CN103786399B - A kind of multi-functional historical relic's protection bag composite membrane and method for making thereof - Google Patents
A kind of multi-functional historical relic's protection bag composite membrane and method for making thereof Download PDFInfo
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- CN103786399B CN103786399B CN201310750437.2A CN201310750437A CN103786399B CN 103786399 B CN103786399 B CN 103786399B CN 201310750437 A CN201310750437 A CN 201310750437A CN 103786399 B CN103786399 B CN 103786399B
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- 238000002844 melting Methods 0.000 claims description 17
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
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- 239000011127 biaxially oriented polypropylene Substances 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
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- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- 239000005025 cast polypropylene Substances 0.000 claims description 4
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 4
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- APVZWAOKZPNDNR-UHFFFAOYSA-L iron(ii) citrate Chemical compound [Fe+2].OC(=O)CC(O)(C([O-])=O)CC([O-])=O APVZWAOKZPNDNR-UHFFFAOYSA-L 0.000 claims description 4
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
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Landscapes
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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Abstract
The invention provides a kind of multi-functional historical relic's protection bag composite membrane and preparation method thereof; this composite membrane comprises adventitia and the inner membrance of lamination; wherein adventitia is high-isolation film; inner membrance is three-layer co-extruded film; add natural rubber, Fe-series catalyst, alkaline earth metal promoter agent and natural accumulation supporting stone powder in the core; make the composite membrane obtained have blocking oxygen simultaneously, intercept steam, absorb the function such as oxygen and uvioresistant, the method preparing this composite membrane is simple to operate, has industrial applicibility.
Description
Technical Field
The invention relates to the field of materials, in particular to a multifunctional composite film for protecting cultural relics and having a gas barrier function, an oxygen absorption function and an ultraviolet barrier function, a preparation method thereof and a cultural relic protection bag made of the film.
Background
China is one of four civilization ancient countries in the world, brilliant ancient civilizations are stored underground, once precious cultural relics leave an underground high-humidity, oxygen-isolated and lightless closed environment, some cultural relics can be instantly extinguished by ash and smoke and instantly disappear in an environment with high oxygen concentration and ultraviolet light irradiation on the ground, even if ageing-resistant cultural relics such as woodware, metal, silk and the like are in the ground environment, the natural damage of the cultural relics is accelerated due to oxidative degradation and light degradation, so that the cultural relics need to be protected in time by oxygen isolation and light protection, and the oxygen isolation and light protection material needs to be portable and can efficiently isolate oxygen and prevent light.
In the prior art, the measures for instantly protecting the cultural relics include coating a protective material on the surface of the cultural relics, transferring the cultural relics into a closed container and the like, the methods are complex to operate and have poor timeliness, and in Chinese patent CN103264565A, a three-layer co-extrusion oxygen absorption film for food packaging and a preparation method thereof are disclosed, wherein the upper layer of the composite film adopts unmodified polyethylene or polypropylene resin; the lower layer is a food contact layer, the polyethylene or polypropylene resin modified by ethylene-vinyl acetate copolymer (EVA) is adopted, the core layer is oxygen absorption resin, the polyethylene or polypropylene resin containing natural rubber and ferrous catalyst ferrite is adopted, and the film is used for food packaging, only has the functions of oxygen absorption and moisture resistance, does not have the function of ultraviolet resistance, and is not suitable for cultural relic protection.
Therefore, portable materials for cultural relic protection, which have the functions of oxygen barrier, water vapor barrier, oxygen absorption and ultraviolet resistance, are in need of development.
Disclosure of Invention
In order to overcome the above disadvantages, the present inventors have conducted extensive studies and found that a high-barrier resin film existing in the prior art is used as an outer film, a three-layer co-extruded film prepared by a multi-layer co-extrusion method is used as an inner film, natural rubber, an iron-based catalyst, an alkaline earth metal cocatalyst and natural rectorite powder are added into a core layer, and a composite film for a cultural relic protection bag is prepared by a dry-process composite process using the outer film and the inner film, so that the prepared composite film has functions of oxygen barrier, water vapor barrier, oxygen absorption, ultraviolet resistance and the like, thereby completing the present invention.
