WO2018028513A1 - Biodegradable polyester thin film and preparation method therefor - Google Patents

Biodegradable polyester thin film and preparation method therefor Download PDF

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WO2018028513A1
WO2018028513A1 PCT/CN2017/095942 CN2017095942W WO2018028513A1 WO 2018028513 A1 WO2018028513 A1 WO 2018028513A1 CN 2017095942 W CN2017095942 W CN 2017095942W WO 2018028513 A1 WO2018028513 A1 WO 2018028513A1
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Prior art keywords
biodegradable polyester
polyester film
film
longitudinal
tear strength
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PCT/CN2017/095942
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French (fr)
Chinese (zh)
Inventor
熊凯
袁志敏
蔡彤旻
黄险波
曾祥斌
焦健
苑仁旭
钟宇科
卢昌利
杨晖
麦开锦
董学腾
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金发科技股份有限公司
珠海万通化工有限公司
天津金发新材料有限公司
上海金发科技发展有限公司
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Publication of WO2018028513A1 publication Critical patent/WO2018028513A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the invention relates to the technical field of polymer materials, in particular to a biodegradable polyester film and a preparation method thereof.
  • Polylactic acid is completely biodegradable and derived from renewable resources such as plants. Its properties are similar to those of general-purpose plastic polypropylene, such as high modulus, high tensile strength and good processability. However, the brittleness of polylactic acid is severe, which severely limits its wide application. It is the main technical means to improve the toughness of polylactic acid by multi-component blending modification.
  • Polyterephthalic acid-adipate-1,4-butanediol terpolymer (PBAT) is also a fully biodegradable material with both PBA segment flexibility and PBT segments. The heat resistance and impact resistance, so the blending of PBAT and polylactic acid can effectively improve the performance of polylactic acid.
  • Patent Application No.: 201080050600.9 discloses a method of producing a shrink film comprising: A) 20-90% by weight biodegradable aliphatic-aromatic polyester; B) 10-80% by weight polylactic acid and C) 0- 2% by weight of compatibilizer, but no vertical and horizontal balance of the tear strength of the film was mentioned.
  • Light transmittance is the percentage of the luminous flux through the film and its incident light flux, which is usually one of the important parameters for characterizing the transparency of the film.
  • the crystallinity, crystal size and preparation process of the film material may cause different microstructures of the film molecules, thereby obtaining films of different light transmittance.
  • the invention discovers unexpectedly that when the light transmittance of the polyester film is controlled within the range of 80% to 90%, the longitudinal and lateral unbalance of the tear strength of the film material when the polyester film is used can be effectively improved.
  • the problem is that the prepared film has a high stiffness and a good longitudinal and lateral balance of the tear strength.
  • An object of the present invention is to provide a biodegradable polyester film having a good longitudinal and lateral balance of tear strength in order to overcome the deficiencies of the above-mentioned conventional film.
  • a biodegradable polyester film comprising, by weight, the following components:
  • the biodegradable polyester film has a light transmittance of 80% to 90% in a film thickness of 20 to 35 ⁇ m, preferably 83% to 88%, the light transmittance is measured according to GB/T 2410-2008.
  • the invention finds that when the light transmittance of the biodegradable polyester film is in the range of 80% to 90%, the crystallinity of the film material in the light transmittance range is low due to the difference in molecular microstructure. Therefore, the problem of the longitudinal and lateral unbalance of the tear strength of the film when the polyester film is used can be effectively improved, and the prepared film has a high stiffness and a good longitudinal and lateral balance of the tear strength.
  • the light transmittance of the biodegradable polyester film of the present invention is preferably in the range of 80% to 90%.
  • the biodegradable polyester film comprises, by weight, the following components:
  • the ratio of the longitudinal and transverse tear strength of the biodegradable polyester film with a film thickness of 20-35 ⁇ m is 1:1 to 1:2, indicating that the longitudinal and transverse balance of the film tear strength is good, and the longitudinal and transverse tear strength is good.
  • Ratio longitudinal tear strength / transverse tear strength, wherein the longitudinal and transverse tear strength is determined according to GB/T 16578.2.
  • the biodegradable polyester film has a film thickness of 20-35 ⁇ m according to GB/T 1040.3, and a longitudinal 10% modulus is between 4 and 10 N, and a lateral 10% modulus is between 2 and 5 N.
