KR100234151B1 - Resin for pellet and composition thereof - Google Patents

Resin for pellet and composition thereof Download PDF

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KR100234151B1
KR100234151B1 KR1019950048798A KR19950048798A KR100234151B1 KR 100234151 B1 KR100234151 B1 KR 100234151B1 KR 1019950048798 A KR1019950048798 A KR 1019950048798A KR 19950048798 A KR19950048798 A KR 19950048798A KR 100234151 B1 KR100234151 B1 KR 100234151B1
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polyethylene
density polyethylene
pallets
polyfunctional acrylate
modified resin
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KR970042632A (en
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김국중
하현수
장재권
정영태
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서갑석
대한유화공업주식회사
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
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    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/08—Butenes
    • C08F210/10—Isobutene
    • C08F210/12—Isobutene with conjugated diolefins, e.g. butyl rubber
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    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/40—Esters of unsaturated alcohols, e.g. allyl (meth)acrylate
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/06—Butadiene
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    • 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
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/08—Isoprene
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F253/00—Macromolecular compounds obtained by polymerising monomers on to natural rubbers or derivatives thereof
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
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    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

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Abstract

본 발명은 폴리에틸렌에 다관능성아크릴레이트게 화합물을 첨가하여 가교 및 체인 익스텐션 반응을 일으켜 높은 생산성 및 고강성을 가질 수 있는 팰릿(Pallet)용 개질 수지 및 폴리에틸렌에 다관능성아크릴레이트계 화합물과 천연 또는 합성 고무 성분 또는 폴리프로필렌을 배합하여 가교 및 체인 익스텐션 반응시켜 얻은 팰릿용수지 조성물에 관한 것이다. 또한 가교 및 체인 익스텐션 반응을 일으킬 때 유기과산화물을 첨가하여 개질화시키는 것도 개시한다. 본 발명의 개질 수지 및 그 조성물은 종래 사용되고 있는 일반적인 폴리에틸렌조성물보다 월등한 충격강도, 인장강도, 굴곡탄성율, 경도를 나타내면서도 멜트 플로우 인덱스의 큰 저하없이 스파이럴 플로우가 아주 양호하여 높은 생산성을 나타낸다.The present invention is natural or synthetic with a polyfunctional acrylate compound in a modified resin for pallets and polyethylene which can add a polyfunctional acrylate crab compound to polyethylene to cause crosslinking and chain extension reactions and thus have high productivity and high rigidity. The present invention relates to a pallet resin composition obtained by blending a rubber component or polypropylene with crosslinking and chain extension reaction. It also discloses the addition and modification of organic peroxides when causing crosslinking and chain extension reactions. The modified resin and the composition of the present invention exhibit superior impact strength, tensile strength, flexural modulus, and hardness than the general polyethylene composition used in the past, and exhibit very high spiral flow without high drop in the melt flow index, resulting in high productivity.

Description

팰릿(Pallet)용 수지 조성물Resin composition for pallet

본 발명은 물품운송 및 저상등에 사용되는 팰릿용 수지조성물에 관한 것이다. 더 상세히는 과거에 나무로 만들어졌던 팰릿을 대체한 플라스틱 팰릿을 제조하는데 사용되는 합성수지를 특별한 방법으로 생산성 및 기계적 물성을 개량시킨 수지조성물에 관한 것이며, 구체적으로는 폴리에틸렌등에 유기과산화물 가교촉진제인 다관능성 아크릴레이트계 모노머를 적량 첨가한 뒤 적절한 전단력하에서 반응압출시켜 고생산성, 고충격성 및 고강성을 나타낼 수 있는 수지조성물에 관한 것이다.The present invention relates to a resin composition for pallets used for transportation of goods and low phase. More specifically, the present invention relates to a resin composition in which productivity and mechanical properties are improved by a special method of synthetic resins used to manufacture plastic pallets replacing wood pallets, and in particular, polyfunctional organic peroxide crosslinking accelerators such as polyethylene. The present invention relates to a resin composition capable of exhibiting high productivity, high impact, and high rigidity by adding an appropriate amount of an acrylate monomer and then extruding the reaction under an appropriate shear force.

