 중량부 이상 약 20 중량부 이하로 포함되는 것을 특징으로 하는, 열가소성 탄성체 조성물을 제공한다. 1. An exemplary embodiment of the present invention is a first SEBS (styrene-ethylene-butylene-styrene) block copolymer resin; Second SEBS (styrene-ethylene-butylene-styrene) block copolymer resin; SBS (styrene-butylene-styrene) block copolymer resin; maleic anhydride grafted polypropylene resin; and a polyolefin resin; wherein the first SEBS block copolymer resin has a weight average molecular weight of about 250,000 g/mol or more and about 450,000 g/mol or less, and the second SEBS block copolymer resin has a weight average molecular weight of about 100,000 g/mol or more and about 200,000 g/mol or less, the maleic anhydride grafting ratio of the maleic anhydride-grafted polypropylene resin is greater than about 1 part by weight and not more than about 5 parts by weight, and the polyolefin resin is the first SEBS block air It provides a thermoplastic elastomer composition, characterized in that it is included in an amount of about 5 parts by weight or more and about 20 parts by weight or less based on 100 parts by weight of the total weight of the copolymer resin and the second SEBS block copolymer resin.
2. 상기 제1 실시상태에서, 상기 폴리올레핀 수지는 호모 폴리프로필렌 수지, 블록 폴리프로필렌 수지 및 랜덤 폴리프로필렌 수지 중 적어도 1종을 포함할 수 있다.2. In the first embodiment, the polyolefin resin may include at least one of a homo polypropylene resin, a block polypropylene resin, and a random polypropylene resin.
3. 상기 제1 또는 제2 실시상태에서, 상기 열가소성 탄성체 조성물은 비방향족 오일을 더 포함할 수 있다.3. In the first or second embodiment, the thermoplastic elastomer composition may further include a non-aromatic oil.
4. 상기 제1 내지 제3 실시상태 중 어느 하나에서, 상기 제1 SEBS 블록 공중합체 수지와 제2 SEBS 블록 공중합체 수지의 중량비는 약 5:5 내지 약 2:8일 수 있다.4. In any one of the first to third embodiments, the weight ratio of the first SEBS block copolymer resin and the second SEBS block copolymer resin may be about 5:5 to about 2:8.
5. 상기 제1 내지 제4 실시상태 중 어느 하나에서, 상기 제1 SEBS 블록 공중합체 수지 및 제2 SEBS 블록 공중합체 수지의 총중량 100 중량부에 대하여, 상기 SBS 블록 공중합체 수지의 함량은 약 5 중량부 이상 약 30 중량부 이하이고, 상기 무수말레산 그라프트된 폴리프로필렌 수지의 함량은 약 20 중량부 이상 약 40 중량부 이하일 수 있다.5. In any one of the first to fourth embodiments, with respect to 100 parts by weight of the total weight of the first SEBS block copolymer resin and the second SEBS block copolymer resin, the content of the SBS block copolymer resin is about 5 The content of the maleic anhydride-grafted polypropylene resin may be about 20 parts by weight or more and about 40 parts by weight or less.
6. 상기 제3 실시상태에서, 상기 제1 SEBS 블록 공중합체 수지 및 제2 SEBS 블록 공중합체 수지의 총중량 100 중량부에 대하여, 상기 비방향족 오일의 함량은 약 80 중량부 이상 약 180 중량부 이하일 수 있다.6. In the third embodiment, with respect to 100 parts by weight of the total weight of the first SEBS block copolymer resin and the second SEBS block copolymer resin, the content of the non-aromatic oil is about 80 parts by weight or more and about 180 parts by weight or less. can
7. 본 발명의 다른 실시상태는, 폴리아미드계 수지 함유 고분자 부재; 및 상기 고분자 부재 상에 상기 열가소성 탄성체 조성물을 이용하여 제조된 탄성체층을 포함하는, 이중 사출 성형품을 제공한다. 7. Another embodiment of the present invention, a polyamide-based resin-containing polymer member; and an elastomer layer prepared using the thermoplastic elastomer composition on the polymer member.
본 발명의 일 실시상태에 따른 열가소성 탄성체 조성물은 내유성이 우수하고, 폴리아미드계 수지 함유 고분자 부재와 이중 사출 성형이 가능하여, 복잡한 조립 공정 없이 상기 고분자 부재와 열가소성 탄성체의 복합 구조물을 제조할 수 있다. 또한, 본 발명의 일 실시상태에 따른 이중 사출 성형품은 별도의 접착제 없이도 폴리아미드계 수지 함유 고분자 부재와 부착되고, 상기 고분자 부재와 매우 우수한 부착력을 가진다. The thermoplastic elastomer composition according to an exemplary embodiment of the present invention has excellent oil resistance and is capable of double injection molding with a polyamide-based resin-containing polymer member, so that a composite structure of the polymer member and the thermoplastic elastomer can be manufactured without a complicated assembly process. . In addition, the double injection molded article according to an exemplary embodiment of the present invention is attached to the polyamide-based resin-containing polymer member without a separate adhesive, and has very good adhesion to the polymer member.
본 명세서 중 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다.In this specification, the singular expression includes the plural expression unless the context clearly dictates otherwise.
본 명세서 중 포함하다 또는 가지다 등의 용어는 명세서 상에 기재된 특징 또는 구성요소가 존재함을 의미하는 것이고, 하나 이상의 다른 특징들 또는 구성요소가 부가될 가능성을 미리 배제하는 것은 아니다.In this specification, terms such as include or have means that the features or components described in the specification are present, and the possibility that one or more other features or components may be added is not excluded in advance.
구성 요소를 해석함에 있어서, 별도의 명시적 기재가 없더라도 오차 범위를 포함하는 것으로 해석한다.In interpreting the components, it is interpreted as including an error range even if there is no separate explicit description.
본 명세서에서 수치범위를 나타내는 "a 내지 b" 및 "a 이상 b 이하"는 ≥ a이고 ≤ b으로 정의한다. In the present specification, "a to b" and "a or more and less than b" indicating a numerical range are defined as ≥ a and ≤ b.
본 명세서에서 단위 "중량부"는 각 성분간의 중량의 비율을 의미할 수 있다.In the present specification, the unit “parts by weight” may mean a ratio of weight between each component.
본 명세서에 있어서, 중량평균분자량(g/mol)은 GPC(gel permeation chromatography)에 의해 측정되는 폴리스티렌에 대한 환산 수치일 수 있다. In the present specification, the weight average molecular weight (g/mol) may be a value converted to polystyrene measured by gel permeation chromatography (GPC).
본 발명자들은 내유성이 우수하고, 폴리아미드계 수지 함유 고분자 부재(이하, '폴리아미드계 부재'로도 지칭됨)와의 부착성이 높으며, 나아가 이중 사출 성형을 통하여 폴리아미드계 부재와 일체형으로 부착되어 제조될 수 있는 열가소성 탄성체에 대한 연구를 지속한 결과, 하기와 같은 발명을 완성하기에 이르렀다. 본 발명에 따른 열가소성 탄성체 조성물은 유동성이 적절히 조절되어, 폴리아미드계 부재의 성형시 이중 사출을 통하여 일체형의 성형체로 제조될 수 있다. 이에 따라, 본 발명에 따른 열가소성 탄성체를 이용하는 경우, 별도의 접착제 및 조립 공정 없이도 폴리아미드계 부재에 일체형으로 구비된 열가소성 탄성체를 제조할 수 있고, 상기 열가소성 탄성체는 우수한 내유성으로 인하여 제품의 손잡이에 적합한 이점이 있다.The present inventors have excellent oil resistance, high adhesion to a polyamide-based resin-containing polymer member (hereinafter also referred to as a 'polyamide-based member'), and furthermore, manufactured by being integrally attached to a polyamide-based member through double injection molding As a result of continuing research on possible thermoplastic elastomers, the following invention was completed. The thermoplastic elastomer composition according to the present invention can be manufactured into an integrated molded body through double injection during molding of a polyamide-based member by appropriately controlling fluidity. Accordingly, when using the thermoplastic elastomer according to the present invention, it is possible to manufacture a thermoplastic elastomer integrally provided with a polyamide-based member without a separate adhesive and assembly process, and the thermoplastic elastomer is suitable for a handle of a product due to its excellent oil resistance. There is an advantage.
