CN101265355A - Polylactic acid mixture and forming articles thereof - Google Patents

Polylactic acid mixture and forming articles thereof Download PDF

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CN101265355A
CN101265355A CN 200710020278 CN200710020278A CN101265355A CN 101265355 A CN101265355 A CN 101265355A CN 200710020278 CN200710020278 CN 200710020278 CN 200710020278 A CN200710020278 A CN 200710020278A CN 101265355 A CN101265355 A CN 101265355A
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polylactic acid
blend
heat treatment
temperature
film
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CN 200710020278
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Chinese (zh)
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天 夏
征 徐
赖铮铮
陈敬禄
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东丽纤维研究所(中国)有限公司
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The invention discloses a poly lactic acid mixture and a heat-resistant transparent formed product prepared by the poly lactic acid mixture. The poly lactic acid mixture is prepared by poly lactic acid in an amount of 100 parts by weight, an amide compount in an amount of 0.1 to 10 parts by weight, and a sorbitol compound in an amount of 0.01 to 5 parts by weight through mixing. The invention further discloses a poly lactic acid formed product prepared by the poly lactic acid mixture through heat treatment during forming or after forming. In addition, the poly lactic acid formed product has high transparency and heat-resistance.

Description

聚乳酸共混物及其成型品技术领域本发明涉及高分子领域,具体的说涉及一种聚乳酸共混物以及由这种共混物所制备的具有耐热性能的透明成型品。 A blend of the polylactic acid molded article TECHNICAL FIELD The present invention relates to the field of polymer, specifically relates to a blend of polylactic acid and a transparent molded article having heat resistance produced from such blends. 背景技术近年来,作为食品、饮料用容器、托盘等以及商品外包装盒材料的聚乙烯、聚丙烯、聚酯、尼龙等的消耗量逐年增加。 BACKGROUND ART In recent years, as a food, beverage consumption increases year by year as polyethylene, polypropylene, polyester, nylon and the like containers, trays and packaging of goods cartridge material. 与此相伴随的是,使用后废弃物的量也在不断的增加。 Along with this is the constantly increasing amount of waste after use. 由于这些废弃物的焚烧以及掩埋,带来了各种各样的环境问题。 Because of these waste incineration and landfill, bringing a wide range of environmental issues. 为了解决这些问题,近年来,能够进行生物分解的聚合物正在不断地被使用。 To solve these problems, in recent years, it can be biodegradable polymer is constantly being used. 其中,聚乳酸由于具有相对较高的熔点及其相对较高的机械性能,在工业上被广泛的应用。 Wherein, since polylactic acid has a relatively high melting point and relatively high mechanical properties, it is widely used in industry. 但是当聚乳酸作为食品、饮料用容器、托盘等以及商品外包装盒,除了要求有较高的透明度以外,还要具有一定的热耐性,以防止集装箱运输或是突然温度升高所带来的变形以及不透明等。 However, when polylactic acid as a food, beverage containers, trays and packaging of goods boxes, high transparency is required in addition to outside, but also has a certain heat resistance, or to prevent a sudden temperature rise container transport brought other modifications and opaque. 但是,聚乳酸本身的耐热性不高, 需要通过双向拉伸结晶、或是通过加入大量的填料来提高。 However, the heat resistance of the polylactic acid itself is not high, crystallization requires biaxial stretching, or improved by adding a large amount of filler. 但是双向拉伸膜的制备,需要庞大的设备费用。 But the two-way stretch film production, requires enormous equipment costs. 而通过加入填料而提高耐热性的方法,会导致成型品透明性的显著降低。 The method of the heat resistance is improved by the addition of a filler, it leads to significant reduction in the transparency of the molded product. 在日本专利2000-008349中提出了一种通过双向拉伸制备的耐热性聚乳酸贴窗膜。 It proposed a process for preparing the heat resistance of polylactic acid by biaxially stretched in Japanese Patent No. 2000-008349 film window stickers. 通过双向拉伸而结晶的聚乳酸膜具有一定的耐热性。 The polylactic acid biaxially stretched film is crystallized by having a certain heat resistance. 但是双向拉伸法无法制备较厚的膜/片材。 However, biaxial stretching can not be prepared thicker films / sheets. 且双向拉伸膜的生产需要庞大的设备和厂房投资。 And two-way stretch film production requires a huge investment in plant and equipment. 更进一步来说,双向拉伸膜由于己经部分或完全结晶,不便于二次成型。 Still further, since the biaxially stretched film had partial or complete crystallization, the secondary molding is not easy. 在日本专利H05-504471中提出在聚乳酸混合滑石粉后注射成型,成型品具有较高的耐热温度,但是添加少量的滑石粉也会大大影响聚乳酸的透明性。 After mixing the polylactic acid is proposed talc injection molding, molded articles having higher heat resistance in Japanese Patent No. H05-504471, but adding a small amount of talc will greatly affect the transparency of the polylactic acid. 且在日本专利H08-193165中将滑石粉等作为成核剂添加到聚乳酸中,当注射成型时,实际的结晶速度较慢,且产品较脆。 In Japanese Patent No. H08-193165 and the like in the talc as a nucleating agent is added to polylactic acid when the injection molding, the actual rate of crystallization is slow, and the product more brittle. 在中国专利CN 1539880A中描述了一种含有酚类抗氧剂和酰胺类化合物的聚乳酸组合物,在注射成型时,将成型机的模具温度设置在该聚乳酸组合物的熔融结晶起始温度和玻璃转化温度之间,通过控制成型品中聚乳酸的熔融结晶来实现耐热性的提高。 Describes a polylactic acid composition containing a phenolic antioxidant compound and amides in the Chinese patent CN 1539880A, during injection molding, the mold temperature is set in a molding machine melt crystallization starting temperature of the poly lactic acid composition and between the glass transition temperature, improve the heat resistance is achieved by control of melt crystallization in the molded article of polylactic acid. 然而,由于聚乳酸及其缓慢的熔融结晶过程, 酰胺类化合物难以单独控制聚乳酸成型过程中的熔融结晶,必须通过添加滑石粉来进一步提高聚乳酸的结晶速度、縮短结晶时间。 