KR100316364B1 - Multilayer sheet improved with impact resistance and weatherability - Google Patents
Multilayer sheet improved with impact resistance and weatherability Download PDFInfo
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- KR100316364B1 KR100316364B1 KR1019970058084A KR19970058084A KR100316364B1 KR 100316364 B1 KR100316364 B1 KR 100316364B1 KR 1019970058084 A KR1019970058084 A KR 1019970058084A KR 19970058084 A KR19970058084 A KR 19970058084A KR 100316364 B1 KR100316364 B1 KR 100316364B1
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- resin
- sheet
- styrene
- multilayer sheet
- butadiene
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- 229920005989 resin Polymers 0.000 claims abstract description 91
- 239000011347 resin Substances 0.000 claims abstract description 91
- 239000004417 polycarbonate Substances 0.000 claims abstract description 42
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 40
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 35
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 35
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims abstract description 30
- 239000002344 surface layer Substances 0.000 claims abstract description 19
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 7
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229920001971 elastomer Polymers 0.000 claims abstract description 3
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 3
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 3
- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 3
- 239000005060 rubber Substances 0.000 claims abstract description 3
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 claims abstract 2
- 229920001577 copolymer Polymers 0.000 claims abstract 2
- 239000010410 layer Substances 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 3
- 238000009966 trimming Methods 0.000 claims description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims 1
- 239000003063 flame retardant Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 5
- 230000032798 delamination Effects 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 238000001125 extrusion Methods 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012994 photoredox catalyst Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
Abstract
Description
본 발명은 내후성 및 내충격성이 향상된 다층시트에 관한 것으로서, 더욱 상세하게는 폴리메틸메타아크릴레이트 수지로 표면층을 구성하고 아크릴로니트릴-부타디엔-스티렌과 폴리카보네이트가 혼합된 혼합수지로 지지층을 구성하고 있어 강성, 내후성 및 내충격성이 향상된 다층시트에 관한 것이다.The present invention relates to a multi-layered sheet having improved weather resistance and impact resistance, and more particularly, to form a support layer using a mixed resin of acrylonitrile-butadiene-styrene and polycarbonate mixed with a surface layer composed of polymethylmethacrylate resin. The present invention relates to a multilayer sheet having improved rigidity, weather resistance, and impact resistance.
종래에는 옥외에 장시간 노출되는 야외용 제품, 차량용 외장부품의 경우에 아크릴로니트릴-부타디엔-스티렌 수지(이하 "ABS 수지"라 함)가 주로 사용되었으나 자외선에 의한 변색과 기계적인 물성의 저하가 초래되는 문제가 있다. 또한, 폴리메틸메타아크릴레이트 수지(이하, "PMMA 수지"라 함)는 내후성은 우수하나 내충격성이 약하고 반면에 폴리카보네이트 수지(이하 "PC 수지"라 함)는 내충격성은 강하나 내후성이 다소 미흡하고 가격이 비싼 단점이 있다.Conventionally, acrylonitrile-butadiene-styrene resins (hereinafter referred to as "ABS resins") are mainly used for outdoor products and automotive exterior parts that are exposed to the outdoors for a long time, but discoloration due to ultraviolet rays and deterioration of mechanical properties are caused. there is a problem. In addition, polymethyl methacrylate resin (hereinafter referred to as "PMMA resin") has excellent weather resistance but low impact resistance, whereas polycarbonate resin (hereinafter referred to as "PC resin") has a high impact resistance but somewhat poor weather resistance. The disadvantage is the high price.
한편, 철도차량의 실내부품의 경우는 유리섬유 강화플라스틱(이하, "FRP"라 함)이 사용되고 있으나, 작업공정상의 어려움과 환경문제 때문에 열가소성 플라스틱으로의 대체가 요구되고 있다. 따라서 FRP와 같은 강성 및 충격특성을 가지면서 또한 내후성도 우수한 열가소성 수지 조성물의 개발이 필요하게 되었다.On the other hand, in the case of the interior parts of the railway vehicle, glass fiber reinforced plastic (hereinafter referred to as "FRP") is used, but due to the difficulties in the work process and environmental problems it is required to replace the thermoplastic plastic. Therefore, it is necessary to develop a thermoplastic resin composition having rigidity and impact characteristics such as FRP and excellent weatherability.