The invention aims to provide the following aspects:
in a first aspect, the invention provides a composite film for a multifunctional cultural relic protection bag, which is characterized by comprising an inner film, wherein the inner film comprises an upper layer, a core layer and a lower layer which are laminated, the lower layer is a cultural relic contact layer, and the inner film is formed by co-extrusion blow molding of an upper layer material, a core layer material and a lower layer material;
wherein, the upper layer is made of polypropylene resin;
the core layer material is prepared from the following components in percentage by weight,
12 to 35 parts by weight of natural rubber powder,
0.06 to 1.75 parts by weight of an iron-based catalyst powder,
0.03 to 1.75 parts by weight of an alkali metal/alkaline earth metal co-catalyst powder,
0.06-3.5 parts by weight of natural rectorite powder,
the balance of polypropylene resin powder,
the parts by weight are based on 100 parts by weight of the core layer,
the ratio of the weight of the iron-based catalyst to the weight of the natural rubber is 0.5:100 to 5:100,
the weight ratio of the alkali metal/alkaline earth metal promoter powder to the iron-based catalyst is 1:1 to 1:2,
the ratio of the weight of the natural rectorite powder to the weight of the alkali metal/alkaline earth metal cocatalyst is 1:2,
wherein,
the iron-based catalyst is selected from: hydrated ammonium ferrous sulfate and hydrated ferrous citrate,
the alkali/alkaline earth metal promoter is selected from: sodium carbonate, potassium carbonate and calcium hydroxide,
the core layer material is prepared by the following steps,
(1-1) drying natural rectorite powder at 300-1000 ℃ for 3-8 hours, grinding to 200-800 meshes,
(1-2) dissolving iron catalyst powder in water to form slurry, pouring the slurry into the natural rectorite powder treated in the step (1-1), drying the slurry in vacuum at the temperature of 30-60 ℃ until the humidity is 40-60% to form an iron salt-natural rectorite mixture,
(1-3) mechanically blending alkali metal/alkaline earth metal powder and the iron salt-natural rectorite mixture prepared in (1-2) to form a mixture,
(1-4) melting and blending the mixture obtained in the step (1-3) with natural rubber powder and polypropylene resin powder to obtain a modified polypropylene resin core layer material;
the lower layer material is polyvinyl alcohol-ethylene-vinyl acetate copolymer modified polypropylene resin, which is prepared by the method comprising the following steps,
(2-1) melting and blending the ethylene-vinyl acetate copolymer and the polyvinyl alcohol resin according to the weight ratio of 1: 1-2: 1,
and (2-2) melting and blending the product obtained in the step (2-1) and polypropylene resin according to the weight ratio of 1: 10-2: 10 to prepare the polyvinyl alcohol-ethylene-vinyl acetate copolymer modified polypropylene resin.
In a second aspect, the present invention provides the above-mentioned composite film for a multifunctional cultural relic protection bag, which is characterized in that the composite film further comprises an upper layer laminated on the core layer,
the upper layer is made of polypropylene resin.
In a third aspect, the present invention provides the above-mentioned composite film for a multifunctional cultural relic protection bag, which is characterized in that the composite film further comprises an outer film laminated on the upper layer,
the outer film is a high-barrier film and is selected from a biaxially oriented polypropylene film coated with polyvinylidene chloride on the surface layer, a vacuum aluminized cast polypropylene film, a vacuum aluminized polyester film, a polyester film plated with silicon oxide on the surface, or a polyester film plated with aluminum oxide on the surface.
In a fourth aspect, the invention provides the composite film for the multifunctional cultural relic protection bag, which is characterized in that the outer film and the inner film are prepared by dry compounding, wherein the upper layers of the outer film and the inner film are bonded by an adhesive.
