CN109968777B - Medical super-tough puncture-resistant high-barrier composite film and preparation method thereof - Google Patents

Medical super-tough puncture-resistant high-barrier composite film and preparation method thereof Download PDF

Info

Publication number
CN109968777B
CN109968777B CN201910175668.2A CN201910175668A CN109968777B CN 109968777 B CN109968777 B CN 109968777B CN 201910175668 A CN201910175668 A CN 201910175668A CN 109968777 B CN109968777 B CN 109968777B
Authority
CN
China
Prior art keywords
melting
film
low
composite film
surface layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910175668.2A
Other languages
Chinese (zh)
Other versions
CN109968777A (en
Inventor
杨金玲
叶青
袁秋环
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong University
Original Assignee
Shandong University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shandong University filed Critical Shandong University
Priority to CN201910175668.2A priority Critical patent/CN109968777B/en
Publication of CN109968777A publication Critical patent/CN109968777A/en
Application granted granted Critical
Publication of CN109968777B publication Critical patent/CN109968777B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2009/00—Layered products
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • 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
    • B32B2307/724—Permeability to gases, adsorption
    • 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
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7248—Odour barrier
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/80—Medical packaging

Abstract

The invention relates to a medical super-tough puncture-resistant high-barrier composite film and a preparation method thereof. The composite film core layer adopts a multilayer laminated structure of high-melting-point crystalline polyester and crystalline polyamide resin, so that the characteristics of puncture resistance and high barrier property of the film are solved; the inner surface layer adopts low-melting-point amorphous polyester, has good low-temperature heat sealability and good bonding force with the core layer, and solves the problem of easy delamination with the core layer; the outer surface layer adopts copolyester with low crystallinity, has good printing performance and barrier performance, and has good adhesion with the core layer. The invention utilizes multilayer coextrusion and lamination technology to carry out the procedures of die head extrusion, stretching and the like, thereby preparing the composite film with controllable thickness, easy molding and higher film rate. Meanwhile, the raw materials are cheap and easy to obtain, the preparation process is easy to control, and the method has great values in industrial production and practical application.