최근에는 ABS 수지, PC 수지, PMMA 수지를 각각 단독으로 시트를 제작하는 대신에 이들 수지의 장점들을 조합할 수 있는 공압출방법을 통하여 PMMA/ABS 수지, PC/ABS 수지 등을 이용한 다층시트가 개발되었다.Recently, multilayer sheets using PMMA / ABS resin, PC / ABS resin, etc. have been developed through co-extrusion method that can combine the advantages of these resins instead of producing sheets of ABS resin, PC resin, and PMMA resin alone. It became.
이러한 종래기술로는 미국특허 제 4,731,213 호, 일본특허공고 소 62-113527호 및 대한민국특허공고 제 90-3824 호에는 PMMA 수지와 ABS 수지의 공압출물이 개시되어 있고, 유럽특허 제 283,861 호에는 ABS 수지와 PMMA 수지 또는 PC 수지의 공압출물이 개시되어 있다. 그리고 미국특허 제 5,069,851 호와 일본특허공고 평 5-501388 호에는 PMMA 수지와 ABS 수지의 라미네이팅된 시트에 관하여 각각 개시되어 있다.As such conventional techniques, US Pat. No. 4,731,213, Japanese Patent Publication No. 62-113527, and Korean Patent Publication No. 90-3824 disclose coextrusion of PMMA resin and ABS resin, and European Patent No. 283,861 discloses ABS resin. And coextrusion of PMMA resin or PC resin. And US Patent No. 5,069,851 and Japanese Patent Application Laid-open No. Hei 5-501388 disclose laminated sheets of PMMA resin and ABS resin, respectively.
그러나, 이러한 공지기술에서는 각 수지간의 상용성 차이에 의한 결합력의 결여 문제, 유동특성의 차이에 기인하는 계면 불안정성과 같은 압출공정상의 어려움 때문에 단지 제한된 수지들간의 조합만이 가능하였다. 옥외용 차량부품이나 철도차량 내장재에 적합하도록 ASTM D256에 따라서 측정한 아이조드 충격강도(Izod impaet, 3.2mm)가 70 kgfcm/cm 이상의 값을 갖고 ASTM D256에 따라서 측정한 변색도 /E(폭로시간 5년)가 2이하의 값을 갖는 다층시트는 아직 개발되지 못하였다.However, in this known technology, only limited combinations of resins were possible due to difficulties in the extrusion process such as lack of bonding force due to compatibility differences between resins and interfacial instability due to differences in flow characteristics. Izod impaet (3.2 mm) measured according to ASTM D256 to be suitable for outdoor vehicle parts or interior materials of railway vehicles with a value of 70 kgfcm / cm or more, and discoloration degree / E measured according to ASTM D256 (5 years exposure time) Has not been developed yet.
본 발명자들은 상기의 문제점을 개선하고자 노력한 결과, 아크릴 수지인 PMMA 수지와 ABS/PC 혼합수지를 이용하여 내후성이 우수하고 내충격성이 뛰어나며 가격 경쟁력을 갖춘 다층시트를 제공하는데 그 목적이 있다.The present inventors have made an effort to improve the above problems, an object of the present invention is to provide a multilayer sheet having excellent weather resistance, excellent impact resistance and competitive price by using PMMA resin and ABS / PC mixed resin, which is an acrylic resin.
도 1은 본 발명에 따른 다층시트의 표면층과 지지층의 폴리메틸메타아크릴레이트 수지(PMMA 수지)와 아크릴로니트릴-부타디엔-스티렌/폴리카보네이트 혼합수지(ABS/PC 혼합수지)의 전단속도 범위와 점도비를 나타낸 그래프이다.1 is a shear rate range and viscosity of a polymethyl methacrylate resin (PMMA resin) and an acrylonitrile-butadiene-styrene / polycarbonate mixed resin (ABS / PC mixed resin) of the surface layer and the support layer of the multilayer sheet according to the present invention. It is a graph showing the ratio.