However, since the polylactic acid and the slow melt crystallization process, it is difficult to individually control the amides of melt crystallization of the polylactic acid molding process, it is necessary to further increase the rate of crystallization of polylactic acid by adding talc, shorten the crystallization time. 因此,所制得的成型品,在改善热耐性的同时,透明性不能得到有效的控制。 Thus, the resulting molded article, while improving the heat resistance, transparency can not be effectively controlled. 发明内容本发明的目的在于克服聚乳酸冷结晶温度高、结晶速度慢的缺点,在不明显降低聚乳酸的玻璃转化温度的基础上,提供一种与基体聚乳酸相比、具有更低的冷结晶温度和更高的结晶速度的聚乳酸共混物。 Object of the present invention is to overcome the high cold crystallization temperature of the polylactic acid, the crystallization speed is slow disadvantage significant loss based on the glass transition temperature of the polylactic acid, there is provided a substrate as compared with polylactic acid having a lower cold blends of polylactic acid crystallization temperature and a higher crystallization rate. 本发明的另一目的在于提供一种该聚乳酸共混物经熔融、成型,并经过成型时和/或成型后的热处理所得到的同时具有良好的透明性与耐热性的聚乳酸成型品。 Another object of the present invention is to provide a blend of polylactic acid by melt molding, and after and / or simultaneously a heat treatment after molding the resultant molding having excellent transparency and heat resistance of the polylactic acid molded article . 本发明的目的可以通过以下的手段得到: 一种聚乳酸共混物,主要由下列重量份的组分组成: 聚乳酸100 份酰胺类化合物0.1~10份山梨醇类化合物0.01~5份。 The object of the present invention can be obtained by the following means: A polylactic acid blend, mainly composed of the following parts by weight of components: 100 parts of the polylactic acid amides of 0.1 to 10 parts sorbitol compound 0.01 to 5 parts. 上述聚乳酸是聚乳酸均聚物、聚乳酸共聚物、聚乳酸立构复合物或者是它们之间的混合物。 Polylactic acid is a polylactic acid homopolymer, a polylactic acid copolymer, poly-lactic acid mixture therebetween stereocomplex or Yes. 聚乳酸的熔点为120〜185°C,重均分子量为2万〜80万。 Melting point of polylactic acid of 120~185 ° C, a weight average molecular weight of 20,000 ~ 80 million. 上述酰胺类化合物选自乙撑双垸基酰胺、饱和脂肪酸单酰胺、不饱和脂肪酸单酰胺或氨基酸酰胺中的一种或几种,优选自月桂酸酰胺、硬脂酸酰胺、 油酸酰胺、芥酸酰胺、蓖麻油酸酰胺、乙撑双月桂酰胺、乙撑双硬脂酰胺、 乙撑双油酸酰胺、赖氨酸月桂酰胺、赖氨酸硬脂酰胺、谷氨酸月桂酰胺、谷氨酸硬脂酸酰胺、亮氨酸氨酸月桂酰胺或亮氨酸硬脂酰胺中的一种或几种。 Of the amide compound is selected from ethylene bis-amide embankment, saturated fatty acid monoamide, one or more unsaturated fatty acid monoamide or amino acid amides, preferably selected from lauric acid amide, stearic acid amide, oleic acid amide, erucic acid amide, ricinoleic acid amide, ethylene bis lauric acid amide, ethylene bis stearamide, ethylene bis oleamide, lauramide lysine, lysine stearic acid amide, lauric acid amide, glutamic acid stearic acid amide, one or more leucine-leucine or leucine laurolactam stearamide. 上述山梨醇类化合物选自含有苄叉基团的山梨醇,如1,3-节叉山梨醇、1,4-苄叉山梨醇、1,3-烷基苄叉山梨醇、1,4-烷基苄叉山梨醇、1,3,2,4-二苄叉山梨醇或1,3,2,4-二(垸基苄叉)山梨醇(其中1,3,2,4-二(烷基苄叉)山梨醇优选l,3,2,4-二(4-甲基苄叉)山梨醇、1,3,2,4-二(4-乙基苄叉)山梨醇、 1,3,2,4-二(3、 4-二甲基苄叉)山梨醇)中的一种或几种。 Sorbitol compound is selected from the above-described benzylidene sorbitol containing groups, such as 1,3-section sorbitol, 1,4-benzylidene sorbitol, 1,3-benzylidene sorbitol alkyl, 1,4 alkyl benzylidene sorbitol, 1,3,2,4-dibenzylidene sorbitol or 1,3,2,4-di (alkyl with benzylidene) sorbitol (wherein the 1,3,2,4-di ( alkyl benzylidene) sorbitol is preferably l, 3,2,4- (4-methyl benzylidene) sorbitol, 1,3,2,4-di (4-ethyl-benzylidene) sorbitol, 1, one or more two 3,2,4- (3,4-dimethyl benzylidene) sorbitol) was added. 上述聚乳酸共混物的共混方法可以是熔融共混、机械共混等或它们的组合。 The method of blending the above-described polylactic acid blend can be melt blended, and other mechanical blending or combinations thereof. 可以通过高速混合机、单螺杆挤出机、双螺杆挤出机、密炼机等机械而实现。 By a high speed mixer, a single screw extruder, a twin screw extruder, mixer, etc. machinery realized. 一种聚乳酸共混物的成型品,由上述聚乳酸共混物在成型时和/或成型后通过热处理得到。 A polylactic acid blend molded article obtained from the polylactic acid blend after molding and / or forming by a heat treatment. 具体的说,先釆用流延成型、压延成型、注塑成型、吹塑成型或热压成型等的方法将聚乳酸共混物熔融成型,再经过成型中和/或成型后的热处理得到。 Specifically, to preclude the use of cast molding, calender molding, injection molding, blow molding or compression molding and other methods will be a blend of the polylactic acid melt-molding, heat treatment and then molding and / or after the molding obtained. 上述成型品的厚度为0.02〜5mm。 The thickness of the molded article is 0.02~5mm. 热处理的温度范围为聚乳酸共混物的冷结晶起始温度以上熔点以下,热处理的时间为2秒到10分钟,优选10~120秒。 The heat treatment temperature range of the cold crystallization of the polylactic acid blend starting temperature above the melting point, the heat treatment time of 2 seconds to 10 minutes, preferably 10 to 120 seconds. 本发明的目的具体可以通过以下措施来达到:通过每IOO重量份聚乳酸与下述(A)和(B)通过共混而形成共混物: (A) 0.1〜10重量份酰胺类化合物,(B) 0.01〜5重量份山梨醇类化合物。 Specific object of the present invention can be achieved by the following measures: and (B) a blend is formed by blending the polylactic acid and the following (A) per IOO parts by weight: (A) 0.1~10 parts by weight of amide-based compound, (B) 0.01~5 parts by weight of a sorbitol-based compound. 通过被添加的(A)酰胺类化合物来降低聚乳酸的冷结晶温度、提高聚乳酸的结晶速度。 To reduce the cold crystallization temperature of polylactic acid by (A) an amide compound is added to improve the crystallization rate of polylactic acid. 包含由上述聚乳酸共混物经成型及热处理所得到的成型品,先釆用流延成型、压延成型、注塑成型、吹塑成型或热压成型的方法将聚乳酸共混物熔融成型后,经过热处理即得。 