  • the polylactic acid has a melt flow rate of 2-5 g/10 min at a temperature of 190 ° C and a load of 2.16 kg;
  • the polyadipate/butylene terephthalate had a melt flow rate of 2-5 g/10 min at a temperature of 190 ° C under a load of 2.16 kg.
  • the biodegradable polyester film of the present invention further comprises (c) an epoxy copolymer of 0 to 2 parts, (d) talc and/or calcium carbonate in an amount of from 0 to 8 parts by weight.
  • the epoxy-based copolymer is an epoxy-based copolymer having 2 to 15 epoxy groups in the structure, and the compatibilizing agent can react with terminal groups of PBAT and PLA such as a hydroxyl group or a carboxyl group to increase compatibility. .
  • the preparation method of the biodegradable polyester film of the invention comprises the following steps:
  • the biodegradable polyester mixture is blown on a double-air ring blown film machine to obtain a film having a film thickness of 20-35 ⁇ m, wherein the air volume of the inner and outer air rings is 1:1 to 1:3.
  • the inflation ratio is between 2.5 and 4.0.
  • the invention has the following beneficial effects:
  • the invention can effectively improve the polyester film by blending polyadipate/butylene terephthalate with polylactic acid and controlling the transmittance of the polyester film to be in the range of 80% to 90%.
  • Vertical and horizontal unevenness of the tear strength of the film when it is used The problem of balance is that the prepared film has a high stiffness and a good vertical and horizontal balance of tear strength.
  • the raw materials used in the present invention are as follows:
  • PBAT BASF, Germany, trade name Ecoflex@, MFR is 3g/10min (190°C/2.16kg);
  • PLA purchased from Natureworks, USA, MFR is 3g/10min (190 ° C / 2.16kg);
  • Talc powder and calcium carbonate are commercially available
  • Epoxy copolymer 9 epoxy groups in the structure, BASF, Germany, trade name ADR-4370;
  • the detection method or standard used in the present invention is:
  • the obtained biodegradable polyester composition is blown on a double air ring blown film machine with a film thickness of 25 ⁇ m, and the air volume of the inner and outer air rings is controlled between 1:1 and 1:3, and the blow ratio is 2.5 to 4.0.
  • the properties of the obtained film are shown in Table 1.
  • Comparative Example 1 The air volume of the inner and outer air rings was controlled to be 1:3.5, and the inflation ratio was 4.0. The rest were the same as in the examples.
  • Comparative Example 2 The air volume of the inner and outer air rings was controlled to be 1:0.8, and the inflation ratio was 4.0. The rest were the same as in the examples.
  • Comparative Example 3 The air volume of the inner and outer air rings was controlled to be 1:4, and the inflation ratio was 2.0. The rest were the same as in the examples.
  • the present invention is modified by blending poly(adipic acid)/butylene terephthalate with polylactic acid, and by controlling the light transmission of the polyester film.
  • the rate is in the range of 80%-90%, which can effectively improve the longitudinal and lateral imbalance of the tear strength of the film when the polyester film is used, and the prepared film has high stiffness and vertical and horizontal tear strength. Balance is good.

Abstract

Disclosed are a biodegradable polyester thin film and a preparation method therefor. The biodegradable polyester thin film comprises the following components: (a) 20-50 parts of polylactic acid; (b) 50-80 parts of polybutylene adipate/terephthalate, wherein the light transmittance of the biodegradable polyester thin film is 80-90 percent when the film thickness is 20-35 μm. As the polybutylene adipate/terephthalate and the polylactic acid are blended and modified, and the light transmittance of the polyester thin film is controlled to be within 80-90 percent, the problems of the film material of the polyester thin film lacking uniformity of longitudinal and transverse tearing strength and having poor transparency when the polyester thin film is used can be effectively improved. The thin film thus prepared has high film stiffness and uniformity of longitudinal and transverse tearing strength.

Description

[根据细则37.2由ISA制定的发明名称]　可生物降解聚酯薄膜及其制备方法[Invention name established by ISA according to Rule 37.2] Biodegradable polyester film and preparation method thereof 技术领域Technical field
本发明涉及高分子材料技术领域，具体涉及一种可生物降解聚酯薄膜及其制备方法。The invention relates to the technical field of polymer materials, in particular to a biodegradable polyester film and a preparation method thereof.