본 발명은 공압출한 다층시트에 있어서, PMMA 수지로 표면층을 구성하고 ABS/PC 혼합수지로 지지층을 구성하고 있는 다층시트를 그 특징으로 한다.The present invention is characterized in that, in the coextruded multilayer sheet, the multilayer sheet constitutes the surface layer of PMMA resin and the support layer of ABS / PC mixed resin.
이와 같은 본 발명을 더욱 상세히 설명하면 다음과 같다.Referring to the present invention in more detail as follows.
본 발명에서는 PMMA 수지를 표면층으로 도입시켜 내후성과 우수한 외관특성의 효과를 얻고, ABS 수지와 PC 수지를 혼합한 혼합수지를 지지층에 도입시켜 이들 각각의 단독 수지를 사용한 경우에서는 기대할 수 없었던 내충격성, 압출성형성, 가격경쟁력을 동시에 만족시키는 효과를 갖는 다층시트에 관한 것이다.In the present invention, the PMMA resin is introduced into the surface layer to obtain the effect of weather resistance and excellent appearance characteristics, and the impact resistance that was not expected in the case of using each of these individual resins by introducing a mixed resin mixed with ABS resin and PC resin to the support layer, The present invention relates to a multilayer sheet having an effect of simultaneously satisfying extrusion molding and cost competitiveness.
본 발명의 표면층으로 사용되는 PMMA 수지는 충격보강을 목적으로 부틸아크릴레이트 고무, 부타디엔 고무가 그라프트 될 수 있다.PMMA resin used as the surface layer of the present invention can be grafted butyl acrylate rubber, butadiene rubber for the purpose of impact reinforcement.
그리고, 지지층에 사용되는 ABS/PC 혼합수지는 ABS 수지와 PC 수지가 혼합형태를 갖는 혼합수지로서, ABS 수지를 단독으로 사용한 경우는 충격이 약하고, PC 수지를 단독으로 사용한 경우는 압출성형성이 떨어지고 가격이 고가인데 반하여 혼합수지는 내충격성, 압출성형설, 가격경쟁력이 모두 우수하다. ABS/PC 혼합수지에는 PC 수지가 50 ∼ 80 중량% 포함되어 있는데, 만일 PC 수지 함유량이 50 중량% 미만이면 목표물성을 얻기 어렵고, 80 중량%를 초과하면 유동성 저하에 의한 성형상의 문제가 발생한다. 또한, ABS/PC 혼합수지는 제품의 요구특성에 따라서 UL 94-5VA의 시험방법에 의해서 특정된 난연도가 HB ∼ V-0 값으로 조절될 수있다.In addition, the ABS / PC mixed resin used in the support layer is a mixed resin in which the ABS resin and the PC resin have a mixed form, and when the ABS resin is used alone, the impact is weak. While the price is low and the price is high, the mixed resin has excellent impact resistance, extrusion molding, and price competitiveness. The ABS / PC blend resin contains 50 to 80 wt% of PC resin, but if the PC resin content is less than 50 wt%, it is difficult to obtain the target properties, and if it exceeds 80 wt%, molding problems occur due to fluidity decrease. . In addition, the ABS / PC mixture resin can be adjusted to the HB to V-0 value specified by the test method of UL 94-5VA according to the required characteristics of the product.
상기와 같은 본 발명의 기술적 핵심은 사용된 각각의 수지의 유동학적 거동 차이를 조절하는데 있다. 첨부도면 도 1에 나타낸 바와 같이 공압출시의 전단 속도의 범위는 10 ∼ 1,000 sec-1이고, 상기 전단속도 범위 내에서의 점도비는 2 : 1 이하를 유지하도록 하는 것이 바람직하다. 즉, 수지의 합류지점인 피드블럭 내에서 각 수지의 상대적인 용융온도에서의 점도값의 비가 일정한 값이하로 유지되어야 하는 바, 이는 계면에서의 유동 안정성이 유지되어야하기 때문이다.The technical core of the present invention as described above is to control the difference in the rheological behavior of each resin used. As shown in FIG. 1, the shear rate at the time of co-extrusion is 10 to 1,000 sec -1 , and the viscosity ratio within the shear rate range is preferably maintained at 2: 1 or less. In other words, the ratio of the viscosity values at the relative melting temperatures of each resin in the feed block, which is the confluence point of the resins, should be kept below a constant value, because the flow stability at the interface should be maintained.
