CN113276526B - One-way water absorption composite membrane and preparation method and application thereof - Google Patents
One-way water absorption composite membrane and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a unidirectional water absorption composite membrane and a preparation method and application thereof. The composite film comprises a surface layer, a first bonding layer, a middle layer, a second bonding layer and an inner layer which are sequentially arranged; the inner layer comprises a composite layer, a functional layer and a heat sealing layer which are arranged in sequence; the composite layer is positioned between the second adhesive layer and the functional layer; the functional layer is a water-absorbent resin layer. The preparation method comprises the following steps: (1) Coating a thermosetting adhesive on any surface of the surface layer, and compounding the thermosetting adhesive with any surface of the aluminum layer to obtain an intermediate; extruding the composite layer material, the functional layer material and the heat sealing layer material to obtain an inner layer; (2) And (2) coating a thermosetting adhesive on one surface of the intermediate obtained in the step (1) far away from the surface layer, compounding the thermosetting adhesive with one surface of the inner layer far away from the heat sealing layer, and curing to obtain the composite film. The composite film provided by the invention has better water and oxygen resistance and higher safety, and is suitable for being used as a packaging material of light-weight medicine and food superfine powder.
Description
Technical Field
The invention belongs to the technical field of packaging materials, and particularly relates to a unidirectional water absorption composite membrane, and a preparation method and application thereof.
Background
With the development of society, the packaging film is widely used in various industries and is suitable for packaging commodities with various shapes, and the sealed and packaged commodities have sanitation, dust prevention and moisture resistance and good protection performance. The barrier property of the packaging film is an important index for measuring the quality of the packaging film, the packaging effect of a product can be directly influenced, and most of reasons for the content change of the packaging film when the product is packaged by the packaging film are that the content changes due to the influence of moisture, oxygen, microorganisms and the like because the barrier property of the packaging film is poor. However, in the current packaging of lightweight (single package of products with less than 2 g) medicine and food ultrafine powder, the requirement for drying the contents is particularly high, and the slight water content can cause the contents to be agglomerated, which affects the consumption experience of the product and the shelf life of the product. And the main sources of the "moisture" are moisture of a certain amount of air in addition to the contents in the actual packaged article, moisture generated by the respiration reaction of the contents, and permeation of external moisture into the contents through the composite film, and the like. Therefore, how to provide a composite film with excellent barrier properties has become a focus of research.
For example, CN110387195A discloses a barrier composite film and a preparation method thereof. The barrier composite membrane sequentially comprises: a polymer layer having a thickness of 5 to 100 μm; a first adhesive layer having a thickness of 5 to 50 μm; a metal layer, the thickness of the metal layer being 10-100 μm; a second adhesive layer having a thickness of 10 to 200 μm. Although the barrier composite film provided by the technical scheme has good water resistance, the barrier composite film can only block external moisture from entering contents, cannot absorb moisture in air in the contents and moisture generated by respiration reaction of the contents, and is not suitable for being used as a packaging material for lightweight medicines and food superfine powder due to the thick metal layer.
CN108995337A discloses a high-resistance water packaging composite film and a preparation method thereof. The high-resistance water packaging composite film comprises a surface layer, an intermediate layer and an inner layer which are sequentially arranged, wherein the surface layer is one of a PE layer, a PET layer, a BOPP layer and a PA layer; the middle layer is one of an aluminum box, a PVA layer and a PET layer; the inner layer comprises a heat sealing layer, a blocking layer and a composite layer which are sequentially arranged from inside to outside; the heat-seal layer is one of a PE layer, a PP layer, an E/VAC layer, a PE and PP co-extrusion layer, and the barrier layer is a PE layer or a PVA layer added with inorganic fillers: the composite layer is a PE layer or a PP layer. Although the composite film provided by the technical scheme has good water resistance, the inorganic filler in the barrier layer is active metal oxide, active metal peroxide and active metal carbide, so that the composite film has low safety and is not suitable for being used as a packaging material for lightweight medicines and food superfine powder, and although the composite film has good water resistance, the water resistance and the safety can not meet the use requirements of the packaging material for lightweight medicines and food superfine powder.
CN201604899U discloses a three-layer composite membrane structure. The three-layer composite membrane structure comprises an outer layer made of PET, a middle layer made of PVDF and an inner layer made of PE; the thickness of the outer layer is 10-14 microns, the thickness of the middle layer is 16-20 microns, and the thickness of the inner layer is 48-52 microns.