본 발명의 일 실시상태는, 제1 SEBS(styrene-ethylene-butylene-styrene) 블록 공중합체 수지; 제2 SEBS(styrene-ethylene-butylene-styrene) 블록 공중합체 수지; SBS(styrene-butylene-styrene) 블록 공중합체 수지; 무수말레산 그라프트된 폴리프로필렌 수지; 및 폴리올레핀 수지; 를 포함하는, 열가소성 탄성체 조성물을 제공한다.An exemplary embodiment of the present invention, a first SEBS (styrene-ethylene-butylene-styrene) block copolymer resin; Second SEBS (styrene-ethylene-butylene-styrene) block copolymer resin; SBS (styrene-butylene-styrene) block copolymer resin; maleic anhydride grafted polypropylene resin; and polyolefin resins; It provides a thermoplastic elastomer composition comprising a.
이하, 본 발명에 대하여 보다 상세히 설명한다. Hereinafter, the present invention will be described in more detail.
SEBS 블록 공중합체 수지SEBS block copolymer resin
본 발명의 일 실시상태에 따른 SEBS 블록 공중합체 수지는 전구체인 SBS의 폴리부타디엔 블록에 완전한 촉매수소화반응을 거치는 과정을 통하여, 폴리에틸렌과 폴리부틸렌으로 이루어진 포화 올레핀 구조를 갖는 것일 수 있다. The SEBS block copolymer resin according to an exemplary embodiment of the present invention may have a saturated olefin structure composed of polyethylene and polybutylene through a process of undergoing a complete catalytic hydrogenation reaction on the polybutadiene block of SBS, which is a precursor.
본 발명의 일 실시상태에 따르면, 상기 SEBS 블록 공중합체는 방향족 비닐 화합물 및 공액 디엔계 화합물을 포함하는 공중합체로서, 상기 열가소성 탄성체 조성물 에 연성을 부여할 수 있다. 구체적으로, 상기 방향족 비닐 화합물은 하드 세그먼트일 수 있으며, 열가소성의 변형을 방지하며 일정 조건 하에 가교체와 같은 물성을 부여하는데 기여할 수 있다. 또한, 상기의 공액 디엔계 화합물은 소프트 세그먼트일 수 있으며, 고무와 같은 연성의 특성을 부여하는데 기여할 수 있다.According to an exemplary embodiment of the present invention, the SEBS block copolymer is a copolymer including an aromatic vinyl compound and a conjugated diene-based compound, and may impart ductility to the thermoplastic elastomer composition. Specifically, the aromatic vinyl compound may be a hard segment, and may contribute to preventing thermoplastic deformation and imparting physical properties such as a crosslinked product under certain conditions. In addition, the conjugated diene-based compound may be a soft segment, and may contribute to imparting ductility properties such as rubber.
본 발명의 일 실시상태에 따른 열가소성 탄성체 조성물은 2종의 서로 다른 SEBS 블록 공중합체 수지를 적용함으로써, 폴리아미드계 부재와의 부착성 및 이중 사출성을 향상시킬 수 있다. By applying two different SEBS block copolymer resins to the thermoplastic elastomer composition according to an exemplary embodiment of the present invention, adhesion to a polyamide-based member and double injection properties can be improved.
본 발명의 일 실시상태에 따르면, 열가소성 탄성체 조성물은 중량평균분자량이 서로 다른 2종의 SEBS 블록 공중합체 수지를 포함할 수 있다. 구체적으로, 본 발명의 일 실시상태에 따르면, 열가소성 탄성체 조성물은 중량평균분자량이 약 250,000 g/mol 이상 약 450,000 g/mol 이하(예를 들면, 250,000 g/mol, 260,000 g/mol, 270,000 g/mol, 280,000 g/mol, 290,000 g/mol, 300,000 g/mol, 310,000 g/mol, 320,000 g/mol, 330,000 g/mol, 340,000 g/mol, 350,000 g/mol, 360,000 g/mol, 370,000 g/mol, 380,000 g/mol, 390,000 g/mol, 400,000 g/mol, 410,000 g/mol, 420,000 g/mol, 430,000 g/mol, 440,000 g/mol 또는 450,000 g/mol), 더욱 구체적으로는 약 300,000 g/mol 이상 약 400,000 g/mol 이하인 SEBS 블록 공중합체 수지(이하, '제1 SEBS 블록 공중합체 수지'로 지칭됨); 및 중량평균분자량이 약 100,000 g/mol 이상 약 200,000 g/mol 이하(예를 들면, 100,000 g/mol, 110,000 g/mol, 120,000 g/mol, 130,000 g/mol, 140,000 g/mol, 150,000 g/mol, 160,000 g/mol, 170,000 g/mol, 180,000 g/mol, 190,000 g/mol 또는 200,000 g/mol), 구체적으로는 약 100,000 g/mol 이상 약 150,000 g/mol 이하인 SEBS 블록 공중합체 수지(이하, '제2 SEBS 블록 공중합체 수지'로 지칭됨)를 포함할 수 있다. 이러한 경우, 폴리아미드계 부재와의 부착성 및 이중 사출성 향상에 보다 유리할 수 있다.According to an exemplary embodiment of the present invention, the thermoplastic elastomer composition may include two types of SEBS block copolymer resins having different weight average molecular weights. Specifically, according to an exemplary embodiment of the present invention, the thermoplastic elastomer composition has a weight average molecular weight of about 250,000 g/mol or more and about 450,000 g/mol or less (eg, 250,000 g/mol, 260,000 g/mol, 270,000 g/mol) mol, 280,000 g/mol, 290,000 g/mol, 300,000 g/mol, 310,000 g/mol, 320,000 g/mol, 330,000 g/mol, 340,000 g/mol, 350,000 g/mol, 360,000 g/mol, 370,000 g/mol mol, 380,000 g/mol, 390,000 g/mol, 400,000 g/mol, 410,000 g/mol, 420,000 g/mol, 430,000 g/mol, 440,000 g/mol or 450,000 g/mol), more specifically about 300,000 g /mol or more and about 400,000 g/mol or less of SEBS block copolymer resin (hereinafter referred to as 'first SEBS block copolymer resin'); and a weight average molecular weight of about 100,000 g/mol or more and about 200,000 g/mol or less (eg, 100,000 g/mol, 110,000 g/mol, 120,000 g/mol, 130,000 g/mol, 140,000 g/mol, 150,000 g/mol) mol, 160,000 g / mol, 170,000 g / mol, 180,000 g / mol, 190,000 g / mol or 200,000 g / mol), specifically, about 100,000 g / mol or more and about 150,000 g / mol or less SEBS block copolymer resin (hereinafter , referred to as 'second SEBS block copolymer resin'). In this case, it may be more advantageous to improve the adhesion to the polyamide-based member and the double injection property.
본 발명의 일 실시상태에 따르면, 상기 제1 SEBS 블록 공중합체 수지와 제2 SEBS 블록 공중합체 수지의 중량비는 약 5:5 내지 약 2:8(예를 들면, 5:5, 4:6, 3:7 또는 2:8)일 수 있다. 상기 제1 SEBS 블록 공중합체 수지와 제2 SEBS 블록 공중합체 수지의 중량비가 상기 범위를 만족하는 경우, 최종 성형품에서의 내유성이 보다 우수하여 유류품 또는 인체와의 접촉에 따라 기계적 물성이 저하되거나 외관 품질이 저하되는 등의 문제가 없을 수 있으나, 이에 제한되는 것은 아니다. According to an exemplary embodiment of the present invention, the weight ratio of the first SEBS block copolymer resin and the second SEBS block copolymer resin is from about 5:5 to about 2:8 (eg, 5:5, 4:6, 3:7 or 2:8). When the weight ratio of the first SEBS block copolymer resin and the second SEBS block copolymer resin satisfies the above range, the oil resistance in the final molded product is better, so that mechanical properties are lowered due to contact with oil products or the human body or appearance quality There may be no problem such as lowering, but is not limited thereto.
