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WO2022247023A1 - 一种双向拉伸可降解薄膜及其制备方法 - Google Patents

一种双向拉伸可降解薄膜及其制备方法 Download PDF

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Publication number
WO2022247023A1
WO2022247023A1 PCT/CN2021/112213 CN2021112213W WO2022247023A1 WO 2022247023 A1 WO2022247023 A1 WO 2022247023A1 CN 2021112213 W CN2021112213 W CN 2021112213W WO 2022247023 A1 WO2022247023 A1 WO 2022247023A1
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layer
agent
polylactic acid
masterbatch
heat
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PCT/CN2021/112213
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English (en)
French (fr)
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赵洁
邢青涛
黎坛
王俊峰
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海南赛诺实业有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/31—Heat sealable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/716—Degradable
    • 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
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/14—Copolymers of propene
    • 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
    • C08J2367/04—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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/55—Boron-containing compounds
    • 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
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • C08K7/20—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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Definitions

  • the invention belongs to the technical field of polymer films, and in particular relates to a biaxially stretched degradable film and a preparation method thereof.
  • BOPP cigarette film is also known as biaxially oriented polypropylene cigarette film, referred to as cigarette film, which is co-extruded and stretched from a variety of polypropylene functional materials.
  • Cigarette film has high transparency and gloss, non-toxic material, stable molecular structure, and has a certain barrier function to odor and moisture, so it is an ideal material for cigarette packaging.
  • the traditional polyolefin packaging cigarette film has excellent mechanical properties, thermal properties and interface smoothness, it has a relatively large negative impact on the environment due to its difficulty in degradation.
  • New degradable cigarette films in response to new national policies, such as polylactic acid degradable cigarette films, although they meet the degradation requirements, the elongation at break, heat seal strength and surface smoothness of the cigarette film itself are difficult to meet the relevant requirements of existing cigarette packaging films.
  • the purpose of the present invention is to provide a biaxially stretched degradable film and its preparation method. While most of the film in the present invention is a degradable material, it also ensures the elongation at break, heat seal strength and surface smoothness of the film itself. .
  • the invention provides a biaxially stretched degradable film, comprising A layer, B layer and C layer in contact with each other in sequence,
  • a layer comprises the raw material of following mass fraction:
  • Heat-sealing masterbatch A 83-85%, slip agent: 2-3%, anti-sticking agent A: 2-3%, antistatic agent A: 3-5%, polylactic acid: 4-10%;
  • B layer comprises the raw material of following mass fraction:
  • Polylactic acid 80-90%, initiator: 1-5%, maleic anhydride: 5-15%;
  • C layer comprises the raw material of following mass fraction:
  • Heat-sealing masterbatch C 85-88%, anti-sticking agent C: 2-5%, antistatic agent C: 3-5%.
  • Polylactic acid 2 to 10%.
  • the heat-sealing masterbatch A and the heat-sealing masterbatch C are independently selected from one of polypropylene and butadiene binary copolymer, ethylene-vinyl acetate copolymer, low-density thread ethylene and cast polypropylene species or several.
  • the slip agent is a silicone slip agent
  • Described release agent A and release agent C are glass microbead class release agent
  • the antistatic agent A and antistatic agent C are ethoxy boron antistatic agents.
  • the initiator is ester peroxide and/or ketone peroxide.
  • the present invention provides the preparation method of the biaxially stretched degradable film as described above, comprising the following steps:
  • the extrusion blending temperature of the layer A is 180-200°C.
  • the extrusion blending temperature of the layer B is 170-190°C.
  • the extrusion blending temperature of the C layer is 180-200°C.
  • the stretch ratio of the longitudinal stretch is 3.5-4.5; the stretch ratio of the transverse stretch is 4.0-5.0.
  • the film is softened at 95-115° C. before longitudinal stretching.
  • the invention provides a biaxially stretched degradable film, which includes layer A, layer B and layer C which are in contact with each other in sequence, and layer A includes the following raw materials in mass fraction: heat-sealing masterbatch A: 83-85%, smoothing agent: 2-3%, anti-sticking agent A: 2-3%, antistatic agent A: 3-5%, polylactic acid: 4-10%; B layer includes the following raw materials in mass fraction: polylactic acid: 80-90%, Initiator: 1-5%, maleic anhydride: 5-15%; C layer includes the following mass fractions of raw materials: heat-sealing masterbatch C: 85-88%, anti-sticking agent C: 2-5%, antistatic agent C: 3 to 5%. Polylactic acid: 2 to 10%.
  • the modified polylactic acid is compounded with the modified polypropylene, so that the longitudinal elongation at break (MD) of the film is kept above 120%, and the transverse elongation at break (TD) is kept above 170%.
  • the heat-sealing strength is above 0.35N/15mm at 80°C, and the surface roughness is below 0.2. While being degradable, other properties of the film also greatly meet the requirements of existing cigarette packaging films.