현재 플라스틱제 팰릿에 사용되는 합성수지로는 폴리에틸렌, 폴리프로필렌, 아크릴로니트릴부타디엔스티렌공중합체, 불포화폴리에스테르, 폴리우레탄, 염화비닐수지, 스티롤수지등이 있으나 가격과 물성의 면에서 가장 많이 사용되고 있는 것은 폴리올레핀이며, 그 중에서도 폴리에틸렌이다. 이러한 합성수지를 사용한 팰릿의 예는 US 5213050A, EP-368595-A, EP-589483A1, DE4207727A1등의 특허에 많이 나타나 있으나 이들은 비범용 또는 범용합성수지를 개질하지 않고 그대로 사용하거나 또는 여러 종류를 브렌드해서 사용하여 팰릿의 모양을 약간씩 바꾸는 수준에 그쳐 실제로 가격과 생산성 및 물성을 모두 만족하지 못하고 있는 실정이다. 또 J05213355의 합성수지로 만든 팰릿에 관한 일본 특허에는 폴리에틸렌을 1.05~1.5 정도로 발포시켜 양호한 강성과 치수안정성을 가지는 팰릿을 제조할 수 있다고 되어 있으나 단순히 알파올레핀이 포함된 폴리에틸렌을 발포시킨 재질로는 충분한 생산성과 기계적물성을 모두 충족시킬 수가 없다. 즉, 생산성이 양호하면 기계적 물성이 저하되고 기계적 물성이 양호하면 생산성이 떨어지는 상반된 결과를 낳고 있는 실정이다.Synthetic resins currently used in plastic pallets include polyethylene, polypropylene, acrylonitrile butadiene styrene copolymers, unsaturated polyesters, polyurethanes, vinyl chloride resins, and styrol resins. Polyolefin, among them, polyethylene. Examples of such pellets using synthetic resins are described in many US Pat. Nos. 52,13050A, EP-368595-A, EP-589483A1, DE4207727A1, etc. Only a slight change in the shape of the pallet does not really satisfy both the price, productivity and properties. In addition, the Japanese patent on pallets made of synthetic resin of J05213355 says that foams with good stiffness and dimensional stability can be produced by foaming polyethylene at about 1.05 to 1.5. Both mechanical and mechanical properties cannot be satisfied. In other words, if the productivity is good, the mechanical properties are lowered, and if the mechanical properties are good, the situation is that the productivity is lowered.

이에 본 발명자들은 가격과 생산성과 기계적물성을 모두 고려하여 가격적인면을 해결하기 위해서는 폴리올레핀을 사용하였고 생산성과 물성의 면을 해결하기위해서는 폴리올레핀을 특수한 방법으로 분자구조를 개질하여 본 발명을 완성하기에 이르렀다.Therefore, the present inventors used polyolefin to solve the price side in consideration of both price, productivity, and mechanical properties, and to solve the aspect of productivity and physical properties, the polyolefin was modified in a special way to complete the present invention. Reached.

