WO2024037440A1 - Anti-sticking master batch for bope film, preparation method therefor, and use thereof - Google Patents

Anti-sticking master batch for bope film, preparation method therefor, and use thereof Download PDF

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Publication number
WO2024037440A1
WO2024037440A1 PCT/CN2023/112485 CN2023112485W WO2024037440A1 WO 2024037440 A1 WO2024037440 A1 WO 2024037440A1 CN 2023112485 W CN2023112485 W CN 2023112485W WO 2024037440 A1 WO2024037440 A1 WO 2024037440A1
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sticking
masterbatch
film
bope
parts
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PCT/CN2023/112485
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French (fr)
Chinese (zh)
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刘小珊
汪晓芳
王微微
陈嘉欣
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汕头市贝斯特科技有限公司
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Publication of WO2024037440A1 publication Critical patent/WO2024037440A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • 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
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2433/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • 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
    • C08K3/36—Silica
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/28—Glass
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/25—Greenhouse technology, e.g. cooling systems therefor

Definitions

  • the invention relates to an anti-sticking masterbatch for BOPE films and its preparation method and application. It specifically relates to the general process of processing and ingredients.
  • BOPE film is a new type of packaging material that can greatly improve the strength of composite packaging bags and has small deformation. It can replace BOPA, PET and other materials. It is an environmentally friendly solution that allows a single material to be recycled. PE films tend to stick during the rewinding process, causing the rolled film to be unable to be unrolled and cut, seriously affecting the later use of the film. In order to reduce the adhesion of the film, a certain amount of anti-adhesive agent needs to be added to the surface of the film. However, the anti-sticking masterbatch used in blown or cast PE films has limited anti-sticking properties and is not suitable for biaxially oriented films. The introduced functional additives are used to prepare BOPE films.
  • the main film materials and functional additives have poor compatibility and dispersion, which will affect the mechanical properties of the film.
  • the anti-adhesive masterbatch currently on the market used in the production of BOPE films still has the problem of insufficient anti-adhesiveness and cannot be used in batches.
  • the dispersion of the anti-adhesive masterbatch in the main material of BOPE film is not good, and there is high haze. There are many defects such as eye crystal spots and poor film surface quality.
  • Chinese invention patent CN111114061B discloses a tear-resistant polyethylene film and its preparation method. Multiple ethylene layers are formed by reacting ethylene/ ⁇ -olefin copolymer linear low-density polyethylene with a cross-linking agent. The formed BOPE film has a high It has high tensile strength and puncture strength, and has good tear resistance. However, using silica as the anti-sticking agent results in a film with poor optical transparency and high haze.
  • Chinese invention patent CN105623069B discloses a spectroscopic ecological agricultural greenhouse energy-concentrating film and its preparation method.
  • the first aspect of the present invention provides an anti-sticking masterbatch for BOPE films, which is characterized in that the preparation raw materials include: 80-100 parts by weight of matrix resin, 5-15 parts of anti-sticking agent, antioxidant 0.5-1.5 parts of the anti-sticking agent, 0.1-1.5 parts of the dispersing agent, the particle size of the anti-sticking agent is 3-8 ⁇ m, and the particle size distribution width is 0.5-2.
  • the matrix resin is PE resin, selected from one or a combination of LDPE, MLLDPE, LLDPE, MDPE, HDPE, modified polyethylene, and ethylene copolymers.
  • the matrix resin is a combination of LDPE and MLLDPE.
  • the weight ratio of the LDPE and MLLDPE is (40-60): (30-45).
  • the weight ratio of the LDPE and MLLDPE is 50:38.
  • the melt index of the matrix resin is 1-8g/10min under the conditions of 190°C and 2.16kg.
  • the melt index of the matrix resin is 1.5-6g/10min under the conditions of 190°C and 2.16kg.
  • the melt index of the LDPE is 4g/10min
  • the melt index of the MLLDPE is 1.5g/10min.
  • the weight ratio of (40-60): (30-45) for LDPE and MLLDPE can reduce the problem of poor dispersion of anti-sticking agents caused by low melt index.
  • the possible reason is that the synergistic effect of LDPE and MLLDPE makes the linear structure of polyethylene entangle on the surface of the anti-adhesive agent, increases the steric hindrance between the anti-adhesive agent particles, prevents the agglomeration of the anti-adhesive agent particles, and allows the anti-adhesive agent to be Evenly dispersed in the matrix resin.
  • the particle size of the anti-adhesive agent is 3-8 ⁇ m, and the particle size distribution width is 0.5-2.
  • the anti-sticking agent is selected from the group consisting of silica, polymer microspheres, glass microspheres, talc, calcium carbonate, diatomaceous earth, kaolin, Yuanming powder, wollastonite, and calcium sulfate. one or a combination of several.
  • the anti-sticking agent is a combination of silica, PMMA polymer microspheres, and glass microspheres.
  • the weight ratio of the silica, polymer microspheres PMMA, and glass microspheres is (2-4): (1-3): (4-6).
  • the weight ratio of silica, polymer microspheres PMMA, and glass microspheres is 3:2:5.
  • the antioxidant is selected from one or a combination of several types of phosphorus antioxidants, phenolic antioxidants, amine antioxidants, and sulfur antioxidants.
  • the amine antioxidant at least includes a hydroxylamine antioxidant.
  • the antioxidant is a hydroxylamine antioxidant.
  • the hydroxylamine antioxidant is a combination of Revonox 420V and Irgastab FS042.
  • the hydroxylamine antioxidant described in this application is a phenol-free antioxidant and has high color protection, which can effectively avoid the discoloration of hindered phenolic antioxidants under NOx gas smoke and will not cause yellowing problems.
  • the hydroxylamine antioxidant of the present application has good compatibility and low volatility with PE materials, which can not only improve the melting stability of the polymer, but also improve the transparency of the product and extend the service life of the product.
  • the dispersant is selected from one or a combination of polyethylene wax, stearic acid, stearate, polyvinyl alcohol, and wax powder.
  • the dispersant is stearate. More preferably, the dispersant is magnesium stearate. More preferably, the dispersant is magnesium hydroxystearate.
  • the magnesium hydroxystearate has a non-linear structure, which is more closely interlocked with the PE resin, and the magnesium hydroxystearate has a bridging effect, which can make the antioxidant, anti-sticking agent and resin form a more uniform whole. Thereby improving the surface properties of the film.