SBS 블록 공중합체 수지SBS block copolymer resin
본 발명의 일 실시상태에 따른 SBS 블록 공중합체 수지는 폴리아미드계 부재에 대한 균일한 접착력을 확보할 수 있도록 할 수 있다. 구체적으로, 상기 열가소성 탄성체 조성물을 이용한 이중 사출 성형품 제조 시, 게이트와 멀어 열이 충분히 공급되지 않는 영역에서 발생할 수 있는 접착력의 편차가 발생할 수 있는데, 상기 SBS 블록 공중합체 수지는 이와 같은 접착력의 편차를 최소화시킬 수 있는 역할을 할 수 있다. The SBS block copolymer resin according to an exemplary embodiment of the present invention can ensure uniform adhesion to the polyamide-based member. Specifically, when manufacturing a double injection molded product using the thermoplastic elastomer composition, there may be a deviation in adhesive strength that may occur in a region where heat is not sufficiently supplied away from the gate. can play a role in minimizing it.
본 발명의 일 실시상태에 따르면, 상기 SBS 공중합체 수지의 함량은 상기 제1 SEBS 블록 공중합체 수지 및 제2 SEBS 블록 공중합체 수지의 총중량 100 중량부에 대하여, 약 5 중량부 이상 약 30 중량부 이하(예를 들면, 5 중량부, 6 중량부, 7 중량부, 8 중량부, 9 중량부, 10 중량부, 11 중량부, 12 중량부, 13 중량부, 14 중량부, 15 중량부, 16 중량부, 17 중량부, 18 중량부, 19 중량부, 20 중량부, 21 중량부, 22 중량부, 23 중량부, 24 중량부, 25 중량부, 26 중량부, 27 중량부, 28 중량부, 29 중량부 또는 30 중량부), 구체적으로 약 10 중량부 이상 약 20 중량부 이하일 수 있다. 상기 SBS 공중합체 수지의 함량이 상기 범위를 만족하는 경우 최종 성형품의 접착면이 균일하여 접착력이 보다 우수할 수 있고, 열가소성 탄성체 조성물의 점도 상승 및 MI(melt index) 하락 등의 문제가 없어 성형성이 보다 우수할 수 있으나, 이에 제한되는 것은 아니다.According to an exemplary embodiment of the present invention, the content of the SBS copolymer resin is about 5 parts by weight or more and about 30 parts by weight based on 100 parts by weight of the total weight of the first SEBS block copolymer resin and the second SEBS block copolymer resin. or less (for example, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, 26 parts by weight, 27 parts by weight, 28 parts by weight parts, 29 parts by weight, or 30 parts by weight), specifically, about 10 parts by weight or more and about 20 parts by weight or less. When the content of the SBS copolymer resin satisfies the above range, the adhesive surface of the final molded article is uniform and thus the adhesive force may be better, and there is no problem such as increase in viscosity and decrease in MI (melt index) of the thermoplastic elastomer composition, so moldability It may be superior to this, but is not limited thereto.
무수말레산 그라프트된 폴리프로필렌 수지Maleic anhydride grafted polypropylene resin
본 발명의 일 실시상태에 따른 무수말레산 그라프트된 폴리프로필렌 수지(MAH-g-PP)은 극성 기재, 구체적으로 폴리아미드계 부재에 대한 접착력을 증가시킬 수 있다. 구체적으로, 상기 무수말레산 그라프트된 폴리프로필렌 수지는 비극성인 열가소성 탄성체 조성물에 극성을 부여하여, 극성 기재에 대한 부착력을 향상시키는 역할을 할 수 있다. The maleic anhydride-grafted polypropylene resin (MAH-g-PP) according to an exemplary embodiment of the present invention may increase adhesion to a polar substrate, specifically, a polyamide-based member. Specifically, the maleic anhydride-grafted polypropylene resin may serve to improve adhesion to a polar substrate by imparting polarity to the non-polar thermoplastic elastomer composition.
본 발명의 일 실시상태에 따르면, 상기 무수말레산 그라프트된 폴리프로필렌 수지의 무수말레산의 그라프트율은 약 1 중량부 초과 약 5 중량부 이하(예를 들면, 1.1 중량부, 2 중량부, 3 중량부, 4 중량부 또는 5 중량부), 구체적으로 약 2 중량부 이상 약 4 중량부 이하일 수 있다. 통상적인 열가소성 수지 조성물에 사용되는 무수말레산 그라프트된 폴리프로필렌 수지는 주로 반응 압출로 제조된 것으로서, 무수말레산의 그라프트율이 0.5 중량부 내지 1.0 중량부로 낮다. 이에 반하여, 본 발명의 일 실시상태에 따른 상기 무수말레산 그라프트된 폴리프로필렌 수지는 용액법을 이용하여, 무수말레산의 그라프트율이 약 1 중량부 초과 약 5 중량부 이하로 높게 제조될 수 있다. 이와 같이 약 1 중량부 초과 약 5 중량부 이하의 그라프트율을 가지는 무수말레산 그라프트된 폴리프로필렌 수지는 높은 그라프트율을 가져 극성 기재에 대한 접착력을 크게 향상시킬 수 있다. According to an exemplary embodiment of the present invention, the maleic anhydride grafting ratio of the maleic anhydride-grafted polypropylene resin is greater than about 1 part by weight and not more than about 5 parts by weight (eg, 1.1 parts by weight, 2 parts by weight, 3 parts by weight). parts by weight, 4 parts by weight, or 5 parts by weight), specifically, about 2 parts by weight or more and about 4 parts by weight or less. The maleic anhydride-grafted polypropylene resin used in a conventional thermoplastic resin composition is mainly prepared by reaction extrusion, and has a low maleic anhydride graft ratio of 0.5 to 1.0 parts by weight. In contrast, the maleic anhydride-grafted polypropylene resin according to an exemplary embodiment of the present invention may be prepared using a solution method, wherein the maleic anhydride grafting ratio is higher than about 1 part by weight and not more than about 5 parts by weight. . As such, the maleic anhydride-grafted polypropylene resin having a graft ratio of greater than about 1 part by weight and less than or equal to about 5 parts by weight has a high graft ratio, thereby greatly improving adhesion to a polar substrate.
본 발명의 일 실시상태에 따르면, 상기 무수말레산 그라프트된 폴리프로필렌 수지의 함량은 상기 제1 SEBS 블록 공중합체 수지 및 제2 SEBS 블록 공중합체 수지의 총중량 100 중량부에 대하여, 약 20 중량부 이상 약 40 중량부 이하(예를 들면, 20 중량부, 21 중량부, 22 중량부, 23 중량부, 24 중량부, 25 중량부, 26 중량부, 27 중량부, 28 중량부, 29 중량부, 30 중량부, 31 중량부, 32 중량부, 33 중량부, 34 중량부, 35 중량부, 36 중량부, 37 중량부, 38 중량부, 39 중량부 또는 40 중량부), 구체적으로 약 25 중량부 이상 약 35 중량부 이하일 수 있다. 상기 무수말레산 그라프트된 폴리프로필렌 수지의 함량이 상기 범위를 만족하는 경우 최종 성형품의 접착력이 충분하고, 최종 성형품의 경도 상승에 따른 그립감 저하, 원가 상승 문제 등이 없을 수 있다. According to an exemplary embodiment of the present invention, the content of the maleic anhydride-grafted polypropylene resin is about 20 parts by weight based on 100 parts by weight of the total weight of the first SEBS block copolymer resin and the second SEBS block copolymer resin. or more and about 40 parts by weight or less (eg, 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, 26 parts by weight, 27 parts by weight, 28 parts by weight, 29 parts by weight , 30 parts by weight, 31 parts by weight, 32 parts by weight, 33 parts by weight, 34 parts by weight, 35 parts by weight, 36 parts by weight, 37 parts by weight, 38 parts by weight, 39 parts by weight or 40 parts by weight), specifically about 25 parts by weight It may be more than about 35 parts by weight or less. When the content of the maleic anhydride-grafted polypropylene resin satisfies the above range, the adhesive force of the final molded article is sufficient, and there may be no problems such as a decrease in grip and a cost increase due to an increase in hardness of the final molded article.
