KR100536605B1 - TPO sheet harded by irradiating electron beam and making method thereof - Google Patents

TPO sheet harded by irradiating electron beam and making method thereof Download PDF

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KR100536605B1
KR100536605B1 KR10-2003-0001012A KR20030001012A KR100536605B1 KR 100536605 B1 KR100536605 B1 KR 100536605B1 KR 20030001012 A KR20030001012 A KR 20030001012A KR 100536605 B1 KR100536605 B1 KR 100536605B1
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electron beam
tpo sheet
tpo
sheet
curable
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KR20040063542A (en
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김기성
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한일이화주식회사
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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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/123—Treatment by wave energy or particle radiation
    • 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
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters

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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)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Laminated Bodies (AREA)

Abstract

본 발명은, TPO 시트 및 그 제조방법에 관한 것으로서, TPO 시트에 전자선을 조사하는 단계를 포함하는 것을 특징으로 한다. 이에 의하여 TPO 시트에 가교가 형성되어 내스크래치성이 향상된 TPO시트가 제공된다.The present invention relates to a TPO sheet and a method of manufacturing the same, characterized by comprising irradiating an electron beam to the TPO sheet. As a result, crosslinking is formed in the TPO sheet, thereby providing a TPO sheet having improved scratch resistance.

Description

전자선 경화형 ＴＰＯ시트 및 그 제조방법{TPO sheet harded by irradiating electron beam and making method thereof}TPO sheet harded by irradiating electron beam and making method

본 발명은 TPO 시트 및 그 제조방법에 관한 것으로서, 더욱 상세하게는 가교효율을 증대시켜 내스크래치성을 향상시킨 자동차 내장재용 TPO 시트 및 그 제조방법에 관한 것이다.The present invention relates to a TPO sheet and a method for manufacturing the same, and more particularly, to a TPO sheet for automotive interiors and a method for manufacturing the same, which has improved cross-linking efficiency to improve scratch resistance.

헤드라이너, 도어트림, 인스트루먼트 패널 등, 자동차 내장 표피재로서 종래에는 폴리비닐 클로라이드(PVC)시트가 주로 사용되어 왔다. 종래에 사용되던 폴리비닐 클로라이드(PVC)시트에는 대개 가공성을 개량하는 물질인 가소제가 첨가되어 있는데, 이러한 가소제는 불쾌한 냄새를 발생시킨다는 단점이 있다. 또한 폴리비닐 클로라이드(PVC)시트는 염소분자를 함유하고 있는 바, 이러한 염소분자는 인체에 유해하다는 문제점이 있다.BACKGROUND ART Polyvinyl chloride (PVC) sheets have conventionally been mainly used as automotive interior skin materials such as headliners, door trims, and instrument panels. Polyvinyl chloride (PVC) sheet used in the prior art is usually added a plasticizer which is a material for improving processability, such a plasticizer has the disadvantage of causing an unpleasant odor. In addition, the polyvinyl chloride (PVC) sheet contains a chlorine molecule, there is a problem that such chlorine molecules are harmful to the human body.

상기와 같은 종래의 자동차 내장재 시트의 문제점을 극복하기 위하여 근래에는 고무 및 올레핀계 수지를 함유한 TPO(ThermoPlastic Olefin)시트를 자동차 내장재용 시트로 사용하고 있다.In order to overcome the problems of the conventional automotive interior sheet as described above, TPO (ThermoPlastic Olefin) sheets containing rubber and olefin resins have recently been used as automotive interior sheets.

한편 자동차 내장 표피재는 자동차 조립시 발생할 수 있는 긁힘이나, 자동차의 사용시 다른 물건과의 마찰, 또는 자외선 등 외부환경으로 부터의 자극에 대해 견딜 수 있는 내성이 있어야 한다. 그러나 종래 자동차 내장재로 사용되고 있는 TPO 시트는 외부자극에 대해 견딜 수 있는 특성, 즉, 내스크래치성이 결여되어 있다는 문제점이 있다.On the other hand, the car interior skin should be resistant to scratches that may occur during car assembly, friction with other objects when using the car, or stimulation from the external environment such as ultraviolet rays. However, the conventional TPO sheet used as a vehicle interior has a problem in that it is resistant to external stimuli, that is, scratch resistance.

