KR102622075B1 - Composite film for vacuum insulation panel with excellent gas barrier properties and adhesion strength - Google Patents

Abstract

The composite film for vacuum insulation panel according to the present invention includes a base layer including a base film, a natural product blocking layer provided on one side of the base layer, a natural product hydrogel and a silane-based coupling agent, and one side of the natural product blocking layer. A first adhesive layer provided on the base layer, a second adhesive layer provided on the other side of the base layer, a first blocking layer provided on one side of the first adhesive layer, and a second blocking layer provided on one side of the second adhesive layer. layer; wherein one side and the other side of the base film are surface treated by corona treatment or plasma treatment, and the natural product blocking layer may be in direct contact with one side of the surface treated base film.

Description

Composite film for vacuum insulation panels with excellent gas barrier properties and interlayer adhesive strength {COMPOSITE FILM FOR VACUUM INSULATION PANEL WITH EXCELLENT GAS BARRIER PROPERTIES AND ADHESION STRENGTH}

The present invention relates to a composite film for vacuum insulation panels with excellent gas barrier properties and interlayer adhesive strength.

[R&D project that supported this invention]

[Assignment identification number] D202073

[Ministry name] Gyeonggi-do

[Research management agency] Gyeonggi Province Economic and Science Promotion Agency

[Research project name] General business-led

[Research project name] Development of an eco-friendly film for vacuum insulation to replace imported metal films

[Contribution rate] 1/1

[Host organization] Everchemtech Co., Ltd.

[Research period] 2020.2.1~2021.5.31

The vacuum insulation panel maintains a vacuum around the core material by the outer skin and sealing material, so the thermal conductivity by gas is very low and the insulation performance is excellent. In order to maintain the insulation performance of such vacuum insulation panels, the inside of the insulation panel must be continuously maintained as a vacuum, so the gas barrier properties of the outer covering material are important.

In the case of conventional vacuum insulation panels, the outer covering material has been composed of a multilayer film containing metal deposition film or aluminum foil. However, in general, in a configuration using metal foil as a gas barrier layer, the amount of heat transmitted through the metal foil is large, so there is a problem in that the insulation effect of the vacuum insulation panel is impaired due to the so-called heat bridging phenomenon.

In addition, when manufacturing a vacuum insulation panel, the outer covering material must withstand the force of vacuum pressure, so the multilayer film constituting the outer covering material needs to have sufficient interlayer adhesive strength and sealing strength.

Accordingly, there is a need to develop a composite film for vacuum insulation panels with excellent gas barrier properties and interlayer adhesion strength.

The present invention provides a composite film for vacuum insulation panels with excellent interlayer adhesion and gas barrier properties.

However, the problem to be solved by the present invention is not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

One embodiment of the present invention includes a base layer including a base film; A natural product blocking layer provided on one side of the base layer and including a natural product hydrogel; A first adhesive layer provided on one side of the natural product blocking layer; a second adhesive layer provided on the other side of the base layer; a first blocking layer provided on one side of the first adhesive layer; and a second blocking layer provided on one surface of the second adhesive layer. It provides a composite film for a vacuum insulation panel including a.

The composite film for vacuum insulation panels according to an exemplary embodiment of the present invention may have excellent interlayer adhesion and gas barrier properties.

Additionally, the composite film for vacuum insulation panels according to an exemplary embodiment of the present invention may have excellent moisture barrier properties.

In addition, the composite film for vacuum insulation panels according to an embodiment of the present invention can be environmentally friendly and easily recycled.

However, the effects of the present invention are not limited to the effects described above, and may be expanded in various ways without departing from the spirit and scope of the present invention.

1 is a cross-sectional view of a composite film for a vacuum insulation panel according to an exemplary embodiment of the present invention.
Figure 2 is a diagram schematically showing the structure of a three-dimensional network structure included in a natural product blocking layer according to an embodiment of the present invention.
Figure 3 is a cross-sectional view of a composite film for a vacuum insulation panel according to an exemplary embodiment of the present invention.
Figure 4 is a cross-sectional view of a composite film for a vacuum insulation panel according to an exemplary embodiment of the present invention.
Figure 5a shows the results of measuring the IR spectrum of the natural product blocking layer prepared in Preparation Example 1, and Figure 5b shows the results of measuring the IR spectrum of the natural product blocking layer prepared in Comparative Preparation Example 1.
Figure 6A is a cross-sectional view of a sample for evaluating the interlayer adhesion of the composite film for a vacuum insulation panel of Example 1 and Comparative Example 1, and Figure 6B is a cross-sectional view of a sample for evaluating the interlayer adhesion of the composite film for a vacuum insulation panel of Comparative Example 2 am.

Throughout the specification of the present application, when a part is said to “include” a certain element, this means that it may further include other elements rather than excluding other elements, unless specifically stated to the contrary.

Throughout this specification, when a member is said to be located “on” another member, this includes not only the case where the member is in contact with the other member, but also the case where another member exists between the two members.

Throughout this specification, “layer” refers to a broad concept including “film, stretched sheet, unstretched sheet, or similar form.”

Hereinafter, the present invention will be described in more detail.

One embodiment of the present invention includes a base layer including a base film; A natural product blocking layer provided on one side of the base layer and including a natural product hydrogel; A first adhesive layer provided on one side of the natural product blocking layer; a second adhesive layer provided on the other side of the base layer; a first blocking layer provided on one side of the first adhesive layer; and a second blocking layer provided on one surface of the second adhesive layer. It provides a composite film for a vacuum insulation panel including a.

The composite film for vacuum insulation panels according to an exemplary embodiment of the present invention may have excellent interlayer adhesion and gas barrier properties. Specifically, interlayer adhesion between the base layer included in the composite film for vacuum insulation panel and the natural product barrier layer may be excellent.