In a fifth aspect, the invention provides the above composite film for a multifunctional cultural relic protection bag, which is characterized in that the core layer material is prepared from the following components in parts by weight,
15-30 parts by weight of natural rubber powder,
0.075 to 1.5 parts by weight of iron-based catalyst powder,
0.0375 to 0.75 part by weight of an alkali metal/alkaline earth metal co-catalyst powder,
0.075-1.5 parts by weight of natural rectorite powder,
the balance of polypropylene resin powder,
the parts by weight are based on 100 parts by weight of the core layer,
the ratio of the weight of the iron-based catalyst to the weight of the natural rubber is 0.5:100 to 5:100,
the weight ratio of the alkali metal/alkaline earth metal promoter powder to the iron-based catalyst is 1:1 to 1:2,
the ratio of the weight of the natural rectorite powder to the weight of the alkali metal/alkaline earth metal promoter is 1: 2.
In a sixth aspect, the invention further provides a preparation method of the composite film for the multifunctional cultural relic protection bag, which is characterized by comprising the following steps,
(1) preparing a core material comprising:
(1-1) treating natural rectorite powder at 300-1000 ℃ for 3-8 hours, grinding to 200-800 meshes,
(1-2) dissolving iron salt catalyst powder in water to form slurry, pouring the slurry into the natural rectorite powder treated in the step (1-1), drying the slurry in vacuum at the temperature of 30-60 ℃ until the humidity is 40-60%, forming an iron salt-natural rectorite mixture,
(1-3) mechanically blending alkali metal/alkaline earth metal promoter powder with the iron salt-natural rectorite mixture prepared in (1-2) to form a mixture,
(1-4) melting and blending the mixture obtained in the step (1-3) with natural rubber powder and polypropylene resin powder to obtain a modified polypropylene resin core layer material;
(2) preparing a lower layer material comprising:
(2-1) melting and blending the ethylene-vinyl acetate copolymer and the polyvinyl alcohol resin according to the weight ratio of 1: 1-2: 1,
(2-2) melting and blending the product obtained in the step (2-1) and polypropylene according to the weight ratio of 1: 10-2: 10 to prepare a vinyl alcohol-ethylene-vinyl acetate copolymer modified polypropylene resin;
(3) preparing an inner membrane: using polypropylene as an upper layer material, and preparing the upper layer material, the core layer material prepared in the step (1) and the lower layer material prepared in the step (2) into an inner film by a multi-layer co-extrusion method;
(4) preparing a composite film for the multifunctional cultural relic protection bag: and (3) compounding the outer membrane of the high-barrier film and the inner membrane prepared in the step (3) by a dry method to prepare the composite membrane for the multifunctional cultural relic protection bag, wherein the upper layers of the outer membrane and the inner membrane are bonded by an adhesive.
In a seventh aspect, the present invention further provides a method for preparing the composite film for the multifunctional cultural relic protection bag, wherein the particle size of the natural rectorite powder is 300 meshes.
In an eighth aspect, the invention also provides the use of the multifunctional composite film for cultural relic protection bags in any one aspect for preparing cultural relic protection bags.
The composite film for the multifunctional cultural relic protection bag and the preparation method thereof have the following beneficial effects:
(1) the composite film automatically starts an oxygen absorption function in an environment with humidity of 50-80%;
(2) the cultural relic protection bag prepared by the composite film has high barrier property to oxygen and water vapor;
(3) the protection bag prepared by the multifunctional composite film has the function of absorbing oxygen in the protection bag, and the oxygen concentration in the protection bag is reduced to zero within 5-10 days;
(4) the protective bag prepared by the multifunctional composite film has the functions of transparency and ultraviolet ray resistance, can prevent cultural relics from being oxidized or degraded by ultraviolet rays, and is particularly suitable for protecting ancient silk, woodware, metal and other cultural relics;
(5) the method for preparing the composite membrane is simple and convenient and has industrial practicability.
Drawings
Fig. 1 shows a schematic structural diagram of a composite film for a multifunctional cultural relic protection bag.
Description of the reference numerals
1-outer membrane;
2-a binder;
3-upper layer;
4-a core layer;
5-lower layer.