A molded article comprising a blend of the polylactic acid obtained by molding and heat treatment, and to preclude flow casting molding, calender molding, injection molding, blow molding or thermoforming method of the polylactic acid after melt-molding the blend, after heat treatment to obtain. 具体的上述聚乳酸共混物的高分子成型制品,例如将该聚乳酸共混物经熔融、成型后得到的厚度为0.02〜5mm的聚乳酸类树脂膜/片材或瓶状、桶状、 盒状聚乳酸成型品,再次成型或不再次成型后,通过成型中和/或成型后热处理引发结晶,通过共混物中的(B)山梨醇类化合物来改善结晶后成型品的透明性。 The polylactic acid resin film of the above-described specific polymer blend of the polylactic acid molded articles such as a blend of the polylactic acid by melt, obtained after forming a thickness of the 0.02~5mm / sheet or bottle-shaped, barrel, a box-shaped molded article of polylactic acid, or again formed after forming again initiate crystallization by heat molding and / or after molding to improve the transparency of the molded product after crystallization by the blend of sorbitol-based compound (B). 作为本发明中的聚乳酸共混物中的聚乳酸,其熔点为120~185度,重均分子量为2万〜80万,以L-乳酸和/或D-乳酸作为主成分,可以是聚乳酸均聚物、聚乳酸共聚物、聚乳酸均聚物与聚乳酸共聚物的共混物、聚乳酸立构复合物(stereocomplex)、聚乳酸立构复合物与聚乳酸均聚物和/或聚乳酸共聚物的共混物。 As the polylactic acid in the present invention is a blend of polylactic acid having a melting point of 120 to 185 degrees, the weight-average molecular weight of 20,000 ~ 80 million, or lactic acid to L- and / or D- lactic acid as a main component, can be poly lactic acid homopolymer, a polylactic acid copolymer, a polylactic acid homopolymer and polylactic acid copolymer blend of polylactic acid stereocomplex (stereocomplex), the polylactic acid stereocomplex polylactic acid homopolymer and / or polylactic acid copolymer blend. L-乳酸单元和D-乳酸单元的构成摩尔比没有特别的限制,可以在100/0〜0/100的范围内选择。 D- and L- lactic acid unit constituting the lactic acid unit molar ratio is not particularly limited, and may be selected within the range of 100 / 0~0 / 100. 但为了保证聚乳酸的熔点,优选L-乳酸单元和D-乳酸单元中的任何一种的含量在90mol。 However, in order to ensure the melting point of the polylactic acid, the content is preferably any of a lactic acid unit and L- lactic acid unit in the D- 90mol. /。 /. 以上。 the above. 本发明中的(A)酰胺类化合物优选极性较低、碳链较长、同时与聚乳酸基体具有适当相容性的酰胺化合物。 In the present invention, (A) the less polar compound is preferably amides, long carbon chain, while the suitable compatibility with the polylactic acid an amide compound having matrix. 该相容性在常温时较小、不起到增塑作用、从而不降低聚乳酸基体的玻璃转化温度;该相容性在高温时较大、使聚乳酸分子链间的相对运动变得容易,从而降低了冷结晶温度、提高了结晶速度。 The compatibility at normal temperature is small, does not function as plasticizing effect, and the decrease in the glass transition temperature of the polylactic acid substrate; the compatibility at high temperature is large, the relative movement between molecular chains becomes easy polylactic acid , thereby reducing the cold crystallization temperature, increased crystallization rate. 上述酰胺化合物可以是饱和脂肪酸单酰胺,如月桂酸酰胺、硬脂酸酰胺、油酸酰胺等;也可以是不饱和脂肪酸单酰胺,如芥酸酰胺、蓖麻油酸酰胺等;也可以是饱和脂肪酸双酰胺,如乙撑双月桂酰胺、乙撑双硬脂酰胺、 乙撑双油酸酰胺等乙撑双烷基酰胺;也可以是氨基酸酰胺,如赖氨酸月桂酰胺、赖氨酸硬脂酰胺、谷氨酸月桂酰胺、谷氨酸硬脂酸酰胺、亮氨酸氨酸月桂酰胺、亮氨酸硬脂酰胺等。 Above amide compound may be a saturated fatty acid monoamide such as lauric acid amide, stearic acid amide, oleic acid amide and the like; may be mono-unsaturated fatty acid amides, such as erucic acid amide, ricinoleic acid amide and the like; may be a saturated fatty acid bis amides such as ethylene bis lauric acid amide, ethylene bis stearamide, ethylene bis oleamide, etc. ethylenebis alkylamide; may be an amino acid amide, lauric acid amide, such as lysine, lysine stearamide , lauric acid amide, stearic acid amide, lauric acid amide leucine-leucine, leucine, stearic acid amide. 本发明中的(B)苄叉山梨醇类化合物是一种众所周知的聚丙烯成核剂, 但是单独使用时,对于聚乳酸的结晶没有明显的促进效果。 (B) benzylidene sorbitol compound of the present invention is a known nucleating agent to polypropylene, when used alone but, for crystallization of polylactic acid without significant promoting effect. 本发明的发明人通过研究发现,通过利用(A)酰胺化合物和(B)山梨醇类化合物这两种成核剂的协同效应,通过热处理、在促进聚乳酸结晶的同时,又明显改善了结晶的均匀程度,从而实现了本发明的目的。 The present inventors found by studies, by using an amide compound (A) and (B) a synergistic effect of these two compounds sorbitol nucleating agent, by heat treatment, while promoting crystallization of polylactic acid, but also significantly improved crystallization the degree of uniformity, thus achieving the purpose of the present invention. 上述山梨醇类化合物可以是含有苄叉基团的山梨醇衍生物:如1,3-苄叉山梨醇、1,4-苄叉山梨醇、1,3-垸基苄叉山梨醇、1,4-垸基苄叉山梨醇、1,3,2,4-二苄叉山梨醇、1,2,3,4-二(垸基苄叉)山梨醇(如1,3,2,4-二(4-甲基苄叉)山梨醇、U,2,4-二(4-乙基苄叉) 山梨醇、1,3,2,4-二(3、 4-二甲基苄叉)山梨醇等),其中所述的垸基优选Cl〜6的烷基,最优选甲基、乙基、丙基或异丙基。 Above may be a compound containing a sorbitol derivative benzylidene sorbitol groups: such as 1,3-benzylidene sorbitol, 1,4-benzylidene sorbitol, 1,3-benzylidene sorbitol embankment yl, 1, alkyl with 4- benzylidene sorbitol, 1,3,2,4-dibenzylidene sorbitol, 1,2,3,4-di (alkyl with benzylidene) sorbitol (e.g. 1,3,2,4 bis (4-methyl benzylidene) sorbitol, U, 2,4- bis (4-ethyl-benzylidene) sorbitol, 1,3,2,4-di (3,4-dimethyl benzylidene) sorbitol, etc.), preferably wherein said alkyl with Cl~6 alkyl, most preferably methyl, ethyl, propyl or isopropyl. 本发明中所述聚乳酸共混物的共混方法可以是熔融共混、机械共混等或它们的组合。 The present invention method of blending polylactic acid blend can be melt blended, and other mechanical blending or combinations thereof. 可以通过高速混合机、单螺杆挤出机、双螺杆挤出机、密炼机等机械而实现。 By a high speed mixer, a single screw extruder, a twin screw extruder, mixer, etc. machinery realized. 本发明所述的成型品,优选是将所述聚乳酸共混物经熔融、成型、成型中和/或成型后热处理得到的具有规则形状或不规则形状的、厚度为0.02~5mm的聚乳酸膜/片材/瓶状/桶状/盒状成型品,或是将乳酸膜/片材/瓶状/桶状/盒状成型品再次成型而得到的其他成型品。 