KR100574681B1 - Polyolefin resin composition with high melt strength and foam produced using the same - Google Patents
Polyolefin resin composition with high melt strength and foam produced using the same Download PDFInfo
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- KR100574681B1 KR100574681B1 KR1020030098652A KR20030098652A KR100574681B1 KR 100574681 B1 KR100574681 B1 KR 100574681B1 KR 1020030098652 A KR1020030098652 A KR 1020030098652A KR 20030098652 A KR20030098652 A KR 20030098652A KR 100574681 B1 KR100574681 B1 KR 100574681B1
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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
- 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
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/22—Thermoplastic resins
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
본 발명은 고용융장력을 지닌, 결정성 에틸렌-프로필렌 랜덤공중합체 부분 65~95중량부와 탄성 에틸렌-프로필렌 공중합체 부분 5~35중량부를 함유하는 공중합체를 포함하는 폴리올레핀 수지조성물 및 상기 수지조성물을 압출발포시켜 제조된 발포체에 관한 것으로서, 본 발명의 수지조성물은, 용융장력이 기존 수지에 비해 우수하여 발포체의 발포배율 및 발포 셀 밀도가 우수하고 발포 공정에서 우수한 발포성을 발현할 뿐만 아니라 종래의 가교를 시키는 방법이 아니므로 열가소성수지의 성질을 그대로 유지할 수 있으며 재활용이 가능하다는 장점이 있다.The present invention provides a polyolefin resin composition comprising a copolymer containing 65 to 95 parts by weight of a crystalline ethylene-propylene random copolymer portion and 5 to 35 parts by weight of an elastic ethylene-propylene copolymer portion having a high melt strength and the resin composition. The present invention relates to a foam produced by extrusion foaming, wherein the resin composition of the present invention has excellent melt tension compared to existing resins, which is excellent in foam ratio and foam cell density of foams, and exhibits excellent foamability in the foaming process. Since it is not a method of crosslinking, the properties of the thermoplastic resin can be maintained as it is and there is an advantage that it can be recycled.
폴리프로필렌 수지조성물, 고용융장력, 발포성, 발포체.Polypropylene resin composition, high melt strength, foamability, foam.
Description
본 발명은 고용융장력을 지닌, 긴 가지가 도입된 폴리올레핀 수지조성물 및 이를 이용하여 제조된 발포체에 관한 것으로, 보다 상세하게는 최적의 알파올레핀 중합용 촉매의 주위에 고분자량 단량체가 캡슐화한 형태의 전중합 촉매를 이용하여 중합된, 결정성 에틸렌-프로필렌 랜덤공중합체 부분 65~95중량부와 탄성 에틸렌-프로필렌 공중합체 부분 5~35중량부를 함유하는 공중합체를 포함하는 수지조성물 및 상기 수지조성물을 압출발포시켜 제조된 발포체에 관한 것이다. The present invention relates to a polyolefin resin composition having a long branching introduced polyolefin resin and a foam produced using the same, more specifically, in a form in which a high molecular weight monomer is encapsulated around an optimum catalyst for alpha olefin polymerization. A resin composition comprising a copolymer containing 65 to 95 parts by weight of a crystalline ethylene-propylene random copolymer portion and 5 to 35 parts by weight of an elastic ethylene-propylene copolymer portion, polymerized using a prepolymerization catalyst, and the resin composition. It relates to a foam produced by extrusion foaming.
일반적으로 발포제품에 사용되는 플라스틱에는, 폴리우레탄, 폴리올레핀, PVC, ABS수지, 요소수지, 페놀수지 등이 있으며, 이중 폴리스티렌과 폴리우레탄이 많이 이용되고 있다. In general, plastics used in foamed products include polyurethanes, polyolefins, PVC, ABS resins, urea resins, phenol resins, and the like, of which polystyrene and polyurethane are widely used.
폴리스티렌은 탄성율이 높아서 높은 단열성과 완충성을 가지며, 또한 고배율의 발포 성형이 가능하여 경량의 발포체를 성형할 수 있을 뿐만 아니라, 독립기포 가 형성되기 때문에 식품용기 등에 많이 적용되고 있다. Polystyrene has high elastic modulus, has high thermal insulation and cushioning properties, and is capable of foaming with high magnification to form lightweight foams, and is widely applied to food containers because independent bubbles are formed.