Description

Medical super-tough puncture-resistant high-barrier composite film and preparation method thereof
Technical Field
The invention belongs to the technical field of medical high polymer materials, and particularly relates to a medical puncture-resistant high-barrier film and a preparation method thereof.
Background
The market of the Chinese non-PVC multilayer co-extrusion medical sterile film is huge, the medical infusion consumption needs to be increased at a speed of 5-8% per year, and the market mainly depends on European, American and Japanese imports at present.
Currently, the mainstream non-PVC multilayer coextruded medical film consists of three layers. The inner layer of the medical needle is required to have good heat sealing property, puncture resistance, inertia and elasticity with the medical liquid, and is generally made of PP, SEBS and other materials; the middle layer is required to have good flexibility, barrier property, transparency and mechanical strength, and mainly adopts materials such as SEBS, PE, PP and the like; the outer layer is required to have good printing property, barrier property, transparency and high-temperature cooking resistance, and is generally made of PP, PET, PA, PS, PC and other materials.
Patent CN104608453A discloses an ultraviolet resistant film for a barrier coat and a preparation method thereof, wherein the upper surface layer is composed of low melting point amorphous polyester modified by nano inorganic substance and EMA copolymer, the core layer is composed of crystalline PET homopolymer, titanium oxide and cyclic olefin copolymer, the lower surface layer is composed of low melting point amorphous polyester modified by nano inorganic substance and EMA copolymer, and the upper and lower surface layers are co-extruded and compounded on the upper and lower surfaces of the core layer.
In the nano inorganic substance modified low-melting-point amorphous polyester, the low-melting-point amorphous polyester is a polyester copolymer obtained by copolymerizing terephthalic acid, isophthalic acid, ethylene glycol and 2, 2-dimethyl-1, 3-propanediol. The nano inorganic substance is nano SiO2And nano calcium carbonate.
Patent CN108841143A discloses a preparation method of microporous membrane for Western Blot, which comprises the following steps: s1, respectively selecting zeolite and light calcium carbonate powder, and carrying out organic treatment by using organic wax; s2, mixing the organically treated zeolite and light calcium carbonate powder with terephthalic acid, 1, 4-naphthalenedicarboxylic acid, 1, 4-cyclohexanedimethanol and 1, 4-butanediol, adding a catalyst and a stabilizer to perform an esterification reaction, and performing a polycondensation reaction under vacuum to obtain amorphous modified copolyester; s3, drying the prepared amorphous modified copolyester, performing melt extrusion, and cooling and forming to obtain a casting sheet with the thickness of 100-500 mu m; s4, preheating, stretching, shaping and cooling the prepared casting sheet to obtain the primary microporous film with the thickness of 10-50 mu m.
The inventor finds that: because the adhesive force between layers of the existing non-PVC multilayer co-extruded film has certain difference, the layers are easy to separate in the film preparation process, so that the preparation of the multilayer co-extruded film is difficult to control and a product with high film yield is obtained, the technical route is mainly mastered by foreign companies, and the domestic preparation cost is high.
Disclosure of Invention
In order to overcome the problems, the invention provides a medical puncture-resistant high-barrier film and a preparation method thereof. The core layer adopts a multilayer laminated structure of high-melting-point crystalline polyester and crystalline polyamide resin, so that the characteristics of puncture resistance and high barrier property of the film are solved; the inner surface layer adopts low-melting-point amorphous polyester, has good low-temperature heat sealability and good bonding force with the core layer, and solves the problem of easy delamination with the core layer; the outer surface layer adopts copolyester with low crystallinity, has good printing performance and barrier property, and has good bonding force with the core layer. The invention utilizes multilayer coextrusion and lamination technology to carry out the procedures of die head extrusion, stretching and the like, thereby preparing the composite film with controllable thickness, easy molding and higher film rate. The novel medical polymer composite material with internal heat sealability, puncture resistance and high barrier property is found, and the preparation method is simple, easy to process and form and has wide application prospect.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
a medical super-tough puncture-resistant high-barrier composite film comprises a core layer, an inner surface layer and an outer surface layer from inside to outside in sequence; the core layer is a multilayer laminated structure of high-melting-point crystalline polyester and crystalline polyamide resin; the inner surface layer is made of low-melting-point amorphous polyester, and the outer surface layer is made of low-crystallinity copolyester.
The composite film is of a sandwich structure and sequentially comprises an inner surface layer, a core layer and an outer surface layer from top to bottom.
In some embodiments, the low crystallinity copolyester is prepared by: carrying out esterification reaction on the silicon dioxide powder after organic treatment, terephthalic acid (PTA), 1, 6-naphthalene dicarboxylic acid (NAP), isophthalic acid (IPA) and ethylene glycol in the presence of a catalyst and a stabilizer, and carrying out polycondensation reaction after the reaction is finished. The copolyester with low crystallinity is adopted as the outer surface layer, so that the outer surface layer has good bonding force with the core layer, the printing performance requirement of the barrier film can be met, and the barrier performance of the barrier film is improved.