The molded article of the present invention, preferably the polylactic acid by melt blend, shaping, molding and / or after forming the heat obtained having a regular shape or an irregular shape, and a thickness of 0.02 ~ 5mm polylactic acid film / sheet / the bottle / barrel / box-shaped molded article, or the acid film / sheet / the bottle / barrel / box-shaped molded article again molded article obtained by molding the other. 本发明所述的熔融、成型的方法,可以是挤出成型,流延成型、压延成型、注塑成型、吹塑成型或热压成型等。 Melt-molding method according to the present invention, it may be extrusion molding, cast molding, calender molding, injection molding, blow molding or thermoforming and the like. 本发明所述的热处理,可以在鼓风烘箱、真空烘箱,隧道烘箱等具有加热功能的密闭或半密闭设备中进行、通过调节处理温度和处理时间以促使成型品部分或完全结晶、从而调节成型品的透明程度与耐热程度。 Heat treatment of the present invention, in a closed or semi-enclosed apparatus having a heating function in a forced air oven, vacuum oven, a tunnel oven or the like, by adjusting the processing temperature and time to cause partial or complete crystallization of the molded article, thereby adjusting the molding the level of transparency and the degree of heat-resistant products. 所述的热处理温度的范围为差示扫描量热仪(DSC)测得的冷结晶起始温度以上熔点以下,热处理的时间为2秒到IO分钟。 The heat treatment temperature range for the measured cooling a differential scanning calorimeter (DSC) crystallization onset temperature above the melting point, the heat treatment time of 2 seconds to IO minutes. 进行热处理时成型品的边缘应被固定以防止热收縮的影响。 Edge of the molded article should be secured to prevent the effects of thermal contraction during the heat treatment. 总体来说本发明是一种本身透明的聚乳酸混合物(不经过热处理时),该混合物由于具有特殊的热特性(比纯聚乳酸低的冷结晶温度),所以可以在通过与此相对应的特殊的热处理工艺(处理温度在差示扫描量热仪(DSC)测得的聚乳酸共混物的冷结晶起始温度以上熔点以下)进行热处理后,同时兼具透明性和耐热性。 Overall, the present invention is transparent to a mixture of polylactic acid itself (without heat treatment), and the mixture due to the special thermal characteristics (pure PLA cold crystallization temperature lower than), this can be by the corresponding special heat treatment process (processing the measured temperature of the cold blend of polylactic acid is crystallized in differential scanning calorimeter (DSC) onset temperature above the melting point) after the heat treatment, while both transparency and heat resistance. 本成型品成型后,通过特殊热处理工艺热处理后得到兼具透明性和耐热性的效果,该热处理工艺对于实现本发明的耐热性的实现来说是不可缺少的, 而山梨醇化合物的加入可以抑制热处理所导致的透明性下降。 This molded article after forming, heat treatment by a heat treatment process to obtain a special effect, both transparency and heat resistance, the heat treatment process to achieve the realization of the present invention, the heat resistance is indispensable, and the addition of a sorbitol compound possible to suppress lowering of transparency caused by a heat treatment. 本发明在不明显降低聚乳酸的玻璃转化温度的基础上,提供一种与基体聚乳酸相比、具有更低的冷结晶温度和更高的结晶速度的聚乳酸共混物,通过本共混物所制得的成型品同时具有良好的透明性与耐热性。 On the basis of the present invention is not significantly lower the glass transition temperature of the polylactic acid, there is provided a substrate as compared with polylactic acid having a lower and higher cold crystallization temperature crystallization speed of the polylactic acid blend, by blending the present It was prepared a molded article having both good transparency and heat resistance. 具体实施方式热处理和评价测试方法热处理:将压制好的薄膜用夹子固定在钢框上,在预先设定好温度并恒温一段时间的鼓风烘箱或隧道烘箱内,加热10-120秒。 DETAILED DESCRIPTION heat treatment and a heat treatment method for evaluation testing: the pressing a good film with clips fixed to the steel frame, a good temperature within a preset temperature and a forced air oven or a tunnel oven a period of 10-120 seconds heating. 所述温度为的范围为差示扫描量热仪(DSC)测得的结晶起始温度以上熔点以下。 The temperature range of a differential scanning calorimeter (DSC) having a crystallization onset temperature above the melting point. 热变形温度:在压制好的膜裁成lcm宽,5cm长的样条,固定在如图(附图)所示的样品台上,放入事先升温到65r的鼓风烘箱(ESPEC)内,放置IO分钟, 观察样条的变形程度,弯曲程度在10° (样条与水平方向的夹角)以内的评价为"©",弯曲程度在10-25。 Heat distortion temperature: good film cut in a press lcm wide, 5cm long spline, fixing the sample stage shown in (drawings) shown placed into the previously heated in a forced air oven 65r (by ESPEC), placing IO min, to observe the degree of deformation of the spline, the degree of bending in the evaluation within 10 ° (the angle with the horizontal direction of the spline) is "©", 10-25 degree bend. 的评价为"A",弯曲程度在25。 It evaluated as "A", 25 degree bend. 以上的评价为"x"。 Above evaluation is "x". 对于评价为"O)"、 "A"的样条,使用上面的方法在8(TC、 IO(TC继续观察并评价耐热性。 透明性:使用雾度来表征成型品的透明性。成型品热处理前后的雾度通过Suga HZ-1型雾度计测定。 热特性:使用TA公司的DSCQIOO,测定结晶温度。把压制好的薄膜用刀片切下大约10mg,制备样盘。氮气流量为50ml/min,在室温下达到平衡,升温速率为20°C/min,升温到20(TC,读出放热峰作为冷结晶温度(Tee),吸热峰作为熔点(Tm),在200。C恒温3分钟消除热历史,冷却速率为20°C/min,降温到室温,读出吸热峰作为熔融结晶温度(Tme),在室温下恒温2分钟,再次以2(TC/min升温,读出玻璃转化温度(Tg)。实施例1将聚乳酸(4032D,Natureworks,重均分子量23.7万)置于真空烘箱中, SO。C干燥10小时后,分别与乙撑双月桂酰胺(EBLA)、 1,3,2,4-二(4-甲基苄叉)山梨醇(NC6,三井化学)通过双螺杆挤出机 For evaluated as "O)", "A" spline, using the above method 8 (TC, IO (TC continue to monitor and evaluate the heat resistance and transparency: to characterize the transparency of the molded product molded using a haze Suga HZ-1 type haze meter measurement of the haze before and after the heat treatment product by thermal properties: using the TA's DSCQIOO, the crystallization temperature was measured good film was cut with a blade pressed at approximately 10mg, samples were prepared disc nitrogen flow was 50ml.. / min, to reach equilibrium at room temperature, heating rate of 20 ° C / min, warmed to 20 (TC, is read out as a cold crystallization exotherm peak temperature (Tee), an endothermic peak as a melting point (Tm), at 200.C 3 minutes isothermal eliminate heat history, the cooling rate of 20 ° C / min, cooled to room temperature, an endothermic peak is read out as melt crystallization temperature (Tme), two minutes at room temperature, again to 2 (TC / min heating, reading a glass transition temperature (Tg). Example 1 the polylactic acid (4032D, Natureworks, weight average molecular weight 237000) was placed in a vacuum oven, SO.C dried for 10 hours respectively, ethylene bis lauramide (Ebla), 1,3,2,4-di (4-methyl benzylidene) sorbitol (NC6, manufactured by Mitsui Chemicals) through a twin screw extruder 挤出、造粒成4032D:EBLA=95/5 (重量份)的母料l, 4032D/NC6=95/5 (重量份)的母料2。