Therefore, it is an urgent technical problem to provide a composite film having good barrier properties and suitable for use as a packaging material for lightweight drugs and food ultrafine powders.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a unidirectional water absorption composite membrane and a preparation method and application thereof. According to the invention, through the design of the components and the structure of the composite film, the prepared composite film has better barrier property and safety, so that external moisture cannot penetrate into contents, and meanwhile, through the special design of the inner layer, the composite film can absorb and lock moisture in one direction, so that the moisture cannot be dispersed reversely, thereby reducing the water content of the contents, drying the contents, prolonging the shelf life of the contents, and being suitable for the packaging material of light-weight medicines and food superfine powder sensitive to moisture.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a unidirectional water absorption composite membrane, which comprises a surface layer, a first bonding layer, a middle layer, a second bonding layer and an inner layer which are arranged in sequence;
the inner layer comprises a composite layer, a functional layer and a heat sealing layer which are arranged in sequence;
the composite layer is positioned between the second adhesive layer and the functional layer;
the functional layer is a water-absorbing resin layer.
According to the invention, through the design of the structure of the unidirectional water absorption composite membrane, the prepared unidirectional water absorption composite membrane has better water resistance and safety, and is suitable for packaging materials of lightweight medicines and food superfine powder which are sensitive to water.
According to the invention, the water-absorbing resin layer is used as a functional layer, so that the water in the air in a packaged article and the water generated by the respiration reaction of the content can be effectively absorbed, and the water is locked and can not be reversely dispersed, thereby reducing the water content of the content, keeping the content dry and prolonging the shelf life of the content.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the object and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
As a preferable technical scheme of the invention, the surface layer is a PET layer, an OPP layer or a nylon layer.
In the present invention, the PET is polyethylene terephthalate, and the OPP is stretched polypropylene.
The thickness of the surface layer is preferably 9 to 23 μm, and may be, for example, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, or 23 μm.
Preferably, the material of the first adhesive layer is a thermosetting adhesive.
Preferably, the thickness of the first adhesive layer is 0.9 to 4.5. Mu.m, and may be, for example, 0.9. Mu.m, 1.2. Mu.m, 1.5. Mu.m, 1.8. Mu.m, 2. Mu.m, 2.2. Mu.m, 2.5. Mu.m, 2.7. Mu.m, 3. Mu.m, 3.3. Mu.m, 3.6. Mu.m, 4. Mu.m, 4.2. Mu.m, 4.5. Mu.m, or the like.
In a preferred embodiment of the present invention, the intermediate layer is an aluminum layer.
The thickness of the intermediate layer is preferably 7 to 20 μm, and may be, for example, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, or 20 μm.
The aluminum has the advantages of moisture resistance, air tightness, shading, abrasion resistance, fragrance retention, no toxicity, no odor and the like, the aluminum layer is used as the middle layer, external moisture can be effectively prevented from permeating into the content through the composite film, the content is enabled to be agglomerated, the quality of the content is affected, meanwhile, the thickness of the middle layer is further controlled within a specific range, if the thickness of the middle layer is too thin, the external moisture can permeate into the content through the composite film, and the water resistance of the composite film is enabled to be poor; if the thickness of the intermediate layer is too thick, on the one hand, the production cost of the composite film is increased, and on the other hand, the prepared composite film is not suitable for being used as a packaging material for lightweight medicines and food ultrafine powder.
Preferably, the material of the second adhesive layer is a thermosetting adhesive.
Preferably, the thickness of the second adhesive layer is 0.9 to 4.5. Mu.m, and may be, for example, 0.9. Mu.m, 1.2. Mu.m, 1.5. Mu.m, 1.8. Mu.m, 2. Mu.m, 2.2. Mu.m, 2.5. Mu.m, 2.7. Mu.m, 3. Mu.m, 3.3. Mu.m, 3.6. Mu.m, 4. Mu.m, 4.2. Mu.m, 4.5. Mu.m, or the like.
In a preferred embodiment of the present invention, the inner layer has a thickness of 30 to 100. Mu.m, for example, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, or 100 μm.
Preferably, the material of the composite layer is selected from PE or PP.
The thickness of the composite layer is preferably 7 to 28 μm, and may be, for example, 7 μm, 8 μm, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, 20 μm, 22 μm, 24 μm, 26 μm, or 28 μm.
Preferably, the material of the functional layer comprises a combination of a water-absorbent resin and a polymer.
Preferably, the water absorbent resin is a synthetic water absorbent resin.
It should be noted that, the synthetic water-absorbent resin in the present application is starch graftAn acrylate polymer cross-linked product, wherein the synthetic water-absorbent resin has a particle size of 50 to 70 mesh (for example, 50 mesh, 60 mesh, 65 mesh, 70 mesh, etc.) and a bulk density of 0.6 to 0.8g/cm 3 (it may be, for example, 0.6g/cm 3 、0.63g/cm 3 、0.65g/cm 3 、0.68g/cm 3 、0.7g/cm 3 、0.72g/cm 3 、0.75g/cm 3 、0.78g/cm 3 Or 0.8g/cm 3 、)。
Preferably, the polymer is selected from PP or PE.
Preferably, the content of the water-absorbent resin in the functional layer is 3 to 10% by mass, and may be, for example, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, or the like.
