KR20000039269A - Polyolefin resin composition excellent in non-polish, impact-resistance, soft touch and products thereof - Google Patents

Polyolefin resin composition excellent in non-polish, impact-resistance, soft touch and products thereof Download PDF

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KR20000039269A
KR20000039269A KR1019980054550A KR19980054550A KR20000039269A KR 20000039269 A KR20000039269 A KR 20000039269A KR 1019980054550 A KR1019980054550 A KR 1019980054550A KR 19980054550 A KR19980054550 A KR 19980054550A KR 20000039269 A KR20000039269 A KR 20000039269A
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ethylene
weight
less
component
container
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KR1019980054550A
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Korean (ko)
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이태근
이규종
김석진
전민호
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남창우
에스케이 주식회사
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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
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/12—Melt flow index or melt flow ratio

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)

Abstract

PURPOSE: Provided is a polyolefin resin composition excellent in non-polish, impact-resistance and soft touch, which can be used for making containers of cosmetic and cleanser. It is not necessary to process the containers by coating and corrosion. CONSTITUTION: A polyolefin resin comprises 20-40 wt% of a random polypropylene resin(component 1) having less than 25 wt% of ethylene and less than 10 dg/min of melt index, 20-45 wt% of high density polyethylene(component 2) having less than 1.0 dg/min of melt index and 10-60 wt% of at least one compound(component 3) selected from the group consisting of an ethylene-propylene block copolymer having less than 25 wt% of ethylene, an ethylene-propylene copolymer having 30-80 wt% of ethylene, an ethylene-propylene-diene copolymer and optionally, 0.01-1 wt% of a coloring agent and SiO2 as a quenching agent having an average particle size of 1-10 micrometer.

Description

무광특성, 내충격성 및 감촉성이 우수한 폴리올레핀 수지 조성물 및 이의 제품Polyolefin resin composition and its products excellent in matt, impact resistance and feel

본 발명은 무광특성, 내충격성 및 감촉성이 우수한 폴리올레핀 수지 조성물 및 이의 제품에 관한 것으로서, 좀 더 상세하게는 랜덤 (random) 폴리프로필렌 수지 (성분 1), 고밀도 폴리에틸렌 (성분 2) 및 에틸렌-프로필렌 블록(block)공중합체, 에틸렌-프로필렌공중합체 (EPR) 또는 에틸렌-프로필렌-다이엔 삼원공중합체 (EPDM) 중 하나 이상의 성분 (성분 3)의 수지 혼합물 (성분 4)로 이루어지며, 중공성형, 사출중공성형, 사출연신중공성형 등의 방법으로 상기 조성물의 단층구조 또는 상기 조성물을 표면 층으로 하여 무광특성을 나타내는 용기를 제조할 수 있으며, 충격강도 및 감촉성 (Soft Touch성)이 우수한 폴리올레핀 수지 조성물 및 이의 제품에 관한 것이다.BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to polyolefin resin compositions and their products having excellent matte properties, impact resistance and feel, and more particularly, to random polypropylene resins (component 1), high density polyethylene (component 2) and ethylene-propylene. Blow molding, consisting of a resin mixture (component 4) of at least one component (component 3) of a block copolymer, ethylene-propylene copolymer (EPR) or ethylene-propylene-diene terpolymer (EPDM) It is possible to manufacture a container exhibiting a matte property using a single layer structure of the composition or the composition as a surface layer by a method such as injection blow molding, injection stretch blow molding, etc., and has excellent impact strength and soft touch (poly touch). It relates to a composition and a product thereof.

일반적으로 폴리프로필렌 수지 (이하 "PP"라 함)는 기계적, 열적, 전기적 특성이 우수하고, 내약품성 및 성형성이 뛰어난 범용수지로 필름, 일회용 용기 등에 많이 사용되고 있다.In general, polypropylene resin (hereinafter referred to as "PP") is a general-purpose resin having excellent mechanical, thermal, and electrical properties, excellent chemical resistance, and moldability, and is widely used in films, disposable containers, and the like.