폴리우레탄은 모노머의 선택을 통해 다양한 발포체를 생산할 수 있는 장점이 있는데, 주로 연질 발포체는 촉감이 뛰어나 완충제 등에 사용되며, 경질 발포체는 건축용 단열재로 사용되고 있다.Polyurethane has the advantage of producing a variety of foams through the selection of monomers, mainly soft foam is excellent in the touch is used for buffers, etc., the rigid foam is used as a building insulation.
이처럼 폴리스티렌과 폴리우레탄은 발포소재로서 뛰어난 특성을 갖기는 하지만 하기와 같은 이유로 특정 용도에는 적용하기 어렵다. 즉, 폴리스티렌은 내유성이 매우 낮기 때문에 사용온도가 100℃가 넘거나 기름에 접촉하는 경우에는 적용이 곤란하며, 또한 폴리우레탄은 발포체 성형 후의 2차 성형이나 재활용이 어려워서 식품용기로 사용하기에는 적용성이 떨어진다.As such, polystyrene and polyurethane have excellent properties as foaming materials, but are difficult to apply to specific applications for the following reasons. That is, polystyrene has very low oil resistance, so it is difficult to apply when the temperature is over 100 ℃ or contact with oil. Also, polyurethane is difficult to be used for food containers because it is difficult to be secondary molded or recycled after foam molding. Falls.
반면에 폴리프로필렌은 기계적 물성의 발란스가 높고 내유성 및 내열성이 우수하다. 또한 2차 성형 및 재활용이 가능하여 자동차 부품, 필름, 사출품 등 넓은 영역에서 사용되고 있다. 그러나 폴리프로필렌은 선형 사슬 구조에 기인하는 약한 용융장력으로 인하여 다른 플라스틱에 비해 만족할 만한 성형성을 확보하지 못하였다. Polypropylene, on the other hand, has a high balance of mechanical properties and excellent oil and heat resistance. In addition, since secondary molding and recycling are possible, it is used in a wide range of fields such as automobile parts, films, and injection molded products. However, polypropylene did not have satisfactory formability compared to other plastics due to the weak melt tension due to the linear chain structure.
이러한 이유로, 폴리프로필렌의 용융장력을 증가시키기 위한 여러 가지 방법이 제시되고 있다. For this reason, various methods for increasing the melt tension of polypropylene have been proposed.
첫 번째는 폴리올레핀에 긴 가지(long chain branch)를 도입하는 방법으로서, 이는 가공공정에서 고분자사슬간의 인력을 감소시켜 이지 플로우(easy flow)특성을 부여하도록 하고, 성형공정(그 중 특히 대형 blow 등과 같은 치수안정성을 요하는 용도)에서 긴 가지가 인접 사슬과의 물리적 가교를 통해 용융장력을 높이는 역할을 하도록 하므로써 고용융장력을 나타내게 하는 방법이다. 이와 같이 긴 가지를 도입하여 고용융장력의 폴리올레핀을 제조하는 구체적인 방법으로는 주로 중합반응기를 거쳐서 나온 폴리올레핀에 전자선이나 반응압출법을 통해 라디칼을 형성시키고, 이들을 다시 반응시켜, 사슬형 폴리올레핀에 긴가지를 형성시키는 방법이 있다. The first is to introduce long chain branches into polyolefins, which reduces the attractive force between the polymer chains in the processing process to give easy flow characteristics, and to the molding process (especially large blows, etc.). In the case where the same dimensional stability is required), long branches have a role of increasing melt tension through physical crosslinking with adjacent chains, thereby showing high melt strength. As a specific method of preparing a polyolefin having high melt strength by introducing a long branch as described above, radicals are mainly formed on the polyolefin from the polymerization reactor through an electron beam or a reaction extrusion method and reacted again to form a long branch on the polyolefin. There is a way to form.
두번째로는 용융지수가 매우 낮은 폴리프로필렌에 폴리에틸렌을 물리적으로 블렌드하는 방법이다. 이 방법은 용융지수가 낮아 가공성이 저하되는 문제점이 있으므로, 이 방법으로 제조된 부드러운 발포체의 사용 용도에는 한계가 있다. The second method is to physically blend polyethylene into polypropylene with a very low melt index. This method has a problem in that workability is lowered because the melt index is low, and thus there is a limit to the use of the soft foam produced by this method.