Detailed Description
According to a first aspect of the present invention, there is provided a composite film for a multifunctional cultural relic protection bag, the composite film comprising:
(1) core layer: comprises the following components in percentage by weight,
12 to 35 parts by weight of a natural rubber,
0.06 to 1.75 parts by weight of an iron-based catalyst,
0.03 to 1.75 parts by weight of an alkaline earth metal co-catalyst,
0.06-3.5 parts by weight of natural rectorite powder,
the balance of polypropylene resin powder,
preferably, the first and second liquid crystal materials are,
15-30 parts by weight of natural rubber powder,
0.075 to 1.5 parts by weight of iron-based catalyst powder,
0.0375 to 0.75 parts by weight of an alkaline earth metal promoter powder,
0.075-1.5 parts by weight of natural rectorite powder,
the balance of polypropylene resin powder,
the parts by weight are based on 100 parts by weight of the core layer,
the ratio of the weight of the iron-based catalyst to the weight of the natural rubber is 0.5:100 to 5:100,
the weight ratio of the alkali metal/alkaline earth metal promoter powder to the iron-based catalyst is 1:1 to 1:2,
the ratio of the weight of the natural rectorite powder to the weight of the alkali metal/alkaline earth metal promoter is 1: 2.
In the core layer material, polypropylene resin is used as a matrix to ensure that the inner film prepared by multilayer coextrusion has higher mechanical strength.
Natural rubber is a natural high molecular compound containing polyisoprene as main ingredient, and has a molecular formula of (C)5H8) And n, wherein 91-94% of the components are rubber hydrocarbon (namely polyisoprene), the rest are non-rubber substances such as protein, fatty acid, ash, saccharide and the like, and each repeating unit of the molecule contains an unsaturated double bond.
The iron catalyst is selected from hydrated ammonium ferrous sulfate and hydrated ferrous citrate, which are ferrous salts, wherein the ferrous salts have active chemical properties and strong reducibility.
The alkali metal/alkaline earth metal cocatalyst is selected from sodium carbonate, potassium carbonate and calcium hydroxide, and can provide a weak alkaline environment for the reaction system after hydrolysis.
The natural rectorite not only has strong ion exchange capacity, but also has strong blocking effect on ultraviolet light, and especially the natural rectorite with the average particle size of 200-800 meshes, preferably 300 meshes, can block 97-99% of ultraviolet light within the range of 300-400 nm.
The composite film provided by the invention has the functions of gas barrier, ultraviolet ray barrier, oxygen absorption and the like, wherein substances in the core layer play an important role.
Because a large number of unsaturated carbon atoms exist in the natural rubber, and hydrogen atoms connected with the unsaturated carbon atoms are very active in chemical property and are easily oxidized by ambient oxygen to form alkyl hydroperoxide, and meanwhile, the ferrous salt can accelerate the decomposition of the alkyl hydroperoxide into hydroxyl free radicals, and the hydroxyl free radicals can perform chain transfer to the natural rubber to form alkyl free radicals and can continue to absorb oxygen until the ambient oxygen is completely consumed.
Because natural rectorite has strong ion exchange capacity, when ferrous salt solutions such as ammonium ferrous sulfate, ferrous citrate and the like are exchanged and adsorbed by the rectorite, the rectorite can effectively prevent the oxidation of ferrous, and ferrous ions can improve the rate of catalytic oxidation of rubber and reduce the activation energy of rubber oxidation reaction; alkaline earth metals such as sodium carbonate, potassium carbonate, calcium hydroxide and the like provide a slightly alkaline environment for the ferrous salt to catalyze the oxidation reaction of the natural rubber, so that the oxidation rate of the rubber is favorably improved; the ferrous salt and the alkaline earth metal are required for catalyzing the rubber oxidation reaction, and the oxidation reaction rate is low under the humidity of less than 50%, so that the other function of the natural rectorite is to keep about 50% of free water, a natural rubber-catalyst system is positioned in the environment with the relative humidity of more than 80%, the ferrous salt and the alkaline earth metal ions around the rectorite are ionized to form metal ions, and the natural rubber is catalyzed to oxidize and absorb oxygen. The oxygen absorption function of the composite membrane comes from the fact that the iron catalyst catalyzes natural rubber to react with oxygen, oxygen near a core layer is consumed, a weak alkaline environment required by oxidation reaction of the natural rubber is provided by alkaline earth metal, and a humidity environment required by the oxidation reaction is provided by crystalline water of hydrated ferrous salt and free water absorbed by natural rectorite.