The functional layer preferably has a thickness of 15 to 44 μm, and may be, for example, 15 μm, 18 μm, 20 μm, 22 μm, 25 μm, 27 μm, 30 μm, 33 μm, 35 μm, 38 μm, 40 μm, 44 μm, or the like.
According to the invention, the thickness of the functional layer is controlled within a specific range, so that the prepared composite film has proper thickness and good water resistance, and is suitable for being used as a packaging material of light-weight medicines and food superfine powder. If the thickness of the functional layer is too small, the prepared composite film cannot completely absorb moisture in the air of the content and moisture generated by the respiration reaction of the content, so that the shelf life of the content is shortened; if the thickness of the functional layer is too large, the production cost of the prepared composite film is high, and the actual production and use are not facilitated.
Preferably, the material of the heat-sealing layer is selected from PE or PP.
The heat-sealable layer preferably has a thickness of 7 to 28 μm, for example 7 μm, 8 μm, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, 20 μm, 22 μm, 24 μm, 26 μm or 28 μm.
In a second aspect, the present invention provides a method for preparing the unidirectional water absorption composite membrane according to the first aspect, comprising the following steps:
(1) Coating a thermosetting adhesive on any surface of the surface layer, and compounding the thermosetting adhesive with any surface of the aluminum layer to obtain an intermediate;
extruding the composite layer material, the functional layer material and the heat sealing layer material to obtain an inner layer;
(2) And (2) coating a thermosetting adhesive on one surface of the intermediate obtained in the step (1) far away from the surface layer, compounding the thermosetting adhesive with one surface of the inner layer far away from the heat sealing layer, and curing to obtain the unidirectional water absorption composite film.
As a preferable embodiment of the present invention, the dry weight of the coating in the step (1) is 1.0 to 5.0g/m 2 For example, it may be 1.0g/m 2 、1.2g/m 2 、1.5g/m 2 、1.8g/m 2 、2.0g/m 2 、2.3g/m 2 、2.5g/m 2 、2.7g/m 2 、3.0g/m 2 、3.3g/m 2 、3.6g/m 2 、4.0g/m 2 、4.2g/m 2 、4.6g/m 2 Or 5.0g/m 2 And so on.
Preferably, the compounding method in step (1) is compounding by a compounding machine.
Preferably, the compounding speed in step (1) is 60-180 m/min, such as 60m/min, 70m/min, 80m/min, 90m/min, 100m/min, 110m/min, 120m/min, 130m/min, 140m/min, 150m/min, 160m/min, 170m/min or 180m/min.
Preferably, the extrusion method in step (1) is extrusion through a three-layer co-extrusion extruder.
Preferably, the temperature of the extrusion is 150 to 200 ℃, for example, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃ or 200 ℃ and the like.
As a preferable embodiment of the present invention, the dry weight of the coating in the step (2) is 1.0 to 5.0g/m 2 For example, it may be 1.0g/m 2 、1.2g/m 2 、1.5g/m 2 、1.8g/m 2 、2.0g/m 2 、2.3g/m 2 、2.5g/m 2 、2.7g/m 2 、3.0g/m 2 、3.3g/m 2 、3.6g/m 2 、4.0g/m 2 、4.2g/m 2 、4.6g/m 2 Or 5.0g/m 2 And so on.
Preferably, the compounding method in the step (2) is compounding through a compounding machine.
Preferably, the compounding speed in step (2) is 80-280 m/min, such as 80m/min, 100m/min, 120m/min, 140m/min, 160m/min, 180m/min, 200m/min, 220m/min, 240m/min, 260m/min or 280m/min.
Preferably, the temperature of the aging in the step (2) is 25 to 55 ℃, and may be, for example, 25 ℃, 27 ℃, 30 ℃, 33 ℃, 35 ℃, 38 ℃, 40 ℃, 42 ℃, 46 ℃, 50 ℃,52 ℃ or 55 ℃.
Preferably, the curing time in the step (2) is 48 to 96 hours, such as 48 hours, 52 hours, 56 hours, 60 hours, 63 hours, 66 hours, 70 hours, 72 hours, 75 hours, 78 hours, 80 hours, 84 hours, 88 hours, 92 hours or 96 hours.
As a preferable technical scheme of the invention, the method also comprises a pretreatment step before the coating in the step (1).
Preferably, the pretreatment method is to coat ink on one surface coated with the thermosetting adhesive and then dry the surface.
Preferably, the temperature for drying is 35-80 ℃, for example, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃.