  • Fig. 1 is a flow chart of the preparation process of the biaxially oriented degradable film in the present invention.
  • the invention provides a biaxially stretched degradable film, comprising A layer, B layer and C layer in sequential contact,
  • a layer comprises the raw material of following mass fraction:
  • Heat-sealing masterbatch A 83-85%, slip agent: 2-3%, anti-sticking agent A: 2-3%, antistatic agent A: 3-5%, polylactic acid: 4-10%;
  • B layer comprises the raw material of following mass fraction:
  • Polylactic acid 80-90%, initiator: 1-5%, maleic anhydride: 5-15%;
  • C layer comprises the raw material of following mass fraction:
  • Heat-sealing masterbatch C 85-88%, anti-sticking agent C: 2-5%, antistatic agent C: 3-5%.
  • Polylactic acid 2 to 10%.
  • the heat-sealing masterbatch A in the A layer is preferably polypropylene and butadiene binary copolymer, ethylene-vinyl acetate copolymer (EVA), low-density linear ethylene (LDPE) and cast polypropylene
  • EVA ethylene-vinyl acetate copolymer
  • LDPE low-density linear ethylene
  • CPP cast polypropylene
  • the slip agent is preferably a silicone slip agent, preferably SAB06554PPR slip agent or PSE-5099RP slip agent; the mass fraction of the slip agent is preferably 2 to 3%;
  • the anti-sticking agent A is preferably glass micro Bead anti-sticking agent, such as ABVT22SC anti-sticking agent; the mass fraction of said anti-sticking agent A is preferably 2 to 3%; said antistatic agent A is preferably an ethoxylated boron antistatic agent,
  • the present invention adds a small amount of polylactic acid in the A layer, the mass fraction of the polylactic acid is preferably 4-10%, preferably 5-9%, such as 4% , 5%, 6%, 7%, 8%, 9%, 10%, preferably a range value with any of the above-mentioned numerical values as the upper limit or the lower limit.
  • the mass fraction of polylactic acid in the B layer is preferably 83 to 85%, such as 83%, 84%, and 85%, and is preferably a range value with any of the above-mentioned values as the upper or lower limit;
  • the initiator It is preferably ester peroxide and/or ketone peroxide, such as one or more of tert-butyl peroxybenzoate, tert-butyl peroxy tert-valerate, methyl ethyl ketone peroxide and cyclohexanone peroxide Several kinds.
  • the function of the initiator is to initiate the grafting of polylactic acid polyester and maleic anhydride, and enhance the compatibility of layer B with layers A and C.
  • the mass fraction of maleic anhydride in the B layer is preferably 5 to 15%, such as 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15% % is preferably a range value with any of the above-mentioned numerical values as the upper limit or the lower limit.
  • the maleic anhydride is a grafted substance, which improves the compatibility between polyesters.
  • the heat-sealing masterbatch C in the C layer is preferably polypropylene and butadiene binary copolymer, ethylene-vinyl acetate copolymer (EVA), low-density linear ethylene (LDPE), cast polypropylene (CPP) etc., specifically, can be Sinopec FS5612 heat-sealing compound;
  • the mass fraction of the heat-sealing masterbatch C is preferably 85-88%, such as 85%, 86%, 87%, 88%, preferably with the above-mentioned any numerical value as the range value of the upper limit or the lower limit;
  • the anti-adhesive agent C is preferably a glass microbead anti-adhesive agent, such as ABS04S anti-adhesive agent;
  • the mass fraction of the anti-adhesive agent C is preferably 2 to 5%, such as 2%, 3%, 4%, 5%, preferably the range value with any of the above-mentione
  • the present invention adds a small amount of polylactic acid in the C layer, the mass fraction of the polylactic acid is preferably 2-10%, preferably 3-9%, such as 2% , 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, preferably a range value with any of the above-mentioned numerical values as the upper limit or the lower limit.
  • the total thickness of the A layer and the C layer is about 1/20 of the total thickness of the entire film.
  • the present invention also provides a method for preparing the biaxially oriented degradable film described above, comprising the following steps:
  • the raw material formulations of the A layer, the B layer and the C layer are consistent with the raw material formulations of the A layer, the B layer and the C layer described above, and will not be repeated here.
  • the above-mentioned components are blended and extruded in a twin-screw extruder according to the proportion to obtain the blended material of the A layer, the blended material of the B layer and the blended material of the C layer.
  • the extrusion blending temperature of the components of the A layer is preferably 180-200°C, more preferably 190-195°C; Agent A and polylactic acid are blended, and then extrusion blended with heat-sealing masterbatch A.