Additionally, the composite film for vacuum insulation panels according to an exemplary embodiment of the present invention may have excellent moisture barrier properties.

In addition, the composite film for vacuum insulation panels according to an embodiment of the present invention can be environmentally friendly and easily recycled. Specifically, the composite film for vacuum insulation panels includes a natural product blocking layer, so that the composite film for vacuum insulation panels can be easily separated by immersing the composite film for vacuum insulation panels in water to dissolve the natural product blocking layer. , it can be recycled and environmentally friendly.

1 is a cross-sectional view of a composite film for a vacuum insulation panel according to an exemplary embodiment of the present invention. Referring to FIG. 1, the composite film 100 for a vacuum insulation panel according to an exemplary embodiment of the present invention includes a base layer 10, a natural product barrier layer 20, a first adhesive layer 31, and a second adhesive layer 32. , may include a first blocking layer 40 and a second blocking layer 50. Specifically, the composite film 100 for a vacuum insulation panel includes a first blocking layer 40, a first adhesive layer 31, a natural product blocking layer 20, a base layer 10, a second adhesive layer 32, and a second adhesive layer 32. The blocking layer 50 may be sequentially stacked.

The composite film for vacuum insulation panels according to an embodiment of the present invention has a structure in which a first blocking layer, a first adhesive layer, a natural product blocking layer, a base layer, a second adhesive layer, and a second blocking layer are stacked, Compared to composite films for vacuum insulation panels, interlayer adhesion, gas barrier properties, and moisture barrier properties can be superior. Specifically, the composite film for a vacuum insulation panel according to an embodiment of the present invention has a sandwich structure in which a natural product barrier layer and a base layer are provided between the first and second barrier layers, thereby comprising the base layer, the barrier layer, and the base layer. Compared to a composite film provided with coating layers sequentially and a composite film provided with a barrier layer between the first and second substrate layers, interlayer adhesion, gas barrier properties, and moisture barrier properties may be superior. In particular, by including the above-described laminated structure, the composite film for vacuum insulation panel can maintain excellent gas barrier properties even under humidity conditions of, for example, 40% to 60%.

According to an exemplary embodiment of the present invention, the base film may include at least one of a polyolefin-based film and a polyester-based film. For example, the polyolefin-based film may include at least one of a polyethylene film and a polypropylene film. Additionally, the polyester-based film may include at least one of a polyethylene terephthalate film, a polybutylene terephthalate film, and a polyethylene-2,6-nathalenedicarboxylate (PEN) film. When using the above-described types of films as the base film, ease of processing and durability of the composite film for vacuum insulation panels can be improved.

According to one embodiment of the present invention, the thickness of the base film may be 10 ㎛ or more and 50 ㎛ or less. Specifically, the thickness of the base film is 12 ㎛ to 50 ㎛, 15 ㎛ to 45 ㎛, 20 ㎛ to 40 ㎛, 20 ㎛ to 30 ㎛, 10 ㎛ to 40 ㎛, 15 ㎛ to 30 ㎛. , it may be 20 ㎛ or more and 50 ㎛ or less, 20 ㎛ or more and 45 ㎛ or less, or 25 ㎛ or more and 35 ㎛ or less. When the thickness of the base film is within the above-mentioned range, the mechanical properties of the composite film for vacuum insulation panel can be further improved.

According to an exemplary embodiment of the present invention, the natural product blocking layer is included in the composite film for the vacuum insulation panel, and may serve to block oxygen and moisture. The natural product blocking layer may include a natural product hydrogel. Specifically, the natural product blocking layer may include a three-dimensional network structure containing a natural product hydrogel. Through this, the oxygen barrier property of the natural product blocking layer can be further improved.

According to one embodiment of the present invention, the natural product blocking layer may include a cured product of a natural product composition containing the natural product and a silane-based coupling agent. Specifically, the natural product may be a raw material for manufacturing the natural product hydrogel, and the natural product barrier layer may include a thermoset (heat-treated product) of the natural product composition. More specifically, by heat-treating the natural product composition, a three-dimensional network structure in which a silane-based coupling agent is dispersed and crosslinked can be formed inside the natural product hydrogel derived from the natural product. That is, the three-dimensional network structure may include a natural hydrogel and a silane-based coupling agent. As described above, when the natural product blocking layer includes a three-dimensional network structure, the physical properties of the natural product blocking layer, such as mechanical properties and oxygen blocking ability, can be further improved.

Figure 2 is a diagram schematically showing the structure of a three-dimensional network structure included in a natural product blocking layer according to an embodiment of the present invention. Referring to FIG. 2, the natural product barrier layer may have a structure in which, for example, a silane-based coupling agent (2) is dispersed and cross-linked inside a protein hydrogel (1). The structure of the three-dimensional network structure can be confirmed from the IR spectrum analysis of Experimental Example 1, which will be described later.

According to one embodiment of the present invention, the natural product hydrogel may include at least one of protein and carbohydrate. Specifically, the natural product hydrogel may contain at least protein. In addition, the natural product, which is a raw material of the natural product hydrogel, may include at least one of the protein and the carbohydrate. Specifically, the natural product may include at least protein.

For example, the protein may include whey protein isolate (WPI), whey protein concentrate (WPC), soy protein isolate (SPI), rice protein isolate (RPI), and oat protein. At least one of oat protein isolate (OPI), pea protein isolate (PPI), casein, sodium caseinate, corn zein, gelatin, and wheat protein (gluten) It can contain one.

