CN112519359B - High-barrier composite hard sheet and preparation method thereof - Google Patents

High-barrier composite hard sheet and preparation method thereof Download PDF

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Publication number
CN112519359B
CN112519359B CN202011223850.XA CN202011223850A CN112519359B CN 112519359 B CN112519359 B CN 112519359B CN 202011223850 A CN202011223850 A CN 202011223850A CN 112519359 B CN112519359 B CN 112519359B
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composite
parts
layer
barrier
hard sheet
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CN112519359A (en
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张友辉
罗雨之
周德辉
吴幸溶
熊小之
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Jiangxi Chunguang New Material Technology Co ltd
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Jiangxi Chunguang New Material Technology Co ltd
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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
    • B32B27/06—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
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • 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
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • 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
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • 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
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • 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
    • B32B2307/718—Weight, e.g. weight per square meter
    • 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
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • 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
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride
    • 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
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/08—Homopolymers or copolymers of vinylidene chloride
    • 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
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2427/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic

Abstract

The invention provides a high-barrier composite hard sheet, which comprises a PVC (polyvinyl chloride) base layer and composite layers arranged on two sides of the PVC base layer, wherein the PVC base layer, a first composite layer and a second composite layer form a composite structure through a multi-layer co-extrusion process, wherein: the PVC base layer comprises the following raw materials in parts by weight: 50-70 parts of polyvinyl chloride, 1-1.5 parts of stabilizer, 0.2-3 parts of calcium stearate/zinc stearate/calcium stearate blend, 3-5 parts of impact modifier and 2-4 parts of vinyl chloride-vinyl acetate resin; the composite layer comprises the following raw materials in parts by weight: 70-90 parts of polyvinylidene chloride, 1-10 parts of nano mesoporous material and 0.2-1 part of dispersing agent. The composite hard sheet can fully exert respective advantages of polyvinyl chloride and polyvinylidene chloride, so that the composite hard sheet has the advantages of good chemical corrosion resistance, good chemical stability, good mechanical property, light weight and the like, thereby having excellent barrier property and greatly prolonging the effective period of the medicine.

Description

High-barrier composite hard sheet and preparation method thereof
Technical Field
The invention relates to the technical field of production and manufacturing of composite hard sheets, in particular to a high-barrier composite hard sheet and a preparation method thereof.
Background
In recent years, with the rapid development of science and technology, china also matures in the technical field of composite material production. Wherein, the composite materials of PVC/PVDC, PCTEF/PVC, CFF and the like have good barrier effect on water vapor and oxygen, so that the composite materials can be widely applied to the fields of medicines, cosmetics, foods and the like.
The composite hard sheet is a high molecular compound prepared from the materials, is mainly applied to the fields of medicines and cosmetics, is a packaging material with excellent comprehensive performance, mainly replaces a common PVC medicine blister package, and is already applied to daily life of people.
However, the conventional composite hard sheet has poor barrier performance when meeting unconventional environments such as high temperature, high humidity and the like, and is not favorable for wide popularization and use.
Disclosure of Invention
Based on this, the invention aims to provide a high-barrier composite hard sheet and a preparation method thereof, so as to solve the problem that the composite hard sheet in the prior art is poor in barrier property.
The utility model provides a high resistant separates compound hard piece, includes the PVC basic unit, and locates respectively the first composite bed and the second composite bed of PVC basic unit both sides, the PVC basic unit the first composite bed the second composite bed forms composite construction through multilayer coextrusion technology, wherein:
the PVC base layer comprises the following raw materials in parts by weight: 50-70 parts of polyvinyl chloride, 1-1.5 parts of stabilizer, 0.2-3 parts of calcium stearate/zinc stearate/calcium stearate blend, 3-5 parts of impact modifier and 2-4 parts of vinyl chloride-vinyl acetate resin;
the composite layer comprises the following raw materials in parts by weight: 70-90 parts of polyvinylidene chloride, 1-10 parts of nano mesoporous material and 0.2-1 part of dispersing agent.