  • the extrusion blending temperature of the components of the B layer is preferably 170-190°C, more preferably 175-185°C, most preferably 180°C;
  • the extrusion blending temperature of the components of the C layer is preferably 180-200°C, more preferably 190-195°C; in the present invention, the anti-sticking agent C, antistatic agent C and polylactic acid are preferably blended first, and then Extrude and blend with heat-sealing masterbatch C.
  • the present invention co-extrudes the above-mentioned three-layer blend material to prepare a three-layer cast sheet material, which is softened at a temperature of 95°C to 115°C after water cooling, and then stretched longitudinally Stretching, then transverse stretching, traction winding, large slitting, and small slitting to prepare biaxially oriented degradable film products.
  • the temperature of the co-extrusion is preferably 190-195°C; the casting is a common film-forming method in the field, and will not be repeated here.
  • the softening temperature is preferably 95-115°C, more preferably 100-110°C;
  • the stretch ratio of the longitudinal stretching is preferably 3.5-4.5, more preferably 4.0-4.5, and the transverse stretching
  • the draw ratio of stretching is preferably 4.0 to 5.0, more preferably 4.5 to 5.0.
  • the biaxially stretched degradable film of the invention can be used as a cigarette film, and has the advantages of degradability, high elongation at break, high heat-sealing strength and excellent surface smoothness.
  • the invention provides a biaxially stretched degradable film, which includes layer A, layer B and layer C which are in contact with each other in sequence, and layer A includes the following raw materials in mass fraction: heat-sealing masterbatch A: 83-85%, smoothing agent: 2-3%, anti-sticking agent A: 2-3%, antistatic agent A: 3-5%, polylactic acid: 4-10%; B layer includes the following raw materials in mass fraction: polylactic acid: 80-90%, Initiator: 1-5%, maleic anhydride: 5-15%; C layer includes the following mass fractions of raw materials: heat-sealing masterbatch C: 85-88%, anti-sticking agent C: 2-5%, antistatic agent C: 3 to 5%. Polylactic acid: 2 to 10%.
  • the non-degradable heat-sealing material and the polylactic acid modified additive are blended in the two surface layers of the A layer and the C layer, and then compounded with the B layer with polylactic acid as the main component, which not only has good compatibility, but also improves the interface bonding strength. High, and while ensuring the degradation performance, it also ensures the elongation at break, heat seal strength and surface smoothness of the film itself.
  • composition of each layer is shown in Table 1:
  • Layer A Blend the blend of anti-sticking agent ABVT22SC, slip agent SAB06554PPR, antistatic agent FASPS2955 and polylactic acid with heat-sealing masterbatch FS5612 in a twin-screw extruder at 190°C;
  • Layer B under the action of an initiator, polylactic acid and maleic anhydride are blended in a twin-screw extruder at 190°C;
  • Layer C Blend the blend of anti-sticking agent ABS04S, antistatic agent DS126T and polylactic acid with polypropylene and butadiene binary copolymer (heat-sealing material FS5612);
  • three-layer co-extrusion is used to prepare a three-layer cast sheet. After water cooling, it is softened at a temperature of 95° C., first stretched longitudinally (controlling the stretching ratio at 3.5), and then Transverse stretching (stretch ratio controlled at 4.5), traction winding, large slitting, and small slitting to prepare biaxially oriented degradable film products.
  • Layer A Blend the blend of anti-sticking agent ABVT22SC, slip agent SAB06554PPR, antistatic agent FASPS2955 and polylactic acid with heat-sealing masterbatch FS5612 in a twin-screw extruder at 190°C;
  • Layer B under the action of an initiator, polylactic acid and maleic anhydride are blended in a twin-screw extruder at 190°C;
  • Layer C Blend the blend of anti-sticking agent ABS04S, antistatic agent DS126T and polylactic acid with polypropylene and butadiene binary copolymer (heat-sealing material FS5612);
  • three-layer co-extrusion is used to prepare a three-layer cast sheet. After water cooling, it is softened at a temperature of 95° C., first stretched longitudinally (controlling the stretching ratio at 3.5), and then Transverse stretching (stretch ratio controlled at 4.5), traction winding, large slitting, and small slitting to prepare biaxially oriented degradable film products.
  • polylactic acid 90 Initiator (cyclohexanone peroxide) 5 maleic anhydride 5 C layer composition Mass fraction/% Heat seal masterbatch FS5612 86 Anti-sticking agent ABS04S 2 Antistatic agent DS126T 3 polylactic acid 9
  • Layer A Blend the blend of anti-sticking agent ABVT22SC, slip agent SAB06554PPR, antistatic agent FASPS2955 and polylactic acid with heat-sealing masterbatch FS5612 in a twin-screw extruder at 190°C;
  • Layer B under the action of an initiator, polylactic acid and maleic anhydride are blended in a twin-screw extruder at 190°C;
  • Layer C Blend the blend of anti-sticking agent ABS04S, antistatic agent DS126T and polylactic acid with polypropylene and butadiene binary copolymer (heat-sealing material FS5612);
  • three-layer co-extrusion is used to prepare a three-layer cast sheet. After water cooling, it is softened at a temperature of 95° C., first stretched longitudinally (controlling the stretching ratio at 3.5), and then Transverse stretching (stretch ratio controlled at 4.5), traction winding, large slitting, and small slitting to prepare biaxially oriented degradable film products.