본 발명은 상기한 바와 같은 문제점을 해결하기 위한 것으로, 용융장력을 증가시켜서 내열성 및 내유성이 우수한 폴리올레핀 수지조성물 및 이로부터 제조된 발포체를 제공하는 것을 목적으로 한다.
The present invention is to solve the problems as described above, an object of the present invention is to provide a polyolefin resin composition excellent in heat resistance and oil resistance by increasing the melt tension and a foam prepared therefrom.
본 발명의 긴 가지가 도입된 수지조성물은 하기 (A) 부분 65~95 중량부와, (B) 부분 5~35 중량부를 함유하는 공중합체 100중량부에, 산화방지제 0.1~1.0중량부, 발포제 1~20중량부 및 발포핵제 0.05~2.0중량부를 포함하여 이루어진 것을 특징으로 한다. The resin composition into which the long branch of the present invention is introduced contains 0.1 to 1.0 part by weight of an antioxidant and a foaming agent to 100 parts by weight of a copolymer containing 65 to 95 parts by weight of the following (A) part and 5 to 35 parts by weight of the (B) part. It is characterized by comprising 1 to 20 parts by weight and 0.05 to 2.0 parts by weight of the foaming nucleating agent.
(A) 하기의 특징을 가진 결정성 에틸렌-프로필렌 랜덤공중합체 부분 (A) A crystalline ethylene-propylene random copolymer moiety having the following characteristics
a) 용융지수가 0.1 ~ 10 g/10분이고, a) the melt index is from 0.1 to 10 g / 10 minutes,
b) 0.5 ~ 10중량%의 에틸렌을 함유하며, b) contains 0.5 to 10% by weight of ethylene,
c) 긴 가지가 도입되고 용융강도가 200mN 이상. c) Long branches are introduced and melt strength is 200 mN or more.
(B) 하기의 특징을 가진 탄성 에틸렌-프로필렌 공중합체 부분 (B) an elastomeric ethylene-propylene copolymer portion having the following characteristics
a) 절대 점도가 0.5 ~ 5.0dl/g이고, a) the absolute viscosity is 0.5 to 5.0 dl / g,
b) 20 ~ 70중량%의 에틸렌을 함유하며, b) contains 20-70% by weight of ethylene,
c) 긴 가지가 도입되고 용융강도가 200mN 이상. c) Long branches are introduced and melt strength is 200 mN or more.
본 발명에서 사용되는 상기의 특징을 가지는 결정성 에틸렌-프로필렌 랜덤 공중합체 부분 및 탄성 에틸렌-프로필렌 공중합체 부분은, 알파 올레핀 중합용 촉매의 주위에 고분자량 단량체가 캡슐화한 형태의 전중합 촉매를 이용하여 중합된 것으로서, 이의 제조에 사용되는 촉매성분의 바람직한 예는 대한민국 특허 출원 번호 제2001-0085640호에 기재되어 있다. 이 촉매성분에 대해 간략히 요약해 보면, 올레핀 중합용 고체 티타늄 촉매를 두 개 이상의 비닐기를 가지는 실란화합물로 표면처리한 다음, 이 표면 처리된 고체 티타늄촉매와 올레핀 단량체 및 디엔 화합물을 전중합시키므로써 촉매주위에 고분자량 단량체를 캡슐화시켜 제조되는 것을 특징으로 하는 알파올레핀 중합용 촉매이다. The crystalline ethylene-propylene random copolymer portion and the elastic ethylene-propylene copolymer portion having the above characteristics used in the present invention employ a prepolymerization catalyst in a form in which a high molecular weight monomer is encapsulated around the catalyst for alpha olefin polymerization. And a preferred example of the catalyst component used for its preparation is described in Korean Patent Application No. 2001-0085640. In summary, the catalyst component is treated by subjecting the solid titanium catalyst for olefin polymerization to a silane compound having two or more vinyl groups and then prepolymerizing the surface treated solid titanium catalyst with an olefin monomer and a diene compound. It is a catalyst for alpha olefin polymerization, which is prepared by encapsulating a high molecular weight monomer around.
본 발명에서 사용되는 상기의 공중합체는, 먼저 (A) 결정성 에틸렌-프로필렌 랜덤 공중합체 부분을 제조하고, 이어지는 일련의 반응장치에서 (B) 탄성 에틸렌-프로필렌 공중합체 부분을 제조하는 것이, 공정상 바람직하다. In the copolymer used in the present invention, first, (A) crystalline ethylene-propylene random copolymer portion is prepared, and in the following series of reaction apparatus, (B) elastic ethylene-propylene copolymer portion is produced in the process Phase is preferred.