  • a second aspect of the invention provides a method for preparing an anti-adhesive masterbatch for BOPE films, which includes the following steps:
  • the traditional preparation process of functional masterbatch is to uniformly mix all the raw materials and then process them at once. Due to the low melt index and poor fluidity of the PE resin, it is difficult to evenly disperse the ultra-high content of anti-sticking agent in the resin carrier. . If the temperature is set too high, the resin will be easily thermally oxidized, resulting in an increase in small molecules and carbon deposits, leaving many black spots in the masterbatch, affecting the preparation of high-quality films downstream.
  • the side feeding method is used to evenly disperse the high-content anti-sticking agent in the matrix resin.
  • the PE resin is fully melted in the extruder first, so that the anti-sticking agent can be evenly and effectively dispersed in the molten matrix resin.
  • the applicant further found that a certain type of anti-sticking agent will produce a pungent smell after being heated at a high temperature of 200-240°C.
  • the side feeding method can greatly shorten the heating time of the anti-sticking agent, thereby reducing the pungent smell from the source.
  • the use of side-feeding processing technology not only ensures that the high-content anti-sticking agent is effectively dispersed in the matrix resin and downstream films, but also avoids the irritating odor caused by excessive heating of the anti-sticking agent.
  • a high-quality anti-adhesive masterbatch with excellent quality, good dispersion, and good film-forming and processing properties during the BOPE film preparation process can be prepared.
  • the third aspect of the present invention provides an application of an anti-adhesive masterbatch for BOPE films, which is used in the preparation of BOPE films.
  • the BOPE films have a 1-5 layer structure and a thickness of 10-80 ⁇ m.
  • the BOPE film has a three-layer structure and a thickness of 20-30 ⁇ m.
  • the BOPE film includes a first surface layer, a core layer and a second surface layer from top to bottom.
  • the anti-sticking masterbatch is added to the first surface layer and the second surface layer, and the thickness of the first surface layer and the second surface layer is 1.0-1.5 ⁇ m.
  • the weight fraction of the anti-sticking masterbatch added to the BOPE film is 1-10%.
  • the added weight fraction of the anti-sticking masterbatch in the BOPE film is 4%.
  • the anti-sticking masterbatch for BOPE films described in this application uses synergistic effects of LDPE and MLLDPE resins with a melt index of 1.5-6g/10min, which improves the compatibility and dispersion of the anti-sticking agent and the carrier resin, and reduces the cost of the masterbatch.
  • the influence on later film processing makes the film have good film surface quality.
  • the anti-sticking masterbatch for BOPE films described in this application uses a combination of synthetic silica, PMMA microspheres and glass microspheres as the anti-sticking agent, which can make the prepared film have excellent anti-sticking properties, and the film surface It has a low friction coefficient and the film surface has highly transparent optical properties.
  • the anti-adhesive masterbatch for BOPE films described in this application uses anti-adhesive particles with an average particle size of 5-6 ⁇ m and a distribution width of ⁇ 1.5, which can make the prepared film have stable anti-adhesive properties, whether it is electrical It is not easy to bond whether the corona surface is on the corona surface or the corona surface is on the non-corona surface.
  • the anti-sticking masterbatch for BOPE films described in this application uses side feeding. After the melted part of the matrix resin is plasticized, anti-sticking agents, antioxidants and dispersants are added, which can reduce the adhesion of the anti-sticking agent particles. Heating time reduces the generation of pungent odors from the source.
  • the anti-adhesive masterbatch for BOPE films described in this application has good compatibility with BOPE main materials.
  • the prepared BOPE film has an excellent film surface without defects such as orange peel lines, mold lip lines, and white spots, and Clear and translucent.
  • the preparation raw materials include: 88.5g of matrix resin, 10g of anti-sticking agent, 1g of antioxidant and 0.5g of dispersant in parts by weight.
  • the matrix resin is a combination of LDPE and MLLDPE.
  • the weight ratio of LDPE and MLLDPE is 50:38.5.
  • the melt index of the LDPE is 4g/10min. It is purchased from China Shipping Shell with the model number LDPE 2420K; the melt index of the MLLDPE is 1.5g/10min, purchased from Dow Chemical, model TF80.
  • the anti-adhesive agent is synthetic silica with a particle size of 5 ⁇ m and a distribution width of 1.36, purchased from Grace in the United States.
  • the antioxidant is a combination of Revonox 420V and Irgastab FS042, with a weight ratio of 1:1.
  • the Revonox 420V is purchased from Qitai (Shanghai) Chemical Technology Co., Ltd.; the Irgastab FS042 is purchased from BASF, Germany.
  • the dispersant is magnesium hydroxystearate, purchased from Jamaicai Chemical (China) Co., Ltd., model number is kpw-12p.
  • a method for preparing anti-adhesive masterbatch for BOPE films including the following steps:
  • An anti-sticking masterbatch for BOPE films The specific steps are the same as in Example 1. The difference is that the anti-sticking agent is PMMA polymer microspheres, with a particle size of 5 ⁇ m and a distribution width of 1.12.
  • An anti-adhesive masterbatch for BOPE films The specific steps are the same as in Example 1. The difference is that the anti-adhesive agent is glass beads with a particle size of 5 ⁇ m and a distribution width of 1.22.
  • An anti-adhesive masterbatch for BOPE films The specific steps are the same as in Example 1. The difference is that the anti-adhesive agent is a combination of synthetic silica, PMMA polymer microspheres and glass microspheres. The weight ratio is 3:2: 5.
  • the synthetic silica has a particle size of 5 ⁇ m and a distribution width of 1.36, purchased from Shantou Best Technology Co., Ltd.; the PMMA polymer microspheres has a particle size of 5 ⁇ m and a distribution width of 1.12; the glass microspheres , the particle size is 5 ⁇ m, and the distribution width is 1.22.
  • the preparation raw materials include: 88.5 parts by weight of matrix resin, 10 parts of anti-adhesive agent, 1 part of antioxidant, and 0.5 part of dispersant.
  • the matrix resin is LLDPE, with a melt index of 1.5g/10min, purchased from Guangzhou Petrochemical, and the model is DFDA-7044.
  • the anti-sticking agent is calcium carbonate, with a particle size of 5 ⁇ m and a distribution width of 3.12.
  • the antioxidant is a combination of antioxidant 1010 and antioxidant 168, with a weight ratio of 1:1.
  • the dispersant was polyethylene wax, purchased from Kunshan Xinkui Polymer New Materials Co., Ltd.
  • a method for preparing anti-sticking masterbatch for BOPE films is the same as Example 1.