본 발명에 사용된 폴리올레핀은 주로 폴리에틸렌이며 여기에는 고밀도폴리에틸렌, 저밀도폴리에틸렌, 성형저밀도폴리에틸렌, 알파올레핀공중합폴리에틸렌 등이 포함되며 폴리에틸렌이 충격강도 향상목적으로 이피엠고무, 이피디엠, 폴리부타디엔, 이소프렌고무, 부틸고무등의 합성고무가 첨가될 수 있으며 폴리에틸렌의 강성향상 목적으로 에틸렌프로필렌블록 및 랜덤공중합체, 호모폴리프로필렌등이 첨가될 수도 있는데, 이 경우 첨가함량은 0~50중량% 범위이면 적당하다. 본 발명에 사용된 폴리에틸렌의 개질방법은 가교반응과 체인익스텐션반응인데, 일반적으로 이러한 목적으로 사용되는 방법으로는 유기과산화물(이하 물질 Ⅰ로 명명)첨가, 실란계화합물첨가, 전자선조사등이 있는데 이러한 방법의 단점은 충분한 물성을 나타낼 수 있을 정도까지 반응을 진행시키면 멜트플로우인덱스가 매우 낮아져서 생산성이 극히 저하된다는 것이다. 이에 본 발명자들은 고생산성을 유지하기 위해 높은 멜트플로우인덱스를 가지면서도 아주 양호한 기계적 물성을 나타낼 수 있도록 다관능성아크릴에티트계화합물(이하 물질Ⅱ로 명명) 단독 혹은 물질Ⅰ과 물질Ⅱ를 병용하여 적절한 전단력하에서 반응압출시켜 본 발명을 완성하였다.Polyolefins used in the present invention are mainly polyethylene, and include high density polyethylene, low density polyethylene, molded low density polyethylene, alpha olefin copolyethylene, etc., and polyethylene is EPM rubber, EPDM, polybutadiene, isoprene rubber, Synthetic rubber such as butyl rubber may be added, and ethylene propylene block, random copolymer, homopolypropylene, etc. may be added for the purpose of improving the rigidity of polyethylene. In this case, the content is appropriate in the range of 0 to 50% by weight. Modification methods of polyethylene used in the present invention are crosslinking reactions and chain extension reactions. Generally, methods used for this purpose include adding organic peroxides (hereinafter referred to as substance I), adding silane compounds, and electron beam irradiation. The disadvantage of the method is that if the reaction proceeds to the extent that sufficient physical properties can be exhibited, the melt flow index is very low and the productivity is extremely low. In order to maintain high productivity, the inventors of the present invention have a high melt flow index and have a good multifunctional acryl ethane compound (hereinafter referred to as substance II) alone or in combination with substance I and substance II so as to exhibit very good mechanical properties. The present invention was completed by reaction extrusion under shear force.

물질 Ⅱ로는 디펜타에리트리톨모노하이드록시아크릴레이트, 트리메틸올프로판트리아크릴레이트, 네오펜틸글리콜하이드록시피바레이트디아크릴레이트, 1,4-부탄디올디아크릴레이트, 1, 6-헥산디올디아크릴레이트, 펜타에리트리톨트리아크릴레이트, 에틸렌글리콜디메타크릴레이트, 트리에틸렌글리콜디메타크릴레이트, 테트라에틸렌글리콜디메타크릴레이트, 1, 3-부틸렌글리콜디메타크릴레이트, 트리메틸올프로판트리메타크릴레이트, 아릴메타크릴레이트 등이 있으며 적절한 함량은 0.001~1.0중량%인데 0.001중량% 이하 첨가되면 충분한 물성을 나타낼 수 없으며, 1.0중량%이상 첨가되면 멜트플로우인덱스가 너무 낮아지는 단점이 있으므로 바람직하게는 0.005~0.4중량% 이다. 또한 물질 Ⅰ과의 병용시에는 상승작용이 일어나므로 이 경우 바람직한 물질 Ⅱ의 함량은 0.005~0.3중량%이며 물질 Ⅰ로는 벤조일퍼록사이드, 디큐밀퍼록사이드,,'-비스(t-부틸퍼록시)-디아이소프로필벤젠, 1, 3-비스(t-부틸퍼록시)벤젠, N-부틸-4, 4-비스(t-부틸퍼록시)발러레이트 같은 현재 사용되고 있는 일반적인 물질 I이 적용될 수 있으나 그 함량은 0.0001~0.1중량%가 적당하며, 물질 II를 2종이상 조합하여 사용할 수도 있다. 그러나 아크릴레이트계 화합물이 아닌 트리아릴시아누레이트, 트리아릴아이소시아누레이트, 엠페닐렌비스말레이미드 같은 다른 종류의 다관능성 모노머를 사용하면 본 발명의 효과를 완성할 수가 없다.As substance II, dipentaerythritol monohydroxyacrylate, trimethylolpropane triacrylate, neopentyl glycol hydroxy pibarate diacrylate, 1,4-butanediol diacrylate, 1, 6-hexanediol diacrylate , Pentaerythritol triacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1, 3-butylene glycol dimethacrylate, trimethylolpropane trimethacrylate , Aryl methacrylate, etc., and the appropriate content is 0.001% to 1.0% by weight, but when added below 0.001% by weight, sufficient physical properties cannot be exhibited, and when it is added above 1.0% by weight, the melt flow index is too low. It is -0.4 weight%. In addition, synergism occurs when used in combination with substance I. In this case, the content of preferred substance II is 0.005 to 0.3% by weight. As substance I, benzoyl peroxide, dicumyl peroxide, , '-Bis (t-butylperoxy) -diaisopropylbenzene, 1, 3-bis (t-butylperoxy) benzene, N-butyl-4, 4-bis (t-butylperoxy) valerate The general substance I used may be applied, but its content is appropriately 0.0001 to 0.1% by weight, and may be used in combination of two or more kinds of substances II. However, the use of other types of multifunctional monomers such as triarylcyanurate, triarylisocyanurate and emphenylenebismaleimide, which are not acrylate compounds, cannot achieve the effects of the present invention.