본 발명에서 사용되는 (A) 결정성 에틸렌-프로필렌 랜덤공중합체 부분은 용융지수가 0.1 ~ 10 g/10분인 것이 바람직하고, 0.3 ~ 5.0 g/10분인 것이 더욱 바람직하다. 상기 용융지수가 0.10 g/분 미만에서는 가공시 부하가 많이 걸리고, 급격한 압력 상승을 수반한다. 융융지수가 10g/10분 이상인 경우에는 용융강도 저하를 수반하여, 발포 가공시 발포체의 셀 형성이 어렵고, 형성된 셀이 열린 형태를 나타낸다. 상기 결정성 에틸렌-프로필렌 랜덤 공중합체 부분의 양은 65~95중량부로 한정지우는 것이 바람직한데, 65중량부 이하일 경우 강성 및 내열성이 현격히 저하되며, 95중량부 이상일 경우 충격 특성 개질에 효과가 없다. The (A) crystalline ethylene-propylene random copolymer portion used in the present invention preferably has a melt index of 0.1 to 10 g / 10 minutes, more preferably 0.3 to 5.0 g / 10 minutes. If the melt index is less than 0.10 g / min, the load is heavy during processing, accompanied by a rapid pressure rise. When the melt index is 10 g / 10 minutes or more, the melt strength is lowered, and thus, the cell formation of the foam is difficult during foaming, and the formed cell is opened. It is preferable to limit the amount of the crystalline ethylene-propylene random copolymer portion to 65 to 95 parts by weight, the stiffness and heat resistance is significantly reduced when the amount is less than 65 parts by weight, and when more than 95 parts by weight is not effective in modifying the impact characteristics.
또한 상기의 결정성 에틸렌-프로필렌 랜덤공중합체 부분은 0.1~10중량%의 에틸렌을 함유하는 것이 바람직하다. 에틸렌 함량이 0.5중량% 미만이면, 투명성이 개선되는 등의 에틸렌 첨가효과를 볼 수가 없고, 10중량% 이상이면 랜덤공중합체 부분의 결정성이 떨어지고, 끈끈해지게 된다. It is also preferable that the above crystalline ethylene-propylene random copolymer portion contains 0.1 to 10% by weight of ethylene. If the ethylene content is less than 0.5% by weight, the effect of ethylene addition such as improving transparency is not seen, and if it is 10% by weight or more, the crystallinity of the random copolymer portion is inferior and becomes sticky.
상기의 (B) 탄성 에틸렌-프로필렌 공중합체 부분은 그 절대점도가 0.5~5,0dl/g인 것이 바람직한데, 이 범위 내에서 (A) 결정성 에틸렌-프로필렌 랜덤공중합체 부분의 점도와 유사한 범위의 절대점도를 나타내어, 양자간의 혼합성이 양호하게 된다. The above-mentioned (B) elastic ethylene-propylene copolymer portion preferably has an absolute viscosity of 0.5 to 5,0 dl / g, and within this range, a range similar to the viscosity of the (A) crystalline ethylene-propylene random copolymer portion. Absolute viscosity is shown, and the mixing property between them becomes favorable.
또한 상기의 탄성 에틸렌-프로필렌 공중합체 부분은 20~70중량%의 에틸렌을 함유하는 것이 바람직하다. 에틸렌 함량이 20중량% 미만이면, 에틸렌 첨가로 인한 탄성의 발현이 불충분하고, 70중량% 이상이면, 상분리가 일어나거나, 가공성이 나빠지는 등 물성이 악화된다. Moreover, it is preferable that the said elastic ethylene propylene copolymer part contains 20 to 70 weight% of ethylene. If the ethylene content is less than 20% by weight, the elasticity due to the addition of ethylene is insufficient, and if the content is 70% by weight or more, phase separation may occur or workability may deteriorate.
본 발명에서 사용되는 상기의 공중합체((A)부분+(B)부분)는, 연신 점도를 측정할 때, 변형율 속도가 어느 정도 이상의 값을 가지면, 점단후화 (Extrension Hardening) 현상이 발현되어 연신점도 값이 선형 곡선의 값보다 많이 커지는 것을 특징으로 하는 것이다.In the copolymer ((A) part + (B) part) used in the present invention, when the strain viscosity has a value of a certain degree or more, an extension hardening phenomenon is expressed and stretched. The viscosity value is characterized by being larger than the value of the linear curve.