As a preferred technical scheme of the invention, the preparation method specifically comprises the following steps:
(1) Coating ink on any surface of the surface layer, drying at 35-80 ℃, coating a thermosetting adhesive on the surface coated with the ink, and compounding with any surface of the aluminum layer by a compounding machine at a speed of 60-180 m/min to obtain an intermediate; wherein the coating dry weight of the coating is 1.0-5.0 g/m 2 ；
Extruding the composite layer material, the functional layer material and the heat sealing layer material by a three-layer co-extrusion extruder at the temperature of 150-200 ℃ to obtain an inner layer;
(2) Coating a thermosetting adhesive on one surface of the intermediate obtained in the step (1) far away from the surface layer, compounding the intermediate with one surface of the inner layer far away from the heat sealing layer by a compounding machine at the speed of 80-280 m/min, and curing at 25-55 ℃ for 48-96 h to obtain the unidirectional water absorption composite membrane; wherein the coating is appliedThe dry weight of the cloth is 1.0 to 5.0g/m 2 。
In a third aspect, the present invention provides a use of the composite membrane for unidirectional water absorption according to the first aspect as a packaging material for lightweight pharmaceutical or food ultrafine powders.
Compared with the prior art, the invention has the following beneficial effects:
the composite membrane prepared by the invention can effectively prevent external moisture from permeating contents through the design of the components and the structure of the unidirectional water absorption composite membrane, and the water vapor permeability of the composite membrane is 0.003-0.1 g/(m) 2 X 24 h), the oxygen transmission capacity is 0.003 to 0.1cm 3 /(m 2 X 24h x 0.1 MPa), further through the special design of the inner layer, the composite film can absorb water in one direction and lock the water, so that the water can not be dispersed reversely, thereby reducing the water content of the content, achieving the drying of the content and improving the quality guarantee period of the content, wherein the water absorption capacity is 69-202.4 g.
Drawings
FIG. 1 is a schematic structural diagram of a unidirectional water-absorbing composite membrane provided by the present invention;
the adhesive comprises a surface layer 1, a first adhesive layer 2, a middle layer 3, a second adhesive layer 4, an inner layer 5, a composite layer 51, a functional layer 52 and a heat sealing layer 53.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings. It should be understood by those skilled in the art that the embodiments are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Some of the component sources in the examples and comparative examples are as follows:
PET: anhui national wind Plastic industry, inc.;
printing ink: shanghai DIC ink Ltd;
polyurethane adhesive: southeast Tong high Union New materials GmbH;
PE: shanghai Zijiang color printing packaging Co., ltd;
water-absorbent resin: sumitomo refinement Co., SA60N.
Example 1
The embodiment provides a unidirectional water absorption composite membrane and a preparation method thereof, and the structural schematic diagram of the unidirectional water absorption composite membrane is shown in fig. 1, the composite membrane comprises a surface layer 1, a first bonding layer 2, an intermediate layer 3, a second bonding layer 4, a composite layer 51, a functional layer 52 and a heat sealing layer 53 which are sequentially arranged;
the surface layer 1 is a PET layer with the thickness of 15 mu m; the first bonding layer 2 is a polyurethane adhesive layer with the thickness of 2.7 mu m; the middle layer 3 is an aluminum layer with the thickness of 15 mu m; the second bonding layer 4 is a polyurethane adhesive layer with the thickness of 2.7 mu m; the composite layer 51 is a PE layer with a thickness of 20 μm; the functional layer 52 is made of a mixture of water-absorbent resin and PE, wherein the water-absorbent resin accounts for 5% of the functional layer 52 by mass, and the functional layer 52 is 35 μm thick; the heat-seal layer 53 was a PE layer having a thickness of 20 μm.
The preparation method of the composite membrane comprises the following steps:
(1) Coating ink on any surface of the PET layer, drying at 60 ℃, coating a polyurethane adhesive on the surface of the PET layer coated with the ink, and compounding with any surface of the aluminum layer by a compounding machine at a speed of 120m/min to obtain an intermediate; wherein the coating has a dry coating weight of 3.0g/m 2 ；
Extruding the composite layer 51 material, the functional layer 52 material and the heat seal layer 53 material by a three-layer co-extrusion extruder at 180 ℃ to obtain an inner layer 5;
(2) Coating a polyurethane adhesive on one surface of the intermediate obtained in the step (1) far away from the surface layer 1, then compounding the intermediate with one surface of the composite layer 51 far away from the functional layer 52 by a compounding machine at the speed of 200m/min, and curing at 40 ℃ for 72 hours to obtain the unidirectional water absorption composite film; wherein the coating has a dry coating weight of 3.0g/m 2 。
Example 2
The embodiment provides a unidirectional water absorption composite film and a preparation method thereof, wherein the composite film comprises a surface layer 1, a first bonding layer 2, a middle layer 3, a second bonding layer 4, a composite layer 51, a functional layer 52 and a heat sealing layer 53 which are sequentially arranged;
the surface layer 1 is a PET layer with the thickness of 18 mu m; the first bonding layer 2 is a polyurethane adhesive layer with the thickness of 0.9 mu m; the middle layer 3 is an aluminum layer with the thickness of 7 mu m; the second bonding layer 4 is a polyurethane adhesive layer with the thickness of 0.9 mu m; the composite layer 51 is a PP layer with a thickness of 7 μm; the functional layer 52 is made of a mixture of water-absorbent resin and PP, wherein the mass percentage of the water-absorbent resin in the functional layer 52 is 5%, and the thickness of the functional layer 52 is 16 μm; the heat seal layer 53 was a PP layer with a thickness of 7 μm.