The modified polypropylene resin core layer material contains natural rubber-iron catalyst-alkali metal/alkaline earth metal cocatalyst-natural rectorite, and the preparation process comprises the following steps:
(1-1) drying natural rectorite powder at 300-1000 ℃ for 3-8 hours, grinding to 200-800 meshes,
(1-2) dissolving iron catalyst powder in water to form slurry, pouring the slurry into the natural rectorite powder treated in the step (1-1), drying the slurry in vacuum at the temperature of 30-60 ℃ until the humidity is 40-60% to form an iron salt-natural rectorite mixture,
(1-3) mechanically blending alkali metal/alkaline earth metal promoter powder with the iron salt-natural rectorite mixture prepared in (1-2) to form a mixture,
(1-4) melting and blending the mixture obtained in the step (1-3) with natural rubber powder and polypropylene resin powder to obtain a modified polypropylene resin core layer material;
in the preparation process, the natural rectorite powder is dried and crushed after being fully prepared, so that particles with the particle size of 200-800 meshes can be prepared conveniently, and the rectorite powder has larger specific surface area, thus having stronger adsorbability and water retention capacity;
the iron salt catalyst is compounded on the natural rectorite in the form of solution, so that the iron catalyst and the natural rectorite powder can be uniformly mixed, and the compounding effect is good;
the iron catalyst, the alkali metal/alkaline earth metal cocatalyst and the natural rectorite powder are sequentially added into the polypropylene resin, and then the core layer material is prepared by a melt blending mode, so that the core layer material has the effects of blocking ultraviolet rays, gases, oxygen and the like, and has strong mechanical properties.
The polyvinyl alcohol-EVA (ethylene-vinyl acetate copolymer) modified polypropylene resin is used as the lower layer of the inner film, and the layer has the function of allowing oxygen in the cultural relic protection bag to penetrate through the lower layer and enter the core layer with the oxygen absorption function; due to the addition of polar polyvinyl alcohol-EVA, the passing rate of polypropylene to water vapor is increased, and the oxygen absorption function is started; due to the addition of the polyvinyl alcohol-EVA, the crystallization of the polypropylene can be hindered, the oxygen passing rate of the modified polypropylene film is increased, and the diffusion of oxygen in the cultural relic protection bag made of the composite film to the core layer is facilitated.
The modified polypropylene material is prepared by the method comprising the following steps:
(1) melting and blending polyvinyl alcohol and EVA resin according to the weight ratio of 1: 1-1: 2,
(2) adding the polyvinyl alcohol/EVA blend prepared in the step (1) into polypropylene resin according to the weight ratio of 1: 10-2: 10, and carrying out melt blending again to prepare the polyvinyl alcohol/EVA resin modified polypropylene resin.
The composite film also comprises an upper layer which is laminated on the core layer and is polypropylene resin,
the three layers of materials are subjected to co-extrusion blow molding to obtain the inner film.
The composite film also comprises an outer film which is a high-barrier resin film and is selected from a biaxially oriented polypropylene film coated with polyvinylidene chloride on the surface layer, a vacuum aluminum-plated cast polypropylene film, a vacuum aluminum-plated polyester film, a polyester film plated with silicon oxide on the surface layer or a polyester film plated with aluminum oxide on the surface layer, and the outer film can prevent most external oxygen and water vapor from entering the protective bag, and even if trace oxygen permeates to the core layer through the high-barrier layer, the oxygen can be absorbed in the core layer and cannot continuously diffuse inwards.
Because the core layer in the inner film of the composite film contains natural rectorite powder which contains adsorbed water and can provide moisture (humidity) necessary for oxygen absorption reaction, after the treatment of a short-time high-humidity environment, the core layer in the inner film can automatically initiate the oxygen absorption function, even if the packaged cultural relic does not contain moisture, oxygen in the air in the cultural relic protection bag made of the composite film can be absorbed within 6-10 days, oxygen diffused to the interior of the protection bag from the external environment is blocked by the outer layer of the protection bag, and trace permeated oxygen is absorbed by the core layer when diffused in the composite film, so that the packaged cultural relic can be in an absolutely oxygen-free and ultraviolet-free environment, and the long-term preservation of the cultural relic is facilitated.