背景技术Background technique
聚乳酸(PLA)可完全生物降解，且来源于植物等可再生资源，本身的性能类似于通用塑料聚丙烯，如模量高、抗张强度大和可加工性能好。但是，聚乳酸的脆性严重，严重的限制了它的广泛应用，采用多组分共混改性的方法提高聚乳酸的韧性是目前的主要技术手段。聚对苯二甲酸-己二酸-1,4-丁二醇三元共聚酯(PBAT)，也是一种可完全生物降解的材料，并兼具了PBA链段的柔顺性及PBT链段的耐热性和抗冲击性，因此将PBAT与聚乳酸共混改性可以有效提高聚乳酸的性能。但是当PLA含量在25％以上时，此类共混材料作为膜或者片材使用时存在其膜材的撕裂强度的纵横向均衡性差，影响了使用性能。专利申请号：201080050600.9公开了生产收缩膜的方法，所述膜包含：A)20-90重量％可生物降解脂族-芳族聚酯；B)10-80重量％聚乳酸和C)0-2重量％增容剂，但是对于膜材的撕裂强度的纵横向均衡性未提及。Polylactic acid (PLA) is completely biodegradable and derived from renewable resources such as plants. Its properties are similar to those of general-purpose plastic polypropylene, such as high modulus, high tensile strength and good processability. However, the brittleness of polylactic acid is severe, which severely limits its wide application. It is the main technical means to improve the toughness of polylactic acid by multi-component blending modification. Polyterephthalic acid-adipate-1,4-butanediol terpolymer (PBAT) is also a fully biodegradable material with both PBA segment flexibility and PBT segments. The heat resistance and impact resistance, so the blending of PBAT and polylactic acid can effectively improve the performance of polylactic acid. However, when the PLA content is above 25%, when such a blend material is used as a film or a sheet, the longitudinal and lateral balance of the tear strength of the film material is poor, which affects the use property. Patent Application No.: 201080050600.9 discloses a method of producing a shrink film comprising: A) 20-90% by weight biodegradable aliphatic-aromatic polyester; B) 10-80% by weight polylactic acid and C) 0- 2% by weight of compatibilizer, but no vertical and horizontal balance of the tear strength of the film was mentioned.
透光率是指透过薄膜的光通量与其入射光通量的百分率，通常是表征薄膜透明性的重要参数之一。影响薄膜透光率的因素有很多，比如，薄膜材料的结晶度、晶体尺寸及制备工艺等不同，均会导致薄膜分子微观结构的不同，从而得到不同透光率的薄膜。本发明通过研究意外的发现，将聚酯薄膜的透光率控制在80％～90％范围内时，可以有效改善聚酯薄膜使用时存在其膜材的撕裂强度的纵横向不均衡性的问题，制备得到的薄膜挺度较高，撕裂强度的纵横向均衡性较好。Light transmittance is the percentage of the luminous flux through the film and its incident light flux, which is usually one of the important parameters for characterizing the transparency of the film. There are many factors affecting the transmittance of the film. For example, the crystallinity, crystal size and preparation process of the film material may cause different microstructures of the film molecules, thereby obtaining films of different light transmittance. The invention discovers unexpectedly that when the light transmittance of the polyester film is controlled within the range of 80% to 90%, the longitudinal and lateral unbalance of the tear strength of the film material when the polyester film is used can be effectively improved. The problem is that the prepared film has a high stiffness and a good longitudinal and lateral balance of the tear strength.
发明内容Summary of the invention
本发明的目的在于克服上述现有膜材存在的不足，提供一种撕裂强度的纵横向均衡性较好的可生物降解聚酯薄膜。SUMMARY OF THE INVENTION An object of the present invention is to provide a biodegradable polyester film having a good longitudinal and lateral balance of tear strength in order to overcome the deficiencies of the above-mentioned conventional film.
本发明是通过以下技术方案实现：The invention is achieved by the following technical solutions:
一种可生物降解聚酯薄膜，按重量份计，包括如下组分：A biodegradable polyester film comprising, by weight, the following components:
(a)聚乳酸      20-50份(a) Polylactic acid 20-50 parts
(b)聚己二酸/对苯二甲酸丁二酯  50～80份。(b) Polybutylene adipate / butylene terephthalate 50 to 80 parts.
其中，所述可生物降解聚酯薄膜在膜厚为20-35μm的透光率为80％～90％，优选为 83％～88％，透光率根据GB/T 2410-2008测定。Wherein, the biodegradable polyester film has a light transmittance of 80% to 90% in a film thickness of 20 to 35 μm, preferably 83% to 88%, the light transmittance is measured according to GB/T 2410-2008.