또한 이러한 방법으로 폴리올레핀을 개질시킬 때는 최종제품의 멜트플로우인스덱스를 고려하여 적절한 가공조건을 부여하는 것이 중요한데 100의 트윈스크류를 기준으로 적당한 체류시간은 1분~10분, 가공온도는 160℃~270℃ 범위내에서 해야 한다. 만약 압출기내 체류시간이 지나치게 길거나 가공온도가 지나치게 높으면 가교 및 체인익스텐션 반응이 과도하게 일어나 멜트플로우인덱스가 너무 떨어져 고생산성을 기대할 수 없으며, 체류시간이 지나치게 짧거나 가공온도가 지나치게 낮으면 원하는 만큼의 물성향상을 얻을 수 없으므로 가공조건의 조절이 필수적이며 이렇게 생산된 최종 개질폴리올레핀의 멜트플로우인덱스는 1~12(그램/10분)가 적당하며, 이 제품으로 팰릿 제조시 발포도가 1~2.0 범위이면 본 발명을 완성할 수가 있다.In addition, when modifying the polyolefin in this way, it is important to give appropriate processing conditions in consideration of the melt flow index of the final product. The proper residence time should be within 1 ~ 10 minutes and the processing temperature should be within 160 ℃ ~ 270 ℃. If the residence time in the extruder is too long or the processing temperature is too high, the crosslinking and chain extension reaction will be excessive and the melt flow index will be too low to expect high productivity.If the residence time is too short or the processing temperature is too low, It is essential to control the processing conditions because it is not possible to obtain the improvement of physical properties, and the melt flow index of the final modified polyolefin produced in this way is 1 to 12 (grams / 10 minutes), and the foaming range when producing pellets with this product is in the range of 1 to 2.0. The present invention can be completed.

이하 본 발명을 실시예를 들어 상세히 설명한다. 본 발명의 실시예에는 폴리올레핀 및 다관능성아크릴레이트계의 몇가지 예만 나타낸 것이며, 전술한 모든 종류의 것은 균동물이므로 이에대한 실시예는 생략하며, 본 발명의 범위가 이들 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples. In the embodiment of the present invention, only a few examples of polyolefins and polyfunctional acrylates are shown, and all of the above-described types are fungal animals, and thus embodiments thereof are omitted, and the scope of the present invention is not limited to these examples.

[실시예 1~3][Examples 1-3]

고밀도플로에틸렌(대한유화 M850)에 펜타에리트리톨트리아크릴레이트를 각각 0.1, 0.2, 0.3중량% 처방하여 1002축 스크류압출기(L/D 30)에서 260℃, 체류시간 8분의 조건으로 콤파운딩을 행한 뒤 각각의 MF1 및 spiral flow를 측정했으며, 40사출기에서 230℃, 1000kgf/㎠의 압력으로 사출시편을 제작한 후 물성을 분석하여 표 2에 나타내었다. 표 2의 각종 항목은 표 1에 나타낸 방법으로 분석하였다. 표 1에서 spiral flow는 사출기에서 일정한 압력으로(500~1300kgf/㎤) 사출을 했을 때 spiral 형태로 성형된 전체길이를 cm로 나타낸 것이며, 이것은 유동성의 척도이며 spiral flow가 높을수록 cycle time을 줄일 수 있어 생산성이 향상된다.100% by formulating 0.1, 0.2, 0.3% by weight of pentaerythritol triacrylate in high density polyethylene (MOH) Compounding was carried out in a twin screw extruder (L / D 30) at 260 ° C and residence time of 8 minutes, and then the respective MF1 and spiral flows were measured. After preparing the injection specimen at 230 ℃, 1000kgf / ㎠ pressure in the injection machine and analyzed the physical properties are shown in Table 2. Various items in Table 2 were analyzed by the method shown in Table 1. In Table 1, the spiral flow shows the total length, in cm, formed in the spiral form when the injection is carried out at a constant pressure (500 to 1300 kgf / cm 3) in the injection molding machine. Productivity is improved.