In some embodiments, the low melting amorphous polyester is prepared by the following steps: carrying out esterification reaction on the silicon dioxide powder after organic treatment, terephthalic acid (PTA), isophthalic acid (IPA), 2-methyl-1, 3-propanediol (NPG), ethylene glycol and 1, 4-Butanediol (BDO) in the presence of a catalyst and a stabilizer, and carrying out polycondensation reaction after the reaction is finished. The low-temperature heat sealability of the copolyester with low crystallinity is utilized to ensure that the copolyester has good bonding force with the core layer, thereby solving the problem of easy delamination with the core layer.
In some embodiments, the core layer is obtained by extruding a high-melting-point crystalline polyester with a melting point of 258-262 ℃ and a crystalline polyamide resin with a melting point of 225-260 ℃ through a double screw and then extruding and molding through a laminator. The method can form a multilayer laminated structure, not only effectively improves the puncture resistance of the barrier film, but also has better cohesiveness with copolyester with low crystallinity and amorphous polyester with low melting point, so that the barrier film has controllable thickness, easy molding and higher film yield.
In some embodiments, the catalyst is one or more of tin oxide, germanium oxide, titanium dioxide, antimony trioxide, antimony glycol, or antimony acetate; the dosage of the catalyst is 300-900 ppm based on the total weight of the acid system in the reaction system.
In some embodiments, the stabilizer is one or more of phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, ammonium phosphate, trimethyl phosphate, dimethyl phosphate, tributyl phosphate and triphenyl phosphate, and the amount of the stabilizer is 200 to 600ppm based on the total weight of the acid system in the reaction system.
In some embodiments, the film has a thickness of 20 to 50 μm.
In some embodiments, the film has an oxygen transmission rate of 3 to 20cc/m at 25 ℃ and 90% humidity2·day·atm, water-gas transmission rate of 5-30 g/m2·day·atm。
The invention also provides a preparation method of the medical super-tough puncture-resistant high-barrier composite film, which comprises the following steps:
mixing the organized silicon dioxide or calcium carbonate powder with terephthalic acid (PTA), 1, 6-naphthalene dicarboxylic acid (TPA), isophthalic acid (IPA) and ethylene glycol, carrying out esterification reaction in the presence of a catalyst and a stabilizer, and after the reaction is finished, carrying out polycondensation reaction to obtain copolyester with low crystallinity;
mixing the silicon dioxide powder subjected to organic treatment with terephthalic acid (PTA), isophthalic acid (IPA), 2-methyl-1, 3-propanediol (NPG), ethylene glycol and 1, 4-Butanediol (BDO), carrying out esterification reaction in the presence of a catalyst and a stabilizer, and carrying out polycondensation reaction after the reaction is finished to obtain low-melting-point amorphous polyester;
extruding high-melting-point crystalline polyester with the melting point of 258-262 ℃ and crystalline polyamide resin with the melting point of 225-260 ℃ by a double screw, and then feeding the extruded high-melting-point crystalline polyester and the crystalline polyamide resin into a laminator to obtain a multilayer laminated structure melt;
the copolyester with low crystallinity, the amorphous polyester with low melting point and the melt with the multilayer laminated structure enter a three-layer adapter together, and then flow out of a die head to be cooled and formed to form a primary casting sheet;
and preheating, stretching, heat setting and cooling the primary casting sheet to form the composite film.
The invention also provides application of any one of the composite films in packaging of medical products, cosmetics, tea, chemical reagents, pesticides, spices, feeds, meat products, dairy products and marinated products.
The invention has the beneficial effects that:
(1) the core layer adopts a multilayer laminated structure of high-melting-point crystalline polyester and crystalline polyamide resin, so that the characteristics of puncture resistance and high barrier property of the film are solved; the inner surface layer is made of low-melting-point amorphous polyester with good low-temperature heat sealability, so that the inner surface layer and the core layer have good bonding force, and the problem of easy delamination with the core layer is solved; the outer surface layer is made of copolyester with low crystallinity, has good printing performance and barrier performance, and has good adhesion with the core layer. The invention utilizes multilayer coextrusion and lamination technology to carry out the procedures of die head extrusion, stretching and the like so as to prepare the composite film with controllable thickness, easy molding and higher film rate; the process simplifies the working procedures, reduces the test requirements and is more convenient for the operation of technical personnel. Meanwhile, the raw materials are cheap and easy to obtain, the preparation process is simple, and the method has great values in industrial production and practical application.
(2) The preparation method is simple, low in cost, universal and easy for large-scale production.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments in accordance with the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As described in the background art, the problem that the preparation of the multilayer co-extruded film is difficult to control and a product with high film yield is obtained is solved because the adhesion force between each layer of the existing non-PVC multilayer co-extruded film has certain difference and the layers are easy to separate in the film preparation process. Therefore, the invention provides a preparation method of a medical puncture-resistant high-barrier composite film, which comprises the following steps:
s1, selecting spherical silicon dioxide or calcium carbonate powder with the particle size range of 0.1-2.0 mu m, and carrying out organic treatment for 1-3 hours by using organic wax;