本发明通过研究发现，当可生物降解聚酯薄膜的透光率在80％～90％范围内时，由于分子微观结构的不同，在此透光率范围内的薄膜材料的结晶度较低，从而可以有效改善聚酯薄膜使用时存在其膜材的撕裂强度的纵横向不均衡性的问题，制备得到的薄膜挺度较高，撕裂强度的纵横向均衡性较好。当薄膜的透光率低于80％或高于90％时，制备得到的薄膜的挺度较低，撕裂强度的纵横向均衡性较差，影响其使用性能。因此，本发明选择可生物降解聚酯薄膜的透光率在80％～90％范围内为宜。The invention finds that when the light transmittance of the biodegradable polyester film is in the range of 80% to 90%, the crystallinity of the film material in the light transmittance range is low due to the difference in molecular microstructure. Therefore, the problem of the longitudinal and lateral unbalance of the tear strength of the film when the polyester film is used can be effectively improved, and the prepared film has a high stiffness and a good longitudinal and lateral balance of the tear strength. When the light transmittance of the film is less than 80% or higher than 90%, the prepared film has lower stiffness and the longitudinal and lateral balance of the tear strength is poor, which affects the use performance. Therefore, the light transmittance of the biodegradable polyester film of the present invention is preferably in the range of 80% to 90%.
优选的，所述可生物降解聚酯薄膜，按重量份计，包括如下组分：Preferably, the biodegradable polyester film comprises, by weight, the following components:
(a)聚乳酸         30-45份(a) Polylactic acid 30-45 parts
(b)聚己二酸/对苯二甲酸丁二酯 55～70份。(b) Polyethylene adipate/butylene terephthalate 55 to 70 parts.
所述可生物降解聚酯薄膜在膜厚为20-35μm的纵横向撕裂强度的比值为1:1～1:2，表明薄膜撕裂强度的纵横向均衡性较好，纵横向撕裂强度的比值＝纵向撕裂强度/横向撕裂强度，其中纵横向撕裂强度根据GB/T 16578.2测定。The ratio of the longitudinal and transverse tear strength of the biodegradable polyester film with a film thickness of 20-35 μm is 1:1 to 1:2, indicating that the longitudinal and transverse balance of the film tear strength is good, and the longitudinal and transverse tear strength is good. Ratio = longitudinal tear strength / transverse tear strength, wherein the longitudinal and transverse tear strength is determined according to GB/T 16578.2.
所述可生物降解聚酯薄膜在膜厚为20-35μm根据GB/T 1040.3测定的纵向10％定伸力在4～10N之间，横向10％定伸力在2～5N之间。The biodegradable polyester film has a film thickness of 20-35 μm according to GB/T 1040.3, and a longitudinal 10% modulus is between 4 and 10 N, and a lateral 10% modulus is between 2 and 5 N.
所述聚乳酸在190℃温度、2.16kg载荷条件下的熔体流动速率为2-5g/10min；The polylactic acid has a melt flow rate of 2-5 g/10 min at a temperature of 190 ° C and a load of 2.16 kg;
所述聚己二酸/对苯二甲酸丁二酯在190℃温度、2.16kg载荷条件下的熔体流动速率为2-5g/10min。The polyadipate/butylene terephthalate had a melt flow rate of 2-5 g/10 min at a temperature of 190 ° C under a load of 2.16 kg.
本发明所述的可生物降解聚酯薄膜，按重量份数计，还包括(c)环氧类共聚物0～2份，(d)滑石粉和/或碳酸钙0～8份。The biodegradable polyester film of the present invention further comprises (c) an epoxy copolymer of 0 to 2 parts, (d) talc and/or calcium carbonate in an amount of from 0 to 8 parts by weight.
所述环氧类共聚物为结构中含有2～15个环氧基团的环氧类共聚物，此类相容剂可以与PBAT和PLA的端基如羟基或羧基反应，从而增加相容性。The epoxy-based copolymer is an epoxy-based copolymer having 2 to 15 epoxy groups in the structure, and the compatibilizing agent can react with terminal groups of PBAT and PLA such as a hydroxyl group or a carboxyl group to increase compatibility. .