  • An anti-adhesive masterbatch for BOPE films The specific steps are the same as Comparative Example 1. The difference is that the matrix resin is a combination of LLDPE and LDPE, and the weight ratio is 50:38.5; the melt index of the LLDPE is 2g/10min, purchased from China Petrochemical, the model is DFDA-7042; the melt index of the LDPE is 1.5g/10min, purchased from Shanghai Petrochemical, the model is LDPE N150.
  • the anti-sticking agent is talc powder, with a particle size of 5 ⁇ m and a distribution width of 3.3.
  • the core layer is made of special material BOPE-3;
  • the main material of the BOPE film is Sinopec's BOPE special material BOPE-3.
  • the thickness ratio of the first surface layer, core layer and second surface layer is 1.5:22:1.5.
  • Adhesion Test the adhesion of the BOPE film obtained after adding the anti-adhesive masterbatch of Examples 1-4 and Comparative Examples 1-2, and test the corona-treated films respectively. Adhesion between film and non-corona treated film.
  • Film friction coefficient The friction coefficient of the BOPE film tested according to the standard GB/T10006-2021.
  • Film surface quality Use visual method to test the appearance quality of BOPE film within an area of 10cm2 .

Abstract

Disclosed in the present invention is an anti-sticking master batch for a BOPE film. The raw materials for preparing same comprises, in parts by weight, 80-100 parts of matrix resin, 5-15 parts of an anti-sticking agent, 0.5-1.5 parts of an antioxidant and 0.1-1.5 parts of a dispersing agent. The present invention uses LDPE and MLLDPE having melt indices of 1.5-6 g/10 min synergistically, so as to improve the compatibility and dispersity of the anti-sticking agent and the matrix resin, thus reducing the impact of the master batch on later film processing, and ensuing the good surface quality of films. In addition, as the combination of synthetic silicon dioxide, PMMA microspheres and glass microbeads serves as the anti-sticking agent, the prepared film has excellent anti-sticking performance, the surface of the film has a relatively low friction coefficient, and the film surface has the optical performance of high transparency.

Description

一种BOPE薄膜用防粘母料及其制备方法和应用An anti-sticking masterbatch for BOPE films and its preparation method and application 技术领域Technical field
本发明涉及一种BOPE薄膜用防粘母料及其制备方法和应用，具体涉及加工，配料的一般工艺过程。The invention relates to an anti-sticking masterbatch for BOPE films and its preparation method and application. It specifically relates to the general process of processing and ingredients.
背景技术Background technique
BOPE薄膜是一种新型的包装材料，可以大幅度提高复合包装袋的强度，并且具有变形小，可替代BOPA，PET等材料，是一种实现单一材质可回收利用的环保解决方案。PE薄膜在收卷过程中容易粘连，导致收卷好的薄膜无法放卷和分切，严重影响薄膜的后期使用，为了降低薄膜的粘结性，需要添加一定的防粘剂到薄膜表层。但是应用于吹膜或流延法PE薄膜的防粘母料，防粘性能有限，并不适合双向拉伸薄膜。引入的功能助剂制备BOPE薄膜，薄膜主料与功能助剂的相容分散性不佳，会影响薄膜的力学性能。目前市面上的防粘母料应用于BOPE薄膜的生产中依旧存在防粘性不够，不能批量使用的问题，并且防粘母料在BOPE薄膜主料中的分散性不好，存在雾度高，鱼眼晶点等缺陷多，膜面质量差等的问题。BOPE film is a new type of packaging material that can greatly improve the strength of composite packaging bags and has small deformation. It can replace BOPA, PET and other materials. It is an environmentally friendly solution that allows a single material to be recycled. PE films tend to stick during the rewinding process, causing the rolled film to be unable to be unrolled and cut, seriously affecting the later use of the film. In order to reduce the adhesion of the film, a certain amount of anti-adhesive agent needs to be added to the surface of the film. However, the anti-sticking masterbatch used in blown or cast PE films has limited anti-sticking properties and is not suitable for biaxially oriented films. The introduced functional additives are used to prepare BOPE films. The main film materials and functional additives have poor compatibility and dispersion, which will affect the mechanical properties of the film. The anti-adhesive masterbatch currently on the market used in the production of BOPE films still has the problem of insufficient anti-adhesiveness and cannot be used in batches. Moreover, the dispersion of the anti-adhesive masterbatch in the main material of BOPE film is not good, and there is high haze. There are many defects such as eye crystal spots and poor film surface quality.
中国发明专利CN111114061B公开了一种耐撕裂聚乙烯薄膜及其制备方法，通过将乙烯/α烯烃共聚的线性低密度聚乙烯与交联剂反应形成多个乙烯层，形成的BOPE薄膜具有较高的拉伸强度和穿刺强度，具有良好的耐撕裂性，但是采用二氧化硅作为防粘剂，形成的薄膜光学透明性不佳，雾度较高。中国发明专利CN105623069B公开了一种分光生态农用大棚聚能膜及其制备方法，通过引入水滑石母料，流变剂母料实现薄膜的防粘性能，但是薄膜采用吹膜的工艺挤出塑化成膜，添加量非常大，成膜性不好，在双向拉伸PE薄膜制备工艺中不适用。Chinese invention patent CN111114061B discloses a tear-resistant polyethylene film and its preparation method. Multiple ethylene layers are formed by reacting ethylene/α-olefin copolymer linear low-density polyethylene with a cross-linking agent. The formed BOPE film has a high It has high tensile strength and puncture strength, and has good tear resistance. However, using silica as the anti-sticking agent results in a film with poor optical transparency and high haze. Chinese invention patent CN105623069B discloses a spectroscopic ecological agricultural greenhouse energy-concentrating film and its preparation method. By introducing hydrotalcite masterbatch and rheological agent masterbatch, the anti-sticking performance of the film is achieved, but the film is extruded and plasticized using a blown film process. Film-forming, the addition amount is very large, the film-forming property is not good, and it is not suitable for the preparation process of biaxially stretched PE film.
发明内容Contents of the invention
为了改善BOPE薄膜的防粘性能，同时使其具有良好的光学性能，适用于大规模工业化生产。本发明的第一个方面提供了一种BOPE薄膜用防粘母料，其特征在于，制备原料以重量份计包括：基体树脂80-100份，防粘剂5-15份，抗氧 剂0.5-1.5份，分散剂0.1-1.5份，所述防粘剂的粒径为3-8μm，粒径分布宽度为0.5-2。In order to improve the anti-sticking properties of BOPE film and at the same time make it have good optical properties, it is suitable for large-scale industrial production. The first aspect of the present invention provides an anti-sticking masterbatch for BOPE films, which is characterized in that the preparation raw materials include: 80-100 parts by weight of matrix resin, 5-15 parts of anti-sticking agent, antioxidant 0.5-1.5 parts of the anti-sticking agent, 0.1-1.5 parts of the dispersing agent, the particle size of the anti-sticking agent is 3-8 μm, and the particle size distribution width is 0.5-2.