The preparation method of the composite membrane comprises the following steps:
(1) Coating ink on any surface of the PET layer, drying at 80 ℃, coating a polyurethane adhesive on the surface of the PET layer coated with the ink, and compounding with any surface of the aluminum layer by a compounding machine at a speed of 60m/min to obtain an intermediate; wherein the coating has a dry coating weight of 1.0g/m 2 ；
Extruding the composite layer 51 material, the functional layer 52 material and the heat seal layer 53 material by a three-layer co-extrusion extruder at 150 ℃ to obtain an inner layer 5;
(2) Coating a polyurethane adhesive layer on one surface of the intermediate obtained in the step (1) far away from the surface layer 1, compounding the intermediate with one surface of the composite layer 51 far away from the functional layer 52 by a compounding machine at the speed of 80m/min, and curing at 25 ℃ for 96 hours to obtain the unidirectional water absorption composite membrane; wherein the coating dry weight of the coating is 1.0g/m 2 。
Example 3
The embodiment provides a unidirectional water absorption composite film and a preparation method thereof, wherein the composite film comprises a surface layer 1, a first bonding layer 2, a middle layer 3, a second bonding layer 4, a composite layer 51, a functional layer 52 and a heat sealing layer 53 which are sequentially arranged;
the surface layer 1 is a PET layer with the thickness of 9 μm; the first adhesive layer 2 is a polyurethane adhesive layer with the thickness of 4.5 mu m; the middle layer 3 is an aluminum layer with the thickness of 12 mu m; the second bonding layer 4 is a polyurethane adhesive layer with the thickness of 4.5 mu m; the composite layer 51 is a PE layer with a thickness of 28 μm; the functional layer 52 is made of a mixture of water-absorbent resin and PE, and has a thickness of 44 μm; the heat-seal layer 53 was a PE layer having a thickness of 28 μm.
The preparation method of the composite membrane comprises the following steps:
(1) Coating ink on any surface of the PET layer, drying at 35 ℃, coating a polyurethane adhesive on the surface of the PET layer coated with the ink, and compounding with any surface of the aluminum layer by a compounding machine at the speed of 180m/min to obtain an intermediate; wherein the coating has a dry coating weight of 5.0g/m 2 ；
Extruding the composite layer 51 material, the functional layer 52 material and the heat seal layer 53 material by a three-layer co-extrusion extruder at 200 ℃ to obtain an inner layer 5;
(2) Coating a polyurethane adhesive layer on one surface of the intermediate obtained in the step (1) far away from the surface layer 1, compounding the intermediate with one surface of the composite layer 51 far away from the functional layer 52 by a compounding machine at the speed of 280m/min, and curing at 55 ℃ for 48h to obtain the unidirectional water absorption composite film; wherein the coating dry weight of the coating is 5.0g/m 2 。
Example 4
The embodiment provides a unidirectional water absorption composite film and a preparation method thereof, wherein the composite film comprises a surface layer 1, a first bonding layer 2, a middle layer 3, a second bonding layer 4, a composite layer 51, a functional layer 52 and a heat sealing layer 53 which are sequentially arranged;
the surface layer 1 is a PET layer with the thickness of 23 μm; the first adhesive layer 2 is a polyurethane adhesive layer with the thickness of 3.6 mu m; the middle layer 3 is an aluminum layer with the thickness of 20 mu m; the first bonding layer 4 is a polyurethane adhesive layer with the thickness of 3.6 mu m; the composite layer 51 is a PE layer with a thickness of 10 μm; the functional layer 52 is made of a mixture of water-absorbent resin and PE, and has a thickness of 15 μm; the heat seal layer 53 was a PE layer having a thickness of 10 μm.
The preparation method of the composite membrane comprises the following steps:
(1) Coating ink on any surface of the PET layer, drying at 50 ℃, coating a polyurethane adhesive on the surface of the PET layer coated with the ink, and compounding the adhesive with any surface of the aluminum layer by a compounding machine at the speed of 150m/min to obtain an intermediate; wherein, theThe dry coating weight of the coating was 4.0g/m 2 ；
Extruding the composite layer 51 material, the functional layer 52 material and the heat seal layer 53 material by a three-layer co-extrusion extruder at 180 ℃ to obtain an inner layer 5;
(2) Coating a polyurethane adhesive layer on one surface of the intermediate obtained in the step (1) far away from the surface layer 1, compounding the intermediate with one surface of the composite layer 51 far away from the functional layer 52 by a compounding machine at the speed of 220m/min, and curing at 50 ℃ for 60 hours to obtain the unidirectional water absorption composite membrane; wherein the coating dry weight of the coating is 4.0g/m 2 。
Example 5
This example provides a unidirectional water-absorbent composite membrane and a method for preparing the same, which is different from example 1 only in that the thickness of an aluminum layer in the composite membrane is 7 μm, and other conditions are the same as example 1.