The high-barrier composite hard sheet is a composite layer framework formed by a multilayer co-extrusion process, and at least comprises three layers, namely a PVC (polyvinyl chloride) base layer positioned in the middle and two composite layers respectively positioned at two sides of the PVC base layer. The raw materials for forming the PVC base layer comprise the following components: polyvinyl chloride (PVC), a stabilizer, a calcium stearate/zinc stearate/calcium stearate blend, an impact modifier, and vinyl chloride-vinyl acetate resin.
Wherein, the polyvinyl chloride is the main component of the PVC base material, and the PVC has better mechanical property, about 60MPa of tensile strength and 5-10 kJ/m < 2 > of impact strength; has excellent dielectric properties.
The calcium stearate/zinc stearate/calcium stearate blend and the vinyl chloride-vinyl acetate resin can be selectively added according to the material requirements. The flexibility, elasticity and weather resistance of a proper amount of vinyl chloride-vinyl acetate resin are added in the material of the PVC base layer; the addition of a proper amount of the calcium stearate/zinc stearate/calcium stearate blend can improve the gas barrier property of the film, and simultaneously, the film has good barrier capability to oxygen, carbon dioxide and water vapor.
The composite layer plays a leading role in gas barrier and mainly comprises 50-80 parts of polyvinylidene chloride, 1-10 parts of nano mesoporous material and 0.2-1 part of dispersing agent. The polyvinylidene chloride has the characteristics of flame resistance, corrosion resistance, good air tightness and the like. Because of its strong polarity, it is insoluble in common solvents at normal temperature. And the barrier property of the barrier layer can be enhanced by adding the nano mesoporous material into the raw material of the composite layer. The nano mesoporous material is a porous material containing mesoporous scale, such as nano mesoporous silica, the pore diameter of which is generally between 2 nanometers and 100 nanometers, and the nano mesoporous material has extremely high specific surface area and regular and ordered pore channel structure, so that polyvinylidene chloride forms a compact barrier structure.
Furthermore, the mass ratio of the calcium stearate, the zinc stearate and the calcium stearate in the calcium stearate/zinc stearate/calcium stearate blend is 6: 4: 3.
Further, the raw material of the PVC base layer also comprises a plasticizer, and the plasticizer is at least one of phthalate, triphenyl phosphate, tri-n-butyl citrate and epoxidized soybean oil.
Furthermore, the raw materials of the composite layer also contain ultramicro sterilization particles.
Furthermore, the raw material of the composite layer also contains polylactic acid, and the polylactic acid forming film layer covers the outermost side of the composite layer.
Further, the dispersing agent is any one or a combination of more of alkylphenol polyoxyethylene ether formaldehyde condensate sulfate, alkylphenol polyoxyethylene ether formaldehyde condensate phosphate, methylene dinaphthyl sodium sulfonate, alkyl naphthalene sulfonate, EO-PO block polyether and styrene phenol polyoxyethylene ether phosphoric acid.
Further, the thickness of the high-barrier composite hard sheet can be 20-350 um, and the thickness of the PVC base layer is 1-3 times of that of the composite layer.
The embodiment of the invention also provides a manufacturing method of the high-barrier composite hard sheet, which comprises the following steps:
step 1: respectively and uniformly mixing the raw materials of the first composite layer, the PVC base layer and the second composite layer according to a set weight part ratio, and respectively adding the raw materials into corresponding double-screw extruders for melting and plasticizing;
and 2, step: extruding the melted and plasticized raw materials of the first base layer, the barrier layer and the second base layer from corresponding double-screw extruders to a die head at the temperature of 150-230 ℃ to converge to form a three-layer composite structure, and cooling at the temperature of 20-70 ℃ through a cooling roller to form a membrane with a three-layer co-extrusion structure;
and 3, step 3: preheating the membrane at 40-90 ℃, longitudinally stretching, heat setting at 20-90 ℃, transversely stretching, and heat setting at 50-160 ℃;
and 4, step 4: and (4) carrying out corona or flame treatment on the stretched membrane and then rolling.