s2, mixing the silicon dioxide powder subjected to organic treatment in the step S1 with terephthalic acid (PTA), 1, 6-naphthalene dicarboxylic acid, isophthalic acid (IPA) and ethylene glycol according to a weight ratio of 0.1-1: 10-50: 5-15: 10-30: 30-65, adding a catalyst and a stabilizer, performing esterification reaction at 240-260 ℃, and performing polycondensation reaction at vacuum degree of 10-100 Pa and temperature of 270-300 ℃ to obtain low-crystallinity copolyester; the intrinsic viscosity of the copolyester with low crystallinity is 0.60-0.85 dl/g; the copolyester with low crystallinity is extruded by a double screw to be used as the outer surface layer of the composite film;
s3, mixing the silicon dioxide powder subjected to organic treatment in the step S1 with terephthalic acid (PTA), isophthalic acid (IPA), 2-methyl-1, 3-propanediol (NPG), ethylene glycol and 1, 4-Butanediol (BDO) according to the weight ratio of 0.1-0.5: 10-50: 5-50: 5:15: 30-65: mixing the raw materials in a ratio of 10-50, adding a catalyst and a stabilizer, carrying out esterification reaction at 230-260 ℃ for 1-3 hours, and carrying out polycondensation reaction at 260-300 ℃ under a vacuum degree of 10-100 Pa to obtain low-melting-point amorphous polyester; the intrinsic viscosity of the low-melting-point amorphous polyester is 0.65-0.85 dl/g; the melting point of the low-melting-point amorphous polyester is 180-190 ℃; the low-melting-point amorphous polyester is extruded by a double screw to be used as the inner surface layer of the composite film;
s4, mixing high-melting-point crystalline polyester with a melting point of 258-262 ℃ and crystalline polyamide resin with a melting point of 225-260 ℃ according to a ratio of 50-90: the length-diameter ratio of 10-50 is respectively 25: 1-42: the double-screw extruder of 1 enters a 128-1024-layer laminator, and the obtained multilayer melt is used as a core layer of the composite film;
s5, enabling the outer surface layer, the core layer and the inner surface layer of the composite film prepared in the steps S1, S3 and S2 to enter a three-layer adapter together, and then enabling the composite film to flow out of a die head to be cooled and formed to obtain a casting sheet with the thickness of 200-400 microns;
s6, preheating, stretching, shaping and cooling the casting sheet prepared in the step S5 on a synchronous stretcher by using hot air to obtain a medical puncture-resistant high-barrier composite film with the thickness of 20-50 mu m; the barrier film has an oxygen transmission rate of 3 to 20cc/m at 25 ℃ and 90% humidity2·day·atm, water-gas transmission rate of 5-30 g/m2·day·atm。
In one embodiment of the present invention, a method for preparing a medical puncture-resistant high-barrier composite film is provided, the method comprising:
s1, selecting spherical silicon dioxide or calcium carbonate powder with the particle size range of 0.1-2.0 mu m respectively, and carrying out organic treatment for 1-3 hours by using organic wax;
s2, mixing the silicon dioxide or calcium carbonate powder subjected to organic treatment in the step S1 with terephthalic acid (PTA), 1, 6-naphthalene dicarboxylic acid (DMB), isophthalic acid (IPA) and ethylene glycol in a weight ratio of 0.1-1: 10-50: 5-15: 10-30: 30-65, adding a catalyst and a stabilizer to perform esterification reaction, and then performing polycondensation reaction under a certain vacuum degree to obtain low-crystallinity copolyester; the intrinsic viscosity of the copolyester with low crystallinity is 0.60-0.85 dl/g; the melting point of the low-crystallinity polyester is 180-220 ℃; the copolyester with low crystallinity is extruded by a double screw to be used as the outer surface layer of the composite film;
s3, mixing the silicon dioxide powder subjected to organic treatment in the step S1 with terephthalic acid (PTA), isophthalic acid (IPA), 2-methyl-1, 3-propanediol (NPG), ethylene glycol and 1, 4-Butanediol (BDO) according to the weight ratio of 0.1-0.5: 10-50: 5-50: 5:15: 30-65: mixing the raw materials in a ratio of 10-50, adding a catalyst and a stabilizer, carrying out esterification reaction at 230-260 ℃ for 1-3 hours, and carrying out polycondensation reaction at 260-300 ℃ under a vacuum degree of 10-100 Pa to obtain low-melting-point amorphous polyester; the intrinsic viscosity of the low-melting-point amorphous polyester is 0.65-0.85 dl/g; the melting point of the low-melting-point amorphous polyester is 180-190 ℃; the low-melting-point amorphous polyester is extruded by a double screw to be used as the inner surface layer of the composite film;
s4, mixing high-melting-point crystalline polyester with a melting point of 258-262 ℃ and crystalline polyamide resin with a melting point of 225-260 ℃ according to a ratio of 50-90: the length-diameter ratio of 10-50 is respectively 25: 1-42: the double-screw extruder of 1 enters a 128-1024-layer laminator, and the obtained multilayer melt is used as a core layer of the composite film;
s5, enabling the outer surface layer, the core layer and the inner surface layer of the composite film prepared in the steps S1, S3 and S2 to enter a three-layer adapter together, and then enabling the composite film to flow out of a die head to be cooled and formed to obtain a primary casting sheet with the thickness of 200-400 microns;
s6, preheating, stretching, heat setting and cooling the casting sheet prepared in the step S5 on a synchronous stretcher by using hot air to obtain the medical puncture-resistant high-barrier composite film with the thickness of 20-50 mu m(ii) a The barrier film has an oxygen transmission rate of 3 to 20cc/m at 25 ℃ and 90% humidity2·day·atm, water-gas transmission rate of 5-30 g/m2·day·atm。
In another embodiment of the present invention, in step s1,
the purity of the spherical silicon dioxide and the calcium carbonate is more than 99.6 percent;
the organic wax is one or more of hydrocarbon mixture with 18-30 carbon atoms, hard partially saponified montan wax, ultra-low molecular weight polyethylene wax and silane coupling agent; preferably, the organic wax is a hard partially saponified montan wax;
in another embodiment of the present invention, in step s2,