作为一种优选的实施方式，所述基体树脂为PE树脂，选自LDPE、MLLDPE、LLDPE、MDPE、HDPE、改性聚乙烯、乙烯共聚物中的一种或几种的组合。As a preferred embodiment, the matrix resin is PE resin, selected from one or a combination of LDPE, MLLDPE, LLDPE, MDPE, HDPE, modified polyethylene, and ethylene copolymers.
作为一种优选的实施方式，所述基体树脂为LDPE、MLLDPE的组合。As a preferred embodiment, the matrix resin is a combination of LDPE and MLLDPE.
作为一种优选的实施方式，所述LDPE和MLLDPE的重量比为(40-60)：(30-45)。As a preferred embodiment, the weight ratio of the LDPE and MLLDPE is (40-60): (30-45).
作为一种优选的实施方式，所述LDPE和MLLDPE的重量比为50：38。As a preferred embodiment, the weight ratio of the LDPE and MLLDPE is 50:38.
作为一种优选的实施方式，所述基体树脂在190℃，2.16kg条件下的熔融指数为1-8g/10min。As a preferred embodiment, the melt index of the matrix resin is 1-8g/10min under the conditions of 190°C and 2.16kg.
作为一种优选的实施方式，所述基体树脂在190℃，2.16kg条件下的熔融指数为1.5-6g/10min。As a preferred embodiment, the melt index of the matrix resin is 1.5-6g/10min under the conditions of 190°C and 2.16kg.
作为一种优选的实施方式，所述LDPE的熔融指数为4g/10min，所述MLLDPE的熔融指数为1.5g/10min。As a preferred embodiment, the melt index of the LDPE is 4g/10min, and the melt index of the MLLDPE is 1.5g/10min.
申请人在实验过程中发现采用熔融指数为1.5-6g/10min的LDPE和MLLDPE材料作为基体树脂可以改善防粘剂在基体树脂中的分散效果，降低母料对后期薄膜加工的影响，形成良好的膜面质量，猜测可能的原因是：熔融指数为2-6g/10min的LDPE和MLLDPE树脂与BOPE主料的熔融指数接近，匹配性较好，将熔融指数接近的母料与BOPE主料混合，加工性能较好，形成较好的膜面质量。但是LDPE和MLLDPE的熔融指数较低，流动性不好，LDPE和MLLDPE采用(40-60)：(30-45)的重量比可以降低熔融指数低造成的防粘剂分散性不佳的问题，可能的原因是：LDPE和MLLDPE协同作用使聚乙烯的线性结构在防粘剂表面缠结，增加防粘剂颗粒间的空间位阻，阻止防粘剂颗粒间的团聚，使防粘剂可以在基体树脂中均匀分散。During the experiment, the applicant found that using LDPE and MLLDPE materials with a melt index of 1.5-6g/10min as the matrix resin can improve the dispersion effect of the anti-sticking agent in the matrix resin, reduce the impact of the masterbatch on later film processing, and form a good Regarding the film surface quality, we speculate that the possible reasons are: the melt index of LDPE and MLLDPE resin with a melt index of 2-6g/10min is close to that of the BOPE main material, and the matching is good. Mix the masterbatch with a similar melt index with the BOPE main material. The processing performance is better and the film surface quality is better. However, LDPE and MLLDPE have low melt index and poor fluidity. The weight ratio of (40-60): (30-45) for LDPE and MLLDPE can reduce the problem of poor dispersion of anti-sticking agents caused by low melt index. The possible reason is that the synergistic effect of LDPE and MLLDPE makes the linear structure of polyethylene entangle on the surface of the anti-adhesive agent, increases the steric hindrance between the anti-adhesive agent particles, prevents the agglomeration of the anti-adhesive agent particles, and allows the anti-adhesive agent to be Evenly dispersed in the matrix resin.
作为一种优选的实施方式，所述防粘剂的粒径为3-8μm，粒径分布宽度为0.5-2。As a preferred embodiment, the particle size of the anti-adhesive agent is 3-8 μm, and the particle size distribution width is 0.5-2.
作为一种优选的实施方式，所述防粘剂选自二氧化硅、聚合物微球、玻璃微珠、滑石粉、碳酸钙、硅藻土、高岭土、元明粉、硅灰石、硫酸钙中的一种或几种的组合。 As a preferred embodiment, the anti-sticking agent is selected from the group consisting of silica, polymer microspheres, glass microspheres, talc, calcium carbonate, diatomaceous earth, kaolin, Yuanming powder, wollastonite, and calcium sulfate. one or a combination of several.
作为一种优选的实施方式，所述防粘剂为二氧化硅、PMMA聚合物微球、玻璃微珠的组合。As a preferred embodiment, the anti-sticking agent is a combination of silica, PMMA polymer microspheres, and glass microspheres.
作为一种优选的实施方式，所述二氧化硅、聚合物微球PMMA、玻璃微珠的重量比为(2-4)：(1-3)：(4-6)。As a preferred embodiment, the weight ratio of the silica, polymer microspheres PMMA, and glass microspheres is (2-4): (1-3): (4-6).
作为一种优选的实施方式，所述二氧化硅、聚合物微球PMMA、玻璃微珠的重量比为3：2：5。As a preferred embodiment, the weight ratio of silica, polymer microspheres PMMA, and glass microspheres is 3:2:5.