  • Layer A Blend the blend of anti-sticking agent ABVT22SC, slip agent SAB06554PPR, antistatic agent FASPS2955 and polylactic acid with heat-sealing masterbatch FS5612 in a twin-screw extruder at 190°C;
  • Layer B under the action of an initiator, polylactic acid and maleic anhydride are blended in a twin-screw extruder at 190°C;
  • Layer C Blend the blend of anti-sticking agent ABS04S, antistatic agent DS126T and polylactic acid with polypropylene and butadiene binary copolymer (heat-sealing material FS5612);
  • three-layer co-extrusion is used to prepare a three-layer cast sheet. After water cooling, it is softened at a temperature of 95° C., first stretched longitudinally (controlling the stretching ratio at 3.5), and then Transverse stretching (stretch ratio controlled at 4.5), traction winding, large slitting, and small slitting to prepare biaxially oriented degradable film products.
  • Layer A Blend the blend of anti-sticking agent ABVT22SC, slip agent SAB06554PPR, antistatic agent FASPS2955 and polylactic acid with heat-sealing masterbatch FS5612 in a twin-screw extruder at 190°C;
  • Layer B Blend polylactic acid in a twin-screw extruder at 190°C;
  • Layer C Blend the blend of anti-sticking agent ABS04S, antistatic agent DS126T and polylactic acid with polypropylene and butadiene binary copolymer (heat-sealing material FS5612);
  • three-layer co-extrusion is used to prepare a three-layer cast sheet. After water cooling, it is softened at a temperature of 95° C., first stretched longitudinally (controlling the stretching ratio at 3.5), and then Transverse stretching (stretch ratio controlled at 4.5), traction winding, large slitting, and small slitting to prepare biaxially oriented degradable film products.
  • the product prepared in Comparative Example 2 also has the defect of poor interface compatibility, that is, there is a risk of peeling off after the interface between the upper and lower surface layers and the core layer. conduct.

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Abstract