PMMA 수지로 구성된 다층시트의 표면층은 전체 두께의 5 ∼ 20% 내로 구성되어야 하매, 단면 또는 양면구조를 사용하여 구성할 수 있다. 만일 표면층이 전체 두께의 5% 미만이면 계면이 불안정하여 파도모양의 불량현상이 나타나며 결합력이 떨어지고 내후성도 저하되는 문제가 있고, 20%를 초과하면 시트의 내충격성이 급격히 저하되는 문제가 있다. 그리고, 표면층을 구성하는 PMMA 수지를 착색하면 내후성이 향상되는 효과를 얻을 수 있다.The surface layer of the multilayer sheet composed of PMMA resin should be composed within 5 to 20% of the total thickness, and can be configured using a single-sided or double-sided structure. If the surface layer is less than 5% of the total thickness, there is a problem that the interface is unstable, the appearance of a wave-like defect, the bonding strength is lowered and the weather resistance is also lowered, if the surface layer exceeds 20% there is a problem that the impact resistance of the sheet is sharply reduced. And when PMMA resin which comprises a surface layer is colored, the effect which weather resistance improves can be acquired.
다층시트의 제조 및 트리밍시에 발생되는 분량을 획수하는 경우에는 회수층을 전체 두께의 50%내로 형성시키며 회수층 내에서의 PMMA 수지 함유량을 5 중량% 이내로 유지하여야 한다. 만일 5 중량%를 초과하면 시트의 물성이 저하되고 내화학성이 떨어져 우레탄이나 FRP에 의한 후보강 작업시에 크랙의 가능성이 있다.In the case of extracting the amount generated during the manufacture and trimming of the multilayer sheet, the recovery layer should be formed within 50% of the total thickness and the PMMA resin content in the recovery layer should be kept within 5% by weight. If it exceeds 5% by weight, the physical properties of the sheet may be lowered and the chemical resistance may be lowered, and there is a possibility of cracking when working with candidate steel by urethane or FRP.
이와 같은 본 발명을 제조과정에 의거하여 더욱 상세하게 설명하면 다음과같다.The present invention will be described in more detail based on the manufacturing process as follows.
피드블럭내에서 융용상태의 PMMA 수지의 온도를 240 ∼ 260℃로 조절하고, ABS/PC 혼합수지의 온도를 220 ∼ 240℃로 조절하여 상기 PMMA 수지의 온도차가 20℃이하가 되도록 한 다음 두 수지를 합류시키면 전단속도의 범위가 상기 범위를 만족하고, 그 범위 내에서의 점도비가 2 : 1 이하로 된다. 만일, PMMA 수지와 ABS/PC 혼합수지간의 온도차가 20℃를 초과하면 낮은 전단속도 영역인 다이내에서의 열전달로 인하여 유동균형이 깨지게 되며 특히 다이의 양 끝부분에서는 점도가 높은 수지가 점도가 낮은 수지를 포위하는 문제가 발생된다. 그리고 다층시트 제조시에 ABS/PC 혼합수지를 220℃ 보다 낮은 온도로 압출하면 유동성 저하에 의하여 압출기내에 심한 부하가 발생되어 바람직하지 않다. 또한 PMMA 수지를 260℃ 이상으로 압출하면 수지의 열화에 의한 가스발생과 표면불량 문제가 발생한다.In the feed block, the temperature of the melted PMMA resin is adjusted to 240 to 260 ° C and the temperature of the ABS / PC mixture is adjusted to 220 to 240 ° C so that the temperature difference of the PMMA resin is 20 ° C or less. When it joins, the range of shear rate satisfy | fills the said range and the viscosity ratio in that range will be 2: 1 or less. If the temperature difference between PMMA resin and ABS / PC mixed resin exceeds 20 ℃, the flow balance is broken due to heat transfer in the die, which is a low shear rate region. Especially, high viscosity resin at both ends of die has low viscosity. Problems surrounding the resin arise. In addition, when the ABS / PC mixed resin is extruded at a temperature lower than 220 ° C. during the manufacture of the multilayer sheet, a heavy load is generated in the extruder due to a decrease in fluidity. In addition, when the PMMA resin is extruded above 260 ° C, gas generation and surface defects due to resin deterioration occur.