The effective components playing the role of isolating ultraviolet and oxygen in the composite film provided by the invention are sandwiched between the high-barrier outer film and the lower layer of the EVA-polyvinyl alcohol modified polypropylene inner film and are blended in the polypropylene resin as the core layer, so that no harm is caused to the encapsulated cultural relics.
The structure of the composite film for the multifunctional cultural relic protection bag is shown in figure 1, and the composite film comprises an outer film and an inner film which are bonded by an adhesive, wherein the inner film comprises an upper layer, a core layer and a lower layer which are laminated from top to bottom.
In order to ensure that the cultural relic protection bag prepared by the multifunctional composite film has the functions of sufficiently blocking oxygen and water vapor, absorbing oxygen and blocking ultraviolet rays, the thicknesses of the outer film, the upper layer of the inner film, the core layer of the inner film and the lower layer of the inner film are respectively 15-30 micrometers, 10 micrometers, 30-70 micrometers and 10 micrometers.
The invention also provides a method for preparing the composite membrane, which is described above.
The invention also provides application of the composite film for the multifunctional cultural relic protection bag in preparation of the cultural relic protection bag.
Examples
1. Experimental Material
Biaxially oriented polypropylene film coated with polyvinylidene chloride on the surface layer, Wuxi packaging materials Co., Ltd;
vacuum aluminizing cast polypropylene film: hening changyu aluminum plating materials ltd;
vacuum aluminizing polyester film: tianjin City Ri Xinda composite packaging materials Co., Ltd;
polypropylene resin: model F280, new space trade ltd, majesty;
EVA resin: model 18-0.3, western chemical instruments (Beijing) science and technology Limited;
natural rectorite powder: 300 mesh, consolidation of Wanyu water purification materials Limited;
polyvinyl alcohol: trade mark 1799, chemical Limited, Guangzhou, China.
2. Procedure for the preparation of the
(1) Preparation of lower layer modified polypropylene resin
Firstly, melting and blending polyvinyl alcohol and EVA resin, then adding the polyvinyl alcohol/EVA blend into polypropylene resin, melting and blending again, and taking the obtained polypropylene modified by the polyvinyl alcohol/EVA resin as an inner layer resin raw material.
(2) Preparation of the core layer
(2-1) treating the natural rectorite powder with the average particle size of 300 meshes at the high temperature of 500 ℃ for 5 hours for later use; dissolving an iron salt catalyst in distilled water to form a saturated solution or slurry, pouring the saturated solution or slurry on the natural rectorite powder pretreated in the step (1), and drying the natural rectorite powder in vacuum at 50 ℃ until the water content (humidity) is 40-60% to obtain an iron salt-natural rectorite catalyst mixture;
(2-2) mechanically blending 300-mesh alkaline earth metal powder with the iron salt-natural rectorite catalyst mixture prepared in (2) to form a catalyst system;
and (2-3) melting and blending the iron salt-natural rectorite-alkaline earth metal catalyst system prepared in the step (2-2) with natural rubber powder and polypropylene resin to obtain modified polypropylene resin as a raw material of the core layer.
(3) Preparation of three-layer co-extruded oxygen absorption film
By utilizing three-layer co-extrusion film blowing equipment, unmodified polypropylene resin is used as an upper layer raw material, Natural Rubber (NR) -iron catalyst-alkaline earth metal cocatalyst-natural rectorite modified polypropylene is used as a core layer raw material, EVA-polyvinyl alcohol modified polypropylene is used as a lower layer raw material, and a raw material film with an oxygen absorption function is formed by one-step extrusion to be used as an inner film.
(4) Preparation of composite membranes
And (3) compounding the inner membrane prepared in the step (3) and a high-barrier film serving as an outer membrane by a dry method to prepare the multifunctional composite membrane, wherein the upper layer of the inner membrane is connected with the outer membrane.