The invention has the beneficial effects that: the high-barrier hard sheet is a composite hard sheet of polyvinyl chloride and polyvinylidene chloride, can fully exert respective advantages of the polyvinyl chloride and the polyvinylidene chloride, and has the advantages of good chemical corrosion resistance, high chemical stability, good mechanical property, light weight and the like, so that the high-barrier hard sheet has excellent barrier property, can greatly prolong the shelf life of food and the effective period of medicines, and has wide application range.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, embodiments of the present invention are described in detail below. Several embodiments of the invention are presented. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Example 1
The utility model provides a high resistant separates compound hard piece, includes the PVC basic unit, and locates respectively the first composite bed and the second composite bed of PVC basic unit both sides, the PVC basic unit the first composite bed the second composite bed forms composite construction through multilayer coextrusion technology, wherein: the PVC base layer comprises the following raw materials in parts by weight: 50 parts of polyvinyl chloride, 1 part of stabilizer, 0.2 part of calcium stearate/zinc stearate/calcium stearate blend, 3 parts of impact modifier and 2 parts of vinyl chloride-vinyl acetate resin;
the composite layer comprises the following raw materials in parts by weight: 70 parts of polyvinylidene chloride, 3 parts of nano mesoporous material and 0.5 part of EO-PO block polyether.
The mass ratio of calcium stearate, zinc stearate and calcium stearate in the calcium stearate/zinc stearate/calcium stearate blend is 6: 4: 3, the gas barrier property of the film can be improved by adding a proper amount of the calcium stearate/zinc stearate/calcium stearate blend, and meanwhile, the film has good barrier capability to oxygen, carbon dioxide and water vapor.
EO-PO block polyether is used as a dispersing agent in the material of the barrier layer, the EO-PO block polyether is composed of polyether, polyoxyethylene (EO) and Polyoxypropylene (PO), the EO and PO are randomly copolymerized to form block polyether, EO is hydrophilic group and EO is hydrophobic group, the EO-PO block polyether has good dispersibility, and the nano mesoporous material is fully dispersed among polyvinylidene chloride molecules.
The manufacturing method of the high-barrier composite hard sheet comprises the following steps:
step 1: respectively and uniformly mixing the raw materials of the first composite layer, the PVC base layer and the second composite layer according to a set weight part ratio, and respectively adding the raw materials into corresponding double-screw extruders for melting and plasticizing, wherein the temperature for melting and plasticizing is 200 ℃;
step 2: extruding the melted and plasticized raw materials of the first base layer, the barrier layer and the second base layer from corresponding double-screw extruders to a die head at 200 ℃ to converge to form a three-layer composite structure, and cooling the three-layer composite structure at 40 ℃ by a cooling roller to form a membrane with a three-layer co-extrusion structure;
and step 3: preheating the membrane at 60 ℃, longitudinally stretching, heat setting at 60 ℃, transversely stretching, and heat setting at 110 ℃;
and 4, step 4: and carrying out corona or flame treatment on the stretched membrane and then rolling to obtain the high-barrier composite hard sheet.
The thickness of the high-barrier composite hard sheet can be 20-350 um, the thickness of the composite layer is larger than that of the PVC base layer, generally speaking, the thickness of the composite layer is 1-3 times of that of the PVC base layer, and therefore the barrier performance of the high-barrier composite hard sheet is guaranteed. The thickness of the high-barrier hard sheet in this embodiment is 200 μm, wherein the thickness of the PVC base layer is 120 μm, and the thickness of both the two composite layers is 40 μm.
The high-barrier hard sheet is a composite hard sheet of polyvinyl chloride and polyvinylidene chloride, can fully exert the respective advantages of polyvinyl chloride and polyvinylidene chloride, has the advantages of good chemical corrosion resistance, higher chemical stability, good mechanical property, light weight and the like, has excellent barrier property, can greatly prolong the shelf life of food and the effective period of medicines, and has wide application range.
Example 2
This embodiment is substantially the same as embodiment 1 except that:
the composite layer comprises 90 parts of polyvinylidene chloride, 8 parts of nano mesoporous material and 1 part of EO-PO block polyether.