所述双螺杆挤出机的进料段温度为170°C,其余各段温度为210。C,挤出过程中抽真空排气。两种母料置于真空烘箱中,8(TC干燥10小时,再与干燥过的聚乳酸(4032D, Natureworks)按一定比例混合成4032D/EBLA/NC6=98/1/1的混合物,通过带有T型模头的单螺杆挤出机挤出并通过流延辊,制得厚度为0.5mm 左右的膜。所述双螺杆挤出机的进料段温度为17(TC,其余各段温度为210°C。 测试热处理前薄膜的冷结晶温度(Tee)为84.8。C,熔点(Tm)为164.5°C。 将制得的薄膜用钢框和夹子固定后,置于隧道烘箱中进行热处理。(1) 热处理温度为110°C, 热处理时间为10秒。测试热处理后薄膜的雾度和耐热性。经测试,雾度为2.5%,耐热性为65。C"A", 80。C"x", 100。C"x"o(2) 热处理温度为ll(TC, 热处理时间为20秒。测试热处 Extruded, granulated to 4032D: EBLA = 95/5 (parts by weight) masterbatch l, 4032D / NC6 = 95/5 (parts by weight) of the masterbatch 2. The temperature of the feed section of the twin screw extruder to 170 ° C, the remaining paragraphs temperature 210.C, the extrusion process a vacuum vent Both masterbatches in a vacuum oven, 8 (TC for 10 hours, and then dried with polylactic acid (4032D, NatureWorks) by mixing into 4032D / EBLA mixture / NC6 = 98/1/1 through a single screw extruder with T-die extrusion and by casting roller, to obtain a thickness of approximately 0.5mm the feed section temperature of the film. the twin screw extruder was 17 (TC, the remaining paragraphs temperature of 210 ° C. cold crystallization temperature of the film before heat treatment tests (Tee) is 84.8.C, melting point (Tm) of 164.5 ° C. the resulting film after the steel frame and the clamps, placed in an oven for heat treatment tunnel (1) a heat treatment temperature of 110 ° C, the heat treatment time is 10 seconds. after the heat treatment the test film haze and heat resistance. after testing, the haze was 2.5%, the heat resistance of 65.C "A", 80.C "x", 100.C "x" o (2) heat treatment temperature is ll (TC, heat treatment time is 20 second test heat 理后薄膜的雾度和耐热性。经测试,雾度为5.6%,耐热性为65。C"(D", 8(TC實,函。C"A"。(3) 热处理温度为12(TC, 热处理时间为10秒。测试热处理后薄膜的雾度和耐热性。经测试,雾度为3.8%,耐热性为65。C"0)", 80。 Haze and heat resistance of the film after treatment. After testing, the haze was 5.6%, the heat resistance of 65.C "(D", 8 (TC solid, letter .C "A". (3) heat treatment temperature is 12 (TC, heat treatment time is 10 seconds after the heat-treated film a haze test and heat resistance. after testing, the haze was 3.8%, the heat resistance is 65.C "0)", 80. C實,腦。 C real brain. C實。 C reality. (4) 热处理温度为12(TC, 热处理时间为20秒。测试热处理后薄膜的雾度和耐热性。经测试,雾度为6.5%,耐热性为65。C實,80。C實,100。C"0)"。 (4) Heat treatment temperature 12 (TC, a heat treatment time of 20 seconds. After the heat-treated film a haze test and heat resistance. After testing, the haze was 6.5%, the heat resistance of the solid 65.C, 80.C solid , 100.C "0)". 实施例2将聚乳酸(4032D,Natureworks)置于真空烘箱中,8(TC干燥IO小时后, 与乙撑双月桂酰胺(EBLA)、 1,3,2,4-二(4-甲基苄叉)山梨醇(NC6,三井化学)按100:1:1(重量份)进行预混合后,通过双螺杆挤出机共挤出、造粒。 所述双螺杆挤出机的进料段温度为H(TC,其余各段温度为210。C,挤出过程中抽真空排气。造粒好的混合物在真空烘箱中,8(TC干燥10小时后,使用手动式热压机压制成膜。热压机的温度为200°C,熔融时间为3min,保压时间为30秒。 压制好的熔体用冰水混合物淬冷后,制得厚度约为0.5mm的膜。薄膜充分干燥后,测试热处理前薄膜的冷结晶温度(Tee)为84.3t:,熔点(TJ为164.5°C,将薄膜用钢框和夹子固定后,置于隧道烘箱中进行热处理。 热处理温度为120°C,热处理时间为20秒。测试热处理后薄膜的雾度和耐热性。经测试,雾度为7.6%,耐热性为65。C實 Example 2 The polylactic acid (4032D, Natureworks) in a vacuum oven, after 8 (TC IO hours drying, and ethylene bis lauric acid amide (EBLA), 1,3,2,4- bis (4-methylbenzyl fork) sorbitol (NC6, manufactured by Mitsui Chemicals) 100: 1: 1 (parts by weight) were premixed, by co-extruding a twin screw extruder, a twin-screw extruder granulation temperature of the feed section of the machine. is H (TC, the remaining paragraphs temperature 210.C, the extrusion process a vacuum vent. good mixture was granulated in a vacuum oven, 8 (TC was dried for 10 hours using a manual hot press forming press after the temperature of the hot press 200 ° C, the melting time of 3min, dwell time of 30 seconds. after the pressing a good melt quenched with ice-water mixture, to obtain a film thickness of about 0.5mm. film sufficiently dried cold crystallization temperature of the film before heat treatment tests (Tee) is 84.3t :, mp (TJ of 164.5 ° C, the film after the steel frame and the clamps, placed in the tunnel oven for heat treatment. the heat treatment temperature of 120 ° C, the heat treatment time is 20 seconds. after the heat-treated film a haze test and heat resistance. after testing, the haze was 7.6%, the heat resistance of the solid 65.C 80。C實,画。C,。 实施例3将聚乳酸(4032D,Natureworks)置于真空烘箱中,8(TC干燥IO小时后, 与乙撑双月桂酰胺(EBLA)、 1,3,2,4-二(4-乙基苄叉)山梨醇(NC4,三井化学)按100:1:0.5(重量份)进行预混合后,通过双螺杆挤出机共挤出、造粒。 所述双螺杆挤出机的进料段温度为H(TC,其余各段温度为210"C,挤出过程中抽真空排气。造粒好的混合物在真空烘箱中,8(TC干燥IO小时后,使用手动式热压机压制成膜。热压机的温度为200°C,熔融时间为3min,保压时间为30秒。 压制好的熔体用冰水混合物淬冷后,制得厚度约为0.5mm的膜。薄膜充分干燥后,测试热处理前薄膜的冷结晶温度(Tec)为87.6"C,熔点CU为164.5°C,将薄膜用钢框和夹子固定后,置于鼓风烘箱中进行热处理。 热处理温度为120°C, 热处理时间为60秒。测试热处理后薄膜的雾度和耐热性。