本发明所述的可生物降解聚酯薄膜的制备方法，包括如下步骤：The preparation method of the biodegradable polyester film of the invention comprises the following steps:
(1)将聚乳酸、聚己二酸/对苯二甲酸丁二酯、环氧类共聚物、滑石粉和/或碳酸钙按重量配比混匀后投入双螺杆挤出机中，于170-210℃挤出、造粒，得到可生物降解聚酯混合物；(1) Mixing polylactic acid, polyadipate/butylene terephthalate, epoxy copolymer, talc and/or calcium carbonate in a weight ratio, and then putting them into a twin-screw extruder at 170 Extrusion and granulation at -210 ° C to obtain a biodegradable polyester mixture;
(2)将可生物降解聚酯混合物在双风环吹膜机上进行吹膜，得到膜厚为20-35μm的薄膜，其中，内风环和外风环的风量在1:1～1:3之间，吹胀比为2.5～4.0。(2) The biodegradable polyester mixture is blown on a double-air ring blown film machine to obtain a film having a film thickness of 20-35 μm, wherein the air volume of the inner and outer air rings is 1:1 to 1:3. The inflation ratio is between 2.5 and 4.0.
本发明与现有技术相比，具有如下有益效果：Compared with the prior art, the invention has the following beneficial effects:
本发明通过将聚己二酸/对苯二甲酸丁二酯与聚乳酸共混改性，并将聚酯薄膜的透光率控制在80％～90％范围内时，可以有效改善聚酯薄膜使用时存在其膜材的撕裂强度的纵横向不均 衡性的问题，制备得到的薄膜挺度较高，撕裂强度的纵横向均衡性较好。The invention can effectively improve the polyester film by blending polyadipate/butylene terephthalate with polylactic acid and controlling the transmittance of the polyester film to be in the range of 80% to 90%. Vertical and horizontal unevenness of the tear strength of the film when it is used The problem of balance is that the prepared film has a high stiffness and a good vertical and horizontal balance of tear strength.
具体实施方式detailed description
下面通过具体实施方式来进一步说明本发明，以下实施例为本发明较佳的实施方式，但本发明的实施方式并不受下述实施例的限制。The invention is further illustrated by the following detailed description of the preferred embodiments of the invention, but the embodiments of the invention are not limited by the following examples.
本发明所采用的原料如下：The raw materials used in the present invention are as follows:
PBAT：德国BASF公司，商品名Ecoflex@，MFR为3g/10min(190℃/2.16kg)；PBAT: BASF, Germany, trade name Ecoflex@, MFR is 3g/10min (190°C/2.16kg);
PLA：购自美国Natureworks公司，MFR为3g/10min(190℃/2.16kg)；PLA: purchased from Natureworks, USA, MFR is 3g/10min (190 ° C / 2.16kg);
滑石粉和碳酸钙均为市购；Talc powder and calcium carbonate are commercially available;
环氧类共聚物：结构中含有9个环氧基团，德国BASF公司，商品名ADR-4370；Epoxy copolymer: 9 epoxy groups in the structure, BASF, Germany, trade name ADR-4370;
本发明所用的检测方法或标准为：The detection method or standard used in the present invention is:
纵向10％定伸力：GB/T 1040.3 塑料 拉伸性能的测定 第3部分：薄膜和薄片的试验条件，膜厚为20-35μm；Longitudinal 10% tensile strength: GB/T 1040.3 Determination of tensile properties - Part 3: Test conditions for film and sheet, film thickness 20-35 μm;
横向10％定伸力：GB/T 1040.3 塑料 拉伸性能的测定 第3部分：薄膜和薄片的试验条件，膜厚为20-35μm；Plastics - Determination of tensile properties - Part 3: Test conditions for film and sheet, film thickness 20-35 μm;
透光率：GB/T 2410-2008 透明塑料透光率和雾度的测定，膜厚为20-35μm；雾度：GB/T 2410-2008 透明塑料透光率和雾度的测定，膜厚为20-35μm；Transmittance: GB/T 2410-2008 Transparent plastic transmittance and haze measurement, film thickness 20-35μm; Haze: GB/T 2410-2008 Transparent plastic transmittance and haze determination, film thickness 20-35 μm;
纵横向撕裂强度比值：根据GB/T 16578.2 塑料 薄膜和薄片 耐撕裂性能的测定 第2部分：埃莱门多夫法，膜厚为20-35μm，分别测定纵横向撕裂强度，然后再根据如下公式计算：纵横向撕裂强度的比值＝纵向撕裂强度/横向撕裂强度；比值越接近1：1，纵横向撕裂强度的均衡性越好。Longitudinal and transverse tear strength ratio: according to GB/T 16578.2 Plastic film and sheet Determination of tearing resistance Part 2: Elemendorf method, film thickness 20-35 μm, respectively, the longitudinal and transverse tear strength, and then Calculated according to the following formula: ratio of longitudinal and transverse tear strength = longitudinal tear strength / transverse tear strength; the closer the ratio is to 1:1, the better the balance of longitudinal and transverse tear strength.
