CN112959786B - Oral liquid PET-PCTFE-PE composite hard sheet and preparation method thereof - Google Patents

Oral liquid PET-PCTFE-PE composite hard sheet and preparation method thereof Download PDF

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Publication number
CN112959786B
CN112959786B CN202110302194.0A CN202110302194A CN112959786B CN 112959786 B CN112959786 B CN 112959786B CN 202110302194 A CN202110302194 A CN 202110302194A CN 112959786 B CN112959786 B CN 112959786B
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polyethylene
polychlorotrifluoroethylene
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pctfe
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CN112959786A (en
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张辉
李中明
张华江
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Sichuan Huili Industrial Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/36Layered products comprising a layer of synthetic resin comprising polyesters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered 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
    • B32B27/08Layered 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/08Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the cooling method
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS 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
    • B65D65/00Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38Packaging materials of special type or form
    • B65D65/40Applications of laminates for particular packaging purposes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/30Properties of the layers or laminate having particular thermal properties
    • B32B2307/302Conductive
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/30Properties of the layers or laminate having particular thermal properties
    • B32B2307/308Heat stability
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/724Permeability to gases, adsorption
    • B32B2307/7242Non-permeable
    • B32B2307/7244Oxygen barrier
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/724Permeability to gases, adsorption
    • B32B2307/7242Non-permeable
    • B32B2307/7246Water vapor barrier
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00Containers; Receptacles
    • B32B2439/80Medical packaging

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention discloses an oral liquid PET-PCTFE-PE composite hard sheet and a preparation method thereof, wherein the PET-PCTFE-PE composite hard sheet comprises an outer polyester layer, a middle polychlorotrifluoroethylene layer and an inner polyethylene layer; the raw materials of the polychlorotrifluoroethylene layer comprise: polychlorotrifluoroethylene, alpha-alumina-loaded copper powder, aluminum powder and polyethylene wax; the polyethylene layer comprises the following raw materials: polyethylene, polyvinyl chloride and aluminum powder; the middle polychlorotrifluoroethylene layer is respectively fixed with the outer polyester layer and the inner polyethylene layer by hot pressing. According to the invention, the PCTFE (polychlorotrifluoroethylene) layer is designed between the PET layer and the PE layer, and the raw material composition of the polychlorotrifluoroethylene layer and the raw material composition of the polyethylene layer are optimally designed, so that the finally obtained composite film material has good barrier property, and meets the requirement of medicine packaging.