본 발명의 긴 가지가 도입된 공중합체 조성물에는 이러한 류의 공중합체에 일반적으로 사용되는 것으로 알려진 공지의 산화방지제를 첨가하는데, 그 양은 상기의 공중합체 100중량부에 대하여 0.1~1.0중량부가 바람직하고, 0.3~0.7 중량부가 더욱 바람직하다. 0.1중량부 미만에서는 산화방지 효과가 불충분할 염려가 있고, 1.0중량부를 넘으면, 산화방지효과가 일정 수준에 달하여 더 이상 증가하지 않기 때문이다. To the copolymer composition in which the long branch of the present invention is introduced, a known antioxidant known to be generally used in this type of copolymer is added, and the amount thereof is preferably 0.1 to 1.0 parts by weight based on 100 parts by weight of the copolymer. 0.3-0.7 weight part is more preferable. If it is less than 0.1 part by weight, there is a fear that the antioxidant effect is insufficient, if it exceeds 1.0 part by weight, the antioxidant effect reaches a certain level and does not increase any more.
본 발명의 긴 가지가 도입된 공중합체 조성물에 통상의 발포제 및 발포핵제를 고온, 고압의 조건하에 혼합하고 적합한 발포온도까지 냉각한 후 대기압 하에서 압출 발포시킴으로써 발포체를 얻을 수 있다. A foam can be obtained by mixing a conventional blowing agent and a foaming nucleating agent in a copolymer composition into which the long branch of the present invention is introduced under high temperature and high pressure conditions, cooling to a suitable foaming temperature, and extruding the foam under atmospheric pressure.
상기 발포제로서 바람직하게는, 부탄, 이소부탄, 펜탄, 헥산 및 헵탄과 같은 지방족 탄화수소류 시클로부탄, 시클로펜탄 및 시클로헥산과 같은 지환족 탄화수소류 및 클로로디플루오로메탄, 디클로로메탄, 디클로로플루오로메탄, 트리클로로플루오로메탄, 클로로에탄, 디클로로트리플루오로에탄 및 퍼플루오로시클로부탄과 같은 할로겐화 탄화수소류로 구성된 군으로부터 선택된 1종 이상의 유기가스, 및/또는 이산화탄소, 질소 및 공기와 같은 무기가스로 구성된 군으로부터 선택된 1종 이상을 사용한다. 발포제의 첨가량은 발포제의 종류 및 목표발포 배율에 의해 선택되며, 일반적으로 상기의 긴가지가 도입된 공중합체 조성물 100중량부에 대하여1~20중량부인 것이 바람직하며, 더욱 바람직하게는 5~10중량부인 것이다. As the blowing agent, aliphatic hydrocarbons such as butane, isobutane, pentane, hexane and heptane and alicyclic hydrocarbons such as cyclobutane, cyclopentane and cyclohexane and chlorodifluoromethane, dichloromethane, dichlorofluoromethane At least one organic gas selected from the group consisting of halogenated hydrocarbons such as trichlorofluoromethane, chloroethane, dichlorotrifluoroethane and perfluorocyclobutane, and / or inorganic gases such as carbon dioxide, nitrogen and air. At least one selected from the group consisting of is used. The addition amount of the blowing agent is selected by the type of blowing agent and the target foaming ratio, and it is generally preferable that it is 1 to 20 parts by weight, more preferably 5 to 10 parts by weight based on 100 parts by weight of the copolymer composition into which the long branches are introduced. I would deny it.
또한 발포 핵제는 특별한 제한 없이 공지의 것을 사용할 수 있으나, 바람직하게는 탈크핵제가 사용될 수 있다. 발포핵제의 첨가량은 상기의 긴 가지가 도입된 공중합체 조성물 100중량부에 대하여 0.05~2.0중량부인 것이 바람직하며, 함량이 0.05중량부 미만에서는 충분한 셀밀도를 얻기 어렵고, 2.0중량부를 초과하면 더 이상 개선된 효과가 발현되지 않는다. In addition, the foaming nucleus may be a known one without particular limitation, but preferably a talc nucleating agent may be used. The addition amount of the foaming nucleating agent is preferably 0.05 to 2.0 parts by weight based on 100 parts by weight of the above-mentioned long branched copolymer composition, and when the content is less than 0.05 parts by weight, it is difficult to obtain a sufficient cell density. No improved effect is expressed.