폴리올레핀은 가격과 성능 면에서 균형이 잡힌 수지로 포장분야에서는 화장품이나 세제 등의 용기에 중공성형용으로 많이 사용되고 있다. 그 대부분은 폴리에틸렌이지만 PP의 성형성이나 내저온 낙하 충격성이 개선되는 동시에 폴리에틸렌과 비교하여 투명성, 내열안정성 및 내크리크성 등이 뛰어난 장점으로 PP의 사용량이 증가되고 있다. 또한, 폴리에틸렌테레프탈레이트 (PET)와 비교하여 성형성 및 재활용 (recycle)성이 우수한 특성을 가지고 있다.Polyolefin is a resin that is balanced in terms of price and performance, and is widely used in the packaging field for blow molding in containers such as cosmetics and detergents. Although most of them are polyethylene, the use of PP is increasing due to the advantages of improving the moldability and impact resistance of cold drop, and excellent transparency, thermal stability, and creek resistance compared to polyethylene. In addition, compared to polyethylene terephthalate (PET) has excellent properties of moldability and recycle (recycle).

표면에 무광특성을 부여하는 방법으로 유리 용기 사용 시에는 일반적으로 유리용기 제조 후 플루오르산계의 부식액으로 처리하여 표면에 미세한 요철을 부여하여, 이에 따라 빛의 난반사가 생겨서 무광 유리 용기 (Frost 용기)를 제조하는 방법이 있다. 최근에는 환경대책을 위한 설비비나 폐액 처리비의 부담증가로 무기계 첨가제를 첨가한 도료를 용기 표면에 코팅하여 광택을 없애는 기술이 실용화되고 있다. 이와 동일한 기술이 폴리에틸렌테레프탈레이트 (PET) 용기에도 응용되고 있다. 그러나, 이는 코팅설비 및 건조설비가 필요하며, 재활용이 어렵고, 비싸다는 단점 등을 가지고 있다.When the glass container is used as a method of imparting matte properties to the surface, after the glass container is manufactured, it is generally treated with a fluoric acid-based corrosion solution to impart fine irregularities to the surface. As a result, diffused reflection of light occurs to form a matte glass container (Frost container). There is a method of manufacturing. In recent years, due to an increase in burden on facility costs and waste liquid treatment costs for environmental measures, a technique of coating gloss by coating a paint with an inorganic additive on the surface of the container has been put to practical use. The same technology is applied to polyethylene terephthalate (PET) containers. However, this requires a coating facility and a drying facility, it is difficult to recycle, and has the disadvantages of being expensive.

이러한 단점을 해결하기 위하여, 부식 또는 코팅 등의 후가공처리 없이 폴리올레핀 수지의 특성을 이용하여 무광특성을 갖는 용기를 제조할 수 있는 기술이 개발되어 왔다.In order to solve this drawback, a technique has been developed that can produce a container having a matte property using the characteristics of the polyolefin resin without post-processing such as corrosion or coating.

이러한 선행 기술의 예로, 일본특개소 제 62-277450호에서는 폴리프로필렌 및 폴리에틸렌 수지를 이용하여 무광특성을 갖는 수지 조성물에 관하여 기술하고 있다. 상기 특허에 게시된 내용에 의하면 분자량분포 (중량평균분자량/수평균분자량)가 16 이상인 호모폴리프로필렌이나 에틸렌, 부텐, 4 메틸 펜텐 등의 알파-올레핀 코폴리머 중 하나의 100 중량부와 분자량분포 16 이상이고 용융지수가 0.2 dg/min 이하인 폴리에틸렌 3-250 중량부의 혼합물의 조성으로 용기를 성형하면 표면 광택이 작은 용기를 성형할 수 있음을 기술하고 있다.As an example of such a prior art, Japanese Patent Laid-Open No. 62-277450 describes a resin composition having matt properties using polypropylene and polyethylene resin. According to the contents disclosed in the patent, 100 parts by weight of one of homopolypropylene having a molecular weight distribution (weight average molecular weight / number average molecular weight) of 16 or more, or an alpha-olefin copolymer such as ethylene, butene or 4 methyl pentene and molecular weight distribution 16 It is described that by molding a container with a composition of 3-250 parts by weight of polyethylene having a melt index of 0.2 dg / min or less, a container having a low surface gloss can be formed.