本发明提供了一种双向拉伸可降解薄膜，包括依次接触的A层、B层和C层，A层包括以下质量分数的原料：热封母料A：83～85％，爽滑剂：2～3％，防粘剂A：2～3％，抗静电剂A：3～5％，聚乳酸：4～10％；B层包括以下质量分数的原料：聚乳酸：80～90％，引发剂：1～5％，马来酸酐：5～15％；C层包括以下质量分数的原料：热封母料C：85～88％，防粘剂C：2～5％，抗静电剂C：3～5％。聚乳酸：2～10％。本发明通过改性聚乳酸与改性聚丙烯复合，在满足可降解的同时，薄膜的其他性能也大大满足现有烟用包装膜的要求。本发明还提供了一种双向拉伸可降解薄膜的制备方法。

Description

一种双向拉伸可降解薄膜及其制备方法
本申请要求于2021年05月26日提交中国专利局、申请号为202110577466.8、发明名称为“一种双向拉伸可降解薄膜及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明属于高分子膜技术领域，尤其涉及一种双向拉伸可降解薄膜及其制备方法。
背景技术
BOPP烟用薄膜又称双向拉伸聚丙烯烟膜，简称烟膜，是由多种聚丙烯功能性材料进行共挤、拉伸成型。烟膜具有高透明度和光泽感，材料无毒、分子结构稳定，对气味及水分有一定的阻隔功能，因此是香烟包装的理想材料。
传统烟膜主要成分为石油提取物聚烯烃，而它们的降解至少要花费上百年时间，这给环境带来极大负荷。2020年1月19日，国家发展改革委、生态环境部发布了新版限塑令—《关于进一步加强塑料污染治理的意见》，规划三个阶段限塑实施目标，以及对四个重点领域(不可降解塑料袋、一次性塑料餐具、宾馆酒店一次性用品、快速塑料包装)的塑料使用进行限制。随着国家相关政策的制定与人们环保意识的加强，可降解材料是大势所趋，它的应用也会越来越广泛。传统聚烯烃包装烟膜虽然力学性能、热学性能与界面光滑性能均较优，但是由于降解比较困难，对环境带来较大的负面影响。响应国家新政策的新降解烟膜，如聚乳酸降解烟膜，虽然满足降解要求，但是烟膜本身断裂伸长率，热封强度与表面光滑度均难以满足现有烟用包装膜相关要求。
发明内容
本发明的目的在于提供一种双向拉伸可降解薄膜及其制备方法，本发明中的薄膜大部分为降解材料的同时，也保证了薄膜本身的断裂伸长率，热封强度与表面光滑度。
本发明提供一种双向拉伸可降解薄膜，包括依次接触的A层、B层和C层，
A层包括以下质量分数的原料：
热封母料A：83～85％，爽滑剂：2～3％，防粘剂A：2～3％，抗静电剂A：3～5％，聚乳酸：4～10％；
B层包括以下质量分数的原料：
聚乳酸：80～90％，引发剂：1～5％，马来酸酐：5～15％；
C层包括以下质量分数的原料：
热封母料C：85～88％，防粘剂C：2～5％，抗静电剂C：3～5％。聚乳酸：2～10％。
优选的，所述热封母料A和热封母料C独立的选自聚丙烯和丁二烯二元共聚物、乙烯-乙酸乙烯共聚物、低密度线乙烯和流延聚丙烯中的一种或几种。
优选的，所述爽滑剂为硅酮类爽滑剂；
所述防粘剂A和防粘剂C为玻璃微珠类防粘剂；
所述抗静电剂A和抗静电剂C为乙氧基硼类抗静电剂。
优选的，所述引发剂为酯类过氧化物和/或酮类过氧化物。
本发明提供如上文所述的双向拉伸可降解薄膜的制备方法，包括以下步骤：
A)按照原料配比将A层、B层和C层的原料分别挤出共混，得到A层共混料、B层共混料和C层共混料；
B)将A层共混料、B层共混料和C层共混料进行三层共挤出，再经过流延、纵向拉伸和横向拉伸，得到双向拉伸可降解薄膜。
优选的，所述A层挤出共混的温度为180～200℃。
优选的，所述B层挤出共混的温度为170～190℃。
优选的，所述C层挤出共混的温度为180～200℃。
优选的，所述纵向拉伸的拉伸比为3.5～4.5；所述横向拉伸的拉伸比为4.0～5.0。
优选的，所述在纵向拉伸之前先对薄膜在95～115℃下软化。
本发明提供了一种双向拉伸可降解薄膜，包括依次接触的A层、B层和C层，A层包括以下质量分数的原料：热封母料A：83～85％，爽滑剂：2～3％，防粘剂A：2～3％，抗静电剂A：3～5％，聚乳酸：4～10％；B层包括以下质量分数的原料：聚乳酸：80～90％，引发剂：1～5％，马来酸酐：5～15％；C层包括以下质量分数的原料：热封母料C：85～88％，防粘剂C：2～5％，抗静电剂C：3～5％。聚乳酸：2～10％。本发明通过改性聚乳酸与改性聚丙烯复合，薄膜的 纵向断裂伸长率(MD)保持在120％以上，横向断裂伸长率(TD)保持在170％以上。热封强度在80℃时在0.35N/15mm以上，表面粗糙度在0.2以下，在满足可降解的同时，薄膜的其他性能也大大满足现有烟用包装膜的要求。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据提供的附图获得其他的附图。