[실시예 4~6]EXAMPLES 4-6

고밀도폴리에틸렌(대한유화 M850)에 EPM(EXXON VISTALON503)을 5중량%혼합한 뒤 펜타에리트리톨트리아크릴레이트를 각각 0.1, 0.2, 0.3중량% 첨가하여 실시예 1~3과 동일한 방법으로 콤파운딩 및 물성분석을 행하여 표 2에 나타내었다.5% by weight of EPM (EXXON VISTALON503) was mixed with high-density polyethylene (Korea Emulsified M850), and then 0.1, 0.2, and 0.3% by weight of pentaerythritol triacrylate were added to the compounding and physical properties in the same manner as in Examples 1 to 3. The analysis is shown in Table 2.

[실시예 7~9]EXAMPLES 7-9

고밀도폴리에틸렌(대한유화 M850)에 물질 I로서 1, 3-비스(t-부틸페록시이소프로필)벤젠을 각각 0.03중량%, 펜타에리트리톨트리아크릴레이트를 각각 0.1, 0.2, 0.3중량%, 첨가하여 실시예 1~3과 동일한 방법으로 콤파운팅 및 물성분석을 행하여 표 2에 나타내었다.0.03% by weight of 1, 3-bis (t-butylperoxyisopropyl) benzene and 0.1, 0.2, 0.3% by weight of pentaerythritol triacrylate, respectively, were added to the high density polyethylene (Korea Emulsification M850) Compounding and physical property analysis were performed in the same manner as in Examples 1 to 3, and the results are shown in Table 2.

[실시예 10~12][Examples 10-12]

물질 Ⅱ로서 펜타에리트리톨트리아크릴레이트 및 프로폭시레이티드글리세롤트리아크릴레이트를 동량으로 혼합하여 이 혼합물을 고밀도폴리에틸렌(대한유화 M850)에 각각 0.1, 0.2, 0.3중량% 첨가하여 실시예 1~3과 동일한 방법으로 콤파운팅 및 물성분석을 행하여 표 2에 나타내었다.As the substance II, pentaerythritol triacrylate and propoxylated glycerol triacrylate were mixed in the same amount, and the mixture was added to the high density polyethylene (Korean emulsified M850) by 0.1, 0.2 and 0.3% by weight, respectively. Compounding and physical property analysis in the same manner is shown in Table 2.

[비교예 1~3][Comparative Examples 1-3]

고밀도폴리에틸렌(대한유화 M850 및 M850P) 단독 미 고밀도폴리에틸렌에EPM(EXXON WISTALON503)을 5중량% 혼합하여 실시예 1~3과 동일한 방법으로 콤파운딩 및 물성분석을 행하여 표 2에 나타내었다.High density polyethylene (Korean emulsification M850 and M850P) 5% by weight of the mixture of EPM (EXXON WISTALON503) in the United States high density polyethylene alone, the compounding and physical properties were analyzed in the same manner as in Examples 1 to 3 shown in Table 2.

[비교예 4~7][Comparative Examples 4-7]

고밀도폴리에틸렌(대한유화 M850)에 물질 Ⅰ인 1,3-비스(t-부틸페록시-이소프로필) 벤젠을 각각 0.01, 0.1, 0.2, 0.3중량% 첨가하여 실시예 1~3과 동일한 방법으로 콤파운딩 및 물성분석을 행하여 표 2에 나타내었다.0.01, 0.1, 0.2, 0.3 wt% of 1,3-bis (t-butylperoxy-isopropyl) benzene as the substance I was added to high-density polyethylene (Korea Emulsification M850), respectively, in the same manner as in Examples 1-3. Compounding and physical property analysis are shown in Table 2.