유사한 기술로 일본특개평 제 2-69549호에서는 용융지수 0.1-100 dg/min의 임팩트폴리프로필렌 (Impact PP) 50-90 중량%와 밀도 0.930 g/cc 이상 및 용융지수 5.0 dg/min 이하의 폴리에틸렌 10-50 중량%을 0.1-5.0의 중량부의 가교조제와 함께 라디칼 발생제 (퍼옥사이드)를 0.001-0.2중량부를 처방한 수지 조성으로 반응압출시킨 수지로 용기를 성형하면 무광특성을 갖는 제품을 성형할 수 있음을 기술하고 있다.Similarly, Japanese Patent Laid-Open No. 2-69549 discloses 50-90 wt% of impact polypropylene (Impact PP) with a melt index of 0.1-100 dg / min, polyethylene with a density of at least 0.930 g / cc and a melt index of 5.0 dg / min. 10-50% by weight of the cross-linking aid with 0.1-5.0 parts by weight of a crosslinking aid and a radical-generating agent (peroxide) by molding the reaction reaction resin with a resin composition prescribed by 0.001-0.2 parts by weight of the molded product having a matt properties It states that it can be done.

또한, 일본특개평 제 9-141766호에서는 다층용기 성형시 무광특성을 부여하기 위해서 안 층에는 폴리에틸렌, 폴리프로필렌, 또는 폴리에틸렌테레프탈레이트의 수지를 사용하고, 최외층에 에틸렌-메타크릴산의 공중합체인 아이오노머 (Ionomer)를 사용하여 무광특성을 갖는 용기를 성형할 수 있음을 기술하고 있다.In Japanese Patent Laid-Open No. 9-141766, polyethylene, polypropylene, or polyethylene terephthalate resin is used for the inner layer, and the copolymer of ethylene-methacrylic acid is used for the outermost layer in order to give matt characteristics when forming a multilayer container. It has been described that ionomers can be used to form containers with matt properties.

그러나, 상기 종래 기술은 폴리프로필렌과 상용성이 없는 폴리에틸렌의 수지 혼합물만으로 용기를 성형하였기 때문에 용기에 내용물을 충진시킨 후, 운송이나 보관 및 사용 중에 발생할 수 있는 충격에 약하여 용기가 쉽게 파손되는 문제점이 있다. 그리고, 라디칼 발생제를 처방하여 반응압출로 제조한 수지 조성물은 미반응 라디칼 개시제가 용기의 내용물과 반응할 수 있으며, 냄새, 변색 문제, 및 표면이 딱딱한 감촉성을 나타내며, 또한, 반응압출로 제조한 수지는 수지 혼합물의 구조가 변하여 충격 강도가 더 약하게 되는 단점이 있다.However, since the prior art has formed the container using only a resin mixture of polyethylene which is not compatible with polypropylene, the container is easily broken because the container is filled with contents, and thus the container is easily damaged due to the shock that may occur during transportation, storage and use. have. In addition, the resin composition prepared by reaction extrusion by prescribing a radical generator has an unreacted radical initiator that can react with the contents of the container, exhibits odor, discoloration problem, and hard feel on the surface, and is also prepared by reaction extrusion. One resin has the disadvantage that the structure of the resin mixture changes, resulting in a weaker impact strength.

이러한 무광특성을 나타내는 유리 및 PET와 종래 기술의 폴리올레핀 수지 조성물의 특성을 하기 표 1에 기재하였다.The properties of glass and PET exhibiting such matting properties and polyolefin resin compositions of the prior art are listed in Table 1 below.

종 류Kinds 무광특성Matte property 충격강도Impact strength 감촉성Touch 중 량weight 가 격price 무광유리Matte Glass 우 수Great 열 세Thirteen 딱딱함crustiness 무겁다heavy 고 가high price 무광 PETMatte PET 우 수Great 우 수Great 딱딱함crustiness 가볍다light 고 가high price 종래기술 (특개소 62-277450 및 특개평 2-69649)Prior art (Japanese Patent Laid-Open No. 62-277450 and Japanese Patent Laid-Open No. 2-69649) 양 호Good 열 세Thirteen 딱딱함crustiness 가볍다light 저 가low price

따라서, 본 발명의 목적은 상술한 종래 기술과는 전혀 다른 방식을 이용하여 용기 제작 후, 부식, 코팅 등의 후가공이 필요 없고, 저 가격에 재활용이 가능한 폴리올레핀 수지 자체를 사용하여 충격강도 및 감촉성이 우수한 무광특성을 갖는 폴리올레핀 수지 조성물을 제공하는데 있다.Accordingly, the object of the present invention is to use a polyolefin resin itself, which can be recycled at a low price without the need for post-processing such as corrosion and coating after the container is manufactured by using a completely different method as described above. It is to provide a polyolefin resin composition having excellent matt properties.