the catalyst is one or more of tin oxide, germanium oxide, titanium dioxide, antimony trioxide, ethylene glycol antimony or antimony acetate; the dosage of the catalyst is 300-900 ppm based on the total weight of the acid system in the reaction system;
the stabilizer is one or more of phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, ammonium phosphate, trimethyl phosphate, dimethyl phosphate, tributyl phosphate and triphenyl phosphate, and the dosage of the stabilizer is 200-600 ppm based on the total weight of an acid system in the reaction system;
the esterification reaction conditions are as follows: the reaction temperature is 230-260 ℃, and the reaction time is 1-4 h;
the polycondensation reaction conditions are as follows: the vacuum degree is 10-50Pa (preferably 10Pa), the reaction temperature is 270-300 ℃, and the reaction time is 2.5-4.5 h (preferably 3.5 h);
in another embodiment of the present invention, in step s3. the step of,
the catalyst is one or more of tin oxide, ethylene glycol antimony or antimony acetate; the dosage of the catalyst is 200-800 ppm based on the total weight of the acid system in the reaction system;
the stabilizer is one or more of trimethyl phosphate, dimethyl phosphate and triphenyl phosphate, and the dosage of the stabilizer is 200-500 ppm based on the total weight of an acid system in the reaction system;
in another embodiment of the present invention, in step s4,
the crystalline polyester has a viscosity of 0.65 to 0.69 dl/g;
the crystalline polyamide resin is obtained by polycondensation of m-xylylenediamine (MXDA) and Adipic Acid (AA), and is preferably a barrier product MXD6 available from Mitsubishi gas chemical corporation;
in another embodiment of the present invention, in step s5, the thickness ratios of the outer surface layer, the core layer, and the inner surface layer are: 10-30: 40-80: 10:30, preferably 10-15: 70-80: 10-15.
In another embodiment of the present invention, the step s6 specifically includes: s5, preheating the obtained primary casting sheet by hot air at 80-130 ℃ for 5-15 s, synchronously stretching the primary casting sheet in hot air at 90-130 ℃ for 5-15 s with the surface stretching ratio of 6-18, shaping the primary casting sheet in hot air at 180-240 ℃ for 5-30s, and cooling and drying the primary casting sheet in cold air at 30-60 ℃ for 5-20 s to obtain a film with the thickness of 20-50 mu m.
In another embodiment of the present invention, the wind speed of the cold air and the wind speed of the hot air are both 10-30 m/s.
In another embodiment of the present invention, the medical puncture-resistant high-barrier composite film prepared by the above preparation method is provided.
In another embodiment of the present invention, the composite film is applied to the market of multi-layer co-extruded sterile films.
Example 1
Respectively selecting spherical silicon dioxide powder with the particle size range of 0.1-1.0 mu m, and performing organic treatment for 1.5 hours by using hard partially saponified montan wax;
mixing the organized silicon dioxide powder with terephthalic acid (PTA), 1, 6-naphthalene dicarboxylic acid (NAP), isophthalic acid (IPA) and ethylene glycol according to the weight ratio of 0.5: 30: 10.6: 15: 44, adding 200ppm of ethylene glycol antimony as a catalyst and 300ppm of tributyl phosphate as a stabilizer to carry out esterification reaction at the esterification temperature of 240-265 ℃ for 3h, and then carrying out polycondensation reaction at the vacuum degree of 20Pa and the temperature of 278-300 ℃ for 3.5h to obtain the copolyester with the intrinsic viscosity of 0.68dl/g and the melting point of 220 ℃ and low crystallinity; the copolyester with low crystallinity is extruded by a double screw to be used as the outer surface layer of the composite film;
mixing the organized silicon dioxide powder with terephthalic acid (PTA), isophthalic acid (IPA), 2-methyl-1, 3-propanediol (NPG), ethylene glycol and 1, 4-Butanediol (BDO) according to the weight ratio of 0.1: 49.9: 20: 15: 10: 10, adding 200ppm of ethylene glycol antimony as a catalyst and 250ppm of trimethyl phosphate as a stabilizer, carrying out esterification reaction at 260 ℃ for 3 hours, and then carrying out polycondensation reaction at 300 ℃ under the vacuum degree of 10Pa for 3.5 hours to obtain low-melting-point amorphous polyester with the melting point of 190 ℃ and the vacuum degree of 0.80 dl/g; the low-melting-point amorphous polyester is extruded by a double screw and then is used as an inner surface layer of the composite film;
a high-melting-point crystalline polyester having a melting point of 258 ℃ and a crystalline polyamide resin MXD6 having a melting point of 225 ℃ were mixed in a ratio of 70: the ratio of 30 is respectively entered into the ratio of length-diameter ratio of 42: 1, entering a 1024-layer laminator to obtain a multilayer melt as a core layer of the composite film;
the outer surface layer, the core layer and the inner surface layer of the prepared composite film enter a three-layer adapter together according to the thickness ratio of 10:80:10, and then flow out of a die head to be cooled and formed to obtain a primary casting sheet with the thickness of 400 mu m;
preheating, stretching, heat setting and cooling the primary casting sheet on a synchronous stretcher by using hot air to obtain a medical puncture-resistant high-barrier composite film with the thickness of 50 mu m; preheating hot air at 105 ℃ for 10s, synchronously stretching in hot air at 120 ℃ for 15s under the condition of surface stretching ratio of 8, shaping in hot air at 240 ℃ for 5s, and cooling and drying in cold air at 30-60 ℃ for 5-20 s; the barrier film has an oxygen transmission rate of 4cc/m at 25 ℃ and 90% humidity2·day·atm, water vapor transmission rate of 6g/m2·day·atm。
The performance of the medical super-tough puncture-resistant high-barrier composite film is shown as 1.1 film in table 1.
Example 2
Respectively selecting spherical silicon dioxide powder with the particle size range of 0.5-1.0 mu m, and carrying out organic treatment for 2.5 hours by using ultra-low molecular weight polyethylene wax;