The protein is a polymer compound in which multiple amino acid units are linked by peptide bonds, and can exhibit excellent oxygen barrier properties due to the multiple peptide bonds. In addition, when forming a natural product barrier layer using a natural product composition containing the protein, hydrogen bonds or covalent bonds may be formed between the peptide bonds, and further, in the hydrogel structure containing a large amount of water, 3 A dimensional network structure can be formed. Through this, the oxygen blocking ability of the composite film for vacuum insulation panels including the natural product blocking layer can be effectively improved.

According to one embodiment of the present invention, the natural hydrogel may contain carbohydrates. Additionally, the natural product may contain carbohydrates. For example, the carbohydrate may include at least one of pullulan, carrageenan, chitosan, starch, agar, and pectin. By using a natural product hydrogel containing the carbohydrate, the mechanical properties of the natural product barrier layer can be improved.

According to one embodiment of the present invention, the content of the natural product included in the natural product composition may be 3 parts by weight or more and 30 parts by weight or less, and 3.5 parts by weight or more and 15 parts by weight or less, based on 100 parts by weight of the natural product composition. When the content of the natural product is within the above-mentioned range, the oxygen barrier property of the natural product barrier layer can be effectively improved.

According to one embodiment of the present invention, the natural product barrier layer may include a silane-based coupling agent. As described above, the natural product barrier layer may include the natural product hydrogel and the silane-based coupling agent dispersed and crosslinked within the natural product hydrogel. By using the silane-based coupling agent, the mechanical properties of the three-dimensional network structure included in the natural product barrier layer can be improved, and the oxygen barrier property of the natural product barrier layer can be improved.

The silane-based coupling agent may include a silane compound containing at least one functional group selected from the group consisting of a vinyl group, an amino group, an epoxy group, an acrylic group, a methacryl group, a methoxy group, an ethoxy group, a trimethoxy group, and a triethoxy group. For example, the silane-based coupling agent may include at least one of aminosilane, epoxy silane, and acrylic acid silane.

According to one embodiment of the present invention, the content of the silane-based coupling agent contained in the natural product composition is 5 parts by weight or more and 30 parts by weight or less, and 5 parts by weight or more and 15 parts by weight or less, based on 100 parts by weight of the natural product composition. You can. When the content of the silane-based coupling agent is within the above-mentioned range, the mechanical properties of the natural product barrier layer can be effectively improved.

According to one embodiment of the present invention, the weight ratio of the natural product and the silane-based coupling agent included in the natural product composition may be 10:1 to 1:10. Specifically, it may be 8:1 to 1:8, 5:1 to 1:5, or 3:1 to 1:3. Additionally, the content of the silane-based coupling agent included in the natural product composition may be greater than the content of the natural product. Specifically, the weight ratio of the natural product and the silane-based coupling agent contained in the natural product composition is 1:1.1 to 1:10, 1:1.5 to 1:8, 1:1.5 to 1:5, or 1:1.5 to 1. :3. When the weight ratio of the natural product and the silane-based coupling agent included in the natural product composition is within the above-mentioned range, the adhesion of the natural product barrier layer to the base layer can be effectively improved, and the gas (oxygen) of the natural product barrier layer can be effectively improved. Blocking properties can be effectively improved.

According to one embodiment of the present invention, the natural product composition may include a filler. The filler includes at least one of sorbitol, fructose, sucrose, mannitol, propylene glycol, glycerol, and polyethylene glycol. can do.

The filler is disposed in the holes between the natural hydrogel three-dimensional network structure and fills the voids, thereby increasing the oxygen barrier property of the natural product barrier layer and smoothing the surface. can play a role.

According to one embodiment of the present invention, the content of the filler may be 3 parts by weight or more and 30 parts by weight or less, and 3.5 parts by weight or more and 15 parts by weight or less, based on 100 parts by weight of the natural product composition. When the content of the filler satisfies the above range, the mechanical properties and oxygen barrier properties of the composite film for vacuum insulation panels can be improved. In addition, when the content of the filler is within the above-mentioned range, the phenomenon of the natural product barrier layer being cracked and peeled off from the base layer can be suppressed, and when the composite film for a vacuum insulation panel is stored for a long period of time, the filler is applied to the surface of the natural product barrier layer. It is possible to prevent the oxygen barrier property from deteriorating by migrating to .

According to one embodiment of the present invention, the method of manufacturing the natural product barrier layer includes the steps of adding a silane-based coupling agent and a filler to a natural product aqueous solution containing a natural product that is a raw material of a natural product hydrogel to prepare a natural product composition; Preparing a natural product composition including the heat-treated product by heat treating and cooling the natural product composition; And it may include preparing a natural product barrier layer by applying a natural product composition containing a heat-treated product to the base layer and drying it. Through the above-described method, a natural product barrier layer can be easily manufactured, and a natural product barrier layer with excellent oxygen barrier properties and excellent adhesion to the base layer can be manufactured.

The contents of the natural product, silane-based coupling agent, and filler contained in the natural product composition are the same as described above.

Distilled water or purified water can be used as a solvent for the aqueous solution of the natural product. The content of the solvent may be 50 parts by weight or more and 99 parts by weight or less, or 70 parts by weight or more and 90 parts by weight or less, based on 100 parts by weight of the natural product composition.

A natural product composition containing a heat-treated product can be prepared by heat treatment and then cooling to ensure sufficient chemical reaction between the components included in the natural product composition. The heat treatment may be performed for 1 to 5 hours at a temperature of 70°C or higher and 120°C or lower. Specifically, the heat treatment may be performed for 2 to 3 hours at a temperature of 80°C or more and 100°C or less. By adjusting the heat treatment temperature and time range within the above-mentioned range, the mechanical properties of the natural product barrier layer can be improved.