본 발명의 또 다른 목적은 무광특성, 충격강도 및 감촉성이 우수한 상기 수지 조성물을 이용한 제품을 제공하는데 있다.Still another object of the present invention is to provide a product using the resin composition having excellent matt properties, impact strength and feel.

상기 목적을 달성하기 위한 본 발명의 조성물은 용융지수 (ASTM D1238)가 10 dg/min 이하이고, 25 중량% 이하의 에틸렌을 포함하는 랜덤 폴리프로필렌 수지 20∼45 중량%, 용융지수가 1.0 dg/min 이하인 고밀도 폴리에틸렌 20∼45 중량% 및 25 중량% 이하의 에틸렌을 포함하는 에틸렌-프로필렌 블록공중합체, 30∼80 중량%의 에틸렌을 포함하는 에틸렌-프로필렌공중합체 (EPR) 또는 에틸렌-프로필렌-다이엔 삼원공중합체 (EPDM)로 이루어진 군으로부터 하나 또는 그 이상 선택되며, 이는 용융지수가 1.0 dg/min 이하인 수지 혼합물 10∼60 중량%로 필수적으로 구성된다.The composition of the present invention for achieving the above object has a melt index (ASTM D1238) of 10 dg / min or less, 20 to 45% by weight of random polypropylene resin containing 25% by weight or less of ethylene, 1.0 dg / Ethylene-propylene block copolymers containing 20 to 45% by weight of high density polyethylene up to min and 25% by weight of ethylene, ethylene-propylene copolymers (EPR) comprising 30 to 80% by weight of ethylene or ethylene-propylene-die One or more selected from the group consisting of ene terpolymers (EPDM), consisting essentially of 10 to 60% by weight of the resin mixture having a melt index of 1.0 dg / min or less.

본 발명의 다른 목적을 달성하기 위한 본 발명의 제품은 본 발명의 조성물을 표면 층으로 하는 2층 이상의 적층구조를 갖도록 중공성형, 사출중공성형 및 사출연신중공성형으로 제조된다.The products of the present invention for achieving another object of the present invention are manufactured by blow molding, injection blow molding and injection stretch hollow molding so as to have a laminated structure of two or more layers using the composition of the present invention as a surface layer.

도 1은 본 발명에 따른 수지를 중공성형으로 제조한 무광 화장품 용기 표면의 전자현미경 사진(×203)이다.1 is an electron micrograph (× 203) of the surface of a matte cosmetic container prepared by blow molding a resin according to the present invention.

이하 본 발명을 좀 더 구체적으로 살펴보면 다음과 같다.Looking at the present invention in more detail as follows.

본 발명의 조성물은 랜덤 폴리프로필렌 수지 (이하 "성분 1"이라 함) 20∼45 중량%, 고밀도 폴리에틸렌 (이하 "성분 2"라 함) 20∼45 중량% 및 에틸렌-프로필렌 블록공중합체, 에틸렌-프로필렌공중합체 (EPR) 또는 에틸렌-프로필렌-다이엔 삼원공중합체 (EPDM) 중 하나 또는 그 이상의 성분 (이하 "성분 3") 10∼60 중량%로 구성되며, 즉, 성분 1, 성분 2 및 성분 3의 혼합물로 필수적으로 구성된다. 필요시 선택적으로 소광제로서 평균입자 크기가 1∼10㎛의 실리카 (SiO2) 및 착색제 0.01∼1 중량%를 더욱 함유할 수 있다.The composition of the present invention comprises 20 to 45% by weight of random polypropylene resin (hereinafter referred to as "component 1"), 20 to 45% by weight of high density polyethylene (hereinafter referred to as "component 2") and ethylene-propylene block copolymer, ethylene- Consisting of 10 to 60% by weight of one or more of the propylene copolymer (EPR) or ethylene-propylene-diene terpolymer (EPDM) (hereinafter "component 3"), ie component 1, component 2 and component It consists essentially of a mixture of three. Optionally, as a matting agent, it may further contain silica (SiO 2 ) having an average particle size of 1 to 10 μm and 0.01 to 1 wt% of a colorant.