Example 6
This example provides a unidirectional water-absorbing composite membrane and a method for preparing the same, which is different from example 1 only in that the thickness of the aluminum layer in the composite membrane is 20 μm, and the other conditions are the same as example 1.
Example 7
This example provides a unidirectional water-absorbing composite membrane and a method for preparing the same, which is different from example 1 only in that the thickness of the aluminum layer in the composite membrane is 5 μm, and the other conditions are the same as example 1.
Example 8
This example provides a unidirectional water-absorbing composite membrane and a method for preparing the same, which is different from example 1 only in that the thickness of the aluminum layer in the composite membrane is 25 μm, and the other conditions are the same as example 1.
Example 9
This example provides a unidirectional water-absorbent composite membrane and a method for preparing the same, which is different from example 1 only in that the thickness of the water-absorbent resin layer in the composite membrane is 15 μm, and the other conditions are the same as example 1.
Example 10
This example provides a unidirectional water-absorbent composite membrane and a method for preparing the same, which is different from example 1 only in that the thickness of the water-absorbent resin layer in the composite membrane is 42 μm, and the other conditions are the same as example 1.
Example 11
This example provides a unidirectional water-absorbent composite membrane and a method for preparing the same, which is different from example 1 only in that the thickness of the water-absorbent resin layer in the composite membrane is 10 μm, and the other conditions are the same as example 1.
Example 12
This example provides a unidirectional water-absorbent composite membrane and a method for preparing the same, which is different from example 1 only in that the thickness of the water-absorbent resin layer in the composite membrane is 50 μm, and the other conditions are the same as example 1.
Comparative example 1
The present comparative example provides a composite film and a method for preparing the same, which are different from example 1 only in that the composite film includes a surface layer, a first adhesive layer, an intermediate layer, a second adhesive layer, and an inner layer, which are sequentially disposed, the inner layer being a PE layer and having a thickness of 75 μm; other conditions were the same as in example 1.
Comparative example 2
The comparative example provides a composite film and a preparation method thereof, and the difference from the embodiment 1 is only that a functional layer in the composite film is a PE layer containing calcium oxide, and the mass percentage content of the calcium oxide in the functional layer is 5%;
the preparation method of the composite membrane comprises the following steps:
(1) Coating ink on any surface of the PET layer, drying at 60 ℃, coating a polyurethane adhesive on the surface of the PET layer coated with the ink, and compounding with any surface of the aluminum layer by a compounding machine at a speed of 120m/min to obtain an intermediate; wherein the coating has a dry coating weight of 3.0g/m 2 ；
Mixing the PE master batches and the calcium oxide particles at 0 ℃ for 30min to obtain functional layer premix, and extruding the functional layer premix, the composite layer material and the heat sealing layer material through a three-layer co-extrusion extruder at 180 ℃ to obtain an inner layer;
(2) Coating a polyurethane adhesive layer on the surface of the intermediate obtained in the step (1) far away from the surface layer, and then carrying out compound machine on the surface of the intermediate and the surface of the composite layer far away from the functional layerCompounding at the speed of 200m/min, and curing at 40 ℃ for 72h to obtain the composite film; wherein the coating has a dry coating weight of 3.0g/m 2 。
The composite membranes provided in the above examples and comparative examples were tested for their performance according to the following test criteria:
water vapor transmission amount: ASTM F1249-01;
oxygen transmission amount: ASTM D3985-02;
heavy metal content: YBB00172002-2015 and YBB00132002-2015;
water absorption capacity: the absorption capacity of the water-absorbent resin is tested according to the GB/T22875-2008 standard, and then the composite membranes of 0.2m provided in the examples and the comparative examples are taken 2 Cutting the composite membrane into 10mm multiplied by 10mm fragments, soaking the fragments in water meeting GB/T6682-2008 standard for 30min, taking out the water-absorbed fragments, placing the fragments on a 50-mesh nylon net on a fixed test container, dripping for 10min in a static state, and measuring the water absorption capacity;
water absorption = (m) 1 -m 2 )/0.2；
Wherein m is 1 Mass (g) of water before soaking the pieces, m 2 The mass (g) of water after removal of the chips.