다층시트 제조시의 압출기의 압출속도는 20 ∼ 100 rpm 으로 조절하고 압출량의 상대적인 비로 다층구조를 조정하며, 로울러의 온도는 50 ∼ 100℃이어야 하는데 온도가 50℃ 미만이면 급냉으로 인하여 수지의 배향현상이 심해지고, 100℃를 초과하면 PMMA 수지가 로울러에 달라붙는 현상이 나타나므로 바람직하지 않다.The extrusion speed of the extruder in the manufacture of the multilayer sheet is adjusted to 20 to 100 rpm and the multilayer structure is adjusted by the relative ratio of the extrusion amount, and the roller temperature should be 50 to 100 ° C. It is not preferable because the phenomenon becomes severe and when the temperature exceeds 100 ° C., the phenomenon that the PMMA resin sticks to the roller appears.
상술한 바와 같이 본 발명의 다층시트는 PMMA 수지를 표면층으로 하고 ABS/PC 혼합수기를 지지층으로 사용하여 공압출을 통하여 제조됨으로써 계면의 접착이 우수하고 충분리가 일어나지 않으며 내후성이 우수하고 내충격성이 향상되어 종래의 스티렌계 단층시트등이 갖지 못하는 여러 장점이 있고 야외용 차량외장품, 열차 내장재 등의 시트로 유용하게 사용할 수 있다.As described above, the multilayer sheet of the present invention is manufactured through coextrusion using PMMA resin as the surface layer and ABS / PC mixed water as the support layer, so that the adhesion of the interface is excellent and does not sufficiently occur, the weather resistance is excellent, and the impact resistance is improved. There are many advantages that the conventional styrene-based single-layer sheet, etc. do not have and can be usefully used as a seat for outdoor vehicle exterior, train interior materials and the like.
이와 같은 본 발명을 실시예에 의거하여 상세하게 설명하겠는 바, 본 발명이 실시예에 한정되는 것은 아니다.Although this invention is demonstrated in detail based on an Example, this invention is not limited to an Example.
실시예 1 : ABS/PC 혼합수지의 혼합비율에 따른 다층시트의 물성 변화Example 1 Change of Physical Properties of Multi-layered Sheet According to Mixing Ratio of ABS / PC Mixed Resin
PMMA 수지를 표면층으로 구성하되, 전체 다층시트 두께의 10 ∼ 20%가 되도록 구성하고, 지지층으로는 ABS/PC 혼합수지로 구성하되, ABS/PC 혼합수지중의 PC 수지를 다음 표 1에 나타낸 함량으로 지지층을 구성하였다. 그리고, 표면층을 구성하는 PMMA 수지와 지지층을 구성하는 ABS/PC 혼합수지의 온도차를 20℃로 공압출하여 다층시트를 제작하였다.The PMMA resin is composed of a surface layer, but is composed of 10 to 20% of the total thickness of the multi-layer sheet, and the support layer is composed of ABS / PC mixed resin, and the PC resin in the ABS / PC mixed resin is shown in Table 1 below. The support layer was constructed. The temperature difference between the PMMA resin constituting the surface layer and the ABS / PC mixed resin constituting the support layer was coextruded at 20 ° C. to prepare a multilayer sheet.
이때 사용한 압출기 1은 ABS/PC 혼합수지용 압출기이고, 압출기 2는 PMMA 수지용 압출기로서 사용조건은 다음과 같다.The extruder 1 used at this time is an extruder for ABS / PC mixed resin, and the extruder 2 is an extruder for PMMA resin.