图1为本发明中双向拉伸可降解薄膜的制备工艺流程图。
具体实施方式
本发明提供了一种双向拉伸可降解薄膜，包括依次接触的A层、B层和C层，
A层包括以下质量分数的原料：
热封母料A：83～85％，爽滑剂：2～3％，防粘剂A：2～3％，抗静电剂A：3～5％，聚乳酸：4～10％；
B层包括以下质量分数的原料：
聚乳酸：80～90％，引发剂：1～5％，马来酸酐：5～15％；
C层包括以下质量分数的原料：
热封母料C：85～88％，防粘剂C：2～5％，抗静电剂C：3～5％。聚乳酸：2～10％。
在本发明中，所述A层中的热封母料A优选聚丙烯和丁二烯二元共聚物、乙烯-乙酸乙烯共聚物(EVA)、低密度线乙烯(LDPE)和流延聚丙烯(CPP)中的一种或几种，具体的，可以是中石化FS5612热封料；所述热封母料A的质量分数优选为83～85％，更优选为84～85％；所述爽滑剂优选为硅酮类爽滑剂，优选为SAB06554PPR爽滑剂或PSE-5099RP爽滑剂；所述爽滑剂的质量分数优选为2～3％；所述防粘剂A优选为玻璃微珠类防粘剂，如ABVT22SC防粘剂；所述防粘剂A的质量分数优选为2～3％；所述抗静电剂A优选为乙氧基硼类抗静电剂，如FASPS2955抗静电剂；所述抗静电剂A的质量分数优选为3～5％，更优选为4～5％。
为保证A层与B层之间的界面相容性，本发明在A层中加入少量聚乳酸，所述聚乳酸的质量分数优选为4～10％，优选为5～9％，如4％、5％、6％、7％、8％、9％、10％，优选为以上述任意数值为上限或下限的范围值。
在本发明中，所述B层中聚乳酸的质量分数优选为83～85％，如83％、84％、85％，优选为以上述任意数值为上限或下限的范围值；所述引发剂优选为为酯类过氧化物和/或酮类过氧化物，如过氧化苯甲酸叔丁酯、过氧化叔戊酸叔丁基酯、过氧化甲乙酮和过氧化环己酮中的一种或几种。所述引发剂的作用为引发聚乳酸类聚酯与马来酸酐接枝，增强B层与A、C层相容性。
所述B层中马来酸酐的质量分数优选为5～15％，如5％、6％、7％、8％、9％、10％、11％、12％、13％、14％、15％，优选为以上述任意数值为上限或下限的范围值。所述马来酸酐为被接枝物，提升聚酯与聚酯之间的相容性。
在本发明中，所述C层中的热封母料C优选聚丙烯和丁二烯二元共聚物、乙烯-乙酸乙烯共聚物(EVA)、低密度线乙烯(LDPE)、流延聚丙烯(CPP)等中的一种或几种，具体的，可以是中石化FS5612热封料；所述热封母料C的质量分数优选为85～88％，如85％、86％、87％、88％，优选为以上述任意数值为上限或下限的范围值；所述防粘剂C优选为玻璃微珠类防粘剂，如ABS04S防粘剂；所述防粘剂C的质量分数优选为2～5％，如2％、3％、4％、5％，优选为以上述任意数值为上限或下限的范围值；所述抗静电剂C优选为乙氧基硼类抗静电剂，如DS126T抗静电剂；所述抗静电剂C的质量分数优选为3～5％，更优选为4～5％。
为保证C层与B层之间的界面相容性，本发明在C层中加入少量聚乳酸，所述聚乳酸的质量分数优选为2～10％，优选为3～9％，如2％、3％、4％、5％、6％、7％、8％、9％、10％，优选为以上述任意数值为上限或下限的范围值。
在本发明中，所述A层和C层的总厚度为整个薄膜总厚度的1/20左右。
本发明还提供了一种上文所述的双向拉伸可降解薄膜的制备方法，包括以下步骤：
A)按照原料配比将A层、B层和C层的原料分别挤出共混，得到A层共混料、B层共混料和C层共混料；
B)将A层共混料、B层共混料和C层共混料进行三层共挤出，再经过流 延、纵向拉伸和横向拉伸，得到双向拉伸可降解薄膜。
在本发明中，所述A层、B层和C层的原料配方与上文所述的A层、B层和C层的原料配方一致，在此不再赘述。
本发明将上述各组分按照配比在双螺杆挤出机中共混挤出，得到A层共混料、B层共混料和C层共混料。
在本发明中，所述A层各成分挤出共混的温度优选为180～200℃，更优选为190～195℃；本发明优选先将所述防粘剂A、爽滑剂、抗静电剂A和聚乳酸共混，然后再与热封母料A进行挤出共混。
在本发明中，所述B层各成分挤出共混的温度优选为170～190℃，更优选为175～185℃，最优选为180℃；
所述C层各成分挤出共混的温度优选为180～200℃，更优选为190～195℃；本发明优选先将所述防粘剂C、抗静电剂C和聚乳酸共混，然后再与热封母料C进行挤出共混。
得到上述三层的共混料之后，本发明将上述三层共混料进行共挤出，制备三层结构流延板材，经水冷后，再在95℃～115℃温度下软化，先纵向拉伸，再横向拉伸，牵引收卷，大分切，小分切后制备双向拉伸可降解薄膜成品。
在本发明中，所述共挤出的温度优选为190～195℃；所述流延为本领域的常用成膜方法，在此不再赘述，