申请人在实验过程中发现，采用合成二氧化硅，PMMA微球和玻璃微珠的组合，并且防粘剂的粒径为5-6μm时，形成的母料应用于薄膜中制得的薄膜具有优异的防粘性能和光学性能，猜测可能的原因是：合成二氧化硅，PMMA微球和玻璃微珠协同作用，在薄膜的表面形成突起，减少薄膜接触面，降低薄膜表面的摩擦系数，在两层薄膜之间形成架桥，使薄膜与薄膜之间有空气层的存在防止薄膜的粘结，并且薄膜母卷卷绕顺畅，减少褶皱。申请人进一步发现，由于玻璃微珠与PE膜折光系数接近，使薄膜表面摩擦系数低的同时，形成的薄膜光学性能佳，具有高透光率，低雾度，高光泽度的特点。The applicant found during the experiment that when a combination of synthetic silica, PMMA microspheres and glass microspheres are used, and the particle size of the anti-sticking agent is 5-6 μm, the resulting masterbatch is applied to the film and the film produced has The possible reasons for the excellent anti-sticking and optical properties are: synthetic silica, PMMA microspheres and glass microspheres work together to form protrusions on the surface of the film, reducing the film contact surface and reducing the friction coefficient on the film surface. A bridge is formed between the two layers of film, so that there is an air layer between the films to prevent the film from adhering, and the film parent roll can be wound smoothly to reduce wrinkles. The applicant further discovered that due to the close refractive index of the glass beads and the PE film, the surface friction coefficient of the film is low, and at the same time, the formed film has excellent optical properties, with high light transmittance, low haze, and high gloss.
作为一种优选的实施方式，所述抗氧剂选自磷类抗氧剂、酚类抗氧剂、胺类抗氧剂、硫类抗氧剂中的一种或几种的组合，优选的，所述胺类抗氧剂至少包括羟胺类抗氧剂。As a preferred embodiment, the antioxidant is selected from one or a combination of several types of phosphorus antioxidants, phenolic antioxidants, amine antioxidants, and sulfur antioxidants. , the amine antioxidant at least includes a hydroxylamine antioxidant.
作为一种优选的实施方式，所述抗氧剂为羟胺类抗氧剂。所述羟胺类抗氧剂为Revonox 420V和Irgastab FS042的组合。As a preferred embodiment, the antioxidant is a hydroxylamine antioxidant. The hydroxylamine antioxidant is a combination of Revonox 420V and Irgastab FS042.
本申请所述羟胺类抗氧剂为不含酚的抗氧剂，具有较高的颜色保护性，可以有效避免受阻酚类抗氧剂在NOx气体烟熏下变色，不会引发黄变的问题。同时本申请羟胺类抗氧剂与PE材质具有良好的相容性和低挥发性，改善聚合物熔融稳定性的同时还可以提高产品的透明度，延长产品的使用寿命。The hydroxylamine antioxidant described in this application is a phenol-free antioxidant and has high color protection, which can effectively avoid the discoloration of hindered phenolic antioxidants under NOx gas smoke and will not cause yellowing problems. . At the same time, the hydroxylamine antioxidant of the present application has good compatibility and low volatility with PE materials, which can not only improve the melting stability of the polymer, but also improve the transparency of the product and extend the service life of the product.
作为一种优选的实施方式，所述分散剂选自聚乙烯蜡、硬脂酸、硬脂酸盐、聚乙烯醇、蜡粉中的一种或几种的组合。As a preferred embodiment, the dispersant is selected from one or a combination of polyethylene wax, stearic acid, stearate, polyvinyl alcohol, and wax powder.
作为一种优选的实施方式，所述分散剂为硬脂酸盐，进一步优选，分散剂为硬脂酸镁，进一步优选，所述分散剂为羟基硬脂酸镁。As a preferred embodiment, the dispersant is stearate. More preferably, the dispersant is magnesium stearate. More preferably, the dispersant is magnesium hydroxystearate.
所述羟基硬脂酸镁具有非线性的结构，与PE树脂的相扣更加紧密，并且羟基硬脂酸镁具有桥梁作用，可以使抗氧剂，防粘剂与树脂形成更加均匀的整体， 从而改善薄膜的表面性能。The magnesium hydroxystearate has a non-linear structure, which is more closely interlocked with the PE resin, and the magnesium hydroxystearate has a bridging effect, which can make the antioxidant, anti-sticking agent and resin form a more uniform whole. Thereby improving the surface properties of the film.
本发明的第二个方面提供了一种BOPE薄膜用防粘母料的制备方法，包括以下步骤：A second aspect of the invention provides a method for preparing an anti-adhesive masterbatch for BOPE films, which includes the following steps:
(1)将基体树脂加入挤出机中，升温至180-190℃，高速熔融剪切10-20s，形成部分塑化的熔体；(1) Add the matrix resin into the extruder, raise the temperature to 180-190°C, and melt and shear at high speed for 10-20 seconds to form a partially plasticized melt;
(2)将防粘剂，抗氧剂和分散剂混合，形成混合物1；(2) Mix the anti-sticking agent, antioxidant and dispersant to form mixture 1;
(3)将混合物1采用侧喂料的方式加入挤出机中，在200-240℃下熔融共混20-30s，通过螺杆挤出机挤出造粒，得防粘母料。(3) Add the mixture 1 into the extruder by side feeding, melt and blend at 200-240°C for 20-30 seconds, and then extrude and granulate through the screw extruder to obtain the anti-stick masterbatch.
传统功能母料的制备工艺是将所有原料均匀混合后一次下料进行加工，这种方法由于PE树脂熔融指数较低、流动性差，很难将超高含量的防粘剂均匀分散在树脂载体中。若温度设置过高，树脂很容易热氧解导致小分子和积碳增多，使母料存在许多黑点，影响下游高品质薄膜的制备。The traditional preparation process of functional masterbatch is to uniformly mix all the raw materials and then process them at once. Due to the low melt index and poor fluidity of the PE resin, it is difficult to evenly disperse the ultra-high content of anti-sticking agent in the resin carrier. . If the temperature is set too high, the resin will be easily thermally oxidized, resulting in an increase in small molecules and carbon deposits, leaving many black spots in the masterbatch, affecting the preparation of high-quality films downstream.
因此，为了保证防粘剂尤其高含量的防粘剂有效分散在基体树脂及下游薄膜里面，采用侧喂料方式将高含量的防粘剂均匀分散在基体树脂中。PE树脂在挤出机内先充分熔融，使防粘剂均匀有效地分散在熔融的基体树脂中。申请人进一步发现某类防粘剂经200-240℃高温加热后会产生一种刺激性味道，而采用侧喂料的方式可以大大缩短防粘剂的受热时间，进而从源头减少刺激性气味的产生，因此，采用侧喂料的加工工艺既保证了高含量的防粘剂有效分散在基体树脂及下游薄膜里面，又避免了防粘剂因过度受热而产生刺激性气味。从而制备出品质优异、分散性好，及在BOPE薄膜制备过程中具有良好的成膜性及加工性能的高品质防粘结母料。Therefore, in order to ensure that the anti-sticking agent, especially the high-content anti-sticking agent, is effectively dispersed in the matrix resin and the downstream film, the side feeding method is used to evenly disperse the high-content anti-sticking agent in the matrix resin. The PE resin is fully melted in the extruder first, so that the anti-sticking agent can be evenly and effectively dispersed in the molten matrix resin. The applicant further found that a certain type of anti-sticking agent will produce a pungent smell after being heated at a high temperature of 200-240°C. The side feeding method can greatly shorten the heating time of the anti-sticking agent, thereby reducing the pungent smell from the source. Therefore, the use of side-feeding processing technology not only ensures that the high-content anti-sticking agent is effectively dispersed in the matrix resin and downstream films, but also avoids the irritating odor caused by excessive heating of the anti-sticking agent. Thus, a high-quality anti-adhesive masterbatch with excellent quality, good dispersion, and good film-forming and processing properties during the BOPE film preparation process can be prepared.