폴리올레핀 수지polyolefin resin
본 발명의 일 실시상태에 따른 폴리올레핀 수지는 열가소성 탄성체 조성물의 가공성을 향상시켜주며, 상기 열가소성 탄성체 조성물을 이용하여 제조된 열가소성 탄성체에 적절한 기계적 강도를 제공할 수 있다.The polyolefin resin according to an exemplary embodiment of the present invention improves the processability of the thermoplastic elastomer composition, and may provide suitable mechanical strength to the thermoplastic elastomer produced using the thermoplastic elastomer composition.
본 발명의 일 실시상태에 따르면, 상기 폴리올레핀 수지는 호모 폴리프로필렌 수지, 블록 폴리프로필렌 수지 및 랜덤 폴리프로필렌 수지 중 적어도 1종을 포함할 수 있으나, 이에 제한되는 것은 아니다.According to an exemplary embodiment of the present invention, the polyolefin resin may include at least one of a homo polypropylene resin, a block polypropylene resin, and a random polypropylene resin, but is not limited thereto.
본 발명의 일 실시상태에 따르면, 상기 폴리올레핀 수지의 중량평균분자량은 약 100,000 g/mol 이상 약 300,000 g/mol 이하(예를 들면, 100,000 g/mol, 110,000 g/mol, 120,000 g/mol, 130,000 g/mol, 140,000 g/mol, 150,000 g/mol, 160,000 g/mol, 170,000 g/mol, 180,000 g/mol, 190,000 g/mol, 200,000 g/mol, 210,000 g/mol, 220,000 g/mol, 230,000 g/mol, 240,000 g/mol, 250,000 g/mol, 260,000 g/mol, 270,000 g/mol, 280,000 g/mol, 290,000 g/mol 또는 300,000 g/mol)일 수 있다. 상기 폴리올레핀 수지의 중량평균분자량이 상기 범위를 만족하는 경우, 상기 열가소성 탄성체 조성물의 점도가 상승하거나 또는 상기 열가소성 탄성체 조성물 내 성분 간의 점도 차이로 인해 혼화도가 저하되는 문제가 없어, 성형성, 표면 젖음성 등이 우수하여 접착력이 우수한 최종 제품을 제공하는데 보다 유리할 수 있다.According to an exemplary embodiment of the present invention, the polyolefin resin has a weight average molecular weight of about 100,000 g/mol or more and about 300,000 g/mol or less (eg, 100,000 g/mol, 110,000 g/mol, 120,000 g/mol, 130,000 g/mol). g/mol, 140,000 g/mol, 150,000 g/mol, 160,000 g/mol, 170,000 g/mol, 180,000 g/mol, 190,000 g/mol, 200,000 g/mol, 210,000 g/mol, 220,000 g/mol, 230,000 g/mol, 240,000 g/mol, 250,000 g/mol, 260,000 g/mol, 270,000 g/mol, 280,000 g/mol, 290,000 g/mol or 300,000 g/mol). When the weight average molecular weight of the polyolefin resin satisfies the above range, there is no problem in that the viscosity of the thermoplastic elastomer composition increases or the miscibility is lowered due to a difference in viscosity between components in the thermoplastic elastomer composition, so that moldability and surface wettability It may be more advantageous in providing a final product having excellent adhesion due to excellent adhesion.
본 발명의 일 실시상태에 따르면, 상기 폴리올레핀 수지는 약 100,000 g/mol 이상 약 300,000 g/mol 이하의 중량평균분자량을 가지는 호모 폴리프로필렌 수지일 수 있으나, 이에 제한되는 것은 아니다.According to an exemplary embodiment of the present invention, the polyolefin resin may be a homo polypropylene resin having a weight average molecular weight of about 100,000 g/mol or more and about 300,000 g/mol or less, but is not limited thereto.
본 발명의 일 실시상태에 따르면, 상기 제1 SEBS 블록 공중합체 수지 및 제2 SEBS 블록 공중합체 수지의 총중량 100 중량부에 대하여, 상기 폴리올레핀 수지의 함량은 약 5 중량부 이상 약 20 중량부 이하(예를 들면, 5 중량부, 6 중량부, 7 중량부, 8 중량부, 9 중량부, 10 중량부, 11 중량부, 12 중량부, 13 중량부, 14 중량부, 15 중량부, 16 중량부, 17 중량부, 18 중량부, 19 중량부 또는 20 중량부), 구체적으로 약 10 중량부 이상 약 20 중량부 이하일 수 있다. 상기 범위에서 열가소성 탄성체 조성물의 가공성을 보다 향상시킬 수 있고, 상기 열가소성 탄성체 조성물을 이용하여 제조된 열가소성 탄성체에 더욱 적절한 기계적 강도를 제공할 수 있으나, 이에 한정되는 것은 아니다.According to an exemplary embodiment of the present invention, with respect to 100 parts by weight of the total weight of the first SEBS block copolymer resin and the second SEBS block copolymer resin, the content of the polyolefin resin is about 5 parts by weight or more and about 20 parts by weight or less ( For example, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight. parts, 17 parts by weight, 18 parts by weight, 19 parts by weight, or 20 parts by weight), specifically about 10 parts by weight or more and about 20 parts by weight or less. In the above range, the processability of the thermoplastic elastomer composition may be further improved, and a more suitable mechanical strength may be provided to a thermoplastic elastomer manufactured using the thermoplastic elastomer composition, but is not limited thereto.
본 발명의 일 실시상태에 따르면, 상기 열가소성 탄성체 조성물은 비방향족 오일을 더 포함할 수 있다.According to an exemplary embodiment of the present invention, the thermoplastic elastomer composition may further include a non-aromatic oil.
비방향족 오일non-aromatic oil
본 발명의 일 실시상태에 따른 비방향족 오일은 열가소성 탄성체의 촉감과 직접적인 연관이 있는 경도와 성형성을 향상시키고, 내유성을 개선시킬 수 있다.The non-aromatic oil according to an exemplary embodiment of the present invention may improve hardness and moldability, which are directly related to the feel of a thermoplastic elastomer, and improve oil resistance.
본 발명의 일 실시상태에 따르면, 상기 비방향족 오일은 파라핀 오일을 포함할 수 있다. 상기 파라핀 오일은 ASTM D445에 의거하여 40 ℃에서 측정한 동점도가 약 90 cSt 이상, 구체적으로는 약 90 cSt 이상 약 180 cSt 이하, 더 구체적으로는 약 100 이상 약 150 cSt 이하일 수 있으며, 상기 범위에서 경도, 성형성, 내유성 개선에 보다 유리할 수 있으나, 이에 제한되는 것은 아니다. According to an exemplary embodiment of the present invention, the non-aromatic oil may include paraffin oil. The paraffin oil may have a kinematic viscosity of about 90 cSt or more, specifically about 90 cSt or more and about 180 cSt or less, more specifically about 100 or more and about 150 cSt or less, measured at 40 ° C. in accordance with ASTM D445, in the above range It may be more advantageous to improve hardness, moldability, and oil resistance, but is not limited thereto.