在本发明中，所述软化的温度优选为95～115℃，更优选为100～110℃；所述纵向拉伸的拉伸比优选为3.5～4.5，更优选为4.0～4.5，所述横向拉伸的拉伸比优选为4.0～5.0，更优选为4.5～5.0。
本发明中的双向拉伸可降解薄膜可作为烟膜使用，具有可降解、断裂伸长率高、热封强度高和表面光滑度优异的优点。
本发明提供了一种双向拉伸可降解薄膜，包括依次接触的A层、B层和C层，A层包括以下质量分数的原料：热封母料A：83～85％，爽滑剂：2～3％，防粘剂A：2～3％，抗静电剂A：3～5％，聚乳酸：4～10％；B层包括以下质量分数的原料：聚乳酸：80～90％，引发剂：1～5％，马来酸酐：5～15％；C层包括以下质量分数的原料：热封母料C：85～88％，防粘剂C：2～5％，抗静电剂C：3～5％。聚乳酸：2～10％。本发明在A层和C层两个表层中将非降解的热封料与 聚乳酸改性添加剂共混后，再与聚乳酸为主要成分的B层复合，不仅相容性好，界面结合强度高，而且在保证了降解性能的同时，还保证了薄膜本身的断裂伸长率，热封强度与表面光滑度。
为了进一步说明本发明，以下结合实施例对本发明提供的一种双向拉伸可降解薄膜及其制备方法进行详细描述，但不能将其理解为对本发明保护范围的限定。
实施例1
各层成分如表1所示：
表1
A层组成成分 质量分数/％
热封母料FS5612 85
爽滑剂SAB06554PPR 2
防粘剂ABVT22SC 3
抗静电剂FASPS2955 5
聚乳酸 5
B层组成成分 质量分数/％
聚乳酸 80
引发剂(过氧化苯甲酸叔丁酯) 5
马来酸酐 15
C层组成成分 质量分数/％
热封母料FS5612 88
防粘剂ABS04S 5
抗静电剂DS126T 5
聚乳酸 2
A层：将防粘剂ABVT22SC、爽滑剂SAB06554PPR、抗静电剂FASPS2955与聚乳酸的共混料在190℃的双螺杆挤出机中与热封母料FS5612共混；
B层：引发剂的作用下，将聚乳酸与马来酸酐在190℃的双螺杆挤出机中共混；
C层：将防粘剂ABS04S、抗静电剂DS126T与聚乳酸的共混料与聚丙烯和丁二烯二元共聚物(热封料FS5612)共混；
在得到三层共混料后，然后采用三层共挤，制备三层结构流延板材，经水冷后，再在95℃温度下软化，先纵向拉伸(控制拉伸比例在3.5)，再横向拉伸(拉伸比控制在4.5)，牵引收卷，大分切，小分切后制备双向拉伸可降解薄膜成品。
实施例2
表2
A层组成成分 质量分数/％
热封母料FS5612 84
爽滑剂SAB06554PPR 3
防粘剂ABVT22SC 3
抗静电剂FASPS2955 3
聚乳酸 6
B层组成成分 质量分数/％
聚乳酸 85
引发剂(过氧化苯甲酸叔丁酯) 3
马来酸酐 12
C层组成成分 质量分数/％
热封母料FS5612 87
防粘剂ABS04S 4
抗静电剂DS126T 4
聚乳酸 5
A层：将防粘剂ABVT22SC、爽滑剂SAB06554PPR、抗静电剂FASPS2955与聚乳酸的共混料在190℃的双螺杆挤出机中与热封母料FS5612共混；
B层：引发剂的作用下，将聚乳酸与马来酸酐在190℃的双螺杆挤出机中共混；
C层：将防粘剂ABS04S、抗静电剂DS126T与聚乳酸的共混料与聚丙烯和丁二烯二元共聚物(热封料FS5612)共混；
在得到三层共混料后，然后采用三层共挤，制备三层结构流延板材，经水冷后，再在95℃温度下软化，先纵向拉伸(控制拉伸比例在3.5)，再横向拉伸(拉伸比控制在4.5)，牵引收卷，大分切，小分切后制备双向拉伸可降解薄膜成品。
实施例3
表3
A层组成成分 质量分数/％
热封母料FS5612 83
爽滑剂SAB06554PPR 2
防粘剂ABVT22SC 2
抗静电剂FASPS2955 3
聚乳酸 10
B层组成成分 质量分数/％
聚乳酸 90
引发剂(过氧化环己酮) 5
马来酸酐 5
C层组成成分 质量分数/％
热封母料FS5612 86
防粘剂ABS04S 2
抗静电剂DS126T 3
聚乳酸 9
A层：将防粘剂ABVT22SC、爽滑剂SAB06554PPR、抗静电剂FASPS2955与聚乳酸的共混料在190℃的双螺杆挤出机中与热封母料FS5612共混；
B层：引发剂的作用下，将聚乳酸与马来酸酐在190℃的双螺杆挤出机中共混；
C层：将防粘剂ABS04S、抗静电剂DS126T与聚乳酸的共混料与聚丙烯和丁二烯二元共聚物(热封料FS5612)共混；
在得到三层共混料后，然后采用三层共挤，制备三层结构流延板材，经水冷后，再在95℃温度下软化，先纵向拉伸(控制拉伸比例在3.5)，再横向拉伸(拉伸比控制在4.5)，牵引收卷，大分切，小分切后制备双向拉伸可降解薄膜成品。
对比例1
A层组成成分 质量分数/％
热封母料FS5612 10
爽滑剂SAB06554PPR 2
防粘剂ABVT22SC 2
抗静电剂FASPS2955 3
聚乳酸 83
B层组成成分 质量分数/％