따라서 본 발명의 목적은, TPO 시트를 구성하는 조성물에 전자선을 조사하여 가교를 형성함으로써 내스크래치성이 향상된 TPO시트 및 그 제조방법을 제공하는 것이다.It is therefore an object of the present invention to provide a TPO sheet having improved scratch resistance and a method for producing the same by irradiating an electron beam to the composition constituting the TPO sheet to form a crosslink.

상기 목적은, 본 발명에 따라, TPO 시트의 제조방법에 있어서, TPO 시트에 전자선을 조사하는 단계에 의하여 달성된다.According to the present invention, in the method for producing a TPO sheet, the object is achieved by irradiating an electron beam to the TPO sheet.

여기서, 상기 전자선은, 25 내지 50℃에서, 300 내지 1000kv의 전압이 2 내지 10Mrad으로 조사되는 것이 바람직하다.Here, the electron beam is preferably irradiated with a voltage of 300 to 1000kv at 2 to 10Mrad at 25 to 50 ° C.

한편, 상기 TPO 시트의 제조시, 가교조제를 첨가하는 단계를 더 포함하는 것이 바람직하며, 상기 가교조제는, 불포화기를 가지며, 전자선에 의해 자유라디칼이 개시가능한 단량체 또는 그 들의 혼합물이다.On the other hand, in the production of the TPO sheet, it is preferable to further include a step of adding a crosslinking aid, the crosslinking aid is a monomer having a unsaturated group, free radicals can be initiated by an electron beam or a mixture thereof.

상기 단량체는, 다관능성 메타크릴레이트 단량체 또는 다관능성 비닐단량체이며 상기 다관능성 메타크릴레이트 단량체는, 디비닐벤젠, 트리알릴시아누레이트, 트리메틸올프로판, 니트로소벤젠, 디페닐구아니딘 또는 에틸렌글리콜디메타크릴레이트로 이루어진 군에서 선택되는 어느 하나이고, 상기 다관능성 비닐단량체는, 비닐부티레이트, 비닐스테아레이트 중 어느 하나인 것이 바람직하다.The monomer is a polyfunctional methacrylate monomer or a polyfunctional vinyl monomer, and the polyfunctional methacrylate monomer is divinylbenzene, triallyl cyanurate, trimethylolpropane, nitrosobenzene, diphenylguanidine or ethylene glycol di It is any one selected from the group which consists of methacrylate, It is preferable that the said polyfunctional vinyl monomer is any one of vinyl butyrate and vinyl stearate.

또한 상기 가교조제는, 0.1 내지 1.5중량부로 첨가되는 것이 효과적이다.In addition, the crosslinking aid is effective to be added at 0.1 to 1.5 parts by weight.

본 발명의 목적은 본 발명의 또 다른 분야에 따르면, 상기 제조방법에 의해 제조되어 가교가 형성된 전자선 경화형 TPO 시트에 의해서 달성된다.According to another field of the present invention, an object of the present invention is achieved by the electron beam-curable TPO sheet prepared by the above production method and crosslinked.

여기서 상기 TPO 시트는 10 내지 40%의 가교율을 가지는 것이 효과적이다.Here, it is effective that the TPO sheet has a crosslinking rate of 10 to 40%.

이하, 본 발명을 상세하게 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

통상의 TPO 시트 수지는 폴리올레핀계 수지와 올레핀계 공중합체 고무와의 혼합물로 조성된다.The usual TPO sheet resin is composed of a mixture of polyolefin resin and olefin copolymer rubber.