본 발명의 일 실시상태에 따르면, 상기 제1 SEBS 블록 공중합체 수지 및 제2 SEBS 블록 공중합체 수지의 총중량 100 중량부에 대하여, 상기 비방향족 오일의 함량은 약 80 중량부 이상 약 180 중량부 이하(예를 들면, 80 중량부, 90 중량부, 100 중량부, 110 중량부, 120 중량부, 130 중량부, 140 중량부, 150 중량부, 160 중량부, 170 중량부 또는 180 중량부), 구체적으로 약 100 중량부 이상 약 150 중량부 이하, 더 구체적으로 약 120 중량부 이상 약 140 중량부 이하일 수 있다. 상기 비방향족 오일의 함량이 상기 범위를 만족하는 경우, 흐름성이 우수하여 생산성 및 가공성을 개선하면서도, 표면 젖음성이 우수하여 이종 소재와의 접착력이 우수하고, 성형품의 품질 또한 우수할 수 있으나, 이에 제한되는 것은 아니다. According to an exemplary embodiment of the present invention, with respect to 100 parts by weight of the total weight of the first SEBS block copolymer resin and the second SEBS block copolymer resin, the content of the non-aromatic oil is about 80 parts by weight or more and about 180 parts by weight or less. (For example, 80 parts by weight, 90 parts by weight, 100 parts by weight, 110 parts by weight, 120 parts by weight, 130 parts by weight, 140 parts by weight, 150 parts by weight, 160 parts by weight, 170 parts by weight or 180 parts by weight), Specifically, it may be about 100 parts by weight or more and about 150 parts by weight or less, more specifically about 120 parts by weight or more and about 140 parts by weight or less. When the content of the non-aromatic oil satisfies the above range, the flowability is excellent to improve productivity and processability, and the surface wettability is excellent to have excellent adhesion to dissimilar materials, and the quality of the molded product may also be excellent. It is not limited.
본 발명의 일 실시상태에 따르면, 상기 제1 SEBS 블록 공중합체 수지 및 제2 SEBS 블록 공중합체 수지의 총중량 100 중량부에 대하여, 상기 SBS 블록 공중합체 수지의 함량은 약 5 중량부 이상 약 30 중량부 이하이고, 상기 무수말레산 그라프트된 폴리프로필렌 수지의 함량은 약 20 중량부 이상 약 40 중량부 이하일 수 있다. According to an exemplary embodiment of the present invention, with respect to 100 parts by weight of the total weight of the first SEBS block copolymer resin and the second SEBS block copolymer resin, the content of the SBS block copolymer resin is about 5 parts by weight or more and about 30 parts by weight. parts, and the content of the maleic anhydride-grafted polypropylene resin may be about 20 parts by weight or more and about 40 parts by weight or less.
본 발명의 다른 실시상태에 따르면, 상기 제1 SEBS 블록 공중합체 수지 및 제2 SEBS 블록 공중합체 수지의 총중량 100 중량부에 대하여, 상기 SBS 블록 공중합체 수지의 함량은 약 5 중량부 이상 약 30 중량부 이하이고, 상기 무수말레산 그라프트된 폴리프로필렌 수지의 함량은 약 20 중량부 이상 약 40 중량부 이하이며, 상기 폴리올레핀 수지의 함량은 약 5 중량부 이상 약 20 중량부 이하이고, 상기 비방향족 오일의 함량은 약 80 중량부 이상 약 180 중량부 이하일 수 있다. According to another exemplary embodiment of the present invention, with respect to 100 parts by weight of the total weight of the first SEBS block copolymer resin and the second SEBS block copolymer resin, the content of the SBS block copolymer resin is about 5 parts by weight or more and about 30 parts by weight. parts, and the content of the maleic anhydride-grafted polypropylene resin is about 20 parts by weight or more and about 40 parts by weight or less, the content of the polyolefin resin is about 5 parts by weight or more and about 20 parts by weight or less, and the non-aromatic The content of the oil may be about 80 parts by weight or more and about 180 parts by weight or less.
본 발명의 일 실시상태에 따르면, 상기 열가소성 탄성체 조성물은 당업계에서 통상적으로 사용되는 첨가제를 더 포함할 수 있다. 구체적으로, 본 발명의 일 실시상태에 따르면, 상기 열가소성 탄성체 조성물은 무기 충전제, 열안정제, 산화 방지제 및 슬립제로 이루어진 군에서 선택되는 첨가제를 더 포함할 수 있다. According to an exemplary embodiment of the present invention, the thermoplastic elastomer composition may further include additives commonly used in the art. Specifically, according to an exemplary embodiment of the present invention, the thermoplastic elastomer composition may further include an additive selected from the group consisting of inorganic fillers, heat stabilizers, antioxidants and slip agents.
본 발명의 일 실시상태에 따르면, 상기 열가소성 탄성체 조성물은 첨가제로서 열가소성 탄성체 조성물의 물성 및 성형 가공성 등을 개선하기 위하여 무기 충전제를 더 포함할 수 있다. 상기 무기 충전제는 탈크, 탄산칼슘, 클레이, 나노클레이 및 카올린으로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있으나, 이에 제한되는 것은 아니다. 상기 무기 충전제의 함량은 상기 제1 SEBS 블록 공중합체 수지 및 제2 SEBS 블록 공중합체 수지의 총중량 100 중량부에 대하여, 약 50 중량부 이상 약 150 중량부 이하, 구체적으로 약 75 중량부 이상 약 125 중량부 이하일 수 있다. 상기 무기 충전제의 함량이 상기 범위를 만족하는 경우 열가소성 탄성체 조성물의 물성 및 성형 가공성 등의 개선 효과가 우수할 수 있으나, 이에 제한되는 것은 아니다.According to an exemplary embodiment of the present invention, the thermoplastic elastomer composition may further include an inorganic filler as an additive to improve physical properties and molding processability of the thermoplastic elastomer composition. The inorganic filler may include at least one selected from the group consisting of talc, calcium carbonate, clay, nanoclay, and kaolin, but is not limited thereto. The content of the inorganic filler is about 50 parts by weight or more and about 150 parts by weight or less, specifically about 75 parts by weight or more and about 125 parts by weight based on 100 parts by weight of the total weight of the first SEBS block copolymer resin and the second SEBS block copolymer resin. may be less than or equal to parts by weight. When the content of the inorganic filler satisfies the above range, the improvement effect such as physical properties and molding processability of the thermoplastic elastomer composition may be excellent, but the present invention is not limited thereto.
본 발명에 따른 열가소성 탄성체 조성물은 상기와 같은 조성의 배합을 통하여, 폴리아미드계 부재와의 이중 사출이 가능하게 되며, 나아가 이중 사출을 이용하여 제조된 열가소성 탄성체는 별도의 접착제 없이도 폴리아미드계 부재와 높은 부착력으로 부착되고, 우수한 내유성을 가질 수 있다.The thermoplastic elastomer composition according to the present invention enables double injection with a polyamide-based member through the blending of the composition as described above, and furthermore, the thermoplastic elastomer manufactured using double injection can be combined with a polyamide-based member without a separate adhesive. It can be attached with high adhesion and have excellent oil resistance.
본 발명의 다른 실시상태는, 폴리아미드계 수지 함유 고분자 부재; 및 상기 고분자 부재 상에 상기 열가소성 탄성체 조성물을 이용하여 제조된 탄성체층을 포함하는, 이중 사출 성형품을 제공한다.Another embodiment of the present invention, a polyamide-based resin-containing polymer member; and an elastomer layer prepared using the thermoplastic elastomer composition on the polymer member.