mixing the organized silicon dioxide powder with terephthalic acid (PTA), 1, 6-naphthalene dicarboxylic acid (NAP), isophthalic acid (IPA) and ethylene glycol according to the weight ratio of 0.5: 26: 9.5: 19: 45, adding 250ppm of antimony trioxide as a catalyst and 350ppm of trimethyl phosphate as a stabilizer to perform esterification reaction at the esterification temperature of 250-255 ℃ for 3.2h, and then performing polycondensation reaction at the vacuum degree of 30Pa and the temperature of 278-290 ℃ for 3.2h to obtain the copolyester with low crystallinity, the intrinsic viscosity of which is 0.69dl/g and the melting point of which is 210 ℃; the copolyester with low crystallinity is extruded by a double screw to be used as the outer surface layer of the composite film;
mixing the organized silicon dioxide powder with terephthalic acid (PTA), isophthalic acid (IPA), 2-methyl-1, 3-propanediol (NPG), ethylene glycol and 1, 4-Butanediol (BDO) according to the weight ratio of 0.1: 49.9: 20: 15: 10: 10, adding 200ppm of antimony trioxide as a catalyst and 250ppm of trimethyl phosphate as a stabilizer, carrying out esterification reaction at 255 ℃ for 3 hours, and then carrying out polycondensation reaction at 295 ℃ under the vacuum degree of 10Pa for 3.5 hours to obtain low-melting-point amorphous polyester with the melting point of 185 ℃ and the concentration of 0.78 dl/g; the low-melting-point amorphous polyester is extruded by a double screw to be used as the inner surface layer of the composite film;
a high-melting-point crystalline polyester having a melting point of 260 ℃ and a crystalline polyamide resin MXD6 having a melting point of 225 ℃ were mixed in a ratio of 80: the ratio of 20 is respectively entered into the ratio of length-diameter ratio of 42: 1, entering a laminator with 512 layers after entering a double-screw extruder, and taking the obtained multilayer melt as a core layer of the composite film;
the outer surface layer, the core layer and the inner surface layer of the prepared composite film enter a three-layer adapter together according to the thickness ratio of 15:70:15, and then flow out of a die head to be cooled and formed to obtain a primary casting sheet with the thickness of 250 mu m;
preheating, stretching, heat setting and cooling the primary casting sheet on a synchronous stretcher by using hot air to obtain a medical puncture-resistant high-barrier composite film with the thickness of 20 mu m; wherein the preheating is carried outPreheating with 100 deg.C hot air for 12s, stretching with 125 deg.C hot air for 10s with surface stretch ratio of 12, shaping with 220 deg.C hot air for 6s, and cooling with 30 deg.C cold air for 20 s; the barrier film has an oxygen transmission rate of 20cc/m at 25 ℃ and 90% humidity2·day·atm, water vapor transmission rate of 25g/m2·day·atm。
The performance of the medical super-tough puncture-resistant high-barrier composite film is shown as 1.2 films in table 1.
Example 3
Selecting spherical silicon dioxide powder with the particle size range of 1.0-2.0 μm, and performing organic treatment for 1.5 hours by using hard partially saponified montan wax;
mixing the organized silicon dioxide powder with terephthalic acid (PTA), 1, 6-naphthalene dicarboxylic acid (NAP), isophthalic acid (IPA) and ethylene glycol according to the weight ratio of 0.2: 24.2: 13.6: 20: 42, adding 400ppm of germanium oxide as a catalyst and 300ppm of dimethyl phosphate as a stabilizer to perform esterification reaction at the esterification temperature of 252-255 ℃ for 2.5-3h, and then performing polycondensation reaction at the vacuum degree of 10Pa and the temperature of 280-288 ℃ for 3-3.5h to obtain the copolyester with low crystallinity, the intrinsic viscosity of which is 0.65dl/g and the melting point of which is 200 ℃; the copolyester with low crystallinity is extruded by a double screw to be used as the outer surface layer of the composite film;
mixing the organized silicon dioxide powder with terephthalic acid (PTA), isophthalic acid (IPA), 2-methyl-1, 3-propanediol (NPG), ethylene glycol and 1, 4-Butanediol (BDO) according to the weight ratio of 0.3: 40: 10: 15: 5.7: 29, adding 400ppm of germanium oxide as a catalyst and 350ppm of trimethyl phosphate as a stabilizer, carrying out esterification reaction at 253 ℃ of 250-3.5 hours, and then carrying out polycondensation reaction at 289 ℃ and vacuum degree of 30Pa for 3.5 hours to obtain low-melting-point amorphous polyester with the melting point of 180 ℃ and the dl/g of 0.75; the low-melting-point amorphous polyester is extruded by a double screw to be used as the inner surface layer of the composite film;
a high-melting-point crystalline polyester having a melting point of 260 ℃ and a crystalline polyamide resin MXD6 having a melting point of 225 ℃ were mixed in a ratio of 90: the ratio of 10 is respectively entered into the ratio of length-diameter ratio of 36: 1, entering a 128-layer laminator to obtain a multilayer melt as a core layer of the composite film;
the outer surface layer, the core layer and the inner surface layer of the prepared composite film are fed into a three-layer adapter together according to the thickness ratio of 12.5:75:12.5, and then flow out of a die head to be cooled and formed, so that a primary casting sheet with the thickness of 300 mu m is obtained;
preheating, stretching, heat setting and cooling the primary casting sheet on a synchronous stretcher by using hot air to obtain a medical puncture-resistant high-barrier composite film with the thickness of 50 mu m; wherein the preheating condition is 95 ℃ hot air preheating 12s, the stretching condition is synchronous stretching 12 with surface stretching ratio of 10 in 115 ℃ hot air, then setting 10s in 180 ℃ hot air, and cooling and drying 15s in 30 ℃ cold air; the barrier film has an oxygen transmission rate of 19cc/m at 25 ℃ and 90% humidity2·day·atm, water vapor transmission rate of 30g/m2·day·atm。
The performance of the medical super-tough puncture-resistant high-barrier composite film is shown as 1.3 films in table 1.
TABLE 1. three medical super-tough puncture-resistant high-barrier composite film performances
Figure BDA0001989511890000091
Figure BDA0001989511890000101
Finally, it should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.