폴리올레핀계 수지는 고분자량의 고체생성물로, 1종 또는 2종 이상의 모노올레핀을 고압법 또는 중압법에 의해 중합하여 얻을 수 있으며, 모노올레핀으로는 에틸렌, 프로필렌, 1-부텐, 1-펜텐, 1-핵산, 1-옥텐, 2-메틸-1-프로펜, 3-메틸-1-펜텐 등이 있다. Polyolefin resin is a high molecular weight solid product, which can be obtained by polymerizing one or two or more monoolefins by a high pressure method or a medium pressure method, and monoolefins are ethylene, propylene, 1-butene, 1-pentene, 1 -Nucleic acid, 1-octene, 2-methyl-1-propene, 3-methyl-1-pentene and the like.

한편 올레핀계 공중합체 고무는 올레핀 단위체를 가지며, 에틸렌-α-올레핀(예컨대, 프로필렌, 1-부텐, 1-헥센, 1-옥텐)공중합체 고무, 에틸렌-α-올레핀(예컨대, 1-부텐, 1-헥센, 1-옥텐)비공액 디엔계 공중합체 고무(예컨대, 에틸렌-프로필렌 공중합체 고무(EPM), 에틸렌 프로필렌 디공액 공중합체 고무(EPDM), 에틸렌-1-부텐 비공액 디엔 공중합체 고무) 및, α-올레핀 공액 디엔 공중합체 고무(예컨대 프로필렌-부타디엔 공중합체 고무로 구성되는 군으로 부터 선택되는 적어도 1종이다.On the other hand, the olefin copolymer rubber has an olefin unit, ethylene-α-olefin (eg propylene, 1-butene, 1-hexene, 1-octene) copolymer rubber, ethylene-α-olefin (eg 1-butene, 1-hexene, 1-octene nonconjugated diene copolymer rubber (e.g., ethylene-propylene copolymer rubber (EPM), ethylene propylene diconjugated copolymer rubber (EPDM), ethylene-1-butene nonconjugated diene copolymer rubber) ) And an α-olefin conjugated diene copolymer rubber (for example, at least one member selected from the group consisting of propylene-butadiene copolymer rubber).

상기의 조성물에 의한 TPO 시트는 내후성 및 내스크래치성이 결여되어 있으므로 내스크래치성 및 내후성을 보강하기 위하여 본 발명은 TPO 시트에 전자선을 조사한다. 전자선을 조사하면 TPO 시트의 표면에 경화가 일어나 내스크래치성이 향상된다.Since the TPO sheet according to the composition lacks weather resistance and scratch resistance, the present invention irradiates an electron beam to the TPO sheet in order to reinforce scratch resistance and weather resistance. Irradiation of an electron beam hardens | cures the surface of a TPO sheet | seat, and scratch resistance improves.

일반적으로 폴리프로필렌 수지에 전자선을 조사하는 경우, 전자선 조사에 의해 폴리프로필렌의 분자가 쉽게 절단되어 분자간격이 크게 벌어지고 폴리머의 착색이 일어나며 열안정성이 저하되므로 폴리프로필렌 수지는 전자선을 조사하기에 적당하지 아니하다. 또한 고무는 우수한 탄성을 가지고 있지만 힘을 가하면 변형된 채의 가소성을 가지며 전자선 조사에 의한 가교효율이 그다지 높지 않으므로 전자선을 조사하여 가교를 형성시키기엔 고무 또한 적당하지 아니하다.In general, when irradiating an electron beam to a polypropylene resin, the polypropylene resin is suitable for irradiating an electron beam because the molecules of the polypropylene are easily cleaved by electron beam irradiation, so that the molecular spacing widens, the coloring of the polymer occurs, and the thermal stability decreases. Not In addition, rubber has excellent elasticity, but plasticity remains deformed when a force is applied, and the crosslinking efficiency by electron beam irradiation is not so high. Therefore, rubber is not suitable to form crosslinks by irradiation with electron beams.

따라서 TPO 시트를 구성하는 조성물에 가교조제를 첨가한 후 전자선을 조사하는 것이 가장 바람직하다. Therefore, it is most preferable to irradiate an electron beam after adding a crosslinking adjuvant to the composition which comprises a TPO sheet.