Table 1 raw material composition for preparing composite membrane
(in the table, the parts are parts by weight, and the total weight of all the raw materials is 100 parts)
Examples of the experiments
Experimental example 1 oxygen absorption Performance test
The composite films obtained in examples 1 to 6 were cut into 50X 50mm, placed in a three-necked flask having a volume of 100 ml, sealed, and tested for headspace oxygen concentration at regular intervals, and the results of the experiments are shown in Table 2,
as can be seen from Table 2, the composite film prepared by the method of the invention has good high oxygen resistance, oxygen absorption performance and ultraviolet ray blocking function, and the larger the catalyst dosage is, the higher the oxygen absorption rate is, and the structural composition of the three-layer co-extruded film can be properly adjusted according to the needs.
TABLE 2 oxygen uptake Performance test results
| Time/day | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| 0 | 20.0 | 20.0 | 20.0 | 20.0 | 20.0 | 20.0 |
| 1 | 13.4 | 9.2 | 11.7 | 10.4 | 9.7 | 8.92 |
| 3 | 9.7 | 5.3 | 8.6 | 7.6 | 7.1 | 5.3 |
| 5 | 7.5 | 4.2 | 7.1 | 6.0 | 5.5 | 4.1 |
Experimental example 2 ultraviolet Barrier Property test
Cutting the film into a square with the thickness of 50 multiplied by 50mm, testing the ultraviolet ray (200 and 400nm) transmittance of the film by using an ultraviolet spectrophotometer, obtaining the barrier rate of the composite film prepared by the invention to the ultraviolet ray according to the transmittance value, and listing the experimental result in table 3,
as shown in Table 3, the UV-blocking ability of the composite film was 97 to 99%.
Table 3 ultraviolet barrier properties test results
| Wavelength of light | Example 1 | Example 2 | Examples3 | Example 4 | Example 5 | Example 6 |
| 200nm | 97.4 | 99.0 | 98.3 | 98.4 | 99.0 | 99.0 |
| 280nm | 97.0 | 99.0 | 99.0 | 99.0 | 99.0 | 99.2 |
| 320nm | 98.0 | 99.2 | 99.0 | 99.0 | 99.1 | 99.0 |
| 400nm | 97.1 | 99.6 | 98.3 | 99.0 | 98.9 | 99.2 |
It should be understood by those skilled in the art that the above-described preferred embodiments are merely illustrative of the present invention and are not to be construed as limiting the present invention. Various changes and equivalents may be made to the technical solution of the present invention without departing from the principle and scope of the technical solution of the present invention, and are intended to be covered by the scope of the claims of the present invention.
Claims (8)
1. The composite film for the multifunctional cultural relic protection bag is characterized by comprising an inner film, wherein the inner film comprises an upper layer, a core layer and a lower layer which are laminated, the lower layer is a cultural relic contact layer, and the inner film is formed by an upper layer material, a core layer material and a lower layer material through co-extrusion blow molding;
wherein, the upper layer is made of polypropylene resin;
the core layer material is prepared from the following components in percentage by weight,
the parts by weight are based on 100 parts by weight of the core layer,
the ratio of the weight of the iron-based catalyst to the weight of the natural rubber is 0.5:100 to 5:100,
the weight ratio of the alkali metal/alkaline earth metal promoter powder to the iron-based catalyst is 1:1 to 1:2,
the ratio of the weight of the natural rectorite powder to the weight of the alkali metal/alkaline earth metal cocatalyst is 1:2,
wherein,
the iron-based catalyst is selected from: hydrated ammonium ferrous sulfate and hydrated ferrous citrate,
the alkali/alkaline earth metal promoter is selected from: sodium carbonate, potassium carbonate and calcium hydroxide,
the core layer material is prepared by a method comprising the steps of,
(1-1) drying natural rectorite powder at 300-1000 ℃ for 3-8 hours, grinding to 200-800 meshes,
(1-2) dissolving iron catalyst powder in water to form slurry, pouring the slurry into the natural rectorite powder treated in the step (1-1), drying the slurry in vacuum at the temperature of 30-60 ℃ until the humidity is 40-60% to form an iron salt-natural rectorite mixture,
(1-3) mechanically blending alkali metal/alkaline earth metal promoter powder with the iron salt-natural rectorite mixture prepared in (1-2) to form a mixture,
(1-4) melting and blending the mixture obtained in the step (1-3) with natural rubber powder and polypropylene resin powder to obtain a modified polypropylene resin core layer material;
the lower layer material is polyvinyl alcohol-ethylene-vinyl acetate copolymer modified polypropylene resin, which is prepared by the method comprising the following steps,
(2-1) melting and blending the ethylene-vinyl acetate copolymer and the polyvinyl alcohol resin according to the weight ratio of 1: 1-2: 1,
and (2-2) melting and blending the product obtained in the step (2-1) and polypropylene resin according to the weight ratio of 1: 10-2: 10 to obtain the polyvinyl alcohol-ethylene-vinyl acetate modified polypropylene resin.