Meanwhile, the natural product blocking layer may be manufactured as follows. For example, the natural product composition can be manufactured in a one-step reaction in which the coating agent is directly performed by inducing a natural product-silane coupling agent reaction simultaneously with the hydrolysis reaction of the silane coupling agent. Alternatively, the natural product composition can be prepared in a two-step reaction in which a hydrolyzed silane-based coupling agent is first prepared, the reaction of the natural product-silane-based coupling agent is sufficiently completed, and then the coating agent is prepared.

The natural product composition can be applied on the base layer through a method used in the art. For example, it may be applied by spin coating, spray coating, dip coating, slit coating, slot die coating, bar coating, etc., but applying the natural composition This does not limit the method.

After applying the natural product composition on the base layer, the natural product composition can be dried to prepare a natural product barrier layer containing a heat-cured product (heat-treated product) of the natural product composition.

According to one embodiment of the present invention, the thickness of the natural product blocking layer may be 1 ㎛ or more and 10 ㎛ or less. Specifically, the thickness of the natural product blocking layer may be 1 ㎛ or more and 8 ㎛ or less, 1 ㎛ or more and 5 ㎛ or less, 1 ㎛ or more and 3 ㎛ or less, or 5 ㎛ or more and 10 ㎛ or less. When the thickness of the natural product blocking layer is within the above-mentioned range, interlayer adhesion between the natural product blocking layer and the base layer can be effectively improved, and the gas barrier property of the composite film for vacuum insulation panel can be further improved.

According to one embodiment of the present invention, the thickness ratio of the natural product blocking layer and the base film may be 1:10 to 1:50. Specifically, the thickness ratio of the natural product blocking layer and the base film is 1:20 to 1:40, 1:25 to 1:35, 1:15 to 1:25, 1:20 to 1:30, and 1:10. to 1:25, or 1:15 to 1:30. When the thickness ratio of the natural product blocking layer and the base film is within the above-mentioned range, it is possible to effectively prevent the interlayer adhesion between the natural product blocking layer and the base layer from decreasing, and during the processing process of the composite film for vacuum insulation panel, It is possible to effectively prevent peeling of the natural product blocking layer from the base layer.

According to one embodiment of the present invention, each of the first adhesive layer and the second adhesive layer may independently include at least one of an oil-based adhesive and a water-based adhesive. Specifically, each of the first adhesive layer and the second adhesive layer is independently made of polyurethane-based resin, polyamide-based resin, ethylene-vinyl acetate-based resin, and polyvinyl acetate. acetate-based resin, phenol-based resin, melamine-based resin, urea-based resin, epoxy-based resin, polyester-based resin, polyvinyl alcohol-based resin , acrylonitrile butadiene rubber (NBR), styrene butadiene rubber (SBR), alkyd, acetyl cellulose, nitro cellulose, starch and hot melt thermoplastic polyurethane. ) may include at least one of the resins. The oil-based adhesive layer may be formed using an oil-based adhesive known in the art. For example, the oil-based adhesive layer may include an oil-based polyurethane-based resin. The water-based adhesive layer may include a water-based adhesive known in the art. For example, it may include water-based polyurethane resin, polyvinylpyrrolidone resin, polyvinyl alcohol resin, water-based acrylic resin, epoxy resin, phenol resin, starch, or a combination thereof.

According to an exemplary embodiment of the present invention, the first adhesive layer and the second adhesive layer may each include a cured product of the adhesive composition. The adhesive composition may include an adhesive and a curing agent. The adhesive may include a polyester-based resin, and the curing agent may include a polyisocyanate-based curing agent. The composite film for vacuum insulation panels including the first adhesive layer and the second adhesive layer formed from the adhesive composition may have excellent interlayer adhesion and sealing strength.

According to one embodiment of the present invention, the weight ratio of the curing agent and the adhesive included in the adhesive composition may be 1:3 to 1:15. Specifically, the weight ratio of the curing agent and the adhesive is 1:5 to 1:13, 1:7.5 to 1:10, 1:3 to 1:10, 1:5.5 to 1:10, and 1:5 to 1:15. , or 1:7.5 to 1:13. When the weight ratio of the curing agent and the adhesive included in the adhesive composition is within the above-mentioned range, the adhesive strength of the first and second adhesive layers containing the cured product of the adhesive composition can be effectively improved.

According to one embodiment of the present invention, based on 100 parts by weight of the adhesive composition, the content of the adhesive may be 30 parts by weight or more and 50 parts by weight or less. Specifically, based on 100 parts by weight of the adhesive composition, the content of the adhesive is 35 parts by weight or more and 47.5 parts by weight or less, 37.5 parts by weight or more and 45 parts by weight or less, 30 parts by weight or more and 45 parts by weight or less, or 40 parts by weight or more and 50 parts by weight. It may be less than one part by weight. By adjusting the content of the adhesive within the above-described range, the adhesive strength of the first and second adhesive layers can be improved.

According to one embodiment of the present invention, based on 100 parts by weight of the adhesive composition, the content of the curing agent may be 3 parts by weight or more and 10 parts by weight or less. Specifically, based on 100 parts by weight of the adhesive composition, the content of the curing agent is 3.5 parts by weight or more and 8.5 parts by weight or less, 5 parts by weight or more and 7 parts by weight or less, 3 parts by weight or more and 6 parts by weight or less, or 5 parts by weight or more and 10 parts by weight. It may be less than one part by weight. When the content of the curing agent is within the above-mentioned range, curing of the adhesive composition can be performed stably, and deterioration of the adhesive strength of the first and second adhesive layers can be effectively prevented.

According to one embodiment of the present invention, the adhesive composition may include a solvent. The solvent may be any solvent used in the art without limitation. For example, ethyl acetate may be used as the solvent, but the type of solvent is not limited. Based on 100 parts by weight of the adhesive composition, the content of the solvent may be 40 parts by weight or more and 60 parts by weight or less. By adjusting the content of the solvent within the above-mentioned range, the coating properties of the adhesive composition can be improved, and the surfaces of the first and second adhesive layers to be manufactured can be formed more flat.