전자선 가교는 상온 및 비교적 높은 온도에서 수행될 수 있으며, 특히 25 내지 50℃의 온도범위가 바람직하다. 전자선 가교시 전압조절에 의해 TPO 시트에 전자선을 전투과 혹은 표면 조사를 수행할 수 있다. 즉, TPO 시트의 두께에 따라 임의의 목적하는 전자선 투과 깊이를 조절할 수 있는데 TPO 시트의 표면경화를 위해서는 표면조사가 바람직하다. Electron beam crosslinking can be carried out at room temperature and relatively high temperature, especially the temperature range of 25 to 50 ℃. By electron beam crosslinking, electron beams can be battled and / or surface irradiated onto the TPO sheet. That is, any desired electron beam penetration depth can be adjusted according to the thickness of the TPO sheet, but surface irradiation is preferable for the surface hardening of the TPO sheet.

전자선의 전투과시 전압의 세기는 500 내지 1,000kv이며, 표면조사시 전압의 세기는 300 내지 400kv, 더욱 바람직하게는 300kv이다.The intensity of the voltage during the battle with the electron beam is 500 to 1,000 kv, and the strength of the voltage during the surface irradiation is 300 to 400 kv, more preferably 300 kv.

전자선 조사시 목적하는 가교율을 발생시키기 위해 전압의 세기에 따라 선량을 2 내지 10Mrad 범위에서 조절할 수 있다.To generate the desired crosslinking rate during electron beam irradiation, the dose may be adjusted in the range of 2 to 10 Mrad depending on the strength of the voltage.

한편 본 발명은 TPO 시트에 전자선을 조사하여 가교를 행하나 상기의 가교율을 높히기 위하여 TPO 시트 조성물에 가교조제 및 보조물질을 첨가하고 동적으로 열처리한 후 압출 및 카렌더 성형장치에 의해 시트를 제조한 다음, 연속적으로 전자선 조사를 적용할 수 있다. 또한 압출 및 카렌더 성형장치에 의해 제조된 TPO시트에 폴리올레핀 발포체를 적층한 후 전자선 조사를 적용할 수 있다.In the present invention, the TPO sheet is crosslinked by irradiation with an electron beam, but in order to increase the crosslinking rate, a crosslinking aid and an auxiliary material are added to the TPO sheet composition and dynamically heat treated, and then the sheet is manufactured by an extrusion and calender forming apparatus. Next, electron beam irradiation can be applied continuously. In addition, the electron beam irradiation may be applied after laminating the polyolefin foam on the TPO sheet produced by the extrusion and calendar molding apparatus.

가교조제는 2개 이상의 불포화기를 갖는 다관능성 모노머로 폴리머들 사이에서 가교역할을 수행하며, 퍼옥사이드 혹은 전자선에 의한 자유 라디칼 개시반응 과정에서 발생되는 폴리머의 분해를 최소화하는 역할을 한다. 가교조제로는 디비닐 벤젠, 트리알릴시아누레이트, 트리메틸올프로판, 니트로소벤젠, 디페닐구아니딘 및, 에틸린 글리콜디메타아크릴레이트, 트리메틸올프로판트리메타크릴레이트, 알릴메타크릴레이트와 같은 다관능성 메타크릴레이트 단량체, 비닐부티레이트, 비닐스테아레이트와 같은 다관능성 비닐단량체가 적합하다. 또한 가교조제의 첨가량은 0.1 내지 1.5중량부이며 더욱 바람직하게는 0.3 내지 0.5중량부이다. 또한 상기 중량부 범위하에서 1종 이상의 가교조제를 혼합 첨가할 수 있다.The crosslinking aid is a multifunctional monomer having two or more unsaturated groups, performs a crosslinking role between the polymers, and minimizes decomposition of the polymer generated during the free radical initiation reaction by peroxide or electron beam. Crosslinking aids include polyvinyl benzene, triallyl cyanurate, trimethylolpropane, nitrosobenzene, diphenylguanidine, and multi-tubes such as ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate. Polyfunctional vinyl monomers such as functional methacrylate monomers, vinyl butyrate, vinyl stearate are suitable. In addition, the addition amount of a crosslinking adjuvant is 0.1-1.5 weight part, More preferably, it is 0.3-0.5 weight part. In addition, one or more crosslinking aids may be mixed and added in the above weight part range.