본 발명의 조성물에는 또한 이러한 류의 조성물에 일반적으로 사용되는 것으로 알려진 다른 첨가물들을 첨가할 수 있다. The composition of the present invention may also be added with other additives known to be generally used in this class of compositions.
본 발명의 발포체를 제조하는 방법에 있어서 특별한 제한은 없고, 보편적으로 알려진 탠덤압출기, 단축압출기 및 2축 압출기 등을 사용하여, 상기 본 발명의 수지조성물을 압출 발포시키는 제조방법을 선택할 수 있다. There is no particular limitation on the method for producing the foam of the present invention, and a production method for extrusion foaming the resin composition of the present invention can be selected using a universally known tandem extruder, single screw extruder, twin screw extruder or the like.
이와 같이 제조된 본 발명의 발포체는 20~40배 이상의 발포배율을 가지며, 이때 발포체의 셀밀도는 1.0E+05cells/cm3 이상이다. The foam of the present invention prepared as described above has a foaming ratio of 20 to 40 times or more, wherein the cell density of the foam is 1.0E + 05 cells / cm 3 or more.
본 발명은 하기의 실시예에 의하여 보다 구체적으로 이해될 수 있으며, 하기의 실시예는 본 발명을 예시하기 위한 예에 지나지 않는 것으로 본 발명의 보호범위를 제한하는 것은 아니다. The present invention can be understood in more detail by the following examples, the following examples are merely examples for illustrating the present invention and do not limit the protection scope of the present invention.
각 실시예 및 비교예에 있어서의 제반 물성의 측정법은 다음과 같다. The measuring method of the physical property in each Example and a comparative example is as follows.
용융지수 측정Melt Index Measurement
ASTM D1238에 의거하여 230℃, 2.16kg에서 측정하였다.It measured at 230 degreeC and 2.16 kg based on ASTMD1238.
용융강도 및 연신점도 측정Melt strength and draw viscosity measurement
특허출원 제1999-0008553호 및 제2001-0030112호 등에 기재된SMER(Samsung Melt Tension Rheometer)을 이용하여 200℃에서 모세관유량계(capillary rheometer)의 판을 통해 나오는 스트랜드에 대하여140℃ 쳄버온도에서 용융강도 및 연신점도를 측정하였다. 이때 판의 L/D는 16이며, 가속비는 1mm/sec였다. Melt strength at 140 ° C. chamber temperature for strands exiting through a plate of capillary rheometer at 200 ° C. using SMER (Samsung Melt Tension Rheometer) described in patent applications Nos. 1999-0008553 and 2001-0030112. The draw viscosity was measured. At this time, the plate had an L / D of 16 and an acceleration ratio of 1 mm / sec.
발포배율Expansion ratio
발포체의 중량과, 수몰법에 의해 구한 체적으로 발포체의 밀도를 측정하고, 발포 전의 수지밀도와의 비를 통해 발포배율을 계산하였다.The density of the foam was measured by the weight of the foam and the volume determined by the water-immersion method, and the foaming ratio was calculated through the ratio of the resin density before foaming.
발포체의 셀 밀도Cell density of foam
발포된 수지의 단위 입방센티미터 당의 셀 수를 나타내는 것으로서, 주사전자현미경으로 발포체의 100×100μm내에 존재하는 셀 수를 측정하여 아래의 식으로 계산하였다.The number of cells per unit cubic centimeter of the foamed resin was measured, and the number of cells present in 100 x 100 µm of the foam was measured by a scanning electron microscope, and the following formula was calculated.
셀 밀도 = (cell의 개수×10μm/l)3/2×109×발포배율 Cell density = (number of cells x 10 μm / l) 3/2 x 109 x expansion ratio
[실시예 1] Example 1
1단계 : 긴가지가 도입된 공중합체 조성물의 제조Step 1: Preparation of Copolymer Composition with Long Branches
결정성 에틸렌-프로필렌 랜덤공중합체(A) 부분의 제조Preparation of Crystalline Ethylene-Propylene Random Copolymer (A) Part
특허 출원 번호 제2001-0085640호에 기재된 전중합촉매를 이용하여 온도 70℃, 압력 38㎏/㎠ 조건하에서 반응장치에 프로필렌과 에틸렌을 동시에 주입하여 반응을 시키되, 생성된 공중합체내의 함량 비율이, 프로필렌 97중량%, 에틸렌 3중량% 비율이 되도록 공중합시켜 긴가지가 도입된 랜덤공중합체(A) 부분을 제조하였다.Using the prepolymerization catalyst described in Patent Application No. 2001-0085640, the reaction was carried out by simultaneously injecting propylene and ethylene into the reactor under a temperature of 70 ° C. and a pressure of 38 kg / cm 2, but the content ratio of the produced copolymer is The copolymer was copolymerized to a ratio of 97% by weight of propylene and 3% by weight of ethylene to prepare a random copolymer (A) having a long branch introduced therein.