Description

Oral liquid PET-PCTFE-PE composite hard sheet and preparation method thereof
Technical Field
The invention relates to a medicine packaging material, in particular to an oral liquid PET-PCTFE-PE composite hard sheet and a preparation method thereof.
Background
Most of the existing liquid medicines are stored in glass bottles or plastic bottles, but the glass bottles are fragile and heavy, and the plastic bottles are mostly formed by compound hard sheets through plastic suction, generally, the plastic bottles are arranged together through one-time plastic suction forming, so that the plastic bottles connected together are firstly separated when the medicine is taken, and then the bottle caps are unscrewed for taking.
At present, some composite hard sheets are used for containing liquid medicines and have high requirements on barrier property, so that a multilayer composite film is generally adopted, and commonly used materials are PET (polyester) and PE (polyethylene).
In the prior art, an inner layer, namely a heat sealing layer PE which is directly contacted with a liquid medicine is generally improved to improve the barrier property of the inner layer. The barrier property is an important project for inspecting the quality of the protective property of the composite film for packaging the medicine, and the quality of the barrier property is directly related to whether the requirement of the moisture-proof property of the medicine can be met or not and the problem of the storage quality of the medicine, so that research and development of a new film material with better barrier property is an important subject.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the invention provides an oral liquid PET-PCTFE-PE composite hard sheet and a preparation method thereof, which solve the problems of improving the barrier property of the PET-PE composite hard sheet.
The invention is realized by the following technical scheme:
an oral liquid PET-PCTFE-PE composite hard sheet comprises an outer polyester layer, a middle polychlorotrifluoroethylene layer and an inner polyethylene layer; the raw materials of the polychlorotrifluoroethylene layer comprise: polychlorotrifluoroethylene, alpha-alumina-loaded copper powder, aluminum powder and polyethylene wax; the polyethylene layer comprises the following raw materials: polyethylene, polyvinyl chloride and aluminum powder; the middle polychlorotrifluoroethylene layer is respectively fixed with the outer polyester layer and the inner polyethylene layer by hot pressing.
Further preferably, the polyethylene wax is polyethylene with a molecular weight of 1800-3000.
Further preferably, the raw materials of the polychlorotrifluoroethylene layer comprise, by weight: 100 parts of polychlorotrifluoroethylene, 8-20 parts of alpha-alumina loaded copper, 3-12 parts of aluminum powder and 2-15 parts of polyethylene wax.
Further preferably, the polyethylene layer comprises the following raw materials in parts by weight: 100 parts of polyethylene, 10-30 parts of polyvinyl chloride and 5-15 parts of aluminum powder.
Further preferably, in the alpha-alumina-supported copper, the mass ratio of alpha-alumina to copper is 1.
A preparation method of an oral liquid PET-PCTFE-PE composite hard sheet is used for preparing the oral liquid PET-PCTFE-PE composite hard sheet and comprises the following steps:
step 1: melting, extruding and cooling the raw materials of the polychlorotrifluoroethylene layer to obtain a polychlorotrifluoroethylene sheet;
step 2: melting, extruding and cooling raw materials of the polyethylene layer to obtain a polyethylene sheet;
and 3, step 3: and sequentially stacking the polyester sheet, the polychlorotrifluoroethylene sheet and the polyethylene sheet, and performing hot pressing, cooling and shaping to obtain the composite film.
More preferably, the particle size of the alpha-alumina-loaded copper powder is larger than 200 meshes; the particle size of the aluminum powder is 50nm-200nm.
Further preferably, the thickness of the polyester layer of the shaped composite film is 80-260 μm; the thickness of the polychlorotrifluoroethylene layer is 45 μm-90 μm; the polyethylene layer has a thickness of 20 μm to 40 μm.
Further preferably, the hot pressing temperature in the step 3 is 150-180 ℃.
The invention has the following advantages and beneficial effects:
the barrier property is an important item for inspecting the quality of the protective property of the composite film for packaging the medicine, and the quality of the barrier property is directly related to whether the requirement of the moisture resistance of the medicine can be met or not and is directly related to the storage quality of the medicine. In the prior art, an inner layer, namely a heat seal layer PE, which is in direct contact with liquid medicine is generally improved so as to improve the barrier property of the inner layer; according to the invention, the PCTFE (polychlorotrifluoroethylene layer) layer is designed between the PET layer and the PE layer, and the raw material composition of the polychlorotrifluoroethylene layer and the raw material composition of the polyethylene layer are optimally designed, so that the heat conductivity and the heat stability of the polychlorotrifluoroethylene layer are improved, the bonding strength of the polyethylene layer and the polychlorotrifluoroethylene layer is improved, and the finally obtained composite film material has good barrier property and meets the requirement of medicine packaging.
In addition, PET refers to polyester material, which is commonly called polyester resin under the English name of Polyethylene terephthalate; PE refers to polyethylene material.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not used as limitations of the present invention.
Example 1
The embodiment provides an oral liquid PET-PCTFE-PE composite hard sheet, which comprises an outer polyester layer, an intermediate polychlorotrifluoroethylene layer and an inner polyethylene layer;
the raw materials of the polychlorotrifluoroethylene layer comprise: polychlorotrifluoroethylene, alpha-alumina-loaded copper powder, aluminum powder and polyethylene wax. The polyethylene wax has an average molecular weight of 2000 to 3000, 2200 in this example; in the alpha-alumina-supported copper, the mass ratio of alpha-alumina to copper is 1. The alpha-alumina carrier is soaked in a copper salt solution (such as a copper nitrate aqueous solution) for impregnation, and the full impregnation loading can be promoted by multiple times of impregnation or ultrasonic oscillation and the like. The weight portions are: 100 parts of polychlorotrifluoroethylene, 8-20 parts of alpha-alumina loaded copper, 5 parts of aluminum powder and 3 parts of polyethylene wax.
The polyethylene layer comprises the following raw materials: polyethylene, polyvinyl chloride and aluminum powder; the weight portions are as follows: 100 parts of polyethylene, 18 parts of polyvinyl chloride and 9 parts of aluminum powder