[비교예 8~10][Comparative Example 8 ~ 10]

고밀도폴리에틸렌에 다른 다관능성모노머인 트리아릴아이소시아누레이트를 0.1, 0.2, 0.3중량%를 첨가하여 실시예 1~3과 동일한 방법으로 콤파운딩 및 물성분석을 행하여 표 2에 나타내었다.Compounds and physical properties were analyzed in the same manner as in Examples 1 to 3 by adding 0.1, 0.2, and 0.3 wt% of triarylisocyanurate, which is another polyfunctional monomer, to high-density polyethylene.

A ; 펜타에리트리톨트리아크릴레이트A; Pentaerythritol triacrylate

B ; 1,3-비스(t-부틸페록시이소프로필)벤젠B; 1,3-bis (t-butylperoxyisopropyl) benzene

C ; 프로폭시레이티드글리세롤트리아크릴레이트C; Propoxylated Glycerol Triacrylate

D ; 트리아릴아이소시아누레이트D; Triarylisocyanurate

상기 표에서 실시예 1~12의 각 항목은 비교예 1~3의 현재 사용되고 있는 일반적인 폴리에틸렌조성물보다 월등한 충격강도, 인장강도, 굴곡탄성율, 경도를 나타내면서도 MFI의 큰 저하없이 spiral flow가 아주 양호하여 고생산성을 나타낼 수 있으며, 비교예 4~10처럼 물질Ⅰ 또는 다른 종류의 다관능성모노머를 사용하면 생산성과물성의 조화를 이룰 수 없다.In the above table, each item of Examples 1 to 12 shows superior impact strength, tensile strength, flexural modulus, and hardness than the general polyethylene composition used in Comparative Examples 1 to 3, but the spiral flow is very good without a significant decrease in MFI. High productivity can be exhibited, and when using the material I or other kinds of multifunctional monomers as in Comparative Examples 4 to 10, the productivity and the physical properties cannot be achieved.

Claims (11)