〈압출기 1〉〈Extruder 1〉
구경 : 120 mmCaliber: 120 mm
스크류 : 40 L/DScrew: 40 L / D
스크류회전수 : 36 rpmScrew rotation speed: 36 rpm
〈압출기 2〉〈Extruder 2〉
구경 : 65 mmCaliber: 65 mm
스크류 : 30 L/DScrew: 30 L / D
스크류회전수 : 25 rpmScrew Speed: 25 rpm
다이온도는 수지의 흐름을 따라 210℃에서 제작하였고, 폴리싱 로울러의 온도는 70℃로 조절하였다. 이와 같은 방법으로 제작된 시트의 두께는 5mm이며 표면층의 두께는 전체 두께의 10%이었다.The die temperature was produced at 210 ° C along the flow of the resin, and the temperature of the polishing roller was adjusted to 70 ° C. The thickness of the sheet produced in this manner was 5 mm and the thickness of the surface layer was 10% of the total thickness.
그런다음, 제작된 다층시트의 물성을 측정하기 위하여 인장강도 및 신율은 ASTM D638에 의하여 측정하였고, 굴곡강도는 ASTM D790에 의하였고, 아이조드 충격 강도는 ASTM D256에 의하였고, 열변형온도는 ASTM D648에 의하였으며 변색도는 ASTM D2565에 의하여 측정하였다.Then, the tensile strength and elongation were measured according to ASTM D638, the flexural strength was according to ASTM D790, the Izod impact strength was according to ASTM D256, and the heat deflection temperature was ASTM D648. Color change was measured according to ASTM D2565.
상기 표 1에 의하면, 지지층을 구성하기 위해 도입된 ABS/PC 혼합수지의 경우 그 혼합비율에 따라 시료의 물성이 크게 달라지는 바, 예컨대 본 발명에 따라PC 수기가 50 ∼ 80 중량% 범위내로 혼합된 경우 아이조드 충격강도가 70 kgfcm/cm 이상의 값을 갖고, 변색도(ΔE)가 2이하의 값을 가지며, 계면불안정성이나 그 밖의 압출공정상의 어려움이 전혀 없어 옥외용 차량부품이나 철도차량 내장재로 유용하다. 그러나. PC 수지의 혼합량이 50 중량% 미만인 경우에는 목표물성이 미달되는 결과를 초래하였고, 80 중량%를 초과하면 유동성 저하로 인한 압출기내에 과부하가 발생하여 시트제작이 불가능하였다.According to the above Table 1, in the case of the ABS / PC mixed resin introduced to form a support layer, the physical properties of the sample largely vary according to the mixing ratio, for example, the PC water group mixed in the range of 50 to 80% by weight according to the present invention. In this case, the Izod impact strength has a value of 70 kgfcm / cm or more, a discoloration degree (ΔE) of 2 or less, and there is no interface instability or other difficulty in the extrusion process, which is useful for outdoor vehicle parts or railway vehicle interior materials. But. When the amount of the PC resin was less than 50% by weight, the target physical properties were less than the result. When the amount of the PC resin was more than 80% by weight, the sheet was impossible due to the overload in the extruder due to the deterioration of the fluidity.
실시예 2Example 2
상기 실시예 1에서 표면층으로 PMMA 수지를 전체 다층시트 두께의 10 ∼ 20%가 되도록 구성하고, 지지층으로는 ABS/PC 혼합수지로 구성하되, ABS/PC 혼합수지중의 PC 수지의 함량이 70 중량%로 구성된 다층시트의 제작과정 중에서 PMMA 수지와 ABS/PC 혼합수지의 유동성을 측정하기 위하여 각 수지의 상대적인 용융온도 즉, 두 수지의 온도차를 20℃ 이내로 하여 전단속도 변화에 따른 정도값을 모세관 점도계로 측정한 다음 그 결과를 첨부도면 도 1에 나타내었다.In Example 1, the surface layer is composed of PMMA resin to be 10 to 20% of the total thickness of the multi-layer sheet, the support layer is composed of ABS / PC mixed resin, the content of PC resin in the ABS / PC mixed resin is 70% by weight In order to measure the fluidity of PMMA resin and ABS / PC mixed resin during the manufacturing process of multi-layered sheets, the relative melting temperature of each resin, that is, the temperature difference between the two resins, should be within 20 ° C. After the measurement, the results are shown in FIG. 1.