经测试,雾度为7.8%, 80.C solid, Example 3 .C ,. Videos polylactic acid (4032D, Natureworks) in a vacuum oven, 8 (TC IO hours after drying, and ethylene bis lauric acid amide (EBLA), 1,3,2 , 4-di (4-ethyl-benzylidene) sorbitol (the NC4, manufactured by Mitsui Chemicals) 100: 1: 0.5 (parts by weight) were premixed, a twin-screw extruder, co-extrusion, the pelletized. after the temperature of the feed section of a twin screw extruder H (TC, the remaining paragraphs temperature of 210 "C, the extrusion process a vacuum vent. good mixture was granulated in a vacuum oven, 8 (TC IO hours drying using a hand press hot press forming. hot press temperature of 200 ° C, the melting time of 3min, dwell time of 30 seconds. after the pressing a good melt quenched with ice-water mixture, to obtain a thickness of about 0.5mm for the film after the film is sufficiently dried, the cold crystallization temperature of the film before heat treatment tests (Tec) of 87.6 "C, a melting point of CU 164.5 ° C, the film after the steel frame and the clamps, placed in a forced air oven a heat treatment. the heat treatment temperature of 120 ° C, the heat treatment time was 60 seconds. the haze and heat resistance after the test of heat-treated films. after testing, the haze was 7.8%, 热性为65。C實,80。C實,IO(TC實。 实施例4将聚乳酸(403 2D, Nature works)置于真空烘箱中,8(TC干燥IO小时后, 与月桂酸酰胺、1,3,2,4-二苄叉山梨醇按100:0.3:0.1(重量份)进行预混合后, 通过双螺杆挤出机共挤出、造粒。所述双螺杆挤出机的进料段温度为no。c,其余各段温度为21(TC,挤出过程中抽真空排气。 65.C heat is real, 80.C solid, IO (the TC solid. Example 4 The polylactic acid (403 2D, Nature works) in a vacuum oven, after 8 (TC IO hours drying, and lauric acid amide, 1,3,2,4-dibenzylidene sorbitol 100: 0.3: 0.1 after (parts by weight) were premixed, a twin-screw extruder, co-extrusion, the granules into a twin screw extruder. feed section temperature was no.c, the remaining paragraphs temperature 21 (TC, the extrusion process a vacuum vent. 造粒好的混合物在真空烘箱中,8(TC干燥10小时后,使用手动式热压机压制成膜。热压机的温度为200°C,熔融时间为3min,保压时间为30秒。 压制好的熔体用冰水混合物淬冷后,制得厚度约为lmm的膜。薄膜充分干燥后,测试热处理前薄膜的冷结晶温度(Tee)为96.2。C,熔点(TJ为164.5°C,将薄膜用钢框和夹子固定后,置于鼓风烘箱中进行热处理。 热处理温度为120°C, 热处理时间为60秒。测试热处理后薄膜的雾度和耐热性。经测试,雾度为3.3%,耐热性为65。C"(D", 80。C"A", 100。C"x',。 实施例5将聚乳酸(4032D,Natureworks)置于真空烘箱中,8(TC干燥10小时后, 与赖氨酸月桂酰胺(Amihope LL, Ajimoto)、 1,3,2,4-二(4-甲基苄叉)山梨醇(NC6,三井化学)按100:9:5(重量份)进行预混合后,通过双螺杆挤出机共挤出、造粒。所述双螺杆挤出机的进料段温度为170°C,其余各段温 Good mixture was granulated in a vacuum oven, 8 (TC was dried for 10 hours using a manual press forming hot press temperature of hot press was 200 ° C, the melting time of 3min, dwell time of 30 seconds. after pressing good melt quenching the mixture with ice-water, to obtain a film thickness of about lmm. film sufficiently dried, heat-treated film before the test cold crystallization temperature (Tee) is 96.2.C, a melting point (TJ of 164.5 ° C the steel frame and the film clamps, placed in a forced air oven for heat treatment. the heat treatment temperature of 120 ° C, the heat treatment time was 60 seconds. after the heat-treated film a haze test and heat resistance. after testing, the haze 3.3%, the heat resistance of 65.C "(D", 80.C "A", 100.C "x ',. Example 5 the polylactic acid (4032D, Natureworks) in a vacuum oven, 8 ( after TC for 10 hours, lauryl lysine amide (Amihope LL, Ajimoto), 1,3,2,4- bis (4-methyl benzylidene) sorbitol (NC6, manufactured by Mitsui Chemicals) 100: 9: 5 after (parts by weight) were premixed, a twin-screw extruder, co-extruder, pelletized. the temperature of the feed section of a twin screw extruder was 170 ° C, the remaining segments temperature 为210°C,挤出过程中抽真空排气。造粒好的混合物在真空烘箱中,8(TC干燥IO小时后,使用手动式热压机压制成膜。热压机的温度为2(XTC,熔融时间为3min,保压时间为30秒。 压制好的熔体用冰水混合物淬冷后,制得厚度约为O.lmm的膜。薄膜充分干燥后,测试热处理前薄膜的冷结晶温度(Tee)为105.9°C, 熔点(TJ为165.9°C。将薄膜用钢框和夹子固定后,置于鼓风烘箱中进行热处理。热处理温度为120°C, 热处理时间为60秒。测试热处理后薄膜的雾度和耐热性。经测试,雾度为6.9%,耐热性为65。C實,80。C實,IO(TC實。 实施例6将聚乳酸(6251D,Natureworks,重均分子量11.8万)置于真空烘箱中, 8(TC干燥10小时后,与乙撑双月桂酰胺(EBLA)、 1,3,2,4-二(4-甲基苄叉) 山梨醇(NC6,三井化学)按100:1:1(重量份)进行预混合后,通过双螺杆挤出机共挤出、造粒。所述双 To 210 ° C, the extrusion process a vacuum vent. Good mixture was granulated in a vacuum oven, 8 (after drying TC IO hours, using a manual press forming hot press temperature of hot press 2 ( XTC, melting time 3min, pressure holding time of 30 seconds. after the pressing a good melt quenched with ice-water mixture, to obtain a film thickness of about O.lmm. after drying sufficiently thin, cold crystallization heat treatment of the film before the test temperature (Tee) of 105.9 ° C, a melting point (TJ of 165.9 ° C. after the film clamps and the steel frame placed in a forced air oven for heat treatment. the heat treatment temperature of 120 ° C, the heat treatment time is 60 seconds. test film haze after heat treatment and heat resistance. after testing, the haze was 6.9%, the heat resistance of the solid 65.C, 80.C solid, IO (TC solid. Example 6 the polylactic acid (6251D, Natureworks, weight average molecular weight 118000) was placed in a vacuum oven 8 (TC after drying for 10 hours and ethylene bis lauric acid amide (EBLA), 1,3,2,4- bis (4-methyl benzylidene) sorbitol ( NC6, Mitsui Chemicals) 100: 1: 1 pre-mixed (parts by weight), by co-extruding a twin screw extruder, pelletizing the double. 杆挤出机的进料段温度为17CTC,其余各段温度为21(TC,挤出过程中抽真空排气。造粒好的混合物在真空烘箱中,8(TC干燥10小时后,使用手动式热压机压制成膜。热压机的温度为200°C,熔融时间为3min,保压时间为30秒。 压制好的熔体用冰水混合物淬冷后,制得厚度约为0.5mm的膜。薄膜充分干燥后,测试热处理前薄膜的冷结晶温度(Tee)为84.0'C,熔点(TJ为167.8°C,将薄膜用钢框和夹子固定后,置于鼓风烘箱中进行热处理。 