Claims (2)

1. A medical super-tough puncture-resistant high-barrier composite film is characterized in that an inner surface layer, a core layer and an outer surface layer are sequentially arranged from top to bottom; the core layer is a multilayer laminated structure of high-melting-point crystalline polyester and crystalline polyamide resin; the inner surface layer is made of low-melting amorphous polyester, and the outer surface layer is made of low-crystallinity copolyester;
the preparation method of the film comprises the following steps: mixing the organized silicon dioxide or calcium carbonate powder with PTA, 1, 6-naphthalenedicarboxylic acid, IPA and ethylene glycol, carrying out esterification reaction in the presence of a catalyst and a stabilizer, and then carrying out polycondensation reaction after the reaction is finished to obtain copolyester with low crystallinity;
mixing the silicon dioxide powder subjected to organic treatment with PTA, IPA, 2-methyl-1, 3-propanediol NPG, glycol and 1, 4-butanediol BDO, carrying out esterification reaction in the presence of a catalyst and a stabilizer, and carrying out polycondensation reaction after the reaction is finished to obtain low-melting-point amorphous polyester;
extruding high-melting-point crystalline polyester with the melting point of 258-262 ℃ and crystalline polyamide resin with the melting point of 225-260 ℃ by a double screw, and then feeding the extruded high-melting-point crystalline polyester and the crystalline polyamide resin into a laminator to obtain a multilayer laminated structure melt;
the copolyester with low crystallinity, the amorphous polyester with low melting point and the melt with the multilayer laminated structure enter a three-layer adapter together, and then flow out of a die head to be cooled and formed to form a primary casting sheet; preheating, stretching, heat setting and cooling the primary casting sheet to form a composite film;
the organic treatment is organic wax treatment;
the catalyst is one or more of tin oxide, germanium oxide, titanium dioxide, antimony trioxide, ethylene glycol antimony or antimony acetate; the dosage of the catalyst is 300-900 ppm based on the total weight of the acid system in the reaction system;
the stabilizer is one or more of phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, ammonium phosphate, trimethyl phosphate, dimethyl phosphate, tributyl phosphate and triphenyl phosphate, and the dosage of the stabilizer is 200-600 ppm based on the total weight of an acid system in the reaction system;
the film has an oxygen transmission rate of 3 to 20cc/m at 25 ℃ and 90% humidity2Atm, and a water-gas transmission rate of 5 to 30g/m2.day.atm。
2. The film of claim 1, wherein the film has a thickness of 20 to 50 μm.
CN201910175668.2A 2019-03-08 2019-03-08 Medical super-tough puncture-resistant high-barrier composite film and preparation method thereof Active CN109968777B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910175668.2A CN109968777B (en) 2019-03-08 2019-03-08 Medical super-tough puncture-resistant high-barrier composite film and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910175668.2A CN109968777B (en) 2019-03-08 2019-03-08 Medical super-tough puncture-resistant high-barrier composite film and preparation method thereof