According to one embodiment of the present invention, the thickness of each of the first adhesive layer and the second adhesive layer may be 1 ㎛ or more and 10 ㎛ or less. Specifically. The thickness of each of the first adhesive layer and the second adhesive layer may be 2 ㎛ or more and 9 ㎛ or less, 3 ㎛ or more and 7 ㎛ or less, 1 ㎛ or more and 5 ㎛ or less, 1 ㎛ or more and 3 ㎛ or less, or 5 ㎛ or more and 10 ㎛ or less. When the thickness of each of the first and second adhesive layers is within the above-mentioned range, the interlayer adhesion and sealing strength of the composite film for vacuum insulation panel can be prevented from being reduced.

According to one embodiment of the present invention, the thickness ratio of the natural product blocking layer and the first adhesive layer may be 1:1 to 1:10. Specifically, the thickness ratio of the natural product blocking layer and the first adhesive layer is 1:2 to 1:8, 1:3 to 1:6, 1:2 to 1:5, 1:2.5 to 1:4.5, 1: It may be 3 to 1:4, 1:2 to 1:3, or 1:3 to 1:5. When the thickness ratio of the natural product barrier layer and the first adhesive layer is within the above-mentioned range, the gas barrier performance and moisture barrier ability of the composite film for vacuum insulation panel are suppressed from being reduced, while the adhesion between the natural product barrier layer and the first adhesive layer is improved. This can effectively improve the sealing strength of the composite film for vacuum insulation panels.

Figure 3 is a cross-sectional view of a composite film for a vacuum insulation panel according to an exemplary embodiment of the present invention. Referring to FIG. 3, the base layer 10 includes a base film 11, a primer layer 12a provided on one side of the base film 11, and a primer layer 12b provided on the other side of the base film 11. It can be included. Additionally, the first blocking layer 40 may include a first base film 41 and a first inorganic blocking layer 42 provided on one surface of the first base film 41. Additionally, the second blocking layer 50 may include a second base film 51 and a second inorganic blocking layer 52 provided on one surface of the second base film 51. Referring to Figure 3, the composite film 100 for a vacuum insulation panel includes a first base film 41, a first inorganic barrier layer 42, a first adhesive layer 31, a natural product barrier layer 20, and a primer layer ( 12a), the base film 11, the primer layer 12b, the second adhesive layer 32, the second inorganic barrier layer 52, and the second base film 51 may be sequentially stacked.

According to one embodiment of the present invention, the base layer includes a primer layer provided on one side and the other side of the base film, and the natural product blocking layer may be provided in direct contact with the primer layer. By providing a primer layer on one side and the other side of the base film, the adhesion to the natural product blocking layer and the second adhesive layer can be effectively improved. Through this, the interlayer adhesion and sealing strength of the composite film for vacuum insulation panels can be further improved.

The primer layer may include a urethane-based primer. By introducing the primer layer containing a urethane-based primer on one side and the other side of the base film, the adhesion of the base layer to the natural product blocking layer and the second adhesive layer can be effectively improved as described above. Meanwhile, a primer layer used in the art may be used as the primer layer.

According to one embodiment of the present invention, one side and the other side of the base film are surface treated by corona treatment or plasma treatment, and the natural product blocking layer may be provided in direct contact with one side of the surface treated base film. By surface treating one side and the other side of the base film with corona treatment or plasma treatment, the adhesion to the natural product blocking layer and the second adhesive layer can be effectively improved. Through this, the interlayer adhesion and sealing strength of the composite film for vacuum insulation panels can be further improved. The method of corona-treating one side and the other side of the base film may be performed through a corona treatment method used in the industry, and the method of plasma treatment may be performed through a plasma treatment method used in the industry.

According to an exemplary embodiment of the present invention, the first blocking layer includes: a first base film; and a first inorganic blocking layer provided on the first base film and containing an inorganic material, wherein the first inorganic blocking layer may be provided on the first adhesive layer.

The first base film may include at least one of a polyolefin-based film and a polyester-based film. For example, the polyolefin-based film may include at least one of a polyethylene film and a polypropylene film. Additionally, the polyester-based film may include at least one of a polyethylene terephthalate film, a polybutylene terephthalate film, and a polyethylene-2,6-nathalenedicarboxylate (PEN) film. When using the above-described type of film as the first base film, ease of processing and durability of the composite film for vacuum insulation panel can be improved.

According to one embodiment of the present invention, the thickness of the first base film may be 5 ㎛ or more and 20 ㎛ or less. Specifically, the thickness of the first base film is 7.5 ㎛ or more and 17.5 ㎛ or less, 10 ㎛ or more and 15 ㎛ or less, 5 ㎛ or more and 15 ㎛ or less, 8 ㎛ or more and 13 ㎛ or less, 10 ㎛ or more and 20 ㎛ or less, or 10 ㎛ or more. It may be 17.5 ㎛ or less. By using the first base film having a thickness in the above-described range, it is possible to prevent deterioration in durability and constructability of the composite film for vacuum insulation panels.

According to an exemplary embodiment of the present invention, the first inorganic blocking layer may include an inorganic material. Specifically, the first inorganic blocking layer may include silicon oxide or aluminum oxide. For example, the silicon oxide is SiO _x , and x may be a real number between 1 and 2. In addition, the aluminum oxide is Al _y O _z , and y and z may be real numbers of 1 to 3. By using the first inorganic barrier layer containing the above-mentioned inorganic material, the gas barrier property of the composite film for vacuum insulation panel can be effectively improved.