이때, 상기 성분 1이 20 중량% 미만 또는 45 중량%를 초과하면 무광특성이 없어지며, 바람직한 상기 성분 1의 함량은 30∼45 중량%이다. 한편, 상기 성분 1은 25 중량% 이하를 갖는 에틸렌을 포함하는 에틸렌-프로필렌 공중합체 (Random PP)이며, 용융수지는 10 dg/min 이하이다. 여기서, 상기 용융수지는 ASTM D1238 (190℃, 2.16kg)에 의거한다. 이때, 상기 용융지수가 10 dg/min을 초과하면 용기 제조시 가공성이 떨어져서 용기 제작이 어렵게 된다.At this time, when the component 1 is less than 20% by weight or more than 45% by weight, the matte properties are lost, the preferred content of the component 1 is 30 to 45% by weight. On the other hand, component 1 is an ethylene-propylene copolymer (Random PP) containing ethylene having 25% by weight or less, and the molten resin is 10 dg / min or less. Here, the molten resin is based on ASTM D1238 (190 ° C., 2.16 kg). At this time, when the melt index exceeds 10 dg / min, the workability during manufacturing the container is poor, making the container difficult.

상기 성분 2는 용융지수 1.0 dg/min 이하인 고밀도 폴리에틸렌 (High Density Polyethylene, HDPE)이며, 여기서 상기 용융지수가 1.0 dg/min을 초과하면 무광특성이 없어지게 된다. 용기의 무광특성은 일차적으로 상기 성분 1과 성분 2의 특성 및 중량비로 결정되어 진다. 즉, 상기 성분 1과 성분 2의 용융지수의 차이가 클수록 용기 제작시 흐름성에 차이가 더 많이 발생하여 무광특성이 양호하게 나타난다.Component 2 is a high density polyethylene (HDPE) having a melt index of 1.0 dg / min or less, and when the melt index exceeds 1.0 dg / min, the matte property is lost. The matting properties of the vessel are primarily determined by the properties and weight ratios of component 1 and component 2 above. That is, the greater the difference between the melt index of the components 1 and 2, the more the difference occurs in the flowability during the manufacturing of the container, the better the matt properties.

상기 성분 3은 25 중량% 이하의 에틸렌 함량을 갖는 에틸렌-프로필렌 블록공중합체 (Impact PP), 에틸렌 함량이 30∼80 중량%의 에틸렌프로필렌공중합체 (이하 EPR) 및 에틸렌-프로필렌-다이엔 삼원공중합체 (이하 EPDM)로 이루어진 군으로부터 하나 또는 그 이상 선택되어 진다. 또한, 상기 성분 3은 용융지수가 1.0 dg/min 이하이다. 여기서, 상기 에틸렌-프로필렌 블록공중합체, EPR 또는 EPDM은 상용화제로서 종래 기술의 문제점인 용기의 충격강도 및 감촉성을 개선하기 위해서 사용하였다. 상기 성분 3으로 인하여 수지 혼합물의 밀도를 낮게 하여 결정화도가 낮아지게 되고, 성분 1과 성분 2의 상 분리 (phase seperation)를 방지하는 상용화제로 작용하고, 그 경계면에서 완충작용을 하여 용기의 충격강도를 향상시키고 우수한 감촉성을 제공한다.Component 3 is an ethylene-propylene block copolymer (Impact PP) having an ethylene content of 25% by weight or less, an ethylene propylene copolymer having an ethylene content of 30 to 80% by weight (hereinafter EPR) and an ethylene-propylene-diene terpolymer One or more selected from the group consisting of coalescing (hereinafter EPDM). In addition, the component 3 has a melt index of 1.0 dg / min or less. Here, the ethylene-propylene block copolymer, EPR or EPDM was used as a compatibilizer to improve the impact strength and feel of the container which is a problem of the prior art. Due to the component 3, the density of the resin mixture is lowered to lower the crystallinity, and acts as a compatibilizer to prevent phase separation of the components 1 and 2, and buffers at the interface to increase the impact strength of the container. Improves and provides excellent feel.