The above examples and comparative examples provide composite film performance test results as shown in table 1:
TABLE 1
The composite membrane prepared by the invention can effectively prevent external moisture from permeating contents through the design of the components and the structure of the unidirectional water absorption composite membrane, and the water vapor permeability of the composite membrane is 0.003-0.1 g/(m) 2 X 24 h), the oxygen transmission capacity is 0.003 to 0.1cm 3 /(m 2 X 24h X0.1 MPa), further passing through the inner layerThe composite membrane has the advantages that the composite membrane is specially designed, water can be absorbed and locked in one direction, the water cannot be dispersed reversely, the water content of the content is reduced, the content is dried, the quality guarantee period of the content is prolonged, the water absorption amount is 69-202.4 g, meanwhile, the composite membrane has high safety, is non-toxic, non-irritant and pollution-free, has low heavy metal content, meets the standard of a medicinal composite membrane, and is suitable for light-weight medicine and food superfine powder packaging materials sensitive to trace water.
If the thickness of the aluminum layer in the composite film is too thin (example 7) as compared to example 1, the composite film prepared has poor water and oxygen blocking properties and has a water vapor transmission rate of 1.02 g/(m) 2 X 24 h), oxygen transmission capacity is 0.98cm 3 /(m 2 X 24h x 0.1 MPa); if the thickness of the aluminum layer in the composite film is too thick (example 8), the prepared composite film has high production cost and large thickness, and is not suitable for being used as a packaging material for light-weight medicines and food ultrafine powder.
If the thickness of the functional layer in the composite film is too thin as compared with example 1 (example 11), the prepared composite film cannot absorb all of the moisture in the air of the contents and the moisture generated by the respiration reaction of the contents, and thus the shelf life of the contents is shortened, and the water absorption amount thereof is 46g; if the thickness of the functional layer in the composite film is too thick (example 12), the production cost of the prepared composite film is high, which is not favorable for practical production and use.
Compared with example 1, if the inner layer of the composite film is of a single-layer structure and is a PE layer (comparative example 1), the prepared composite film cannot absorb moisture in the air of the contents and moisture generated by the respiration reaction of the contents, and thus the shelf life of the contents is shortened; if the water-absorbing resin in the functional layer is replaced by calcium oxide (comparative example 2), the prepared composite membrane has poor safety and high heavy metal content, and does not meet the standard of a medicinal composite membrane.
In conclusion, through the design of the components and the structure of the composite film, the prepared composite film can effectively prevent external moisture from permeating into contents, and meanwhile, through the special design of the inner layer, the composite film can absorb water in one direction and lock the moisture, so that the moisture can not be dispersed reversely, the moisture content of the contents is reduced, the contents are dried, the quality guarantee period of the contents is prolonged, and the composite film provided by the application has higher safety and is suitable for being used as a packaging material of light-weight medicines and food superfine powder.
The applicant states that the present invention is illustrated by the above examples to show the detailed structure and material characteristics of the composite film provided by the present invention, but the present invention is not limited to the above detailed structure and material, i.e. it does not mean that the present invention must rely on the above detailed structure and material to be implemented. It will be appreciated by those skilled in the art that any modifications to the invention, equivalents of the materials selected for use in the invention, and the like, are within the scope and disclosure of the invention.
Claims (31)
1. A one-way water-absorbing composite film used as a light-weight medicine or food superfine powder packaging material is characterized by comprising a surface layer, a first bonding layer, a middle layer, a second bonding layer and an inner layer which are sequentially arranged;
the inner layer comprises a composite layer, a functional layer and a heat sealing layer which are arranged in sequence;
the composite layer is positioned between the second adhesive layer and the functional layer;
the functional layer is a water-absorbent resin layer;
the material of the functional layer comprises a composition of a water-absorbent resin and a polymer;
the mass percentage of the water-absorbing resin in the functional layer is 3-10%;
the thickness of the functional layer is 15-44 μm;
the middle layer is an aluminum layer.
2. The unidirectional water absorption composite film according to claim 1, wherein the surface layer is a PET layer, an OPP layer or a nylon layer.
3. The unidirectional water absorption composite film according to claim 1, wherein the thickness of the surface layer is 9 to 23 μm.
4. The unidirectional water absorption composite film according to claim 1, wherein the material of the first adhesive layer is a thermosetting adhesive.
5. A unidirectional water absorption composite film according to claim 1 wherein the thickness of the first adhesive layer is 0.9 to 4.5 μm.
6. A unidirectional water absorption composite membrane according to claim 1 wherein the thickness of the intermediate layer is 7 to 20 μm.
7. The unidirectional water absorption composite film according to claim 1, wherein the material of the second adhesive layer is a thermosetting adhesive.
8. A unidirectional water absorption composite film according to claim 1 wherein the thickness of the second adhesive layer is 0.9 to 4.5 μm.
9. A unidirectional water absorption composite membrane according to claim 1 wherein the thickness of the inner layer is 30 to 100 μm.
10. A unidirectional water absorption composite membrane according to claim 1 wherein the material of the composite layer is selected from PE or PP.
11. A unidirectional water absorbent composite membrane according to claim 1, wherein the thickness of the composite layer is 7 to 28 μm.