첨부도면 도 1에 나타낸 바와 같이 공압출시의 전단속도 범위는 10 ∼ 1,000 sec-1이었고, PMMA 수지와 ABS/PC 수지의 점도비는 2 : 1 이하로 되었다.As shown in FIG. 1, the shear rate range during coextrusion was 10 to 1,000 sec −1, and the viscosity ratio of PMMA resin and ABS / PC resin was 2: 1 or less.
상술한 바와 같이, 본 발명의 다층시트는 PMMA 수지를 표면층으로 하고 ABS/PC 혼합수지를 지지층으로 사용하고 이를 공압출을 통하여 제조함으로써 계면 접착이 우수하고 층분리가 일어나지 않으며 내후성이 우수하고 내충격성이 향상되어 종래의 스티렌계 단층시트등이 갖지 못하는 여러 장점이 있고 야외용 차량외장품, 열차 내장재 등의 시트로 유용하게 사용할 수 있음을 알 수 있다.As described above, the multi-layered sheet of the present invention uses the PMMA resin as the surface layer and the ABS / PC mixed resin as the support layer and manufactured by co-extrusion, so that the interfacial adhesion is excellent, the layer separation does not occur, the weather resistance and the impact resistance are excellent. This is improved and it can be seen that there are many advantages that the conventional styrene-based single-layer sheet, etc. do not have and can be usefully used as a seat for outdoor vehicle exterior, train interior materials and the like.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101712416B1 (en) * | 2016-04-22 | 2017-03-06 | 박용필 | Composite sheet having excellent weather-ability |
| KR101712419B1 (en) * | 2016-04-22 | 2017-03-06 | 박용필 | Composite sheet having excellent weather-ability |
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| KR20040019204A (en) * | 2002-08-27 | 2004-03-05 | 주식회사에버그로스 | Multi sheet with excellent UV resistance and impact resistance and Manufacturing thereof |
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| EP0454520A1 (en) * | 1990-04-27 | 1991-10-30 | Société dite : TECHNOPLAST (Société Anonyme) | Method for producing a composite sheet comprising a cast polymethylmethacrylate sheet and a thermoplastic support layer and product obtained in such a way |
| WO1992000843A1 (en) * | 1990-07-09 | 1992-01-23 | Aristech Chemical Corporation | Abs/acrylic lamination process |
| US5318737A (en) * | 1990-05-25 | 1994-06-07 | Rohm And Haas Company | Feedblock coextrusion of modified acrylic capstock |
| JPH08290532A (en) * | 1995-04-21 | 1996-11-05 | Shin Kobe Electric Mach Co Ltd | Transparent multilayered sheet and manufacture thereof |
| KR100222240B1 (en) * | 1995-11-15 | 1999-10-01 | 하영준 | Method for preparing engineering plastic sheets |
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| JPS52144077A (en) * | 1976-05-26 | 1977-12-01 | Sumitomo Chem Co Ltd | Flame-retardant resin composites |
| EP0454520A1 (en) * | 1990-04-27 | 1991-10-30 | Société dite : TECHNOPLAST (Société Anonyme) | Method for producing a composite sheet comprising a cast polymethylmethacrylate sheet and a thermoplastic support layer and product obtained in such a way |
| US5318737A (en) * | 1990-05-25 | 1994-06-07 | Rohm And Haas Company | Feedblock coextrusion of modified acrylic capstock |
| WO1992000843A1 (en) * | 1990-07-09 | 1992-01-23 | Aristech Chemical Corporation | Abs/acrylic lamination process |
| JPH08290532A (en) * | 1995-04-21 | 1996-11-05 | Shin Kobe Electric Mach Co Ltd | Transparent multilayered sheet and manufacture thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101712416B1 (en) * | 2016-04-22 | 2017-03-06 | 박용필 | Composite sheet having excellent weather-ability |
| KR101712419B1 (en) * | 2016-04-22 | 2017-03-06 | 박용필 | Composite sheet having excellent weather-ability |
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