聚乳酸 90
引发剂(过氧化苯甲酸叔丁酯) 5
马来酸酐 5
C层组成成分 质量分数/％
热封母料FS5612 86
防粘剂ABS04S 2
抗静电剂DS126T 3
聚乳酸 9
A层：将防粘剂ABVT22SC、爽滑剂SAB06554PPR、抗静电剂FASPS2955与聚乳酸的共混料在190℃的双螺杆挤出机中与热封母料FS5612共混；
B层：引发剂的作用下，将聚乳酸与马来酸酐在190℃的双螺杆挤出机中共混；
C层：将防粘剂ABS04S、抗静电剂DS126T与聚乳酸的共混料与聚丙烯和丁二烯二元共聚物(热封料FS5612)共混；
在得到三层共混料后，然后采用三层共挤，制备三层结构流延板材，经水冷后，再在95℃温度下软化，先纵向拉伸(控制拉伸比例在3.5)，再横向拉伸(拉伸比控制在4.5)，牵引收卷，大分切，小分切后制备双向拉伸可降解薄膜成品。
对比例2
A层组成成分 质量分数/％
热封母料FS5612 83
爽滑剂SAB06554PPR 2
防粘剂ABVT22SC 2
抗静电剂FASPS2955 3
聚乳酸 10
B层组成成分 质量分数/％
聚乳酸 100
C层组成成分 质量分数/％
热封母料FS5612 86
防粘剂ABS04S 2
抗静电剂DS126T 3
聚乳酸 9
A层：将防粘剂ABVT22SC、爽滑剂SAB06554PPR、抗静电剂FASPS2955与聚乳酸的共混料在190℃的双螺杆挤出机中与热封母料FS5612共混；
B层：将聚乳酸在190℃的双螺杆挤出机中共混；
C层：将防粘剂ABS04S、抗静电剂DS126T与聚乳酸的共混料与聚丙烯和丁二烯二元共聚物(热封料FS5612)共混；
在得到三层共混料后，然后采用三层共挤，制备三层结构流延板材，经水冷后，再在95℃温度下软化，先纵向拉伸(控制拉伸比例在3.5)，再横向拉伸(拉伸比控制在4.5)，牵引收卷，大分切，小分切后制备双向拉伸可降解薄膜成品。
对实施例和比较例得到的薄膜进行性能检测，结果如表4所示：
表4
Figure PCTCN2021112213-appb-000001
比较例2制备的产品还存在界面相容性较差的缺陷，也就是后续存在上下表层与芯层界面粘接存在剥落的风险，这个隐患导致在烟用包装膜里面走机的时候完全没法进行。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (10)

  1. 一种双向拉伸可降解薄膜，包括依次接触的A层、B层和C层，
    A层包括以下质量分数的原料：
    热封母料A：83～85％，爽滑剂：2～3％，防粘剂A：2～3％，抗静电剂A：3～5％，聚乳酸：4～10％；
    B层包括以下质量分数的原料：
    聚乳酸：80～90％，引发剂：1～5％，马来酸酐：5～15％；
    C层包括以下质量分数的原料：
    热封母料C：85～88％，防粘剂C：2～5％，抗静电剂C：3～5％，聚乳酸：2～10％。
  2. 根据权利要求1所述的双向拉伸可降解薄膜，其特征在于，所述热封母料A和热封母料C独立的选自聚丙烯和丁二烯二元共聚物、乙烯-乙酸乙烯共聚物、低密度线乙烯和流延聚丙烯中的一种或几种。
  3. 根据权利要求1所述的双向拉伸可降解薄膜，其特征在于，所述爽滑剂为硅酮类爽滑剂；
    所述防粘剂A和防粘剂C为玻璃微珠类防粘剂；
    所述抗静电剂A和抗静电剂C为乙氧基硼类抗静电剂。
  4. 根据权利要求1所述的双向拉伸可降解薄膜，其特征在于，所述引发剂为酯类过氧化物和/或酮类过氧化物。
  5. 如权利要求1～4任意一项所述的双向拉伸可降解薄膜的制备方法，包括以下步骤：
    A)按照原料配比将A层、B层和C层的原料分别挤出共混，得到A层共混料、B层共混料和C层共混料；
    B)将A层共混料、B层共混料和C层共混料进行三层共挤出，再经过流延、纵向拉伸和横向拉伸，得到双向拉伸可降解薄膜。
  6. 根据权利要求5所述的制备方法，其特征在于，所述A层挤出共混的温度为180～200℃。
  7. 根据权利要求5所述的制备方法，其特征在于，所述B层挤出共混的 温度为170～190℃。
  8. 根据权利要求5所述的制备方法，其特征在于，所述C层挤出共混的温度为180～200℃。
  9. 根据权利要求5所述的制备方法，其特征在于，所述纵向拉伸的拉伸比为3.5～4.5；所述横向拉伸的拉伸比为4.0～5.0。
  10. 根据权利要求5所述的制备方法，其特征在于，所述在纵向拉伸之前先对薄膜在95～115℃下软化。
PCT/CN2021/112213 2021-05-26 2021-08-12 一种双向拉伸可降解薄膜及其制备方法 WO2022247023A1 (zh)

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