본 발명은 소광제로서 평균입자 크기가 1∼10㎛의 실리카 (SiO2) 및 착색제 0.01∼1 중량%를 더욱 함유할 수 있으며, 이때, 상기 실리카의 평균입자의 크기가 1㎛ 미만이면 소광효과가 나타나지 않는 문제가 있으며, 10㎛를 초과하면 분산의 문제를 초래할 수 있다.The present invention may further contain silica (SiO 2 ) having an average particle size of 1 to 10 μm and a coloring agent of 0.01 to 1 wt% as a matting agent, wherein the average particle size of the silica is less than 1 μm to provide a matting effect. There is a problem that does not appear, if it exceeds 10㎛ may cause the problem of dispersion.

상기 본 발명의 조성물은 단층구조, 또는 상기 조성물을 표면 층으로 하는 2층 이상의 적층구조를 갖도록 중공성형, 사출중공성형 및 사출연신중공성형으로 제품을 제작하여 표면에 미세한 요철을 갖게 하여 이에 따른 빛의 난반사에 의해 용기에 무광특성을 제공한다.The composition of the present invention has a single layer structure, or two or more layers of the laminated layer of the composition as a surface layer to produce a product by blow molding, injection molding and injection-stretching hollow molding to have a fine concave-convex on the surface to thereby light The diffuse reflection of light provides the container with a matte property.

이하 실시예를 통하여 본 발명을 좀 더 상세히 설명하겠지만, 이에 본 발명의 범주가 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited thereto.

상기 수지 조성물을 30ψ2축 혼련기 (Twin Screw Compounder)를 이용하여 200∼240℃에서 혼련하였고, 중공성형기, 사출중공성형기 또는 사출연신중공성형기를 이용하여 무광 용기를 제조하였다. 하기 실시예에서는 이중 대표적인 것을 기술하였다.The resin composition was kneaded at 200-240 ° C. using a 30-screw twin screw compounder, and a matt container was prepared using a blow molding machine, an injection blow molding machine, or an injection stretching hollow molding machine. The following examples describe a representative of these.

비교예 1∼3Comparative Examples 1 to 3

성분 1로는 호모폴리프로필렌 (이하 호모 PP) 및 랜덤폴리프로필렌 (이하 랜덤 PP)을, 성분 2로는 선형 고밀도 폴리에틸렌 (이하 HDPE)을 사용하여 이들의 구성비를 1:1로 하여 중공성형으로 용기를 제조하여 각 특성을 평가하여 하기 표 2에 나타내었다. 비교예 2 및 3의 무광특성은 우수하였으나, 충격강도 및 감촉성은 비교예 1, 2 및 3 모두 열세로 나타났다.Component 1 was used as homopolypropylene (hereinafter homo PP) and random polypropylene (hereinafter random PP), and component 2 was linear high density polyethylene (hereafter HDPE) to make a container in blow molding with a composition ratio of 1: 1. Each property was evaluated and shown in Table 2 below. Although the matt properties of Comparative Examples 2 and 3 were excellent, the impact strength and the touchability were inferior in all of Comparative Examples 1, 2 and 3.

비교예Comparative example 구성비Composition ratio 무광특성Matte property 충격강도Impact strength 감촉성Touch 성분 1Ingredient 1 성분 2Component 2 성분 3Ingredient 3 1One 호모 PP 50%1)(용융지수2)16)Homo PP 50% 1) (melt index 2) 16) HDPE 50%(용융지수 0.3)HDPE 50% (melt index 0.3) -- 중medium 하Ha 딱딱함crustiness 22 랜덤 PP 50%(용융지수 1.8)Random PP 50% (melt index 1.8) HDPE 50%(용융지수 0.04)HDPE 50% (melt index 0.04) -- 상Prize 하Ha 딱딱함crustiness 33 랜덤 PP 40%(용융지수 6.0)Random PP 40% (melt index 6.0) HDPE 40%(용융지수 0.04)HDPE 40% (melt index 0.04) 라디칼 개시제400 ppmRadical initiator400 ppm 상Prize 하Ha 딱딱함crustiness

1) %는 중량%이다.1)% is% by weight.