탄성 에틸렌-프로필렌 공중합체(B) 부분의 제조 및 결과 공중합체의 제조Preparation of the Elastomeric Ethylene-Propylene Copolymer (B) Part and Preparation of the Resulting Copolymer
1단계 중합이 이루어진 후, 이어지는 일련의 반응장치에서 온도 80℃, 압력 17㎏/㎠ 조건하에서 반응을 시키되, 생성되는 탄성 공중합체내의 에틸렌과 프로필렌의 함량 비율이 에틸렌 30중량%, 프로필렌 70중량%가 되도록 하고, 동시에 절대점도가 0.88dl/g이 되도록 에틸렌-프로필렌 탄성 공중합체(B) 부분을 제조하되, 상기 (A)와 (B)의 함량 비율이, (A) 90중량%, (B) 10중량%가 되도록 각 단계의 중합량을 조절하여, 용융지수가 2g/10min인 결과 공중합체를 얻었다.After the one-stage polymerization, the reaction was carried out in the following series of reactors at a temperature of 80 ° C. and a pressure of 17 kg / cm 2, wherein the content ratio of ethylene and propylene in the resulting elastomeric copolymer was 30% by weight of ethylene and 70% by weight of propylene. And at the same time to prepare an ethylene-propylene elastic copolymer (B) portion such that the absolute viscosity is 0.88 dl / g, wherein the content ratio of (A) and (B) is (A) 90% by weight, (B The amount of polymerization in each step was adjusted to 10% by weight to obtain a copolymer having a melt index of 2 g / 10 min.
2단계 : 펠렛 및 발포체의 제조Step 2: Preparation of Pellets and Foams
상기의 긴 가지가 도입된 공중합체 100중량부에, 산화방지제 0.5중량부를 함께 혼합한 후 2축 압출기를 통해 용융 혼합하여 펠렛화하였다. 이 펠렛을 사용하여 상기의 방법으로 용융지수, 용융강도를 측정하고 그 측정결과를 표 1에 나타내었다.To 100 parts by weight of the above-mentioned long branched copolymer, 0.5 parts by weight of antioxidant was mixed together and then melt mixed through a twin screw extruder to pelletize. Using this pellet, the melt index and melt strength were measured by the above method, and the measurement results are shown in Table 1.
상기의 수지 펠렛을 20kg/h로 25mm 텐덤형 압출기에 발포핵제로 탈크 0.5중량부와 함께 공급하고 제1단 압출기에서 220℃로 가소화한 후, 상기 공중합체 조성물 100중량부에 대하여 발포제로서 n-부탄 10중량부를 압입한 다음, 기어펌프를 통해 제2단 압출기로 정량적으로 공급하였다. 40mm 제2단 압출기의 온도를 180℃로 냉각시킨 후 스테틱 믹서 및 판의 온도를 130℃까지 냉각시켜 발포 스트렌드를 얻었다. 이와 같이 제조된 발포체에 대하여 발포배율 및 발포체 셀 밀도를 상기와 같이 측정하고 그 결과도 표 1에 나타내었다.The resin pellets were supplied with 0.5 parts by weight of talc as a foaming nucleating agent to a 25 mm tandem extruder at 20 kg / h and plasticized at 220 ° C. in a first stage extruder, and then n was used as a foaming agent with respect to 100 parts by weight of the copolymer composition. 10 parts by weight of butane was press-fitted and then quantitatively fed through a gear pump to a second stage extruder. After cooling the temperature of the 40 mm 2nd stage extruder to 180 degreeC, the temperature of the static mixer and plate was cooled to 130 degreeC, and foamed strand was obtained. The foaming ratio and foam cell density of the foam thus prepared were measured as described above, and the results are also shown in Table 1.