实施例1-10Examples 1-10
按表1所示配比，将PBAT、PLA、滑石粉或碳酸钙、环氧类共聚物混匀后投入双螺杆挤出机中，于170-210℃挤出、造粒，可生物降解聚酯混合物；According to the ratio shown in Table 1, PBAT, PLA, talc or calcium carbonate, epoxy copolymer are mixed, put into a twin-screw extruder, extruded at 170-210 ° C, granulated, biodegradable Ester mixture
将得到的生物降解聚酯组合物在双风环吹膜机上进行吹膜，膜厚为25μm，控制内风环和外风环的风量在1:1～1:3之间，吹胀比为2.5～4.0。所得薄膜各性能如表1所示。The obtained biodegradable polyester composition is blown on a double air ring blown film machine with a film thickness of 25 μm, and the air volume of the inner and outer air rings is controlled between 1:1 and 1:3, and the blow ratio is 2.5 to 4.0. The properties of the obtained film are shown in Table 1.
对比例1 控制内风环和外风环的风量为1:3.5，吹胀比为4.0，其余同实施例。Comparative Example 1 The air volume of the inner and outer air rings was controlled to be 1:3.5, and the inflation ratio was 4.0. The rest were the same as in the examples.
对比例2 控制内风环和外风环的风量为1:0.8，吹胀比为4.0，其余同实施例。Comparative Example 2 The air volume of the inner and outer air rings was controlled to be 1:0.8, and the inflation ratio was 4.0. The rest were the same as in the examples.
对比例3 控制内风环和外风环的风量为1：4，吹胀比为2.0，其余同实施例。Comparative Example 3 The air volume of the inner and outer air rings was controlled to be 1:4, and the inflation ratio was 2.0. The rest were the same as in the examples.
表1 实施例及对比例各组分组成及性能结果 Table 1 Example and Comparative Example Composition and Performance Results of Each Component
Figure PCTCN2017095942-appb-000001
Figure PCTCN2017095942-appb-000001
续表1： Continued Table 1:
Figure PCTCN2017095942-appb-000002
Figure PCTCN2017095942-appb-000002
由对比例1-3和实施例1-10对比可以看出，本发明通过将聚己二酸/对苯二甲酸丁二酯与聚乳酸共混改性，并通过控制聚酯薄膜的透光率在80％-90％范围内，可以有效改善聚酯薄膜使用时存在其膜材的撕裂强度的纵横向不均衡性的问题，制备得到的薄膜挺度较高，撕裂强度的纵横向均衡性较好。 It can be seen from the comparison between Comparative Examples 1-3 and Examples 1-10 that the present invention is modified by blending poly(adipic acid)/butylene terephthalate with polylactic acid, and by controlling the light transmission of the polyester film. The rate is in the range of 80%-90%, which can effectively improve the longitudinal and lateral imbalance of the tear strength of the film when the polyester film is used, and the prepared film has high stiffness and vertical and horizontal tear strength. Balance is good.

Claims (8)

  1. 一种可生物降解聚酯薄膜，其特征在于，按重量份计，包括如下组分：A biodegradable polyester film characterized by comprising the following components by weight:
    (a)聚乳酸   20-50份(a) Polylactic acid 20-50 parts
    (b)聚己二酸/对苯二甲酸丁二酯   50～80份(b) Polyadipate/butylene terephthalate 50-80 parts
    其中，所述可生物降解聚酯薄膜在膜厚为20-35μm的透光率为80％～90％，优选为83％～88％，透光率根据GB/T 2410-2008测定。Wherein, the biodegradable polyester film has a light transmittance of 80% to 90%, preferably 83% to 88%, and a light transmittance according to GB/T 2410-2008.