The temperature of the feed section of the extruder rod is 17CTC, the remaining paragraphs temperature 21 (TC, the extrusion process a vacuum vent. Good mixture was granulated in a vacuum oven, 8 (TC dried after 10 hours, using a manual pressing hot press forming. hot press temperature of 200 ° C, the melting time of 3min, dwell time of 30 seconds. after the pressing a good melt quenched with ice-water mixture, to obtain a thickness of about 0.5mm film after the film is sufficiently dried, the cold crystallization temperature of the film before heat treatment tests (Tee) of 84.0'C, a melting point (TJ of 167.8 ° C, the film after the steel frame and the clamps, placed in a forced air oven heat treatment . 热处理温度为120°C, 热处理时间为60秒。 The heat treatment temperature of 120 ° C, the heat treatment time is 60 seconds. 测试热处理后薄膜的雾度和耐热性。 After the heat-treated film a haze test and heat resistance. 经测试,雾度为8.3%,耐热性为65。 After testing, the haze was 8.3%, the heat resistance is 65. C"0)", 80°C"€>", 100。 C "0)", 80 ° C "€>", 100. C實。 C reality. 实施例7将聚乳酸均聚物(重均分子量9.8万)置于真空烘箱中,8(TC干燥10小时后,与乙撑双月桂酰胺(EBLA)、 1,3,2,4-二(4-甲基苄叉)山梨醇(NC6, 三井化学)按100:1:1(重量份)进行预混合后,通过双螺杆挤出机共挤出、造粒。所述双螺杆挤出机的进料段温度为170°C,其余各段温度为21(TC,挤出过程中抽真空排气。造粒好的混合物在真空烘箱中,80'C干燥IO小时后,使用手动式热压机压制成膜。热压机的温度为200°C,熔融时间为3min,保压时间为30秒。 压制好的熔体用冰水混合物淬冷后,制得厚度约为0.5mm的膜。薄膜充分干燥后,测试热处理前薄膜的冷结晶温度(T^)为82.(C,熔点(TJ为150.2°C,将薄膜用钢框和夹子固定后,置于鼓风烘箱中进行热处理。 热处理温度为120°C , 热处理时间为60秒。测试热处理后薄膜的雾度和耐热性。经测试,雾度为8.0%,耐热 Example 7 The polylactic acid homopolymer (weight average molecular weight 98,000) was placed in a vacuum oven, 8 (TC was dried for 10 hours and ethylene bis lauric acid amide (EBLA), 1,3,2,4- bis ( 4-methyl benzylidene) sorbitol (NC6, manufactured by Mitsui Chemicals) 100: 1: 1 (parts by weight) were premixed, by co-extruding a twin screw extruder, a twin-screw extruder granulation. the feed section temperature was 170 ° C, the remaining paragraphs temperature 21 (TC, the extrusion process a vacuum vent. good mixture was granulated in a vacuum oven, after drying 80'C IO hours, with hand hot pressing the press forming. hot press temperature of 200 ° C, the melting time of 3min, dwell time of 30 seconds. after the pressing a good melt quenched with ice-water mixture, to obtain a film thickness of about 0.5mm after the thin film is sufficiently dried, the cold crystallization temperature of the film before heat treatment tests (T ^) is 82. (C, melting point (TJ of 150.2 ° C, the film after the steel frame and the clamps, placed in a forced air oven heat treatment the heat treatment temperature is 120 ° C, the heat treatment time was 60 seconds. after the heat-treated film a haze test and heat resistance. after testing, the haze of 8.0%, the heat 为65。C實,80。C"(D", IO(TC實。 比较例(1)将聚乳酸(4032D,Natureworks)置于真空烘箱中,8(TC干燥10小时后, 使用手动式热压机压制成膜。热压机的温度为20(TC,熔融时间为3min,保压时间为30秒。压制好的熔体用冰水混合物淬冷后,制得厚度约为0.5mm 的膜。薄膜充分干燥后,测试热处理前薄膜的冷结晶温度(Tee)为U0.5'C, 熔点(TJ为H0.(TC。所制得的膜不进行热处理。经测试,该薄膜的雾度为3.0%,耐热性为65。C"x", 80。C"x", 100。C"x"。 比较例(2)将比较例(1)中制得的膜在鼓风烘箱中进行热处理。热处理温度为120°C,热处理时间为60秒。经测试,该薄膜的雾度为3.2%,耐热性为65。C"x", 80。C"x", 100。C"x"。 比较例(3)将聚乳酸(4032D,Natureworks)置于真空烘箱中,80。C干燥10小时后, 分别与乙撑双月桂酰胺(EBLA)、 1,3,2,4-二(4-甲基苄叉)山梨醇(NC6, 三井化学) 65.C is real, 80.C "(D", IO (TC solid. Comparative Example (1) polylactic acid (4032D, Natureworks) in a vacuum oven, 8 (TC was dried for 10 hours using the manual heat pressing the press forming. hot press temperature 20 (TC, melting time 3min, pressure holding time of 30 seconds. after the pressing a good melt quenched with ice-water mixture, to obtain a film thickness of about 0.5mm after the film was sufficiently dried, heat-treated film before the test cold crystallization temperature (Tee) is U0.5'C, a melting point (TJ of H0. (TC. the resulting film was not heat-treated. after testing, the haze of the film 3.0%, the heat resistance of 65.C "x", 80.C "x", 100.C "x". Comparative Example (2) Comparative Example (1) prepared in the film in a forced air oven a heat treatment. the heat treatment temperature of 120 ° C, the heat treatment time was 60 seconds. after testing, the haze of the film was 3.2%, the heat resistance of 65.C "x", 80.C "x", 100.C " X. "Comparative Example (3) the polylactic acid (4032D, Natureworks) in a vacuum oven, 80.C for 10 hours after, respectively, ethylene bis lauric acid amide (EBLA), 1,3,2,4- two (4-methyl benzylidene) sorbitol (NC6, Mitsui Chemicals) 通过双螺杆挤出机共挤出、造粒成4032D:EBLA=95/5 (重量份) 的母料l, 4032D/NC6=95/5 (重量份)的母料2。所述双螺杆挤出机的进料段温度为170。C,其余各段温度为21(TC,挤出过程中抽真空排气。两种母料置于真空烘箱中,8(TC干燥10小时,再与干燥过的聚乳酸(4032D, Natureworks)按一定比例混合成4032D/EBLA/NC6=98/1/1的混合物,通过带有T型模头的单螺杆挤出机挤出并通过流延辊,制得厚度为0.5mm 左右的膜。 Co-extrusion through a twin screw extruder, pelletized to 4032D: EBLA = 95/5 (parts by weight) masterbatch l, 4032D / NC6 = 95/5 (parts by weight) of the masterbatch 2. The twin-screw extruder the temperature of the feed section of the machine of 170.C, the remaining paragraphs temperature 21 (TC, during extrusion vacuum exhaust Both masterbatches in a vacuum oven, 8 (TC for 10 hours, and then dried over polylactic acid (4032D, Natureworks) according to a certain ratio to 4032D / EBLA / NC6 = mixture of 98/1/1, extruded through a single screw extruder with T-die and by casting rollers, Ltd. to give a film thickness of about 0.5mm. 所述双螺杆挤出机的进料段温度为170。 The twin-screw extruder feed zone temperature was 170. C,其余各段温度为210°C。 C, balance temperature of each of 210 ° C. 薄膜充分干燥后,测试热处理前薄膜的冷结晶温度(Tw)为89.4",熔点CU为165.5'C。所制得的膜不进行热处理。经测试,该薄膜的雾度为2.5%, 耐热性为65。C"x", 8(TC"x", 100°C"x"。 比较例(4)将聚乳酸(4032D,Natureworks)置于真空烘箱中,80。C干燥IO小时后, 与乙撑双月桂酰胺(EBLA)按IOO:I(重量份)进行预混合后,通过双螺杆挤出机共挤出、造粒。所述双螺杆挤出机的进料段温度为17(TC,其余各段温度为21(TC,挤出过程中抽真空排气。造粒好的混合物在真空烘箱中,8(TC干燥IO小时后,使用手动式热压机压制成膜。