2. The composite film for a multifunctional cultural relic protection bag according to claim 1, which further comprises an upper layer laminated on the core layer, wherein the upper layer is polypropylene resin.
3. The composite film for a multifunctional cultural relic protection bag according to claim 1, which further comprises an outer film laminated on the upper layer,
the outer film is a high-barrier film and is selected from a biaxially oriented polypropylene film coated with polyvinylidene chloride on the surface layer, a vacuum aluminized cast polypropylene film, a vacuum aluminized polyester film, a polyester film plated with silicon oxide on the surface, or a polyester film plated with aluminum oxide on the surface.
4. The composite film for a multifunctional cultural relic protection bag according to claim 3, wherein the outer film and the inner film are prepared by dry compounding, and the upper layers of the outer film and the inner film are bonded by an adhesive.
5. The composite film for a multifunctional cultural relic protection bag as claimed in claim 1, wherein the core layer material is prepared from the following components in the following weight ratio,
the parts by weight are based on 100 parts by weight of the core layer,
the ratio of the weight of the iron-based catalyst to the weight of the natural rubber is 0.5:100 to 5:100,
the weight ratio of the alkali metal/alkaline earth metal promoter powder to the iron-based catalyst is 1:1 to 1:2,
the ratio of the weight of the natural rectorite powder to the weight of the alkali metal/alkaline earth metal promoter is 1: 2.
6. A preparation method of a composite film for a multifunctional cultural relic protection bag is characterized by comprising the following steps,
(1) preparing a core material comprising:
(1-1) drying natural rectorite powder at 300-1000 ℃ for 3-8 hours, grinding to 200-800 meshes,
(1-2) dissolving iron catalyst powder in water to form slurry, pouring the slurry into the natural rectorite powder treated in the step (1-1), drying the slurry in vacuum at the temperature of 30-60 ℃ until the humidity is 40-60% to form an iron salt-natural rectorite mixture,
(1-3) mechanically blending alkali metal/alkaline earth metal promoter powder with the iron salt-natural rectorite mixture prepared in (1-2) to form a mixture,
(1-4) melting and blending the mixture obtained in the step (1-3) with natural rubber powder and polypropylene resin powder to obtain a modified polypropylene resin core layer material;
(2) preparing a lower layer material comprising:
(2-1) melting and blending the ethylene-vinyl acetate copolymer and the polyvinyl alcohol resin according to the weight ratio of 1: 1-2: 1,
(2-2) melting and blending the product obtained in the step (2-1) and polypropylene resin powder according to the weight ratio of 1: 10-2: 10 to prepare polyvinyl alcohol-ethylene-vinyl acetate copolymer modified polypropylene resin;
(3) preparing an inner membrane: using polypropylene as an upper layer material, and preparing the upper layer material, the core layer material prepared in the step (1) and the lower layer material prepared in the step (2) into an inner film by a multi-layer co-extrusion method;
(4) preparing a composite film for the multifunctional cultural relic protection bag: and (3) compounding the high-barrier film serving as an outer film and the inner film prepared in the step (3) by a dry method to prepare the multifunctional composite film for the cultural relic protection bag, wherein the outer film and the upper layer of the inner film are bonded by an adhesive.
7. The method for preparing a composite film for a multifunctional cultural relic protection bag as claimed in claim 6, wherein the particle size of the natural rectorite powder is 300 mesh.
8. The use of the composite film for the multifunctional cultural relic protection bag according to any one of claims 1 to 5 in the preparation of the cultural relic protection bag.
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