本发明的第三个方面提供了一种BOPE薄膜用防粘母料的应用，应用于BOPE薄膜的制备中，所述BOPE薄膜为1-5层结构，厚度为10-80μm。The third aspect of the present invention provides an application of an anti-adhesive masterbatch for BOPE films, which is used in the preparation of BOPE films. The BOPE films have a 1-5 layer structure and a thickness of 10-80 μm.
作为一种优选的实施方式，所述BOPE薄膜为3层结构，厚度为20-30μm。As a preferred embodiment, the BOPE film has a three-layer structure and a thickness of 20-30 μm.
作为一种优选的实施方式，所述BOPE薄膜自上至下依次包括第一表层，芯层和第二表层。所述防粘母料添加到第一表层和第二表层中，第一表层和第二表层的厚度为1.0-1.5μm。As a preferred embodiment, the BOPE film includes a first surface layer, a core layer and a second surface layer from top to bottom. The anti-sticking masterbatch is added to the first surface layer and the second surface layer, and the thickness of the first surface layer and the second surface layer is 1.0-1.5 μm.
作为一种优选的实施方式，所述防粘母料在BOPE薄膜中的添加重量分数为1-10％。 As a preferred embodiment, the weight fraction of the anti-sticking masterbatch added to the BOPE film is 1-10%.
作为一种优选的实施方式，所述防粘母料在BOPE薄膜中的添加重量分数为4％。As a preferred embodiment, the added weight fraction of the anti-sticking masterbatch in the BOPE film is 4%.
与现有技术相比，本申请具有以下有益效果：Compared with the existing technology, this application has the following beneficial effects:
(1)本申请所述BOPE薄膜用防粘母料，通过采用熔融指数为1.5-6g/10min的LDPE和MLLDPE树脂协同作用，改善了防粘剂与载体树脂的相容分散性，降低母料对后期薄膜加工的影响，使薄膜具有良好的膜面质量。(1) The anti-sticking masterbatch for BOPE films described in this application uses synergistic effects of LDPE and MLLDPE resins with a melt index of 1.5-6g/10min, which improves the compatibility and dispersion of the anti-sticking agent and the carrier resin, and reduces the cost of the masterbatch. The influence on later film processing makes the film have good film surface quality.
(2)本申请所述BOPE薄膜用防粘母料，采用合成二氧化硅，PMMA微球和玻璃微珠的组合作为防粘剂，可以使制备的薄膜具有极佳的防粘性能，薄膜表面具有较低的摩擦系数，膜面具有高透明的光学性能。(2) The anti-sticking masterbatch for BOPE films described in this application uses a combination of synthetic silica, PMMA microspheres and glass microspheres as the anti-sticking agent, which can make the prepared film have excellent anti-sticking properties, and the film surface It has a low friction coefficient and the film surface has highly transparent optical properties.
(3)本申请所述BOPE薄膜用防粘母料，采用平均粒径为5-6μm，分布宽度≤1.5的防粘剂颗粒，可以使制备的薄膜具有稳定的防粘合性能，不论是电晕面对电晕面还是电晕面对非电晕面都不易粘结。(3) The anti-adhesive masterbatch for BOPE films described in this application uses anti-adhesive particles with an average particle size of 5-6 μm and a distribution width of ≤1.5, which can make the prepared film have stable anti-adhesive properties, whether it is electrical It is not easy to bond whether the corona surface is on the corona surface or the corona surface is on the non-corona surface.
(4)本申请所述BOPE薄膜用防粘母料，采用侧喂料的方式，在基体树脂熔融部分塑化后加入防粘剂，抗氧剂和和分散剂，可以降低防粘剂粒子的受热时间，从源头减少刺激性气味的产生。(4) The anti-sticking masterbatch for BOPE films described in this application uses side feeding. After the melted part of the matrix resin is plasticized, anti-sticking agents, antioxidants and dispersants are added, which can reduce the adhesion of the anti-sticking agent particles. Heating time reduces the generation of pungent odors from the source.
(5)本申请所述BOPE薄膜用防粘母料，与BOPE主料的相容性较好，制备的BOPE薄膜膜面极佳，无橘皮纹、模唇线，白点等缺陷，且清晰透亮。(5) The anti-adhesive masterbatch for BOPE films described in this application has good compatibility with BOPE main materials. The prepared BOPE film has an excellent film surface without defects such as orange peel lines, mold lip lines, and white spots, and Clear and translucent.
具体实施方式Detailed ways
实施例1Example 1
一种BOPE薄膜用防粘母料，制备原料以重量份计包括：基体树脂88.5g，防粘剂10g，抗氧剂1g，分散剂0.5g。An anti-sticking masterbatch for BOPE films. The preparation raw materials include: 88.5g of matrix resin, 10g of anti-sticking agent, 1g of antioxidant and 0.5g of dispersant in parts by weight.
所述基体树脂为LDPE、MLLDPE的组合，LDPE和MLLDPE的重量比为50：38.5，所述LDPE的熔融指数为4g/10min，购自中海壳牌，型号为LDPE 2420K；所述MLLDPE的熔融指数为1.5g/10min，购自陶氏化学，型号为TF80。The matrix resin is a combination of LDPE and MLLDPE. The weight ratio of LDPE and MLLDPE is 50:38.5. The melt index of the LDPE is 4g/10min. It is purchased from China Shipping Shell with the model number LDPE 2420K; the melt index of the MLLDPE is 1.5g/10min, purchased from Dow Chemical, model TF80.
所述防粘剂为合成二氧化硅，粒径为5μm，分布宽度为1.36，购自美国格雷斯。The anti-adhesive agent is synthetic silica with a particle size of 5 μm and a distribution width of 1.36, purchased from Grace in the United States.