  2. 根据权利要求1所述的可生物降解聚酯薄膜，其特征在于，按重量份计，包括如下组分：The biodegradable polyester film according to claim 1, which comprises, by weight, the following components:
    (a)聚乳酸   30-45份(a) Polylactic acid 30-45 parts
    (b)聚己二酸/对苯二甲酸丁二酯   55～70份。(b) Polyethylene adipate/butylene terephthalate 55 to 70 parts.
  3. 根据权利要求1或2所述的可生物降解聚酯薄膜，其特征在于：所述可生物降解聚酯薄膜在膜厚为20-35μm的纵横向撕裂强度的比值为1:1～1:2，纵横向撕裂强度的比值＝纵向撕裂强度/横向撕裂强度，其中纵横向撕裂强度根据GB/T 16578.2测定。The biodegradable polyester film according to claim 1 or 2, wherein the ratio of the longitudinal and transverse tear strength of the biodegradable polyester film to a film thickness of 20 to 35 μm is 1:1 to 1: 2, the ratio of longitudinal and transverse tear strength = longitudinal tear strength / transverse tear strength, wherein the longitudinal and transverse tear strength is determined according to GB/T 16578.2.
  4. 根据权利要求1或2所述的可生物降解聚酯薄膜，其特征在于：所述可生物降解聚酯薄膜在膜厚为20-35μm根据GB/T 1040.3测定的纵向10％定伸力在4～10N之间，横向10％定伸力在2～5N之间。The biodegradable polyester film according to claim 1 or 2, wherein the biodegradable polyester film has a film thickness of 20-35 μm and a longitudinal 10% modulus determined according to GB/T 1040.3. Between 10N and 10% in the lateral direction is between 2 and 5N.
  5. 根据权利要求1或2所述的可生物降解聚酯薄膜，其特征在于：所述聚乳酸在190℃温度、2.16kg载荷条件下的熔体流动速率为2-5g/10min；所述聚己二酸/对苯二甲酸丁二酯在190℃温度、2.16kg载荷条件下的熔体流动速率为2-5g/10min。The biodegradable polyester film according to claim 1 or 2, wherein the polylactic acid has a melt flow rate of 2 to 5 g/10 min at a temperature of 190 ° C and a load of 2.16 kg; The melt flow rate of diacid/butylene terephthalate at a temperature of 190 ° C under a load of 2.16 kg was 2-5 g/10 min.
  6. 根据权利要求1或2所述的可生物降解聚酯薄膜，其特征在于：按重量份数计，还包括(c)环氧类共聚物0～2份，(d)滑石粉和/或碳酸钙0～8份。The biodegradable polyester film according to claim 1 or 2, which further comprises (c) an epoxy copolymer of 0 to 2 parts by weight, (d) talc and/or carbonic acid. Calcium 0 to 8 parts.
  7. 根据权利要求6所述的可生物降解聚酯薄膜，其特征在于：所述环氧类共聚物为结构中含有2～15个环氧基团的环氧类共聚物。The biodegradable polyester film according to claim 6, wherein the epoxy-based copolymer is an epoxy-based copolymer having 2 to 15 epoxy groups in its structure.
  8. 根据权利要求1-7任一项所述的可生物降解聚酯薄膜的制备方法，其特征在于：包括如下步骤：The method for preparing a biodegradable polyester film according to any one of claims 1 to 7, comprising the steps of:
    (1)将聚乳酸、聚己二酸/对苯二甲酸丁二酯、环氧类共聚物、滑石粉和/或碳酸钙按重量配比混匀后投入双螺杆挤出机中，于170-210℃挤出、造粒，得到可生物降解聚酯混合物；(1) Mixing polylactic acid, polyadipate/butylene terephthalate, epoxy copolymer, talc and/or calcium carbonate in a weight ratio, and then putting them into a twin-screw extruder at 170 Extrusion and granulation at -210 ° C to obtain a biodegradable polyester mixture;
    (2)将可生物降解聚酯混合物在双风环吹膜机上进行吹膜，得到膜厚为20-35μm的薄膜，其中，内风环和外风环的风量在1:1～1:3之间，吹胀比为2.5～4.0。 (2) The biodegradable polyester mixture is blown on a double-air ring blown film machine to obtain a film having a film thickness of 20-35 μm, wherein the air volume of the inner and outer air rings is 1:1 to 1:3. The inflation ratio is between 2.5 and 4.0.
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