Example 3
This embodiment is substantially the same as embodiment 1 except that:
the dispersant is a mixture of sodium methylene dinaphthalene sulfonate and alkyl naphthalene sulfonate.
Example 4
This embodiment is substantially the same as embodiment 1 except that:
3 parts of the calcium stearate/zinc stearate/calcium stearate blend.
Example 5
This embodiment is substantially the same as embodiment 1 except that:
4 parts of vinyl chloride-vinyl acetate resin.
Example 6
This embodiment is substantially the same as embodiment 1 except that:
the base layer is also added with 2 parts of plasticizer, 1.5 parts of stabilizer and 5 parts of impact modifier, wherein the plasticizer is triphenyl phosphate.
Example 7
This embodiment is substantially the same as embodiment 1 except that:
the raw materials of the composite layer also contain ultrafine bactericidal particles.
Example 8
This example is substantially the same as example 1, except that:
the raw material of the composite layer also contains polylactic acid, and the polylactic acid forms a film layer to cover the outermost side of the composite layer.
Comparative example 1
This embodiment is substantially the same as embodiment 1 except that:
the high-barrier composite hard sheet does not contain a composite layer.
Comparative example 2
This embodiment is substantially the same as embodiment 1 except that:
the raw material of the barrier layer is not added with the nano mesoporous material.
Comparative example 3
This embodiment is substantially the same as embodiment 1 except that:
the raw materials of the PVC base layer are not added with vinyl chloride-vinyl acetate resin.
The environment-friendly high-barrier films obtained in the above examples and comparative examples were subjected to gas barrier property test, tensile property test and antibacterial property test.
The gas barrier property test measures primarily the barrier properties of the rigid sheet to oxygen, carbon dioxide, and water vapor. As shown in table 1, it is understood from examples 1 to 7 that the high barrier prepared in the present application has excellent barrier properties against oxygen, carbon dioxide and water vapor, and the high barrier has a permeability of oxygen of 30cm 3/(m 2 · 24h · atm) or less, a permeability of carbon dioxide of 233cm 3/(m 2 · 24h · atm) or less and a permeability of water vapor of 25cm 3/(m 2 · 24h · atm) or less.
In addition, as can be seen from examples 1 and 2 and comparative example 2, the polyvinylidene chloride uniformly dispersed in the composite layer under the action of the dispersant of the nano mesoporous material forms a barrier structure with dense arrangement with the nano mesoporous material under the action of the porous channel of the nano mesoporous material, and the barrier performance of the composite hard sheet is greatly improved.
TABLE 1
Figure BDA0002763001640000061
Figure BDA0002763001640000071
Further, as shown in table 2, the film was stretched in the longitudinal direction by the tensile properties test, and it can be seen that the high-barrier composite hard sheets of examples 1 to 8 all had good tensile properties, and particularly, the tensile properties were significantly improved after adding a proper amount of plasticizer and vinyl chloride-vinyl acetate resin. Different plasticizers have different influences on the stretching performance, and the effect of improving the stretching performance of the hard sheet material by the triphenyl phosphate in the embodiment of the invention is better than that of other plasticizers.
In addition, as can be seen from table 2, the barrier properties of the hard sheet are also improved after the plasticizer, the stabilizer and the impact modifier are added to the raw materials of the composite layer, and particularly when the plasticizer is triphenyl phosphate, the barrier properties of the hard sheet are significantly improved, because triphenyl phosphate can significantly improve the fusion degree of the components and the aggregation degree of the components.
TABLE 2
Tensile strength Mpa Elongation at break%
Example 1 32 223
Example 2 35 231
Example 3 26 213
Example 4 24 213
Example 5 28 221
Example 6 15 215
Example 7 20 209
Example 8 25 214
Comparative example 1 33 256
Comparative example 2 32 225
Comparative example 3 31 212
Further, as shown in table 3, the film was tested for antibacterial performance from the outside to the inside through an antibacterial performance test, and it can be seen that the high-barrier composite hard sheets in examples 1 to 8 all have good antibacterial performance, and especially after a proper amount of ultrafine bactericidal particles are added, the antibacterial performance is significantly improved. And after the polylactic acid film is added on the outer side of the composite layer, the antibacterial performance is also obviously improved.