所述抗氧剂为Revonox 420V和Irgastab FS042的组合，重量比为1：1，所述Revonox 420V购自奇钛(上海)化学科技有限公司；所述Irgastab FS042购自德国巴斯夫。 The antioxidant is a combination of Revonox 420V and Irgastab FS042, with a weight ratio of 1:1. The Revonox 420V is purchased from Qitai (Shanghai) Chemical Technology Co., Ltd.; the Irgastab FS042 is purchased from BASF, Germany.
所述分散剂为羟基硬脂酸镁，购自日彩化工(中国)有限公司，型号为kpw-12p。The dispersant is magnesium hydroxystearate, purchased from Ricai Chemical (China) Co., Ltd., model number is kpw-12p.
一种BOPE薄膜用防粘母料的制备方法，包括以下步骤：A method for preparing anti-adhesive masterbatch for BOPE films, including the following steps:
(1)将基体树脂加入挤出机中，升温至190℃，高速剪切20s，形成部分塑化的熔体；(1) Add the matrix resin into the extruder, raise the temperature to 190°C, and shear at high speed for 20 seconds to form a partially plasticized melt;
(2)将防粘剂，抗氧剂和分散剂混合，形成混合物1；(2) Mix the anti-sticking agent, antioxidant and dispersant to form mixture 1;
(3)将混合物1采用侧喂料的方式加入挤出机中，在220℃下混合30s，通过螺杆挤出机挤出造粒，得防粘母料。(3) Add the mixture 1 into the extruder by side feeding, mix at 220°C for 30 seconds, and then extrude and granulate through the screw extruder to obtain the anti-stick masterbatch.
实施例2Example 2
一种BOPE薄膜用防粘母料，具体步骤同实施例1，不同点在于所述防粘剂为PMMA聚合物微球，粒径为5μm，分布宽度为1.12。An anti-sticking masterbatch for BOPE films. The specific steps are the same as in Example 1. The difference is that the anti-sticking agent is PMMA polymer microspheres, with a particle size of 5 μm and a distribution width of 1.12.
实施例3Example 3
一种BOPE薄膜用防粘母料，具体步骤同实施例1，不同点在于所述防粘剂为玻璃微珠，粒径为5μm，分布宽度为1.22。An anti-adhesive masterbatch for BOPE films. The specific steps are the same as in Example 1. The difference is that the anti-adhesive agent is glass beads with a particle size of 5 μm and a distribution width of 1.22.
实施例4Example 4
一种BOPE薄膜用防粘母料，具体步骤同实施例1，不同点在于所述防粘剂为合成二氧化硅，PMMA聚合物微球和玻璃微珠的组合，重量比为3：2：5。所述合成二氧化硅，粒径为5μm，分布宽度为1.36，购自汕头市贝斯特科技有限公司；所述PMMA聚合物微球，粒径为5μm，分布宽度为1.12；所述玻璃微珠，粒径为5μm，分布宽度为1.22。An anti-adhesive masterbatch for BOPE films. The specific steps are the same as in Example 1. The difference is that the anti-adhesive agent is a combination of synthetic silica, PMMA polymer microspheres and glass microspheres. The weight ratio is 3:2: 5. The synthetic silica has a particle size of 5 μm and a distribution width of 1.36, purchased from Shantou Best Technology Co., Ltd.; the PMMA polymer microspheres has a particle size of 5 μm and a distribution width of 1.12; the glass microspheres , the particle size is 5μm, and the distribution width is 1.22.
对比例1Comparative example 1
一种BOPE薄膜用防粘母料，制备原料以重量份计包括：基体树脂88.5份，防粘剂10份，抗氧剂1份，分散剂0.5份。An anti-adhesive masterbatch for BOPE films. The preparation raw materials include: 88.5 parts by weight of matrix resin, 10 parts of anti-adhesive agent, 1 part of antioxidant, and 0.5 part of dispersant.
所述基体树脂为LLDPE，熔融指数为1.5g/10min，购自广州石化，型号为DFDA-7044。The matrix resin is LLDPE, with a melt index of 1.5g/10min, purchased from Guangzhou Petrochemical, and the model is DFDA-7044.
所述防粘剂为碳酸钙，粒径为5μm，分布宽度为3.12。The anti-sticking agent is calcium carbonate, with a particle size of 5 μm and a distribution width of 3.12.
所述抗氧剂为抗氧剂1010和抗氧剂168的组合，重量比为1：1。The antioxidant is a combination of antioxidant 1010 and antioxidant 168, with a weight ratio of 1:1.
所述分散剂为聚乙烯蜡，购自昆山鑫葵高分子新材料有限公司。The dispersant was polyethylene wax, purchased from Kunshan Xinkui Polymer New Materials Co., Ltd.
一种BOPE薄膜用防粘母料的制备方法，同实施例1。 A method for preparing anti-sticking masterbatch for BOPE films is the same as Example 1.
对比例2Comparative example 2
一种BOPE薄膜用防粘母料，具体步骤同对比例1，不同点在于基体树脂为LLDPE和LDPE的组合，重量比为50：38.5；所述LLDPE的熔融指数为2g/10min，购自中国石化，型号为DFDA-7042；所述LDPE的熔融指数为1.5g/10min，购自上海石化，型号为LDPE N150。An anti-adhesive masterbatch for BOPE films. The specific steps are the same as Comparative Example 1. The difference is that the matrix resin is a combination of LLDPE and LDPE, and the weight ratio is 50:38.5; the melt index of the LLDPE is 2g/10min, purchased from China Petrochemical, the model is DFDA-7042; the melt index of the LDPE is 1.5g/10min, purchased from Shanghai Petrochemical, the model is LDPE N150.
所述防粘剂为滑石粉，粒径为5μm，分布宽度为3.3。The anti-sticking agent is talc powder, with a particle size of 5 μm and a distribution width of 3.3.
性能测试Performance Testing
BOPE薄膜的制备方法：Preparation method of BOPE film:
(1)将实施例1-4，对比例1-2制备的防粘母料与BOPE薄膜主料混合，制备BOPE薄膜的第一表层和第二表层，防粘母料与BOPE薄膜主料的重量比为4：96；(1) Mix the anti-sticking masterbatch prepared in Examples 1-4 and Comparative Examples 1-2 with the BOPE film main material to prepare the first surface layer and the second surface layer of the BOPE film. The anti-sticking masterbatch and the BOPE film main material are The weight ratio is 4:96;
(2)芯层的制备原料为专用料BOPE-3；(2) The core layer is made of special material BOPE-3;
(3)按配比称重下料，熔融混合，过滤，挤出，预热纵拉(拉伸倍率5)，冷却牵引，预热横拉(拉伸倍率8)，电晕处理，收卷。(3) Weigh and cut materials according to the proportion, melt and mix, filter, extrusion, preheat longitudinal drawing (stretch ratio 5), cooling traction, preheat transverse drawing (stretch ratio 8), corona treatment, and winding.