The middle polychlorotrifluoroethylene layer is respectively fixed with the outer polyester layer and the inner polyethylene layer by hot pressing.
The preparation method of the oral liquid PET-PCTFE-PE composite hard sheet comprises the following specific steps:
step 1: melting, extruding and cooling the raw materials of the polychlorotrifluoroethylene layer to obtain a polychlorotrifluoroethylene sheet; the grain diameter of the alpha-alumina loaded copper powder is 400 meshes; the average grain diameter of the aluminum powder is 80nm-120nm.
Step 2: melting, extruding and cooling raw materials of the polyethylene layer to obtain a polyethylene sheet; the average grain diameter of the aluminum powder is 80nm-120nm.
And 3, step 3: and sequentially stacking the polyester sheet, the polychlorotrifluoroethylene sheet and the polyethylene sheet, and performing hot pressing, cooling and shaping to obtain the composite film. The hot pressing temperature is 150-180 ℃. In the shaped composite film, the thickness of the polyester layer is 110 mu m; the thickness of the polychlorotrifluoroethylene layer was 55 μm; the thickness of the polyethylene layer was 25 μm.
Example 2
The embodiment provides an oral liquid PET-PCTFE-PE composite hard sheet, which comprises an outer polyester layer, an intermediate polychlorotrifluoroethylene layer and an inner polyethylene layer;
the raw materials of the polychlorotrifluoroethylene layer comprise: polychlorotrifluoroethylene, alpha-alumina-supported copper powder, aluminum powder and polyethylene wax. The polyethylene wax has an average molecular weight of 2000 to 3000, 2200 in this example; in the alpha-alumina-loaded copper, the mass ratio of alpha-alumina to copper is 1. The weight portions are as follows: 100 parts of polychlorotrifluoroethylene, 16 parts of alpha-alumina-loaded copper, 10 parts of aluminum powder and 8 parts of polyethylene wax.
The polyethylene layer comprises the following raw materials: polyethylene, polyvinyl chloride and aluminum powder; the weight portions are as follows: 100 parts of polyethylene, 25 parts of polyvinyl chloride and 12 parts of aluminum powder
The middle polychlorotrifluoroethylene layer is respectively fixed with the outer polyester layer and the inner polyethylene layer by hot pressing.
The preparation method of the oral liquid PET-PCTFE-PE composite hard sheet comprises the following specific steps:
step 1: melting, extruding and cooling the raw materials of the polychlorotrifluoroethylene layer to obtain a polychlorotrifluoroethylene sheet; the grain diameter of the alpha-alumina loaded copper powder is 400 meshes; the average grain diameter of the aluminum powder is 80nm-120nm.
Step 2: melting, extruding and cooling raw materials of the polyethylene layer to obtain a polyethylene sheet; the average grain diameter of the aluminum powder is 80nm-120nm.
And step 3: and sequentially stacking the polyester sheet, the polychlorotrifluoroethylene sheet and the polyethylene sheet, and performing hot pressing, cooling and shaping to obtain the composite film. The hot pressing temperature is 150-180 ℃. In the shaped composite film, the thickness of the polyester layer is 200 mu m; the thickness of the polychlorotrifluoroethylene layer was 80 μm; the thickness of the polyethylene layer was 35 μm.
Example 3
The present example differs from example 2 in that: the raw material of the polychlorotrifluoroethylene layer is only polychlorotrifluoroethylene; the polyethylene layer is made of polyethylene only.
Example 4
This example differs from example 2 in that: the raw material of the polychlorotrifluoroethylene layer is not added with alpha-alumina-loaded copper powder.
Example 5
The present example differs from example 2 in that: the polyethylene layer is made of polyethylene only, and polyvinyl chloride and aluminum powder are not added.
Performance testing
The composite membranes prepared in examples 1-5 above were tested for performance as follows:
1. test method
1. Water vapor transmission amount (film): the method adopts the method standard released by the State food and drug administration: water vapor Transmission amount measurement (YBB 0092003) the measurement was carried out according to the first method, and B was selected as the test conditions. The water vapor barrier capability of the packaging material is inspected under the condition of higher humidity so as to meet the requirement of the medicine on moisture resistance.
2. Oxygen transmission amount: taking a composite film product, and carrying out the measurement according to the specification of a gas permeability measurement method (YBB 00082003-2015) first method or second method. The oxygen permeability is an important index of the composite membrane, the gas barrier property of the composite membrane is ensured by controlling the index, the oxidation reaction of the medicine is avoided, and the stability of the medicine quality can be effectively controlled.
3. The microbial limit: taking the composite film product, and opening with an area of 20cm 2 The sterilized metal template is pressed on the inner layer surface, a sterile cotton swab is slightly wetted by sodium chloride injection, the sterile cotton swab is wiped in a half-hole range for 5 times, 1 cotton swab is replaced and wiped for 5 times, 2 cotton swabs are wiped for 10 times in each position, 5 positions are wiped for 5 times, and the length of each position is 100cm 2 . Each cotton swab is cut short (or burned) immediately after being smeared, and is put into a conical flask (or a large test tube) filled with 30ml of sterile normal saline. And after all the swabs are wiped and put into the bottle, quickly shaking the bottle for 1 minute to obtain the test solution. The extract was measured by the microorganism limitation method (the general guidelines 1105 and 1106 in the fourth part of the 2015, chinese pharmacopoeia). The microbial limit test is used to check the degree of contamination of the product by microorganisms, thereby ensuring the hygienic safety of the product.
2. Test results
1. Results of barrier and strength Properties tests
Table 1 results of performance test of composite membranes prepared in examples 1 to 5
Figure BDA0002986700900000041
Remarking: the unit of each performance index is as follows:
water vapor barrier property, i.e. water vapor transmission capacity, g/(m) 2 ·24h);
Oxygen barrier property, i.e. oxygen transmission capacity, cm 3 /(m 2 ·24h·0.1MPa);
Total aerobic bacteria cfu/100cm 2
The total number of the mold and the yeast cfu/100cm 2
Escherichia coli cfu/100cm 2
The above-mentioned embodiments, objects, technical solutions and advantages of the present invention are further described in detail, it should be understood that the above-mentioned embodiments are only examples of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (5)