2) 용융지수의 단위는 dg/min이다.2) The unit of melt index is dg / min.

실시예 1∼5Examples 1-5

하기 실시예에서는 성분 1로 용융지수 1.8 dg/min의 랜덤폴리프로필렌 (랜덤 PP) 수지를 사용하고, 성분 2로는 용융지수 0.04 dg/min의 고밀도 폴리에틸렌 (HDPE) 및 성분 3으로는 임팩트폴리프로필렌 (임팩트 PP), 에틸렌-프로필렌공중합체 (EPR) 또는 에틸렌-프로필렌-다이엔 삼원공중합체 (EPDM)를 사용하였다. 상기 조성물을 용융압출시켜 제품을 만든 후, 중공성형기기에서 압출온도는 160∼230℃로, 금형온도는 0∼20℃로 하여 중공성형 용기를 제조하였다.In the examples below, random polypropylene (random PP) resin with a melt index of 1.8 dg / min is used as component 1, high density polyethylene (HDPE) with a melt index of 0.04 dg / min and component polyimpact polypropylene (component 3) Impact PP), ethylene-propylene copolymer (EPR) or ethylene-propylene-diene terpolymer (EPDM). After melt-extruding the composition to make a product, a blow molding container was prepared at an extrusion temperature of 160 to 230 ° C. and a mold temperature of 0 to 20 ° C. in a blow molding machine.

성분 1, 2 및 3의 조성비의 변화에 따라서 중공성형으로 성형된 용기의 무광특성, 충격강도 및 감촉성을 평가한 결과를 하기 표 3에 나타내었다.Table 3 shows the results of evaluating the matting properties, impact strength, and feel of the containers molded by blow molding according to the change of the composition ratios of the components 1, 2, and 3.

본 발명의 폴리올레핀 수지 조성물의 무광특성은 종래의 기술과 동등 또는 동등 이상으로 나타났으며, 종래 기술의 문제점인 충격강도가 현저히 개선되었고, 감촉성도 아주 부드러운 결과가 얻어졌다. 도 1은 실시예 1에 따라 제조된 화장품 용기 표면의 전자현미경 사진이다.The matte properties of the polyolefin resin composition of the present invention appeared to be equivalent or equivalent to that of the prior art, and the impact strength, which is a problem of the prior art, was remarkably improved, and the feel was also very soft. 1 is an electron micrograph of the surface of the cosmetic container prepared according to Example 1.

실시예Example 구성비Composition ratio 무광특성Matte property 충격강도Impact strength 감촉성Touch 성분 1Ingredient 1 성분 2Component 2 성분 3Ingredient 3 1One 랜덤PP 40%Random PP 40% HDPE 40%HDPE 40% 임팩트PP 20%Impact PP 20% 상Prize 중medium 약간 부드러움Slightly soft 22 랜덤PP 30%1) Random PP 30% 1) HDPE 30%HDPE 30% 임팩트PP 40%Impact PP 40% 상Prize 상Prize 약간 부드러움Slightly soft 33 랜덤PP 40%Random PP 40% HDPE 40%HDPE 40% EPR 20%EPR 20% 상Prize 상Prize 부드러움Softness 44 랜덤PP 30%Random PP 30% HDPE 30%HDPE 30% EPR 40%EPR 40% 상Prize 상Prize 부드러움Softness 55 랜덤PP 40%Random PP 40% HDPE 40%HDPE 40% EPDM 20%EPDM 20% 상Prize 상Prize 부드러움Softness

1) %는 중량%이다.1)% is% by weight.