한편 가교조제와 TPO 수지의 혼합 방법으로는 반바리 믹서 혹은 통상의 혼련믹서가 사용되며 필요에 따라 무기 충전제, 산화방지제, 내후제, 대전방지제, 착색제를 배합할 수 있다. On the other hand, as a method of mixing the crosslinking aid and the TPO resin, a short-barrier mixer or a conventional kneading mixer is used, and an inorganic filler, an antioxidant, a weathering agent, an antistatic agent, and a coloring agent may be blended as necessary.

상기의 조성물을 압출 혹은 카렌더 성형 방식에 의해 소정의 시트를 제조한 다음 TPO조성물을 가교결합시킨다. The sheet is prepared by extrusion or calender molding, and then crosslinks the TPO composition.

상기의 전자선 조사 과정을 통하여 가교된 TPO 시트의 가교율은 10 내지 40%가 적당하며 더욱 바람직하게는 10 내지 20%가 적당하다. 조사된 TPO 시트의 가교도는 ASTM D-2765에 따른 용매 추출법에 의해 측정될 수 있다.The crosslinking ratio of the TPO sheet crosslinked through the electron beam irradiation process is appropriately 10 to 40%, more preferably 10 to 20%. The degree of crosslinking of the irradiated TPO sheets can be measured by solvent extraction according to ASTM D-2765.

이하는 실시예로서 본 발명을 더욱 상세히 설명하며 본 발명의 범위를 한정짓는 것은 아니다.The following describes the invention in more detail by way of examples and does not limit the scope of the invention.

실시예 1Example 1 실시예 2Example 2 비교실시예1Comparative Example 1 비교실시예2Comparative Example 2 비교실시예3Comparative Example 3 비교실시예4Comparative Example 4 TPO(phr)TPO (phr) 100100 100100 100100 100100 100100 100100 가교조제((phr)Crosslinking Aid ((phr) 0.30.3 0.40.4 0.50.5 0.50.5 -- -- 전압(kv)Voltage (kv) 300300 800800 300300 500500 -- 300300 선량(Mrad)Dose (Mrad) 5.05.0 2.22.2 5.05.0 2.52.5 -- 4.04.0 연필경도Pencil hardness BB BB HH BB 3B3B 2B보다 연성Softer than 2B

상기에 의해서 제조된 TPO 시트는 내스크래치성, 내후성 및 내약품성이 향상되어 외부자극에 의해 쉽게 크랙이 발생되지 않는다. 따라서 표면 특성이 우수한 자동차 내장재인 도어트림, 헤드라이너, 인스트루먼트 패널 등을 제조할 수 있다. The TPO sheet manufactured by the above has improved scratch resistance, weather resistance, and chemical resistance, so that cracks are not easily generated by external stimulation. Therefore, it is possible to manufacture a door trim, a headliner, an instrument panel, etc., which have excellent surface properties.

이상 설명한 바와 같이, 본 발명에 따르면, TPO 시트를 구성하는 조성물에 전자선을 조사하여 가교를 형성함으로써 내스크래치성이 향상된 TPO시트를 제공할 수 있다.As described above, according to the present invention, a TPO sheet having improved scratch resistance can be provided by irradiating an electron beam to the composition constituting the TPO sheet to form a crosslink.