According to one embodiment of the present invention, the thickness ratio of the first base film and the base film may be 5:1 to 1:5. Specifically, the thickness ratio of the first base film and the base film is 4:1 to 1:4, 3:1 to 1:3, 2:1 to 1:2, 1:1.5 to 1:5, 1: It may be 2 to 1:4, 1:2 to 1:3, 1:1.5 to 1:3, or 1:1.5 to 1:2. When the thickness ratio of the first base film and the base film is within the above-described range, durability of the composite film for a vacuum insulation panel can be improved and processability can be suppressed from being deteriorated.

According to an exemplary embodiment of the present invention, the second blocking layer includes a second base film; and a second inorganic blocking layer provided on the second base film and containing an inorganic material, wherein the second inorganic blocking layer may be provided on the second adhesive layer.

The second base film may include at least one of a polyolefin-based film and a polyester-based film. For example, the polyolefin-based film may include at least one of a polyethylene film and a polypropylene film. Additionally, the polyester-based film may include at least one of a polyethylene terephthalate film, a polybutylene terephthalate film, and a polyethylene-2,6-nathalenedicarboxylate (PEN) film. When using the above-described type of film as the second base film, ease of processing and durability of the composite film for vacuum insulation panel can be improved.

According to an exemplary embodiment of the present invention, the thickness of the second base film may be 5 ㎛ or more and 20 ㎛ or less. Specifically, the thickness of the second base film is 7.5 ㎛ or more and 17.5 ㎛ or less, 10 ㎛ or more and 15 ㎛ or less, 5 ㎛ or more and 15 ㎛ or less, 8 ㎛ or more and 13 ㎛ or less, 10 ㎛ or more and 20 ㎛ or less, or 10 ㎛ or more. It may be 17.5 ㎛ or less. By using a second base film having a thickness in the above-described range, it is possible to prevent deterioration in durability and constructability of the composite film for vacuum insulation panels.

According to one embodiment of the present invention, the second inorganic blocking layer may include an inorganic material. Specifically, the second inorganic blocking layer may include silicon oxide or aluminum oxide. For example, the silicon oxide is SiO _x , and x may be a real number between 1 and 2. In addition, the aluminum oxide is Al _y O _z , and y and z may be real numbers of 1 to 3. By using the second inorganic barrier layer containing the above-mentioned inorganic material, the gas barrier property of the composite film for vacuum insulation panel can be effectively improved.

According to one embodiment of the present invention, the thickness ratio of the second base film and the base film may be 5:1 to 1:5. Specifically, the thickness ratio of the second base film and the base film is 4:1 to 1:4, 3:1 to 1:3, 2:1 to 1:2, 1:1.5 to 1:5, 1: It may be 2 to 1:4, 1:2 to 1:3, 1:1.5 to 1:3, or 1:1.5 to 1:2. When the thickness ratio of the second base film and the base film is within the above-described range, durability of the composite film for a vacuum insulation panel can be improved while processability can be suppressed from being deteriorated.

According to one embodiment of the present invention, the composite film for a vacuum insulation panel is provided with the first blocking layer on one side of the natural product blocking layer and a second blocking layer on the other side of the natural product blocking layer, thereby reducing moisture permeability. can be reduced, and through this, a decrease in the gas (oxygen) blocking ability of the natural product blocking layer can be effectively suppressed.

Figure 4 is a cross-sectional view of a composite film for a vacuum insulation panel according to an exemplary embodiment of the present invention. Referring to FIG. 4 , the first blocking layer 40 may include a first base film 41, a first inorganic blocking layer 42, and a first protective layer 43. Additionally, the second blocking layer 50 may include a second base film 51, a second inorganic blocking layer 52, and a second protective layer 53.

According to one embodiment of the present invention, the first blocking layer may include a first protective layer provided on one surface of the first inorganic blocking layer. Additionally, the second blocking layer may include a second protective layer provided on one surface of the second inorganic blocking layer. By providing a first protective layer on one side of the first inorganic barrier layer and a second protective layer on one side of the second inorganic layer, the moisture barrier ability of the first and second barrier layers is effectively improved. You can do it. As the first protective layer and the second protective layer, any configuration having the ability to block moisture in the art can be used without limitation.

According to one embodiment of the present invention, the composite film for vacuum insulation panels may be a film for food packaging materials. As described above, the composite film for vacuum insulation panels has excellent interlayer adhesion, oxygen barrier properties, and gas barrier properties, and can be easily applied as a film for food packaging materials.

Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention may be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of this specification are provided to more completely explain the present invention to those skilled in the art.

Manufacturing example

Preparation of natural compositions

Manufacturing Example 1

A natural product aqueous solution was prepared by slowly adding 5 g of whey protein as a natural product to 92 g of distilled water and stirring. 8 g of amino silane as a silane-based coupling agent was added and dissolved in the natural product aqueous solution, and then 5 g of sorbitol was added as a filler to prepare a natural product composition. The pH was adjusted to 9 by adding 1N NaOH to the natural product composition. Thereafter, the pH-adjusted natural product composition was stirred using a mechanical stirrer at 300 rpm, heated at 90° C. for 120 minutes, and then cooled to room temperature to prepare a natural product composition containing the heat-treated product.

Comparative Manufacturing Example 1

A natural product composition containing a heat-treated product was prepared in the same manner as Preparation Example 1, except that the silane-based coupling agent was not added.

Preparation of adhesive composition

Production example 2

TM-585-60K-S (Toyo INK), a polyester resin, was prepared as an adhesive, CAT-10 (Toyo INK), a polyisocyanate-based curing agent, and ethyl acetate as a solvent. Afterwards, 21.2 g of ethyl acetate was added to the beaker, the beaker and impeller were set on a stirrer, and the mixture was stirred at 300 rpm. 18 g of adhesive and 2.2 g of hardener were sequentially added to the stirring solvent at 3-minute intervals and stirred for 10 minutes to prepare an adhesive composition.