TABLE 3
Bacterial test body volume Bacterial transmittance (%)
Example 1 1 30
Example 2 1 23
Example 3 1 33
Example 4 1 25
Example 5 1 20
Example 6 1 18
Example 7 1 5
Example 8 1 10
Comparative example 1 1 65
Comparative example 2 1 50
Comparative example 3 1 53
The above-described embodiments describe the technical principles of the present invention, and these descriptions are only for the purpose of explaining the principles of the present invention and are not to be construed as limiting the scope of the present invention in any way. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive effort, which would fall within the scope of the present invention.

Claims (7)

1. A high resistant separates compound hard piece which characterized in that: including the PVC basic unit, and locate respectively the first composite bed and the second composite bed of PVC basic unit both sides, the PVC basic unit first composite bed the second composite bed forms composite construction through multilayer crowded technology altogether, wherein:
the PVC base layer comprises the following raw materials in parts by weight: 50-70 parts of polyvinyl chloride, 1-1.5 parts of stabilizer, 0.2-3 parts of calcium stearate/zinc stearate/calcium stearate blend, 3-5 parts of impact modifier and 2-4 parts of vinyl chloride-vinyl acetate resin;
the composite layer comprises the following raw materials in parts by weight: 70-90 parts of polyvinylidene chloride, 1-10 parts of nano mesoporous material and 0.2-1 part of dispersing agent;
the preparation method of the high-barrier composite hard sheet comprises the following steps:
step 1: respectively and uniformly mixing the raw materials of the first composite layer, the PVC base layer and the second composite layer according to a set weight part ratio, and respectively adding the raw materials into corresponding double-screw extruders for melting and plasticizing;
and 2, step: extruding the melted and plasticized raw materials of the first base layer, the barrier layer and the second base layer from corresponding double-screw extruders to a die head at the temperature of 150-230 ℃ to converge to form a three-layer composite structure, and cooling the three-layer composite structure at the temperature of 20-70 ℃ by a cooling roller to form a membrane with a three-layer co-extrusion structure;
and 3, step 3: preheating the membrane at 40-90 ℃, longitudinally stretching, heat setting at 20-90 ℃, transversely stretching, and heat setting at 50-160 ℃;
and 4, step 4: and (4) carrying out corona or flame treatment on the stretched membrane and then rolling.
2. The high-barrier composite hard sheet according to claim 1, characterized in that: the mass ratio of the calcium stearate, the zinc stearate and the calcium stearate in the calcium stearate/zinc stearate/calcium stearate blend is 6: 4: 3.
3. The high-barrier composite hard sheet according to claim 1, characterized in that: the PVC base layer is characterized by also comprising a plasticizer, wherein the plasticizer is at least one of phthalate, triphenyl phosphate, tri-n-butyl citrate and epoxidized soybean oil.
4. The high-barrier composite hard sheet according to claim 1, wherein: the raw materials of the composite layer also contain ultramicro sterilization particles.
5. The high-barrier composite hard sheet according to claim 1, wherein: the raw materials of the composite layer also contain polylactic acid, and the polylactic acid forming film layer covers the outermost side of the composite layer.
6. The high-barrier composite hard sheet according to claim 1, wherein: the dispersing agent is any one or combination of more of alkylphenol polyoxyethylene ether formaldehyde condensate sulfate, alkylphenol polyoxyethylene ether formaldehyde condensate phosphate, methylene dinaphthalene sodium sulfonate, alkyl naphthalene sulfonate, EO-PO block polyether and styrene phenol polyoxyethylene ether phosphoric acid.
7. The high-barrier composite hard sheet according to claim 1, wherein: the thickness of the high-barrier composite hard sheet is 20-350 um, and the thickness of the PVC base layer is 1-3 times of the thickness of the composite layer.
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