Claims (11)

TPO 시트의 제조방법에 있어서,In the manufacturing method of the TPO sheet, 상기 TPO 시트에 300 내지 400kV의 전압으로 전자선을 조사하여 상기 TPO 시트의 표면을 경화시키는 단계를 포함하는 것을 특징으로 하는 전자선 경화형 TPO 시트의 제조방법.Irradiating an electron beam to the TPO sheet at a voltage of 300 to 400 kV to harden the surface of the TPO sheet. 제1항에 있어서,The method of claim 1, 상기 전자선은, 25 내지 50℃에서 조사되는 것을 특징으로 하는 전자선 경화형 TPO 시트의 제조방법.Said electron beam is irradiated at 25-50 degreeC, The manufacturing method of the electron beam curable TPO sheet | seat characterized by the above-mentioned. 삭제delete 제1항에 있어서,The method of claim 1, 상기 전자선은, 2 내지 10Mrad인 것을 특징으로 하는 전자선 경화형 TPO 시트의 제조방법.The electron beam is a method of producing an electron beam curable TPO sheet, characterized in that 2 to 10Mrad. 제1항에 있어서,The method of claim 1, 상기 TPO 시트의 제조시, 가교조제를 첨가하는 단계를 더 포함하는 것을 특징으로 하는 전자선 경화형 TPO 시트의 제조방법.In the production of the TPO sheet, a method for producing an electron beam-curable TPO sheet further comprising the step of adding a crosslinking aid. 제5항에 있어서,The method of claim 5, 상기 가교조제는, 불포화기를 가지며, 전자선에 의해 자유라디칼이 개시가능한 단량체 또는 그들의 혼합물인 것을 특징으로 하는 전자선 경화형 TPO 시트의 제조방법.The crosslinking aid is an electron beam-curable TPO sheet production method, characterized in that it has a unsaturated group and is a monomer or a mixture thereof in which free radicals can be initiated by an electron beam. 제6항에 있어서,The method of claim 6, 상기 단량체는, 다관능성 메타크릴레이트 단량체 또는 다관능성 비닐단량체인 것을 특징으로 하는 전자선 경화형 TPO 시트의 제조방법.The said monomer is a polyfunctional methacrylate monomer or a polyfunctional vinyl monomer, The manufacturing method of the electron beam hardening type TPO sheet characterized by the above-mentioned. 제7항에 있어서,The method of claim 7, wherein 상기 다관능성 메타크릴레이트 단량체는, 디비닐벤젠, 트리알릴시아누레이트, 트리메틸올프로판, 니트로소벤젠, 디페닐구아니딘 또는 에틸렌글리콜디메타크릴레이트로 이루어진 군에서 선택되는 어느 하나이고, 상기 다관능성 비닐단량체는, 비닐부티레이트, 비닐스테아레이트 중 어느 하나인 것을 특징으로 하는 전자선 경화형 TPO 시트의 제조방법.The polyfunctional methacrylate monomer is any one selected from the group consisting of divinylbenzene, triallyl cyanurate, trimethylolpropane, nitrosobenzene, diphenylguanidine or ethylene glycol dimethacrylate, and the polyfunctional The vinyl monomer is any one of vinyl butyrate and vinyl stearate, The manufacturing method of the electron beam hardening type TPO sheet | seat characterized by the above-mentioned. 제5항에 있어서,The method of claim 5, 상기 가교조제는, 0.1 내지 1.5중량부로 첨가되는 것을 특징으로 하는 전자선 경화형 TPO 시트의 제조방법.The crosslinking aid is added to 0.1 to 1.5 parts by weight of the electron beam curable TPO sheet production method. TPO 시트에 있어서,In the TPO sheet, 상기 제1항, 제2항 및 제4항 내지 제9항 중 어느 한 항에 의해 제조되는 상기 TPO 시트는 가교가 형성된 것을 특징으로 하는 전자선 경화형 TPO 시트.The electron beam-curable TPO sheet according to any one of claims 1, 2 and 4 to 9, wherein the TPO sheet is crosslinked. 제10항에 있어서,The method of claim 10, 상기 TPO 시트는 10 내지 20%의 가교율을 가지는 것을 특징으로 하는 전자선 경화형 TPO 시트.Electron beam curable TPO sheet, characterized in that the TPO sheet has a crosslinking rate of 10 to 20%.
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