1. An oral liquid PET-PCTFE-PE composite hard sheet comprises an outer polyester layer, a middle polytrifluorochloroethylene layer and an inner polyethylene layer, and is characterized in that the outer polyester layer is a polyester layer;
the raw materials of the polychlorotrifluoroethylene layer include: polychlorotrifluoroethylene, alpha-alumina-loaded copper powder, aluminum powder and polyethylene wax;
the polyethylene layer comprises the following raw materials: polyethylene, polyvinyl chloride and aluminum powder;
the middle polychlorotrifluoroethylene layer is respectively fixed with the outer polyester layer and the inner polyethylene layer by hot pressing;
the polyethylene wax is polyethylene with the molecular weight of 1800-3000;
the polychlorotrifluoroethylene layer comprises the following raw materials in parts by weight: 100 parts of polychlorotrifluoroethylene, 8-20 parts of alpha-alumina loaded copper, 3-12 parts of aluminum powder and 2-15 parts of polyethylene wax;
the polyethylene layer comprises the following raw materials in parts by weight: 100 parts of polyethylene, 10-30 parts of polyvinyl chloride and 5-15 parts of aluminum powder;
in the alpha-alumina loaded copper, the mass ratio of alpha-alumina to copper is 1.
2. A method for preparing an oral liquid PET-PCTFE-PE composite hard sheet as claimed in claim 1, comprising the steps of:
step 1: melting, extruding and cooling the raw materials of the polychlorotrifluoroethylene layer to obtain a polychlorotrifluoroethylene sheet;
step 2: melting, extruding and cooling raw materials of the polyethylene layer to obtain a polyethylene sheet;
and step 3: and sequentially stacking the polyester sheet, the polychlorotrifluoroethylene sheet and the polyethylene sheet, and carrying out hot pressing, cooling and shaping to obtain the composite hard sheet.
3. The method for preparing the oral liquid PET-PCTFE-PE composite hard sheet as claimed in claim 2, wherein the particle size of the alpha-alumina supported copper powder is more than 200 meshes; the particle size of the aluminum powder is 50nm-200nm.
4. The method for preparing an oral liquid PET-PCTFE-PE composite hard sheet as claimed in claim 2, wherein the thickness of the polyester layer of the shaped composite hard sheet is 80 μm to 260 μm; the thickness of the polychlorotrifluoroethylene layer is 45 μm-90 μm; the polyethylene layer has a thickness of 20 μm to 40 μm.
5. The method for preparing an oral liquid PET-PCTFE-PE composite hard sheet as claimed in claim 2, wherein the hot pressing temperature in the step 3 is 150-180 ℃.
CN202110302194.0A 2021-03-22 2021-03-22 Oral liquid PET-PCTFE-PE composite hard sheet and preparation method thereof Active CN112959786B (en)

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Denomination of invention: An oral liquid PET-PCTFE-PE composite hard tablet and its preparation method

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