Example 1

A base layer (SH86; SKC) provided with a primer layer containing a urethane primer was prepared on one side and the other side of a polyethylene terephthalate film with a thickness of 23 ㎛.

An inorganic film (Seoil Co., Ltd.) in which aluminum oxide was deposited on one side of a polyethylene terephthalate (PET) film with a thickness of 12 ㎛ was prepared as a first and second blocking layer.

The natural product composition prepared in Preparation Example 1 was coated on the primer layer of the prepared base layer using an applicator (YBA-5). Thereafter, the base layer coated with the natural product composition was placed in an oven and dried at 100° C. for 3 minutes to prepare a base layer equipped with a natural product blocking layer with a thickness of 1 μm.

The adhesive composition prepared in Preparation Example 2 was coated on the first inorganic blocking layer (aluminum oxide deposition layer) of the prepared first blocking layer using a bar coater. Thereafter, the first blocking layer coated with the adhesive composition was placed in an oven and heat treated at 80° C. for 5 seconds to prepare a first blocking layer provided with a first adhesive layer. Thereafter, a second blocking layer provided with a second adhesive layer was manufactured in the same manner as above.

Fixing the first blocking layer with the first adhesive layer on a flat plate, stacking the base layer with the natural product blocking layer on the first blocking layer so that the natural product blocking layer is in contact with the first adhesive layer, and first lamination using the dry lamination method. did.

The first laminated laminate is fixed to a flat plate, and a second blocking layer provided with a second adhesive layer is applied to the primer of the first laminated laminate so that the second adhesive layer is in contact with the exposed primer layer of the first laminated laminate. The composite film for the vacuum insulation panel shown in FIG. 3 was manufactured by stacking the layers on top of each other and secondary lamination using a dry lamination method. At this time, the thickness of the first adhesive layer and the second adhesive layer after dry lamination were each 3 ㎛.

Thereafter, the composite film for vacuum insulation panel was aged at 40° C. for 3 days to finally prepare the composite film for vacuum insulation panel.

Comparative Example 1

In Example 1, a composite film for a vacuum insulation panel was manufactured in the same manner as Example 1, except that the natural product composition prepared in Comparative Preparation Example 1 was used instead of the natural product composition prepared in Preparation Example 1.

Comparative Example 2

A composite film for a vacuum insulation panel was manufactured in the same manner as in Example 1, except that a base layer without a primer layer was used in Example 1.

Comparative Example 3

The primary laminated laminate (first blocking layer/first adhesive layer/natural product blocking layer/base layer with primer layer on both sides) prepared in Example 1 was aged at 40°C for 3 days, A composite film for vacuum insulation panels was prepared.

Experiment example

Experimental Example 1: IR spectrum analysis

IR spectra were measured for the base layer provided with the natural product blocking layer prepared in Example 1 and the base layer provided with the natural product blocking layer prepared in Comparative Example 1 to confirm whether crosslinking was present. The results are shown in Figures 5a and 5b, respectively.

Figure 5a shows the results of measuring the IR spectrum of the natural product blocking layer prepared in Preparation Example 1, and Figure 5b shows the results of measuring the IR spectrum of the natural product blocking layer prepared in Comparative Preparation Example 1.

Referring to Figures 5a and 5b, the natural product blocking layer of Example 1 showed a higher peak at 900 to 1200 cm ^-1 corresponding to the CN bond compared to the natural product blocking layer of Comparative Example 1, and the peak peak was observed at 2800 cm -1 corresponding to the CH bond. It was confirmed that the peak appeared high at 3000 cm ^-1 .

Through this, it can be confirmed that the natural product barrier layer of Example 1 has a structure in which a silane-based coupling agent is dispersed and cross-linked inside a protein hydrogel with a three-dimensional network structure.

Experimental Example 2: Evaluation of interlayer adhesion strength

Figure 6A is a cross-sectional view of a sample for evaluating the interlayer adhesion of the composite film for a vacuum insulation panel of Example 1 and Comparative Example 1, and Figure 6B is a cross-sectional view of a sample for evaluating the interlayer adhesion of the composite film for a vacuum insulation panel of Comparative Example 2 am.

As shown in FIGS. 6A and 6B, when manufacturing the composite film for vacuum insulation panel of Example 1, Comparative Example 1, and Comparative Example 2, the ends of the first adhesive layer and the second adhesive layer are 30 mm from the outside. By spacing them apart (d), samples for evaluating the interlayer adhesion strength were prepared.

Afterwards, the peel strength of the first adhesive layer and the second adhesive layer was measured through the T-Peel Test, and the results are shown in Tables 1 and 2 below.

Example 1 first adhesive layer second adhesive layer Peel strength
(gf/25mm) 798 582 Whether peeling or not peel peel

Comparative Example 1 Comparative Example 2 first adhesive layer second adhesive layer first adhesive layer second adhesive layer Peel strength
(gf/25mm) 221.67 850.32 840 618 Whether peeling or not complete delamination peel partial delamination partial delamination

Referring to Tables 1 and 2, in Example 1 in which a primer layer was introduced into the base layer, it was confirmed that the first adhesive layer and the second adhesive layer did not peel off from the adjacent layer during the interlayer adhesive strength evaluation process.

On the other hand, in the case of Comparative Example 1 using the natural product composition prepared in Comparative Preparation Example 1 without adding a silane-based coupling agent, a primer layer was introduced into the base layer, but in the process of evaluating the interlayer adhesion strength, the first adhesive layer was separated from the natural product barrier layer. It was confirmed that it was completely peeled off.

In addition, in the case of Comparative Example 2 in which the primer layer was not introduced into the base layer, it was confirmed that the first adhesive layer and the second adhesive layer were partially separated from the adjacent layer by about 2 cm during the interlayer adhesive strength evaluation process.