BOPE薄膜主料为中石化BOPE专用料BOPE-3，第一表层，芯层和第二表层的厚度比值为1.5：22：1.5。The main material of the BOPE film is Sinopec's BOPE special material BOPE-3. The thickness ratio of the first surface layer, core layer and second surface layer is 1.5:22:1.5.
1.粘合力：测试添加实施例1-4，对比例1-2的防粘母料后得到的BOPE薄膜的粘合力，分别测试经过电晕处理的薄膜之间，经过电晕处理的薄膜与未经电晕处理的薄膜之间的粘合力。1. Adhesion: Test the adhesion of the BOPE film obtained after adding the anti-adhesive masterbatch of Examples 1-4 and Comparative Examples 1-2, and test the corona-treated films respectively. Adhesion between film and non-corona treated film.
2.薄膜雾度：依据标准GB/T 2410-2008测试制得的BOPE薄膜的雾度。2. Film haze: The haze of the BOPE film was tested according to the standard GB/T 2410-2008.
3.薄膜摩擦系数：依据标准GB/T10006-2021测试制得的BOPE薄膜的摩擦系数。3. Film friction coefficient: The friction coefficient of the BOPE film tested according to the standard GB/T10006-2021.
4.膜面质量：使用目视法，测试10cm2面积范围内的BOPE薄膜的外观形态质量。4. Film surface quality: Use visual method to test the appearance quality of BOPE film within an area of 10cm2 .
测试结果见表1。The test results are shown in Table 1.
表1
Table 1

Claims (8)

  1. 一种BOPE薄膜用防粘母料，其特征在于，制备原料以重量份计包括：基体树脂80-100份，防粘剂5-15份，抗氧剂0.5-1.5份，分散剂0.1-1.5份，所述防粘剂为二氧化硅、PMMA聚合物微球、玻璃微珠的组合；所述防粘剂的粒径为3-8μm，粒径分布宽度为0.5-2。An anti-sticking masterbatch for BOPE films, characterized in that the preparation raw materials include: 80-100 parts by weight of matrix resin, 5-15 parts of anti-sticking agent, 0.5-1.5 parts of antioxidant, and 0.1-1.5 parts of dispersant part, the anti-sticking agent is a combination of silica, PMMA polymer microspheres, and glass microspheres; the particle size of the anti-sticking agent is 3-8 μm, and the particle size distribution width is 0.5-2.
  2. 根据权利要求1所述BOPE薄膜用防粘母料，其特征在于，所述基体树脂为PE树脂，选自LDPE、MLLDPE、LLDPE、MDPE、HDPE、改性聚乙烯、乙烯共聚物中的一种或几种的组合。The anti-adhesive masterbatch for BOPE films according to claim 1, characterized in that the matrix resin is PE resin, selected from one of LDPE, MLLDPE, LLDPE, MDPE, HDPE, modified polyethylene, and ethylene copolymer. or a combination of several.
  3. 根据权利要求1所述BOPE薄膜用防粘母料，其特征在于，所述基体树脂在190℃，2.16kg条件下的熔融指数为1-8g/10min。The anti-sticking masterbatch for BOPE films according to claim 1 is characterized in that the melt index of the matrix resin under the conditions of 190°C and 2.16kg is 1-8g/10min.
  4. 根据权利要求1所述BOPE薄膜用防粘母料，其特征在于，所述抗氧剂选自磷类抗氧剂、酚类抗氧剂、胺类抗氧剂、硫类抗氧剂中的一种或几种的组合，优选的，所述胺类抗氧剂至少包括羟胺类抗氧剂。The anti-sticking masterbatch for BOPE films according to claim 1, wherein the antioxidant is selected from the group consisting of phosphorus antioxidants, phenolic antioxidants, amine antioxidants, and sulfur antioxidants. One or a combination of several, preferably, the amine antioxidant at least includes a hydroxylamine antioxidant.
  5. 根据权利要求1所述BOPE薄膜用防粘母料，其特征在于，所述分散剂选自聚乙烯蜡、硬脂酸、硬脂酸盐、聚乙烯醇、蜡粉中的一种或几种的组合。The anti-stick masterbatch for BOPE films according to claim 1, characterized in that the dispersant is selected from one or more of polyethylene wax, stearic acid, stearate, polyvinyl alcohol, and wax powder. The combination.
  6. 一种根据权利要求1-5任一项所述BOPE薄膜用防粘母料的制备方法，其特征在于，包括以下步骤：A method for preparing anti-sticking masterbatch for BOPE films according to any one of claims 1-5, characterized in that it includes the following steps:
    (1)将基体树脂加入挤出机中，升温至180-190℃，高速熔融剪切10-20s，形成部分塑化的熔体；(1) Add the matrix resin into the extruder, raise the temperature to 180-190°C, and melt and shear at high speed for 10-20 seconds to form a partially plasticized melt;
    (2)将防粘剂，抗氧剂和分散剂混合，形成混合物1；(2) Mix the anti-sticking agent, antioxidant and dispersant to form mixture 1;
    (3)将混合物1采用侧喂料的方式加入挤出机中，在200-240℃下熔融共混20-30s，通过螺杆挤出机挤出造粒，得防粘母料。(3) Add the mixture 1 into the extruder by side feeding, melt and blend at 200-240°C for 20-30 seconds, and then extrude and granulate through the screw extruder to obtain the anti-stick masterbatch.
  7. 一种根据权利要求1-5任一项所述BOPE薄膜用防粘母料的应用，其特征在于，应用于BOPE薄膜的制备中，所述BOPE薄膜为1-5层结构，厚度为10-80μm。An application of anti-adhesive masterbatch for BOPE films according to any one of claims 1-5, characterized in that it is used in the preparation of BOPE films, and the BOPE films have a 1-5 layer structure and a thickness of 10- 80μm.
  8. 根据权利要求7所述BOPE薄膜用防粘母料的应用，其特征在于，所述防粘母料在BOPE薄膜中的添加重量分数为1-10％。 The application of anti-sticking masterbatch for BOPE films according to claim 7, characterized in that the added weight fraction of the anti-sticking masterbatch in the BOPE film is 1-10%.
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