전술한 바와 같이, 본 발명에 따른 열가소성 탄성체 조성물은 폴리아미드계 부재와의 이중 사출성 및 접착력이 뛰어나므로, 이중 사출법을 통하여 폴리아미드계 부재 상에 별도의 접착제 없이 열가소성 탄성체를 제조할 수 있다. 본 명세서에서의 이중 사출법은 당업계에 일반적으로 알려진 이중 사출법을 제한 없이 적용할 수 있다. As described above, since the thermoplastic elastomer composition according to the present invention has excellent double injection property and adhesion with the polyamide-based member, a thermoplastic elastomer can be manufactured without a separate adhesive on the polyamide-based member through the double injection method. . The double injection method in the present specification may be applied without limitation to the double injection method generally known in the art.
본 발명의 일 실시상태에 따르면, 상기 폴리아미드계 수지 함유 고분자 부재는 폴리아미드계 수지 외에 폴리올레핀계 수지(예를 들어, 폴리에틸렌계 수지, 폴리프로필렌계 수지 등), 폴리카보네이트계 수지, 이들의 공중합체, 이들의 조합을 더 포함할 수 있다. 다만, 추가 가능한 수지의 종류가 이에 한정되는 것은 아니며, 당업계에서 일반적으로 사용되는 다양한 수지를 더 포함할 수 있다. According to an exemplary embodiment of the present invention, the polyamide-based resin-containing polymer member is a polyolefin-based resin (eg, a polyethylene-based resin, a polypropylene-based resin, etc.), a polycarbonate-based resin, in addition to the polyamide-based resin, It may further include a coalescence, a combination thereof. However, the type of resin that can be added is not limited thereto, and various resins generally used in the art may be further included.
본 발명의 일 실시상태에 따르면, 상기 폴리아미드계 수지 함유 고분자 부재는 유리 섬유를 더 포함할 수 있다. 상기 폴리아미드계 수지 함유 고분자 부재는 유리 섬유를 더 포함함으로써, 강성을 보다 향상시킬 수 있다. 상기 유리 섬유의 함량은 최종 제품에 요구되는 물성에 따라 적절하게 조절될 수 있다.According to an exemplary embodiment of the present invention, the polyamide-based resin-containing polymer member may further include glass fibers. When the polyamide-based resin-containing polymer member further includes glass fibers, rigidity may be further improved. The content of the glass fiber may be appropriately adjusted according to the physical properties required for the final product.
상기 이중 사출 성형품은 폴리아미드계 수지 함유 고분자 부재에 열가소성 탄성체가 결합된 것일 수 있다. 상기 이중 사출 성형품의 열가소성 탄성체는 손잡이와 같이 사람의 접촉이 많은 부위에 적용될 수 있고, 상기 열가소성 탄성체는 내유성이 우수하여 빈번한 사용에도 물성 저하가 최소화될 수 있다. The double injection molded article may be one in which a thermoplastic elastomer is bonded to a polyamide-based resin-containing polymer member. The thermoplastic elastomer of the double injection-molded article may be applied to a portion with a lot of human contact, such as a handle, and the thermoplastic elastomer has excellent oil resistance, so that deterioration of physical properties can be minimized even with frequent use.
상기와 같은 이중 사출 성형품은 자동차용 내장재 또는 전동 드릴, 드라이버 등와 같은 공구일 수 있으며, 이의 손잡이 부분은 열가소성 탄성체로 구성될 수 있다. The double injection molded article as described above may be an automobile interior material or a tool such as an electric drill or driver, and the handle portion thereof may be composed of a thermoplastic elastomer.
이하, 본 발명을 구체적으로 설명하기 위해 실시예를 들어 상세하게 설명하기로 한다. 그러나, 본 발명에 따른 실시예들은 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 아래에서 기술하는 실시예들에 한정되는 것으로 해석되지 않는다. 본 명세서의 실시예들은 당업계에서 평균적인 지식을 가진 자에게 본 발명을 보다 완전하게 설명하기 위해 제공되는 것이다.Hereinafter, examples will be given to describe the present invention in detail. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention is not to be construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely explain the present invention to those of ordinary skill in the art.
실시예 및 비교예 Examples and Comparative Examples
하기 표의 구성 성분 및 함량에 따라 혼합하고, 약 52의 L/D, 약 40mm 직경의 이축 압출기를 이용하여 가공온도 약 220℃의 온도에서 약 350 rpm의 스크류 회전속도 및 50 kg/hr의 공급 속도의 조건으로 압출하여 펠렛을 제조하였다.Mix according to the components and contents in the table below, and a screw rotation speed of about 350 rpm and a feed rate of 50 kg/hr at a processing temperature of about 220° C. using a twin-screw extruder having an L/D of about 52 and a diameter of about 40 mm. Pellets were prepared by extrusion under the conditions of
상기 제조된 펠렛을 약 80 ℃에서 약 2시간 동안 건조시킨 후 150 ton의 사출기에서 약 260 ℃의 사출 온도로 사출하여 물성 평가용 시편을 제작하고, 이의 물성을 측정하여 하기 표 1에 나타내었다. The prepared pellets were dried at about 80 ° C. for about 2 hours and then injected at an injection temperature of about 260 ° C. in a 150 ton injection machine to prepare a specimen for evaluation of physical properties, and the physical properties thereof were measured and shown in Table 1 below.
중량부parts by weight 실시예 1Example 1 비교예 1Comparative Example 1 비교예 2Comparative Example 2 비교예 3Comparative Example 3 비교예 4Comparative Example 4 비교예 5Comparative Example 5 비교예 6Comparative Example 6
조성Furtherance 제1 SEBS1st SEBS 3030 3030 100100 3030 100100 -- 3030
제2 SEBS2nd SEBS 7070 7070 -- 7070 -- 100100 7070
SBSSBS 1515 1515 1515 -- 1515 1515 1515
MAH-g-PP(3중량부)MAH-g-PP (3 parts by weight) 3030 -- 3030 3030 -- 3030 3030
MAH-g-PP(1중량부)MAH-g-PP (1 part by weight) -- 3030 -- -- -- -- --
Homo PPHomo PP 12.512.5 12.512.5 12.512.5 12.512.5 42.542.5 12.512.5 4040
파라핀 오일paraffin oil 130130 130130 130130 130130 130130 130130 130130
무기 충전제inorganic filler 100100 100100 100100 100100 100100 100100 100100
물성Properties 용융흐름지수(g/10min.)Melt flow index (g/10min.) 170170 140140 3737 210210 -- 300300 180180
경도(Shore A)Hardness (Shore A) 6464 6363 6363 6666 6262 6565 8080
인장강도(MPa)Tensile strength (MPa) 4.84.8 4.54.5 6.36.3 4.54.5 4.14.1 3.53.5 6.56.5
연신율(%)Elongation (%) 500500 500500 550550 503503 480480 400400 480480
접착력(90° peel)(N/mm)Adhesion (90° peel) (N/mm) 9.679.67 2.12.1 3.33.3 9.39.3 ×× 3.23.2 1111
내유성(IRM 903)(@ 80℃, 22hr)Oil resistance (IRM 903) (@ 80℃, 22hr) 9090 9191 170170 9090 150150 7878 8383
성형성formability ○○ ○○ ×× ○○ △△ ○○ ○○
<조성 성분><Composition Ingredients>
제1 SEBS 블록 공중합체 수지(제1 SEBS): Kraton사 G1651 (중량평균분자량: 350,000 g/mol)First SEBS block copolymer resin (first SEBS): Kraton G1651 (weight average molecular weight: 350,000 g/mol)
제2 SEBS 블록 공중합체 수지(제2 SEBS): Kraton사 G1650 (중량평균분자량: 130,000 g/mol)Second SEBS block copolymer resin (second SEBS): Kraton G1650 (weight average molecular weight: 130,000 g/mol)
SBS 블록 공중합체 수지(SBS): LCY 사 GP7533 (중량평균분자량: 130,000 g/mol)SBS block copolymer resin (SBS): LCY GP7533 (weight average molecular weight: 130,000 g/mol)
3 중량부의 무수말레산이 그라프트된 폴리프로필렌 수지(MAH-g-PP (3 중량부)): 롯데케미칼사 PH-2003 parts by weight of maleic anhydride grafted polypropylene resin (MAH-g-PP (3 parts by weight)): Lotte Chemical PH-200
1 중량부의 무수말레산이 그라프트된 폴리프로필렌 수지(MAH-g-PP (1 중량부)): 롯데케미칼사 CM-1120H1 part by weight of maleic anhydride grafted polypropylene resin (MAH-g-PP (1 part by weight)): Lotte Chemical CM-1120H
호모 폴리프로필렌 수지(Homo PP): 롯데케미칼사 SJ-170 (중량평균분자량: 190,000 g/mol)Homo polypropylene resin (Homo PP): Lotte Chemical SJ-170 (weight average molecular weight: 190,000 g/mol)
파라핀 오일: Shell사 Catenex T145Paraffin oil: Shell Catenex T145
무기 충전제: 탄산칼슘, KOCH사 CMS-8000Inorganic filler: Calcium carbonate, KOCH CMS-8000
<물성 측정 방법><Method of measuring physical properties>
- 용융흐름지수(MFI): ISO 1133 에 의거, 230 ℃에서 5 kg 무게추를 이용하여 정해진 규격의 시간에 흐른 수지의 무게를 측정하였다.- Melt flow index (MFI): In accordance with ISO 1133, the weight of the resin that flowed at 230 ℃ at the specified time using a 5 kg weight was measured.