In Tables 1 and 2, the peel strength measured in Example 1, Comparative Example 1, and Comparative Example 2 refers to the peel strength measured at the point when the PET film of the first blocking layer is torn during the interlayer adhesion strength evaluation process. do. Referring to Table 2, it was confirmed that Comparative Example 2 had a higher peel strength from the first adhesive layer and the second adhesive layer compared to Example 1. However, as partial peeling occurred in Comparative Example 2, the peel strength was greater. You can see that it was measured.

Through this, it can be seen that the composite film for vacuum insulation panels according to an exemplary embodiment of the present invention has excellent interlayer adhesive strength.

Experimental Example 3: Evaluation of oxygen barrier property (barrier property) and moisture barrier property (barrier property)

For the composite films for vacuum insulation panels prepared in Example 1 and Comparative Example 3, oxygen permeability and moisture permeability were measured through the following method.

Oxygen permeability evaluation method: The oxygen permeability was evaluated from the results of measuring the oxygen permeability using an OXTRAN 2/21 oxygen permeability tester from MOCON. The oxygen permeability indicates the amount of oxygen in the composite film for vacuum insulation panels for 24 hours under the conditions of a temperature of 23 ± 1 ℃, humidity (relative humidity) of 0% and 50%, and O ₂ concentration of 100%.

Water permeability evaluation method: The water permeability was evaluated from the results of measuring the water permeability using a PERMATRAN-W 3/34G permeability tester from MOCON. The moisture permeability refers to the amount of moisture that permeates the composite film for vacuum insulation panels per unit time under the conditions of a temperature of 38 ± 1 °C and a humidity of 100%.

oxygen permeability
(cc/m ² ·day) moisture permeability
(g/m ² ·day) 23℃/
RH 0% 23℃/
RH 50% 38℃ Example 1 0.06 0.08 0.9309 Comparative Example 3 0.12 0.42 2.1989

Referring to Table 3, it can be seen that the composite film for vacuum insulation panels prepared in Example 1 has low oxygen permeability and moisture permeability compared to the composite film for vacuum insulation panels prepared in Comparative Example 3. In particular, it can be seen that the acid permeability of the composite film for vacuum insulation panels prepared in Example 1 under 50% relative humidity conditions is about 5 times lower than that of the composite film for vacuum insulation panels prepared in Comparative Example 3.

Through this, it can be seen that the composite film for vacuum insulation panels according to an embodiment of the present invention has excellent oxygen barrier properties and moisture barrier properties.

The foregoing detailed description illustrates and explains the invention. In addition, the foregoing merely shows and describes preferred embodiments of the present invention, and as described above, the present invention can be used in various other combinations, modifications, and environments, and the scope and scope of the inventive concept disclosed in this specification. Changes or modifications may be made within the scope of equivalent disclosure and/or skill or knowledge in the art. Accordingly, the above detailed description of the invention is not intended to limit the invention to the disclosed embodiments. Additionally, the appended claims should be construed to include other embodiments as well.

100: Composite film for vacuum insulation panels
1: Protein hydrogel of three-dimensional network structure
2: Cross-linked silane-based coupling agent
10: base layer 11: base film
12a, 12b: Primer layer 20: Natural product blocking layer
31: first adhesive layer 32: second adhesive layer
40: first blocking layer 41: first base film
42: first inorganic blocking layer 43: first protective layer
50: second blocking layer 51: second base film
52: second inorganic blocking layer 53: second protective layer

Claims (10)

A base layer including a base film;
A natural product blocking layer provided on one side of the base layer and containing a natural product hydrogel and a silane-based coupling agent;
A first adhesive layer provided on one side of the natural product blocking layer;
a second adhesive layer provided on the other side of the base layer;
a first blocking layer provided on one side of the first adhesive layer; and
It includes; a second blocking layer provided on one surface of the second adhesive layer,
One side and the other side of the base film are surface treated by corona treatment or plasma treatment,
A composite film for a vacuum insulation panel, wherein the natural product blocking layer is provided in direct contact with one side of the surface-treated base film. According to paragraph 1,
A composite film for a vacuum insulation panel, wherein the thickness ratio of the natural product blocking layer and the first adhesive layer is 1:1 to 1:10. According to paragraph 1,
The base film is a composite film for a vacuum insulation panel comprising at least one of a polyolefin-based film and a polyester-based film. According to paragraph 1,
The first blocking layer is,
first base film; and
A first inorganic blocking layer provided on the first base film and containing an inorganic material,
The first inorganic blocking layer is a composite film for a vacuum insulation panel, wherein the first inorganic blocking layer is provided on the first adhesive layer. According to paragraph 4,
A composite film for a vacuum insulation panel, wherein the thickness ratio of the first base film and the base film is 5:1 to 1:5. According to paragraph 1,
The second blocking layer is,
second base film; and
It includes a second inorganic blocking layer provided on the second base film and containing an inorganic material,
The second inorganic blocking layer is a composite film for a vacuum insulation panel, wherein the second inorganic blocking layer is provided on the second adhesive layer. According to clause 6,
A composite film for a vacuum insulation panel, wherein the thickness ratio of the second base film and the base film is 5:1 to 1:5. According to paragraph 1,
The natural hydrogel is a composite film for a vacuum insulation panel, wherein the natural hydrogel contains at least one of protein and carbohydrate. According to paragraph 1,
The natural product blocking layer is,
A composite film for vacuum insulation panels comprising a cured product of a natural product composition containing a natural product and a silane-based coupling agent. According to clause 9,
A composite film for a vacuum insulation panel, wherein the weight ratio of the natural product and the silane-based coupling agent is 10:1 to 1:10.