폴리에틸렌에 다관능성 아크릴레이트계 화합물을 첨가하여 가교 및 체인 익스텐션 반응시켜 얻은 멜트 플로우 인덱스가 2~7인 팰릿용 개질 수지.A modified resin for pallets having a melt flow index of 2 to 7 obtained by adding a polyfunctional acrylate compound to polyethylene and crosslinking and chain extension reaction. 제1항에 있어서, 폴리에틸렌이 고밀도 폴리에틸렌임이 특징인 팰릿용 개질수지.The modified resin for pallets according to claim 1, wherein the polyethylene is a high density polyethylene. 제1항에 있어서, 폴리에틸렌이 고밀도 폴리에틸렌과 선형 저밀도 폴리에틸렌, 중밀도 폴리에틸렌, 저밀도 폴리에틸렌으로 구성된 군에서 선택된 1종 또는 2종 이상을 조합한 것을 사용함이 특징인 팰릿용 개질 수지.The modified resin for pallets according to claim 1, wherein the polyethylene is one selected from the group consisting of high density polyethylene, linear low density polyethylene, medium density polyethylene, and low density polyethylene. 제1항에 있어서, 고밀도폴리에틸렌에 대해 선형 저밀도 폴리에틸렌, 중밀도 폴리에틸렌, 저밀도 폴리에틸렌으로 구성된 군에서 선택된 1종 또는 2종이상이 20중량% 이하로 배합된 것을 사용함이 특징인 개질 수지.The modified resin according to claim 1, wherein one or two or more selected from the group consisting of linear low density polyethylene, medium density polyethylene, and low density polyethylene is used in an amount of 20% by weight or less based on high density polyethylene. 제1항에 있어서, 다관능성 아크릴레이트계 화합물이 헥사아크릴레이트카프로락톤모디파이드디펜타에리트리톨, 디펜타에리트리톨모노하이드록시아크릴레이트, 트리메틸올프로판트리아크릴레이트, 네오펜틸글리콜하이드록시피바레이트디아크릴레이트, 1, 4-부탄디올디아크릴레이트, 1, 6-헥산디올디아크릴레이트, 펜타에리트리톨트리아크릴레이트, 에틸렌글리콜디메타크릴레이트, 트리에틸렌글리콜디메타크릴레이트, 테트라에틸렌글리콜디메타크릴레이트, 1, 3-부틸렌글리콜디메타크릴레이트, 트리메틸올프로판트리메타크릴레이트, 아릴메타크릴레이트로 이루어진 군에서 선택되고, 그 함량이 0.001~1,0중량%를 사용하여 제조한 개질 수지.2. The polyfunctional acrylate compound according to claim 1, wherein the polyfunctional acrylate compound is hexaacrylate caprolactone modified dipentaerythritol, dipentaerythritol monohydroxy acrylate, trimethylol propane triacrylate, neopentyl glycol hydroxy pibarate Diacrylate, 1, 4- butanediol diacrylate, 1, 6-hexanediol diacrylate, pentaerythritol triacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimetha Modified by using acrylate, 1, 3-butylene glycol dimethacrylate, trimethylolpropane trimethacrylate, aryl methacrylate, the content is prepared using 0.001 to 1,0% by weight Suzy. 제1항에 있어서 개질화 반응에 개시제로서 유기 과산물을 사용하여 제조한 팰릿용 개질 수지.The modified resin for pallets of Claim 1 manufactured using organic peroxide as an initiator in a reforming reaction. 제6항에 있어서, 개시제로서 벤조일퍼옥사이드, 디큐밀퍼옥사이드,,'-비스(t-부틸퍼옥시)-디아이소프로필벤젠, 1, 3-비스(t-부틸퍼옥시이소프로필)벤젠 또는 N-부틸-4, 4-비스(t-부틸퍼옥시) 발러레이트를 사용하여 제조한 팰릿용 개질 수지.The method of claim 6, wherein as the initiator benzoyl peroxide, dicumyl peroxide, , '-Bis (t-butylperoxy) -diaisopropylbenzene, 1, 3-bis (t-butylperoxyisopropyl) benzene or N-butyl-4, 4-bis (t-butylperoxy) valerate Modified resin for pallets prepared using. 폴리에틸렌에 다관능성아크릴레이트계 화학물과 천연 또는 합성 고무성분을 배합하여 가교 및 체인 익스텐션 반응시켜 얻은 팰릿용 수지 조성물.A resin composition for pallets obtained by blending polyfunctional acrylate-based chemicals with polyethylene or natural or synthetic rubber components and carrying out crosslinking and chain extension reactions. 제8항에 있어서, 합성고무가 에틸렌프로필렌고무, 에틸렌프로필렌디엔고무, 폴리부타디엔, 이소프렌고무, 부틸고무에서 선택되고, 그 함량이 50중량% 이하인 것이 특징인 팰릿용 수지조성물.The resin composition according to claim 8, wherein the synthetic rubber is selected from ethylene propylene rubber, ethylene propylene diene rubber, polybutadiene, isoprene rubber, and butyl rubber, and its content is 50% by weight or less. 폴리에틸렌에 다관능성아크릴레이트계 화합물과 폴리프로필렌을 배합하여 가교 및 체인 익스텐션 반응시켜 얻은 팰릿용 수지 조성물.A resin composition for pallets obtained by blending a polyfunctional acrylate compound and a polypropylene with polyethylene, followed by crosslinking and chain extension reaction. 제10항에 있어서, 폴리프로필렌이 에틸렌프로필렌랜덤 또는 블록공중합체, 호모폴리프로필렌에서 선택되고, 그 함량이 20중량% 이하인 팰릿용 수지조성물.The resin composition according to claim 10, wherein the polypropylene is selected from ethylene propylene random or block copolymer and homo polypropylene, and its content is 20% by weight or less.
KR1019950048798A 1995-12-12 1995-12-12 Resin for pellet and composition thereof KR100234151B1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR970065596A (en) * 1996-03-20 1997-10-13 마르코위츠 스티븐 에이치 Masterbatch Blends for the Production of Polyolefin Products

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR970065596A (en) * 1996-03-20 1997-10-13 마르코위츠 스티븐 에이치 Masterbatch Blends for the Production of Polyolefin Products

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