热压机的温度为200°C,熔融时间为3min,保压时间为30秒。 压制好的熔体用冰水混合物淬冷后,制得厚度约为0.5mm的膜。薄膜充分干燥后,测试热处理前薄膜的冷结晶温度(Tee)为84.7'C,熔点(Tm)为164.5°C,将薄膜用钢框和夹子固定后,置于隧道烘箱中进行 After sufficiently drying the film, the cold crystallization temperature of the film before heat treatment tests (Tw) of 89.4 ", a melting point of CU 165.5'C. The resulting film was not heat-treated. After testing, the haze of the film was 2.5%, the heat resistance to 65.C "x", 8 (TC "x", 100 ° C "x". Comparative Example (4) the polylactic acid (4032D, Natureworks) in a vacuum oven, after drying 80.C IO hours, lauramide and ethylene bis (Ebla) by IOO: after I (parts by weight) is pre-mixed by a twin screw extruder co-extruded, pelletized feed section of the twin-screw extruder a temperature of 17 (. TC, the remaining section 21 is a temperature (TC, the extrusion process a vacuum vent. good mixture was granulated in a vacuum oven, 8 (after drying TC IO hours, using a manual press hot press forming. thermocompression after the temperature of the dryer is 200 ° C, the melting time of 3min, dwell time of 30 seconds. after the pressing a good melt quenched with ice-water mixture, to obtain a film thickness of about 0.5mm. film sufficiently dried, heat-treated test cold crystallization temperature of the film before (Tee) of 84.7'C, the melting point (Tm) of 164.5 ° C, the film after the steel frame and the clamps, placed in the tunnel oven for 处理。 热处理温度为120°C, 热处理时间为20秒。测试热处理后薄膜的雾度和耐热性。经测试,雾度为13.3%,耐热性为65。C"0)", 8(TC實,10(TC實o通过对比以上的实施例和比较例,发明人发现纯的聚乳酸薄膜,即使通过热处理,也不具有65。C的耐热性(比较例l、 2)。而当聚乳酸薄膜中含有乙撑双月桂酰胺(EBLA)时,冷结晶温度(Tee)显著降低(比较例3),从而可以使薄膜中的聚乳酸组分能够在相同热处理温度的条件下,更快,更容易的结晶。并且,通过在含有乙撑双月桂酰胺(EBLA)的聚乳酸薄膜中, 进一步添加苄叉山梨醇类化合物,热处理所导致的雾度上升被明显抑制,聚乳酸薄膜的透明性得到了维持(比较例4、实施例l)。并且,通过控制热处理温度和热处理时间,本发明可以自由的调节制品的耐热程度和透明性。 Treatment. The heat treatment temperature of 120 ° C, the heat treatment time is 20 seconds. The haze and heat resistance after the test of heat-treated films. After testing, the haze was 13.3%, the heat resistance is 65.C "0)", 8 ( TC solid, 10 (TC solid o the above Comparative Examples and Comparative Examples, the inventors have found that pure polylactic acid film, even by heat treatment, nor 65.C having heat resistance (Comparative Example l, 2). and when the polylactic acid film containing ethylene bis lauramide (Ebla), cold crystallization temperature (Tee) was significantly decreased (Comparative Example 3), thereby the thin film of the polylactic acid component can be at the same heat treatment temperature, more faster, easier crystallization. further, the polylactic acid film comprising ethylene bis lauramide (Ebla) is further added benzylidene sorbitol compound, heat treatment caused the haze increase was significantly inhibited, the polylactic acid film transparency was maintained (Comparative Example 4, Example l embodiment). Further, by controlling the heat treatment temperature and heat treatment time, the present invention can be freely adjusted and the degree of transparency of the heat-resistant products.

Claims (8)

1. 一种聚乳酸共混物,其特征在于所述的共混物主要由下列重量份的组分组成: 聚乳酸100 份酰胺类化合物0.1~10份山梨醇类化合物0.01~5份。 1. A polylactic acid blend, wherein said blend consists of the following main parts by weight of components: 100 parts of the polylactic acid amides of 0.1 to 10 parts sorbitol compound 0.01 to 5 parts.
2、 根据权利要求1所述的聚乳酸共混物,其特征在于所述的聚乳酸是聚乳酸均聚物、聚乳酸共聚物、聚乳酸立构复合物或者是它们之间的混合物。 2, the blend of the polylactic acid according to claim 1, wherein the polylactic acid is a polylactic acid homopolymer, a polylactic acid copolymer, a stereocomplex polylactic acid or a mixture therebetween.
3、 根据权利要求1所述的聚乳酸共混物,其特征在于所述的聚乳酸的重均分子量为2万〜80万。 3. The blend of polylactic acid according to claim 1, characterized in that the weight of the polylactic acid average molecular weight of 20,000 ~ 80 million.
4、 根据权利要求1所述的聚乳酸共混物,其特征在于所述的酰胺类化合物选自乙撑双垸基酰胺、饱和脂肪酸单酰胺、不饱和脂肪酸单酰胺或氨基酸酰胺中的一种或几种。 4, the polylactic acid according to claim blend according to claim 1, wherein the amide compound is selected from ethylene bis-amide embankment, saturated fatty acid monoamide, an unsaturated fatty acid monoamide or amino acid amides or more.
5、 根据权利要求1所述的聚乳酸共混物,其特征在于所述的山梨醇类化合物选自含有苄叉基团的山梨醇类化合物中的一种或几种。 5, the polylactic acid according to claim blend according to claim 1, wherein said sorbitol-based compound selected from the group comprising one or more benzylidene sorbitol compound in the group.
6、 一种聚乳酸共混物的成型品,其特征在于由权利要求1~5任意一项所述的聚乳酸共混物在成型时和/或成型后通过热处理得到。 6 A polylactic acid molded article of the blend, from 1 to 5, wherein the polylactic acid blend according to any one of claims obtained by a heat treatment after molding and / or shaping.
7、 根据权利要求6所述的成型品,其特征在于所述的成型品厚度为0.02~5mm。 7. The molded article according to claim 6, wherein said molded article having a thickness of 0.02 ~ 5mm.
8、 根据权利要求6所述的成型品,其特征在于热处理的温度范围为聚乳酸共混物的冷结晶起始温度以上熔点以下,热处理的时间为2秒钟到10分钟。 8. The molded article according to claim 6, characterized in that the heat treatment temperature range for the cold blend of polylactic acid crystallization starting temperature above the melting point, the heat treatment time of 2 seconds to 10 minutes.
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CN101857715A (en) * 2010-05-26 2010-10-13 上海大学 Method for quickly crystallizing polylactic acid
US9951184B2 (en) 2013-10-10 2018-04-24 International Business Machines Corporation Methods of preparing polyhemiaminals and polyhexahydrotriazines

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