- 경도: 쇼어 경도계 A Type 을 사용하여, ISO 868의 규격에 따라 평가하였다. 시편의 두께는 2T의 사출 시편을 3장 겹쳐 측정 시작 후 15초의 값을 활용하였다.- Hardness: Using Shore hardness tester A Type, it was evaluated according to the standard of ISO 868. For the thickness of the specimen, the value of 15 seconds after the start of measurement was used by overlapping 3 2T injection specimens.
- 인장강도 및 연신율: 인스트론 시험기를 사용하여, ISO 37 규격에 준하여 측정하였다.- Tensile strength and elongation: Measured according to the ISO 37 standard using an Instron tester.
- 접착력: 이종 소재간 접착력 평가를 위해 Lanxess 사의 AKV30을 10×15×2 mm 의 규격으로 시편을 제작하여 폴리아미드계 부재(70 wt%의 나일론 6 및 30 wt%의 유리 섬유) 상에 인서트 이중 사출하였으며, 90°방향으로 100 mm/min. 속도로 VDI2019에 따라 접착력을 측정하였다.- Adhesion: For the evaluation of adhesion between different materials, a specimen of Lanxess' AKV30 with a size of 10×15×2 mm was prepared and double inserts were placed on a polyamide-based member (70 wt% nylon 6 and 30 wt% glass fiber). injection, and 100 mm/min in the 90° direction. Adhesion was measured according to VDI2019 with speed.
- 내유성: 50×30×2 (mm) 면적의 시편을 80 ℃로 예열한 ASTM #3 규격 Oil에 담지하여 22시간 방치한 후, 시편의 부피 변화를 확인하였다. - Oil resistance: A 50×30×2 (mm) specimen was immersed in ASTM #3 standard oil preheated to 80 ℃ and left for 22 hours, then the volume change of the specimen was checked.
- 성형성: 150 MT 유압식 사출기에 노즐부 260 ℃부터 10 ℃ 간격으로 하향된 온도로 설정하여 평가하였다. 동일 조건에서의 충진여부, 냉각정도, 외관(Sink 등)으로 상대 비교하였다.- Moldability: In a 150 MT hydraulic injection machine, the nozzle part was evaluated by setting the temperature from 260 ℃ to the lowered temperature at 10 ℃ intervals. Comparisons were made based on the filling condition, cooling degree, and appearance (Sink, etc.)
<평가><Evaluation>
실시예 1 및 비교예 1에 따르면, 무수말레산 그라프트된 폴리프로필렌 수지의 무수말레산의 그라프트율이 1 중량부인 경우 접착력이 지나치게 낮은 것을 확인할 수 있으며, 무수말레산의 그라프트율이 3 중량부인 경우 우수한 접착력을 구현할 수 있음을 알 수 있다. 이에 따라 실제 사용을 위한 처방 시, 무수말레산의 그라프트율이 1 중량부 초과인 무수말레산 그라프트된 폴리프로필렌을 처방하는 것이 접착력 향상 측면에서 유리한 것임을 알 수 있다. According to Example 1 and Comparative Example 1, when the maleic anhydride graft ratio of the maleic anhydride-grafted polypropylene resin is 1 part by weight, it can be confirmed that the adhesive strength is too low, and when the maleic anhydride grafting ratio is 3 parts by weight, excellent It can be seen that adhesion can be implemented. Accordingly, it can be seen that when prescribing for actual use, it is advantageous in terms of adhesion improvement to prescribe maleic anhydride-grafted polypropylene having a maleic anhydride graft ratio of more than 1 part by weight.
나아가, 제2 SEBS 블록 공중합체 수지를 함유하지 않은 비교예 2의 경우, 실시예 1에 비하여 매우 낮은 용융흐름지수에 따라 열악한 성형성을 나타내는 것을 확인할 수 있으며, 실시예 1에 비하여 상당히 낮은 접착력을 나타내는 것을 확인할 수 있다. Furthermore, in the case of Comparative Example 2, which does not contain the second SEBS block copolymer resin, it can be confirmed that it exhibits poor moldability according to a very low melt flow index compared to Example 1, and has significantly lower adhesion compared to Example 1 can be seen to indicate.
또한, 제2 SEBS 블록 공중합체 수지 및 무수말레산 그라프트된 폴리프로필렌을 함유하지 않은 비교예 4의 경우, 접착력이 거의 없어 접착력 테스트를 수행할 수 없었으며, 내유성 테스트 시 부피 팽창이 상당히 심한 것을 확인할 수 있었다. In addition, in the case of Comparative Example 4, which did not contain the second SEBS block copolymer resin and the maleic anhydride-grafted polypropylene, the adhesion test could not be performed because there was little adhesion, and the volume expansion during the oil resistance test was quite severe. could check
참고로, 제2 SEBS 블록 공중합체 수지 없이 제1 SEBS 블록 공중합체 수지 만을 함유하는 비교예 2는 내유성이 매우 저조한 것을 확인할 수 있다. 그리고, 제1 SEBS 블록 공중합체 수지 없이 제2 SEBS 블록 공중합체 수지만을 함유하는 비교예 5는 내유성은 향상되지만, 연신율, 인장 강도 및 접착력 등의 물성이 매우 저조한 것을 확인할 수 있다. 그러므로, 실시예와 같이 제1 SEBS 블록 공중합체 수지와 제2 SEBS 블록 공중합체 수지를 적절하게 혼합하는 경우, 열가소성 탄성체의 접착력 및 기계적 물성이 동시에 만족될 수 있음을 확인할 수 있다. For reference, it can be seen that Comparative Example 2 containing only the first SEBS block copolymer resin without the second SEBS block copolymer resin has very poor oil resistance. And, Comparative Example 5 containing only the second SEBS block copolymer resin without the first SEBS block copolymer resin has improved oil resistance, but it can be confirmed that physical properties such as elongation, tensile strength and adhesion are very poor. Therefore, it can be confirmed that when the first SEBS block copolymer resin and the second SEBS block copolymer resin are properly mixed as in the example, the adhesive strength and mechanical properties of the thermoplastic elastomer can be simultaneously satisfied.