[실시예 2] Example 2
실시예 1과 동일하게 펠렛화한 후, 발포핵제로 탈크 0.8중량부를 제1단 압출기에 함께 공급한 것 이외에는, 실시예 1과 동일하게 하여 발포체를 제조한 후, 발포배율 및 발포체의 셀밀도를 측정하여, 그 결과를 표 1에 나타내었다.After pelletizing in the same manner as in Example 1, foam was prepared in the same manner as in Example 1 except that 0.8 parts by weight of talc was fed together with the foaming nucleating agent in the first stage extruder, and then the foaming ratio and the cell density of the foam were measured. It measured and the result is shown in Table 1.
[비교예 1] Comparative Example 1
긴가지가 도입된 공중합체 대신에 용융지수가 1.7g/10분인 프로필렌 단독 중합체 100중량부를 사용한 것 이외에는 상기 실시예1과 동일하게 펠렛화하여 용융지수, 용융강도, 및 연신점도를 측정하고, 상기 펠렛을 이용하여 실시예 1과 동일하게 발포체를 제조한 후, 발포배율 및 발포체의 셀밀도를 측정하여, 그 결과를 표1에 나타내었다.In the same manner as in Example 1 except that 100 parts by weight of a propylene homopolymer having a melt index of 1.7 g / 10 minutes was used instead of the long branched copolymer, the melt index, melt strength, and elongation viscosity were measured. After the foam was produced in the same manner as in Example 1 using the pellet, the foaming ratio and the cell density of the foam were measured, and the results are shown in Table 1.
[비교예 2] Comparative Example 2
상기 (A)로서 용융지수가 1.7g/10분인 프로필렌 단독 중합체를 사용한 것 이외에는 상기 실시예1과 동일하게 펠렛화하여 용융지수, 용융강도, 및 연신점도를 측정하고, 상기 펠렛을 이용하여 실시예 1과 동일하게 발포체를 제조한 후, 발포배율 및 발포체의 셀밀도를 측정하여 그 결과를 표1에 나타내었다.Except for using a propylene homopolymer having a melt index of 1.7 g / 10 min as (A), pelletized in the same manner as in Example 1 to measure the melt index, melt strength, and elongation viscosity, and the pellet was used as an example. After preparing the foam in the same manner as in 1, the foaming ratio and the cell density of the foam were measured, and the results are shown in Table 1.
(표1)Table 1
본 발명의 수지 조성물은, 용융장력이 기존 수지에 비해 우수하여 발포체의 발포배율 및 발포 셀 밀도가 우수하고 발포 공정에서 우수한 발포성을 발현할 뿐만 아니라 종래의 가교를 시키는 방법이 아니므로 열가소성수지의 성질을 그대로 유지할 수 있으며 재활용이 가능하다는 장점이 있다.
Since the resin composition of the present invention has excellent melt tension compared to existing resins, it has excellent foaming ratio and foam cell density of the foam, and excellent foamability in the foaming process. It can be kept intact and can be recycled.
Claims (7)
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| KR1020030098652A KR100574681B1 (en) | 2003-12-29 | 2003-12-29 | Polyolefin resin composition with high melt strength and foam produced using the same |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101068714B1 (en) * | 2009-03-09 | 2011-09-28 | 삼성토탈 주식회사 | Polypropylene resin composition for foaming molding and a foam prepared using the same |
| KR101372137B1 (en) * | 2011-12-20 | 2014-03-10 | 삼성토탈 주식회사 | Polypropylene Resin Composition for Expandable Bead |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100727895B1 (en) | 2006-01-04 | 2007-06-14 | 삼성토탈 주식회사 | Polypropylene resin composition for extrusion blow molding |
| KR101352682B1 (en) * | 2011-12-27 | 2014-01-17 | 삼성토탈 주식회사 | Polypropylene resin Composition |
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- 2003-12-29 KR KR1020030098652A patent/KR100574681B1/en active IP Right Grant
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101068714B1 (en) * | 2009-03-09 | 2011-09-28 | 삼성토탈 주식회사 | Polypropylene resin composition for foaming molding and a foam prepared using the same |
| KR101372137B1 (en) * | 2011-12-20 | 2014-03-10 | 삼성토탈 주식회사 | Polypropylene Resin Composition for Expandable Bead |
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| KR20050067654A (en) | 2005-07-05 |
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