상기 비교예 및 실시예에서 알 수 있는 바와 같이, 본 발명에 따른 조성물을 이용하여 제조된 제품은 용기제작 후 부식, 코팅 등의 후가공처리 없이 표면에 미세한 요철이 형성하게 되어 빛이 난반사 되어 무광특성을 가지게 되며, 종래 기술의 문제점인 충격강도가 우수하게 되어 보관, 운송 및 사용할 때 발생할 수 있는 용기의 파손 문제가 개선되었고, 감촉성이 우수하여 고급스러운 용기 제조가 가능하게 되었다.As can be seen in the comparative examples and examples, the product manufactured by using the composition according to the present invention after the container is manufactured, fine irregularities are formed on the surface without post-processing such as corrosion, coating, so that the light is diffusely reflected to the matte characteristics It will have a, the impact strength of the problem of the prior art has been improved, the problem of breakage of the container that can occur when storage, transport and use is improved, and the excellent texture is possible to manufacture a high-quality container.

Claims (4)

용융지수가 10 dg/min 이하이고, 25 중량% 이하의 에틸렌을 포함하는 랜덤 폴리프로필렌 수지 20∼45 중량%;20-45 wt% of a random polypropylene resin having a melt index of 10 dg / min or less and containing 25 wt% or less of ethylene; 용융지수가 1.0 dg/min 이하인 고밀도 폴리에틸렌 20∼45 중량%; 및20 to 45% by weight of high density polyethylene having a melt index of 1.0 dg / min or less; And 25 중량% 이하의 에틸렌을 포함하는 에틸렌-프로필렌 블록공중합체, 30∼80 중량%의 에틸렌을 포함하는 에틸렌-프로필렌공중합체(EPR) 또는 에틸렌-프로필렌-다이엔 삼원공중합체(EPDM)로 이루어진 군으로부터 하나 또는 그 이상이 10∼60 중량%로 필수적으로 구성되는 것을 특징으로 하는 무광특성, 충격강도 및 감촉성이 우수한 중공성형용 폴리올레핀 수지 조성물.Group consisting of ethylene-propylene block copolymers containing up to 25% by weight of ethylene, ethylene-propylene copolymers containing 30 to 80% by weight of ethylene (EPR) or ethylene-propylene-diene terpolymers (EPDM) The polyolefin resin composition for blow molding excellent in matt, impact strength and feel, characterized in that consisting essentially of one to more than 10 to 60% by weight from. 제 1항에 있어서, 상기 조성물이 소광제로 평균입자크기가 1∼10㎛의 실리카(SiO2) 및 착색제 0.01∼1 중량%를 더욱 포함하는 것을 특징으로 하는 무광특성, 충격강도 및 감촉성이 우수한 중공성형용 폴리올레핀 수지 조성물.2. The composition of claim 1, wherein the composition further comprises silica (SiO 2 ) having a mean particle size of 1 to 10 μm and a coloring agent of 0.01 to 1 wt% as a matting agent. Polyolefin resin composition for blow molding. 제 1항에 따른 조성물을 단층구조 또는 표면 층으로 하는 2층 이상의 적층구조를 갖도록 중공성형, 사출중공성형 및 사출연신중공성형한 것을 특징으로 하는 제품.The product according to claim 1, wherein the composition according to claim 1 has a single layer structure or a laminated structure having two or more layers as a surface layer. 제 3항에 있어서, 상기 제품은 일회용 용기, 화장품 용기 및 세제 용기인 것을 특징으로 하는 제품.4. The product of claim 3, wherein the product is a disposable container, a cosmetic container, and a detergent container.
KR1019980054550A 1998-12-11 1998-12-11 Polyolefin resin composition excellent in non-polish, impact-resistance, soft touch and products thereof KR20000039269A (en)

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KR100645663B1 (en) * 2001-12-14 2006-11-13 에스케이 주식회사 Compositions for wrap film and method for preparing wrap film using the same
KR100842161B1 (en) * 2007-03-27 2008-06-27 삼성토탈 주식회사 Excellent izod impact strength polypropylene composition having superior flowability and glossless property
KR100855333B1 (en) * 2007-09-06 2008-09-04 현대이피 주식회사 Polypropylene complex resin composition without glossing for automobile
US8674028B2 (en) 2007-10-22 2014-03-18 Dow Global Technologies Llc Polymeric compositions and processes for molding articles
KR102255797B1 (en) * 2020-01-07 2021-05-25 주식회사 천경 Resin composition for mascara container and mascara container made from the resin

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