나아가, SBS 블록 공중합체 수지를 함유하지 않은 비교예 3의 경우, 게이트와 가까워 지속적으로 열을 받는 중심 부분 외의 게이트와 먼 사출 위치에서는 다소 접착 형태에 편차가 있는 문제점이 있었다. 또한, 비교예 3의 경우 경도가 소폭 상승하여 쿠션감 등의 품질적인 특성이 다소 저하되는 것을 확인할 수 있었다. 그러므로, 열가소성 탄성체에 전반적으로 균일한 접착성을 발현시키고, 그립감 등의 품질을 개선하기 위하여, 실시예 1과 같이 SBS 블록 공중합체 수지를 처방하는 것이 필요함을 확인할 수 있다.Furthermore, in the case of Comparative Example 3, which did not contain the SBS block copolymer resin, there was a problem in that there was a slight deviation in the adhesion form at the injection location far from the gate except for the central portion that was continuously heated close to the gate. In addition, in the case of Comparative Example 3, the hardness was slightly increased, and it was confirmed that the quality characteristics such as cushioning feeling were slightly decreased. Therefore, it can be confirmed that it is necessary to prescribe the SBS block copolymer resin as in Example 1 in order to express the overall uniform adhesion to the thermoplastic elastomer and to improve the quality such as grip.
또한, 호모 폴리프로필렌의 함량이 과도하게 처방된 비교예 6의 경우, 경도가 지나치게 상승하여 쿠션감 저하 등의 촉감적 품질에 문제가 발생할 수 있음을 확인할 수 있었다. In addition, in the case of Comparative Example 6, in which the content of homopolypropylene was excessively prescribed, it was confirmed that the hardness was excessively increased, so that a problem in tactile quality such as a decrease in cushion feeling may occur.
이제까지 본 발명에 대하여 실시예들을 중심으로 살펴보았다. 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자는 본 발명이 본 발명의 본질적인 특성에서 벗어나지 않는 범위에서 변형된 형태로 구현될 수 있음을 이해할 수 있을 것이다. 그러므로 개시된 실시예들은 한정적인 관점이 아니라 설명적인 관점에서 고려되어야 한다. 본 발명의 범위는 전술한 설명이 아니라 특허청구범위에 나타나 있으며, 그와 동등한 범위 내에 있는 모든 차이점은 본 발명에 포함된 것으로 해석되어야 할 것이다. Up to now, the present invention has been looked at mainly with respect to the embodiments. Those of ordinary skill in the art to which the present invention pertains will understand that the present invention can be implemented in modified forms without departing from the essential characteristics of the present invention. Therefore, the disclosed embodiments are to be considered in an illustrative rather than a restrictive sense. The scope of the present invention is indicated in the claims rather than the foregoing description, and all differences within the scope equivalent thereto should be construed as being included in the present invention.

Claims (7)

  1. 제1 SEBS(styrene-ethylene-butylene-styrene) 블록 공중합체 수지;First SEBS (styrene-ethylene-butylene-styrene) block copolymer resin;
    제2 SEBS(styrene-ethylene-butylene-styrene) 블록 공중합체 수지; Second SEBS (styrene-ethylene-butylene-styrene) block copolymer resin;
    SBS(styrene-butylene-styrene) 블록 공중합체 수지;SBS (styrene-butylene-styrene) block copolymer resin;
    무수말레산 그라프트된 폴리프로필렌 수지; 및maleic anhydride grafted polypropylene resin; and
    폴리올레핀 수지;를 포함하고,Including; polyolefin resin;
    상기 제1 SEBS 블록 공중합체 수지는 중량평균분자량이 약 250,000 g/mol 이상 약 450,000 g/mol 이하이고,The first SEBS block copolymer resin has a weight average molecular weight of about 250,000 g/mol or more and about 450,000 g/mol or less,
    상기 제2 SEBS 블록 공중합체 수지는 중량평균분자량이 약 100,000 g/mol 이상 약 200,000 g/mol 이하이고,The second SEBS block copolymer resin has a weight average molecular weight of about 100,000 g/mol or more and about 200,000 g/mol or less,
    상기 무수말레산 그라프트된 폴리프로필렌 수지의 무수말레산 그라프트율은 약 1 중량부 초과 약 5 중량부 이하이고,The maleic anhydride grafting ratio of the maleic anhydride-grafted polypropylene resin is greater than about 1 part by weight and not more than about 5 parts by weight,
    상기 폴리올레핀 수지는 상기 제1 SEBS 블록 공중합체 수지 및 제2 SEBS 블록 공중합체 수지의 총중량 100 중량부에 대하여 약 5 중량부 이상 약 20 중량부 이하로 포함되는 것을 특징으로 하는, 열가소성 탄성체 조성물.The polyolefin resin is a thermoplastic elastomer composition, characterized in that it is included in an amount of about 5 parts by weight to about 20 parts by weight based on 100 parts by weight of the total weight of the first SEBS block copolymer resin and the second SEBS block copolymer resin.
  2. 청구항 1에 있어서,The method according to claim 1,
    상기 폴리올레핀 수지는 호모 폴리프로필렌 수지, 블록 폴리프로필렌 수지 및 랜덤 폴리프로필렌 수지 중 적어도 1종을 포함하는 것을 특징으로 하는, 열가소성 탄성체 조성물.The polyolefin resin comprises at least one of a homo polypropylene resin, a block polypropylene resin, and a random polypropylene resin, a thermoplastic elastomer composition.
  3. 청구항 1 또는 2에 있어서, The method according to claim 1 or 2,
    비방향족 오일을 더 포함하는 것을 특징으로 하는, 열가소성 탄성체 조성물.A thermoplastic elastomer composition, characterized in that it further comprises a non-aromatic oil.
  4. 청구항 1 내지 3 중 어느 한 항에 있어서, 4. The method according to any one of claims 1 to 3,
    상기 제1 SEBS 블록 공중합체 수지와 제2 SEBS 블록 공중합체 수지의 중량비는 약 5:5 내지 약 2:8인 것을 특징으로 하는, 열가소성 탄성체 조성물. The thermoplastic elastomer composition, characterized in that the weight ratio of the first SEBS block copolymer resin and the second SEBS block copolymer resin is about 5:5 to about 2:8.
  5. 청구항 1 내지 4 중 어느 한 항에 있어서, 5. The method according to any one of claims 1 to 4,
    상기 제1 SEBS 블록 공중합체 수지 및 제2 SEBS 블록 공중합체 수지의 총중량 100 중량부에 대하여, 상기 SBS 블록 공중합체 수지의 함량은 약 5 중량부 이상 약 30 중량부 이하이고, 상기 무수말레산 그라프트된 폴리프로필렌 수지의 함량은 약 20 중량부 이상 약 40 중량부 이하인 것을 특징으로 하는, 열가소성 탄성체 조성물.With respect to 100 parts by weight of the total weight of the first SEBS block copolymer resin and the second SEBS block copolymer resin, the content of the SBS block copolymer resin is about 5 parts by weight or more and about 30 parts by weight or less, and the maleic anhydride graft The thermoplastic elastomer composition, characterized in that the content of the modified polypropylene resin is about 20 parts by weight or more and about 40 parts by weight or less.
  6. 청구항 3에 있어서, 4. The method according to claim 3,
    상기 제1 SEBS 블록 공중합체 수지 및 제2 SEBS 블록 공중합체 수지의 총중량 100 중량부에 대하여, 상기 비방향족 오일의 함량은 약 80 중량부 이상 약 180 중량부 이하인 것을 특징으로 하는, 열가소성 탄성체 조성물.Based on 100 parts by weight of the total weight of the first SEBS block copolymer resin and the second SEBS block copolymer resin, the content of the non-aromatic oil is about 80 parts by weight or more and about 180 parts by weight or less, The thermoplastic elastomer composition.
  7. 폴리아미드계 수지를 포함하는 고분자 부재; 및 상기 고분자 부재 상에 청구항 1 내지 6 중 어느 한 항에 따른 열가소성 탄성체 조성물을 이용하여 제조된 탄성체층을 포함하는, 이중 사출 성형품. a polymer member including a polyamide-based resin; and an elastomer layer prepared using the thermoplastic elastomer composition according to any one of claims 1 to 6 on the polymer member.
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