12. The unidirectional water absorption composite film according to claim 1, wherein the water absorption resin is a synthetic water absorption resin.
13. A unidirectional water absorbing composite film according to claim 1 wherein said polymer is selected from PP or PE.
14. A unidirectional water absorbing composite film according to claim 1 wherein the material of the heat seal layer is selected from PE or PP.
15. A unidirectional water absorbent composite film according to claim 1, wherein the thickness of the heat seal layer is 7 to 28 μm.
16. A method for preparing a unidirectional water absorption composite membrane according to any one of claims 1 to 15, characterized in that the method comprises the following steps:
(1) Coating a thermosetting adhesive on any surface of the surface layer, and compounding the thermosetting adhesive with any surface of the aluminum layer to obtain an intermediate;
extruding the composite layer material, the functional layer material and the heat sealing layer material to obtain an inner layer;
(2) Coating a thermosetting adhesive on one surface of the intermediate obtained in the step (1) far away from the surface layer, compounding the thermosetting adhesive with one surface of the inner layer far away from the heat sealing layer, and curing to obtain the unidirectional water absorption composite membrane;
the functional layer is a water-absorbent resin layer;
the material of the functional layer comprises a composition of a water-absorbent resin and a polymer;
the mass percentage of the water-absorbing resin in the functional layer is 3-10%;
the thickness of the functional layer is 15-44 μm.
17. The method according to claim 16, wherein the coating in the step (1) is carried out in a dry coating amount of 1.0 to 5.0g/m 2 。
18. The method according to claim 16, wherein the compounding in step (1) is performed by a compounding machine.
19. The method of claim 16, wherein the compounding speed in step (1) is 60 to 180m/min.
20. The method for preparing the polypropylene composition according to claim 16, wherein the extruding in the step (1) is performed by a three-layer co-extrusion extruder.
21. The method of claim 16, wherein the temperature of the extrusion is 150 to 200 ℃.
22. The method according to claim 16, wherein the coating in the step (2) is carried out in a dry coating amount of 1.0 to 5.0g/m 2 。
23. The method according to claim 16, wherein the compounding in step (2) is performed by a compounding machine.
24. The method of claim 16, wherein the compounding speed in the step (2) is 80 to 280m/min.
25. The method according to claim 16, wherein the temperature of the aging in the step (2) is 25 to 55 ℃.
26. The method according to claim 16, wherein the aging time in the step (2) is 48 to 96 hours.
27. The method of claim 16, further comprising a step of pre-treating before the coating in step (1).
28. The preparation method of claim 27, wherein the pretreatment comprises applying ink to the surface coated with the thermosetting adhesive and drying.
29. The method as claimed in claim 28, wherein the temperature of the drying is 35 to 80 ℃.
30. The method according to claim 16, comprising the steps of:
(1) Coating ink on any surface of the surface layer, drying at 35-80 ℃, coating a thermosetting adhesive on the surface coated with the ink on the surface layer, and compounding the thermosetting adhesive with any surface of the aluminum layer by a compound machine at the speed of 60-180 m/min to obtain an intermediate; wherein the coating dry weight of the coating is 1.0-5.0 g/m 2 ；
Extruding the composite layer material, the functional layer material and the heat-sealing layer material by a three-layer co-extrusion extruder at the temperature of 150-200 ℃ to obtain an inner layer;
(2) Coating a thermosetting adhesive on one surface of the intermediate obtained in the step (1) far away from the surface layer, compounding the intermediate with one surface of the composite layer far away from the functional layer by a compound machine at the speed of 80-280 m/min, and curing at 25-55 ℃ for 48-96 h to obtain the unidirectional water absorption composite membrane; wherein the coating dry weight of the coating is 1.0-5.0 g/m 2 。
31. Use of a unidirectional water-absorbing composite film according to any one of claims 1 to 15 as a packaging material for lightweight pharmaceutical or food ultrafine powders.
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| CN208101252U (en) * | 2017-12-04 | 2018-11-16 | 江阴升辉包装材料有限公司 | A kind of sheet material for plastics sucking moulding |
| CN109177415A (en) * | 2018-09-29 | 2019-01-11 | 浙江金石包装有限公司 | A kind of package compound film and preparation method thereof |
| CN111038054A (en) * | 2019-12-23 | 2020-04-21 | 常州市华健药用包装材料股份有限公司 | Visual environment-friendly medicinal composite membrane based on temperature-sensitive technology and processing technology thereof |
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Denomination of invention: A unidirectional water absorbing composite film and its preparation method and application Granted publication date: 20230324 Pledgee: Minhang Branch of Shanghai Rural Commercial Bank Co.,Ltd. Pledgor: SHANGHAI ZIJIANG COLOUR PRINTING & PACKAGING Co.,Ltd. Registration number: Y2024310000053 |
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