Publications (2)

Publication Number Publication Date
CN109968777A CN109968777A (en) 2019-07-05
CN109968777B true CN109968777B (en) 2020-01-07

Family

ID=67078317

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910175668.2A Active CN109968777B (en) 2019-03-08 2019-03-08 Medical super-tough puncture-resistant high-barrier composite film and preparation method thereof

Country Status (1)

Country Link
CN (1) CN109968777B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114400416B (en) * 2021-12-08 2023-02-28 四川大学 Lithium battery diaphragm with thermal shutdown property and preparation method

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101274501A (en) * 2000-03-16 2008-10-01 巴克斯特国际公司 Multilayer film of new non-pvc material
DE602005006573D1 (en) * 2004-07-15 2008-06-19 Du Pont COMPOSITION, CONTAINING ETHYLENE COPOLYMERS AND POLYOLEFINES
CN1817637A (en) * 2006-03-11 2006-08-16 宁波市奕盛电子科技发展有限公司 Multi-layer coextrusion film with high impedance and production thereof
CN201922599U (en) * 2010-11-23 2011-08-10 富维薄膜（山东）有限公司 Heat-sealing type polyester film for capacitor housing
CN105082693B (en) * 2015-08-19 2017-11-03 树业环保科技股份有限公司 A kind of antimildew and antibacterial polyester film and preparation method thereof

Also Published As

Publication number Publication date
CN109968777A (en) 2019-07-05

Similar Documents

Publication Publication Date Title
CN1222408C (en) High moisture barrier films
CN102070882B (en) Polyester film for being adhered to surface of metal thin plate and manufacture method thereof
CN109476857A (en) Encapsulant film and preparation method
CN102225648A (en) High-barrier polyester film and its preparation method
CN103203934A (en) Heat shrinkage copolyester film and preparation method thereof
CN103897322B (en) A kind of resin combination and solar energy backboard prepared therefrom
CN103715287A (en) Humidity-resistant and heat-resistant solar cell panel and manufacturing method thereof
CN102152579A (en) Co-extruded and bidirectional-stretched composite film and preparation method thereof
CN109968777B (en) Medical super-tough puncture-resistant high-barrier composite film and preparation method thereof
CN109411558A (en) A kind of solar cell backboard and preparation method thereof
EP3250377A1 (en) Multilayer film structures comprising renewable polyester compositions
CN211518752U (en) Heat-sealable co-extruded biaxially oriented composite film
CN102825877A (en) Multi-layer plastic composite isolating sheet and production process thereof
CN201587630U (en) Extinction blocking five-layer coextruded composite film
CN112590341B (en) Recyclable high-barrier composite sheet with high composite strength and preparation method thereof
CN112848580B (en) PETG/PET co-extrusion self-sealing multilayer film and preparation method thereof
CN105504249B (en) A kind of fluorine-containing conjugated polyester resin of hydrolysis, the fluorine-containing copolyesters compound substrate membranes of hydrolysis and preparation method thereof
CN110385905B (en) Laminated co-extrusion film containing double-protection core barrier layers and production process thereof
CN114290784A (en) High-barrier bio-based nylon film with antibacterial property and preparation method and application thereof
CN214111840U (en) Thick low-thermal-shrinkage polyester film
CN108909114A (en) A kind of carbon dioxide-base composite material and preparation method
CN115556455B (en) Full-plastic transparent high-barrier coating composite film and preparation method thereof
KR20170009003A (en) Heat-shrinkable laminated film and heat-shrinkable label using same
CN115489188B (en) Polyester film for household protection and preparation method thereof
CN102814958A (en) Method for improving polyolefin gas barrier properties

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant