JP4677738B2 - Vacuum insulator exterior and vacuum insulator - Google Patents

Description

  The present invention relates to an exterior body for a vacuum heat insulating material that is attached to a refrigerator, a low temperature container or the like and exhibits a heat insulating effect.

  Conventionally, various heat insulating materials have been used for refrigerators, low temperature containers, etc. Especially, as a heat insulating material with excellent heat insulating performance, a heat insulating core material is enclosed in the exterior body, and the inside is evacuated Vacuum insulation is used.

  The exterior body needs to be excellent in gas barrier properties in order to prevent ingress of gas (air) from the outside and keep the inside in a vacuum state for a long time.

  The gas barrier material is roughly divided into a barrier resin film, a vapor deposition film, and a metal foil laminated film. When a normal gas barrier property is required, a barrier resin film can be used.

  For example, among the barrier resin films, a polyvinylidene chloride resin film (PVDC) and a vinyl alcohol resin film, which are relatively excellent in gas barrier properties, are often used.

  Examples of the vinyl alcohol resin film include a polyvinyl alcohol film (PVA) and an ethylene / vinyl alcohol copolymer film (EVOH).

  The polyvinylidene chloride resin film (PVDC) includes an extruded film of polyvinylidene chloride resin and a K coat film in which various plastic films are coated with polyvinylidene chloride resin.

  Among the vinyl alcohol resin films, the polyvinyl alcohol film (PVA) has low chargeability, excellent transparency, and the best gas barrier property in the dry state, but has high hygroscopicity and high It has the disadvantage that barrier properties and mechanical strength are reduced under humidity.

  In addition, the ethylene-vinyl alcohol copolymer film (EVOH) is copolymerized with ethylene in order to improve the deterioration of the barrier property of the polyvinyl alcohol film under high humidity, compared to other barrier resins. Good extrudability.

  However, when a high gas barrier property is required to maintain the degree of vacuum inside, as in a vacuum heat insulating material, the barrier resin film as described above cannot obtain a sufficient gas barrier property. As the gas barrier layer, an aluminum vapor deposition film in which an aluminum metal foil having a thickness of about 7 to 20 μm or aluminum is vapor-deposited on a resin film by a vacuum vapor deposition method or the like is used.

  However, the laminated film obtained by laminating the above aluminum metal foil and aluminum vapor-deposited film has excellent gas barrier properties. However, since any laminated film includes an aluminum layer having a high thermal conductivity, an exterior using the laminated film. The heat conductivity of the body also increases, and the vacuum heat insulating material using these exterior bodies has a problem that heat leaks easily through the exterior body in the thickness direction.

  In particular, in the case of using an aluminum vapor deposition film, which is noticeable with aluminum foil and has relatively small problems, there has been a problem when the panel size of the vacuum heat insulating material is small.

  For example, as a conventional laminated film structure, ONy 15 μm // ONy 25 μm // AL 6 μm // LLDPE 50 μm, or ONy 25 μm // VM-PET 12 μm // VM-EVOH 12 μm // LLDPE 50 μm Used to indicate lamination).

  Therefore, for the purpose of solving this problem, a method of using a stainless steel foil or the like having a low thermal conductivity for the gas barrier layer of the outer package (see, for example, Patent Document 1), a method of using a glass deposition film (for example, a patent) Document 2) has been proposed.

Prior art documents are shown below.
JP-A-8-159376 JP-A-7-113493

  However, in the method using a stainless steel foil or the like, the thermal conductivity of the stainless steel is still large, so that the reduction of the heat conduction (heat bridge) is insufficient.

  In addition, in the method using the vapor deposition film of glass, the reduction of the heat bridge is sufficient, but the gas barrier property is insufficient due to the presence of pinholes and cracks in the vapor deposition film, and over the long term, It was impossible to keep the inside in a vacuum state.

  Furthermore, if the heat insulating core material is vacuum degassed and the wrapping material is formed along the irregularities of the core material to form a convex portion, it may be rubbed during the manufacturing process or transportation, causing pinholes.

  Furthermore, when the film is laminated with any number of layers, the film becomes hard and a pinhole is likely to be generated.

  The present invention is intended to solve such problems of the prior art, and provides an inexpensive outer package for vacuum heat insulating material that is excellent in heat insulation, pinhole resistance, and abrasion resistance.

  The present invention has been made to solve the above problems, and the invention according to claim 1 of the present invention is composed of a multilayer sheet comprising an inner layer (B) and an outer layer (A) having gas barrier properties. The vacuum heat insulating material exterior body (E), wherein the multilayer sheet has a non-adhesive portion (air layer) (6) between the inner layer (B) and the outer layer (A). This is an exterior body for a heat insulating material.

  The invention according to claim 2 of the present invention is the exterior body for a vacuum heat insulating material according to claim 1, wherein the multilayer sheet is formed on a support layer (3) made of a synthetic resin material, a gas barrier layer (4), and a sealant. It is composed of an inner layer (B) obtained by sequentially laminating layers (5) and an outer layer (A) comprising a base material layer (1) of a synthetic resin material, and further laminated via a partial adhesive layer (2). It is for vacuum heat insulating materials characterized by being made.

According to a third aspect of the present invention, there is provided the vacuum insulator exterior body according to the first aspect, wherein the multilayer sheet is formed on the resin layer (7) made of a synthetic resin material, the gas barrier layer (4), and the sealant layer. An inner layer (B) obtained by sequentially laminating (5) and an outer layer (A) obtained by laminating the resin layer (7) on the base material layer (1) of a synthetic resin material, It is the exterior body for vacuum heat insulating materials characterized by being laminated | stacked through the heat sealing | fusion layer (8).

  The exterior body for a vacuum heat insulating material of the present invention is an exterior body for a vacuum heat insulating material composed of a multilayer sheet composed of an inner layer and an outer layer having gas barrier properties, and the multilayer sheet is non-adhered between the inner layer and the outer layer. By having a part (air layer), heat insulation, pinhole resistance, and abrasion resistance are excellent, and it can be manufactured at a lower cost.

  An embodiment of the present invention will be described in detail with reference to FIGS.

  FIG. 1 is a side sectional view showing one embodiment of a vacuum heat insulating material using a multilayer sheet constituting the vacuum heat insulating material exterior body according to the present invention shown in FIG. 3, and FIG. 2 is a view before assembling the vacuum heat insulating material. FIG. 3 is a side sectional view showing one embodiment of the layer structure of the multilayer sheet constituting the exterior body for a vacuum heat insulating material according to the present invention, and FIG. 4 is for the vacuum heat insulating material according to the present invention. It is a sectional side view which shows the other Example of the layer structure of the multilayer sheet which comprises an exterior body.

  As the vacuum insulator outer body (E) according to the present invention, for example, as shown in FIG. 1, a pair of multilayer sheets (C) composed of an inner layer (B) having gas barrier properties and an outer layer (A) It has a non-adhesive part (air layer) (6) between the inner layer (B) and the outer layer (A).

  For example, as shown in FIG. 3, the multilayer sheet (C) has an inner layer (4) and a sealant layer (5) sequentially laminated on a support layer (3) made of a synthetic resin material. B) and an outer layer (A) composed of a base material layer (1) of a synthetic resin material are laminated via a partial adhesive layer (2).

  The material used for the support layer (3) is not particularly limited, but a single film and various laminated films can be used in consideration of processability and the like.

  For example, polyesters such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polyolefins such as polyethylene (PE), polypropylene (PP), polystyrene (PS), nylon-6, nylon Polyamide (PA) such as -66, polycarbonate (PC), polyacrylonitrile (PAN), polyimide (PI), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyvinyl alcohol (PVA), ethylene-vinyl alcohol A polymer (EVOH), polyether sulfone (PES), polymethyl methacrylate (PMMA), or a copolymer thereof is an unstretched or stretched film.

  Usually, these are used after being processed into a film shape, and it is preferable to use a polyethylene terephthalate film (PET) arbitrarily stretched in the biaxial direction from the viewpoints of heat resistance, strength, cost and the like.

  The thickness of the support layer (3) is preferably in the range of 3 to 200 [mu] m, more preferably 6 to 30 [mu] m, in consideration of workability when forming the gas barrier layer (4).

Further, in order to improve the adhesion to the gas barrier layer (4), the surface of the support layer (3) is subjected to corona discharge treatment, glow discharge treatment, low temperature plasma treatment, flame treatment, chemical treatment, solvent treatment, etc. In some cases, the pretreatment is performed by a known method.

  Furthermore, various known additives and stabilizers such as antistatic agents, ultraviolet absorbers, plasticizers, and lubricants can be used on the front and back surfaces of the support layer (3).

  Next, the gas barrier layer (4) includes an aluminum foil layer, an aluminum vapor deposition layer, an inorganic oxide vapor deposition layer (all not shown), and the like.

  In particular, the gas barrier layer (4) composed of an inorganic oxide vapor deposition layer having a high gas barrier property and a good heat insulating effect will be described in detail.

  As the deposited layer of the inorganic oxide, it is basically possible to use a metal oxide, for example, aluminum, silicon, magnesium, calcium, potassium, tin, sodium, boron, titanium, lead, zirconium, An oxide such as yttrium or a mixture thereof may be mentioned.

  In general, it is preferable to use aluminum oxide or silicon oxide from the standpoint of productivity and physical properties.

  As a method of forming such a vapor deposition layer, a vacuum vapor deposition method, a sputtering method, or the like can be used. However, in consideration of productivity, the vacuum vapor deposition method is preferable.

  There are three types of vacuum deposition methods, depending on the form of the body to be vapor-deposited. 1) Batch method: vapor deposition method of molded products, 2) take-up semi-continuous method: vacuum for roll-shaped film (web) After unwinding, vapor deposition, and winding in the system, return to the atmospheric system again and take out the vapor deposition product. 3) Unwinder (unwinding device) for roll type film (web) ) And a rewinder (winding device) are arranged in the atmospheric system, and a vapor deposition drum and an evaporation source are arranged in a vacuum system to vaporize the evaporated substance on a roll film (web). This is a completely continuous method called a to-air method and has a feature of high productivity.

  When evaporating a vaporized material on a roll-shaped film (web), a take-up semi-continuous method is particularly widespread. Describes the internal structure.

  First, the constituent elements are a roll film (web), an evaporation source, an evaporation substance, a vapor deposition drum, a vacuum system, an unwinder (unwinding device), a rewinder (winding device), a guide roll, and the like.

  Next, the outline of the work process will be described. First, as a preparatory step, the door of the vacuum evaporation apparatus is opened, a roll-shaped film (web) is set in the unwinder (unwinding apparatus), and it is arranged between the unwinder and the evaporation drum. The web is caused to travel to the vapor deposition drum through a guide roll that is wound around the rewinder (winding device) via a guide roll disposed between the web and the rewinder (winding device). Preparation of vapor deposition of the evaporating substance on is completed.

  Next, the door of the vacuum deposition apparatus is closed, and the vacuum suction chamber in the vacuum deposition apparatus and the vacuum deposition chamber divided by the partition walls are set to a predetermined vacuum environment by a vacuum pump, and the web is unwound from the unwinder. The evaporating substance is evaporated on the web by evaporating the evaporating substance from the evaporation source disposed at the lower part of the evaporating drum on the web that has been run through the guide roll.

  Since the vapor deposition drum is cooled, the vaporized substance is recrystallized and fixed on the web, and the vapor deposited on the rewinder side guide roll is wound around the rewinder.

  The internal structure of the vacuum deposition apparatus is divided into a vacuum suction constant pressure chamber and a vacuum deposition chamber by partition walls. The vacuum suction constant pressure chamber is composed of an unwinder, guide roll, tension control device, speed control device, position control device, and vapor deposition drum. Some rewinders are arranged.

In the vacuum deposition chamber, a part of the deposition drum, an evaporation source, and a heating device thereof are arranged. The vacuum suction constant pressure chamber has a degree of vacuum of 1 by a vacuum pump arranged around the vacuum deposition apparatus main body. × 10 ⁰ MPa about, the vacuum deposition chamber provided via the partition wall is set to a degree 1 × 10 ^-2 MPa (SI units).

  Since the two chambers are divided by the partition walls, impurities (dust) such as gas generated from the web in the vacuum suction constant pressure chamber are unlikely to adversely affect the deposition in the vacuum deposition chamber.

  On the contrary, the radiant heat from the evaporation source arranged in the vacuum deposition chamber has little influence on the vacuum suction constant pressure chamber, so that the influence of the heat on the web is small.

  The vacuum deposition method is also a heating method: 1) Indirect resistance method, 2) Direct resistance heating method (wire feed method), 3) High frequency induction heating method, 4) Electron beam method (Electoron Beam, EB method for short) 4 There are two methods, but when the evaporated substance uses an insulating metal oxide such as silicon oxide or aluminum oxide, the electron beam method with high energy conversion efficiency is optimal.

  The wound-up electron beam vacuum deposition method is a method in which the evaporative material is directly irradiated with an electron beam and scanned on the surface of the evaporative material, and the surface of the evaporative material is heated. And evaporating the evaporated substance.

  Although the thickness of this vapor deposition layer is suitably selected by the end use of a vapor deposition film, it is preferable that it is the range of 50-2,000 mm.

  If the film thickness is less than 50 mm, a uniform film cannot be provided, so that a sufficient gas barrier property cannot be obtained. If the film thickness exceeds 2,000 mm, flexibility is lost, and vapor deposition occurs due to external factors such as bending and pulling. This is not preferable because cracks and peeling easily occur in the film.

  Next, the layer structure of the gas barrier layer (4) is, for example, a two-layer structure of vapor deposition layer / intermediate layer (not shown) or a three-layer structure of first vapor deposition layer / intermediate layer / second vapor deposition layer (not shown). And a four-layer structure (not shown) of first vapor deposition layer / first intermediate layer / second vapor deposition layer / second intermediate layer, etc., a more preferable high gas barrier property can be obtained.

  The intermediate layer (not shown) is formed by applying a coating agent containing at least a water-soluble polymer.

  The thickness of the intermediate layer at that time is preferably in the range of 0.01 to 50 μm after drying.

  Examples of the water-soluble polymer include polyvinyl alcohol, polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, and sodium alginate.

  In particular, polyvinyl alcohol (PVA) is preferable because of its excellent gas barrier properties. The polyvinyl alcohol (PVA) here is generally obtained by saponifying polyvinyl acetate.

  Examples of the polyvinyl alcohol (PVA) include fully saponified polyvinyl alcohol (PVA) in which only a few percent of acetic acid groups remain from so-called partially saponified polyvinyl alcohol (PVA) in which several tens of percent of acetate groups remain. There is no particular limitation.

  The intermediate layer is coated with a coating agent containing a water-soluble polymer such as polyvinyl alcohol (PVA) on the vapor deposition layer by a known method such as a gravure coating method, a reverse roll coating method, an air knife coating method, and the like. , Formed by drying.

  More preferably, the coating agent is prepared by dissolving water-soluble polymer and tin chloride with water or a water-alcohol mixed solution, or water-soluble polymer and metal alkoxide directly or in advance by hydrolysis, and water or water. -A solution dissolved with an alcohol mixed solution may be prepared as a coating agent.

  The tin chloride is stannous chloride, stannic chloride, or a mixture thereof, and anhydrides and hydrates of these tin chlorides can also be used.

  Next, as the metal alkoxide, tetraethoxysilane, triisopropoxyaluminum and the like that are relatively stable in an aqueous solvent after hydrolysis are preferable.

  Furthermore, known additives such as isocyanate compounds, silane coupling agents, or dispersants, stabilizers, viscosity modifiers, colorants and the like are added to the coating agent as necessary, as long as the gas barrier properties are not impaired. Can be added.

  As the isocyanate compound added to the coating agent, those having two or more isocyanate groups in the molecule are preferable.

  Examples of such isocyanate compounds include monomers such as tolylene diisocyanate, triphenylmethane triisocyanate, and tetramethylxylene diisocyanate, and polymers and derivatives thereof.

  Next, a primer layer (not shown) can be provided between the support layer (3) and the vapor deposition layer.

  When the primer layer is provided, it is possible to improve the adhesion between the support layer (3) and the vapor deposition layer, and prevent the occurrence of peeling between the support layer (3) and the vapor deposition layer due to heat or the like. be able to.

  A composition comprising a polyester polyol or acrylic polyol, an isocyanate compound, and a silane coupling agent can be preferably used as the primer layer.

Examples of the polyester polyol include terephthalic acid, isophthalic acid, phthalic acid, methylphthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, succinic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, Acid raw materials of hexahydrophthalic acid and reactive derivatives thereof, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-hexanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, neo Of polyester resins obtained by known production methods from alcohol raw materials such as pentyl glycol, bishydroxyethyl terephthalate, trimethylol methane, trimethylol propane, glycerin and pentaerythritol Those having 2 or more hydroxyl groups in the end, is intended to react with the isocyanate groups of the isocyanate compound added later.

  The acrylic polyol is a polymer compound obtained by polymerizing an acrylic acid derivative monomer, or a polymer compound obtained by copolymerizing with an acrylic acid derivative monomer and other monomers, and having a hydroxyl group at the terminal, It reacts with the isocyanate group of the isocyanate compound added later.

  Among them, an acrylic polyol obtained by polymerizing an acrylic acid derivative monomer such as ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, or hydroxybutyl methacrylate alone, or an acrylic polyol copolymerized by adding other monomers such as styrene is preferably used. .

  In consideration of reactivity with an isocyanate compound, the hydroxyl value is preferably between 5 and 200 (KOHmg / g).

  Next, the isocyanate compound is added in order to increase the adhesion to the support layer (3) or the vapor deposition layer by a urethane bond formed by reacting with a polyester polyol or an acrylic polyol. Acts as a curing agent.

  As such an isocyanate compound, monomers such as aromatic tolylene diisocyanate, diphenylmethane diisocyanate, aliphatic xylene diisocyanate, hexadiene isocyanate, isophorone diisocyanate, and polymers and derivatives thereof are used. Used alone or as a mixture.

  As described above, the support layer (3) composed of a laminated film in which an aluminum foil layer is laminated on the support layer (3), an aluminum vapor deposition film in which aluminum is vapor-deposited, and a synthetic resin film such as a polyethylene terephthalate film (PET). An adhesive layer comprising an inorganic oxide vapor-deposited film on which an inorganic oxide such as aluminum oxide or silicon oxide is vapor-deposited, a gas barrier layer (4) including an intermediate layer made of PVA, and the like, and a sealant layer (5). Lamination is performed through a layer (not shown) to obtain an inner layer (B) of the multilayer film (C).

  The sealant layer (5) is a polyolefin resin such as low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene (L-LDPE), unstretched polypropylene ( CPP), ethylene-vinyl acetate copolymer (EVA), ionomer, cyclic polyolefin, and the like can be used.

  By the way, a coating layer containing a support layer (3) made of the above-described polyethylene terephthalate film (PET), a vapor deposition layer made of an inorganic oxide such as aluminum oxide or silicon oxide, and polyvinyl alcohol (PVA) is applied. Inorganic oxide vapor-deposited film consisting of an intermediate layer formed when the film is bent due to bending force, and in some cases, the shape of the coating agent layer also deteriorates, such as oxygen gas and water vapor. It has the property that it becomes easy to permeate the broken part.

  Therefore, when the inner layer (B) produced by laminating the sealant layer (5) on the inorganic oxide vapor-deposited film is subjected to bending force, or the heat insulating core material is vacuum degassed, it is wrapped in the irregularities of the core material. If a convex part is formed along the material, it may be rubbed during the manufacturing process or transportation, causing pinholes, and the gas barrier property of the inner layer (B) may not be sufficient.

  Since it is considered that the hardness greatly affects the flexibility of the laminate, the sealant layer (5) is used to suppress a decrease in gas barrier properties even when the inorganic oxide vapor-deposited film repeatedly receives bending force. Among the polyolefin-based resins, it is preferable to use a linear low density polyethylene film (L-LDPE) having relatively high mechanical strength and high rigidity.

  The linear low-density polyethylene film (L-LDPE) has excellent mechanical strength, high rigidity (waist strength), heat resistance, cold resistance, stress cracking resistance, heat sealability, hot sealability. Excellent sealing performance for impurities.

  Next, an adhesive for laminating such as polyurethane, polyester, epoxy, polyacryl, polyvinyl acetate, cellulose, etc. can be used for the adhesive layer.

  The lamination method may be a known method such as a dry lamination method, a non-solvent dry lamination method, a hot melt lamination method, or an extrusion lamination method.

  For example, the dry lamination method includes three sections: a coating unit that applies an adhesive on a film, a drying device, and a nip roller unit, and an unwinding, winding, and tension control system.

  The coating portion generally employs a gravure coating method or a reverse coating method.

  As the lamination adhesive, a solvent type adhesive or a solventless type adhesive is used. However, when a solventless type adhesive is used, a drying apparatus is not necessary, and this is called a non-solvent dry lamination method. Yes.

  The hot melt lamination method is a method in which a hot melt adhesive such as a heat-melted ethylene-vinyl acetate copolymer (EVA) is applied onto a film, and another film is immediately laminated.

  The extrusion lamination method involves heating a thermoplastic resin such as polyethylene or polypropylene, melting it in a cylinder called a cylinder, extruding it by applying pressure with a screw, and forming a narrow slit called a T die at the tip of the cylinder. The resin melted in the form of a curtain is extruded and laminated into a film.

  As described above, as a method of laminating the laminated film including the gas barrier layer (4) and the sealant layer (5), a dry lamination method, a non-solvent dry lamination method, a hot melt lamination method, an extrusion lamination method, or the like can be used. However, the dry lamination method is preferable in view of adhesiveness, heat resistance, cost, and the like.

As another lamination method, a sandwich lamination method can also be used.

  Next, the outer layer (A) which comprises the said multilayer sheet (C) is comprised with the base material layer (1) of a synthetic resin material, as shown in FIG.

  The material used for the substrate layer (1) is not particularly limited, but a single film and various laminated films can be used in consideration of processability and the like.

  For example, polyesters such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polyolefins such as polyethylene (PE), polypropylene (PP), polystyrene (PS), nylon-6, nylon Polyamide (PA) such as -66, polycarbonate (PC), polyacrylonitrile (PAN), polyimide (PI), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyvinyl alcohol (PVA), ethylene-vinyl alcohol A polymer (EVOH), polyether sulfone (PES), polymethyl methacrylate (PMMA), or a copolymer thereof is an unstretched or stretched film.

  Usually, these are processed into a film and used, and it is particularly preferable to use polyamide (PA) such as biaxially stretched nylon-6 or nylon-66, which has excellent piercing strength.

  The thickness of the base material layer (1) is preferably in the range of 3 to 200 μm, more preferably 6 to 30 μm in view of strength and workability.

  A multilayer film (C) is produced by laminating the outer layer (A) obtained as described above and the inner layer (B) described above through a partial adhesive layer (2).

  In the present invention, the adhesive is not applied to the entire surface of the outer layer (A), and as shown in FIG. 3, the adhesive is applied only to the peripheral edge of the outer layer (A), and the adhesive is partially applied. A layer (2) is formed and lamination is performed to provide a non-adhesive portion (air layer) (6) between the outer layer (A) and the inner layer (B).

  Thus, the multilayer film (C) provided with the air layer (6) has a heat insulating effect, and the outer layer (A) is coated on the entire surface of the outer layer (A) and laminated with the inner layer (B). Compared with the multilayer film in which the air layer (6) to be obtained is not obtained, there is no heat transfer and the heat insulating effect is excellent.

  In addition, when a multilayer film is laminated with an adhesive, the multilayer film becomes hard and pinholes are likely to occur. However, in the case of the multilayer film (C) of the present invention, the air layer (6) is a cushioning material. Even if the outer layer (A) is damaged, the outer layer (A) and the inner layer (B) can be prevented from being damaged, thereby preventing the barrier layer from being damaged.

  Furthermore, since the expensive adhesive is only partially used, the manufacturing cost of the multilayer film (C) is reduced.

The method for partially applying the adhesive to the outer layer (A) is not particularly limited as long as the base layer (1) can be pattern-coated, but copper is applied on the surface of the iron cylinder (cylinder). Plating is applied to form a base, a release layer is provided on the copper plating surface, copper plating is performed, and the surface is mirror-polished to form a recess (cell) by engraving or corrosion. A gravure roll coating method is preferable, in which the adhesive in the cell is transferred to the base material layer (1) and applied.

  At this time, the side on which the adhesive is applied is not limited to the outer layer (A) side, but may be the support layer (3) side of the inner layer (B).

  The lamination method between the outer layer (A) and the support layer (3) of the inner layer (B) may be a dry lamination method, a non-solvent dry lamination method, a hot melt lamination method, an extrusion lamination method, or the like. However, it is preferable to use a dry lamination method in consideration of adhesiveness, heat resistance, cost and the like.

  For the adhesive layer (2), polyurethane, polyester, epoxy, polyacryl, polyvinyl acetate, cellulose, and other dry lamination adhesives can be used.

  In addition, the multilayer film (C) may contain a printing layer (not shown), an anchor coating layer (not shown), etc. in addition.

  When the printing layer is provided on the base material layer (1), the printing surface of the base material layer (1) can be printed on either the front surface or the back surface. However, when printing on a general plastic film bag, Similarly, it is preferable to provide a printing layer on the back surface of the base material layer (1) in consideration of the friction resistance and weather resistance of the ink.

  As the printing ink for forming the printing layer, a color material composed of a pigment or a dye that gives color to the ink, a resin that adheres to the printing medium while dispersing and holding the color material in fine particles, and the resin are used. A vehicle composed of a solvent that can stably dissolve, disperse the pigments and dyes, maintain the fluidity of the ink, and transfer an appropriate amount of ink from the printing plate, and further disperse the coloring material. The pigment is formed from an auxiliary agent such as a surfactant for the purpose of improving color development, preventing precipitation, and improving fluidity. In particular, the colorant is preferably a pigment having good weather resistance.

  The printing method for providing the printing layer is not particularly limited as long as it is a printing method capable of printing on the base material layer (1), but copper plating is applied to the surface of an iron cylinder (cylinder) to form a base, A release layer is provided on the copper-plated surface, and further copper-plated, and the surface is mirror-polished to create a recess (cell) by engraving or corrosion, and the printing ink in the cell is applied. A gravure printing method is preferable in which the substrate layer (1) is transferred to the base layer (1) so that it can be printed in a colorful manner and has a high appealing effect.

  In addition, when printing on the base material layer (1), if necessary to improve the adhesion between the base material layer (1) and the ink, ozone treatment is performed on the printing surface side of the base material layer (1). Pretreatment such as corona treatment is preferably performed, and an anchor coating agent or the like may be further coated.

  Examples of the anchor coat agent include isocyanate-based (urethane-based), polyethyleneimine-based, polybutadiene-based, and organic titanium-based anchor coat agents, or polyurethane-based, polyacrylic-based, polyester-based, epoxy-based, and polyvinyl acetate-based. , Cellulosic, and other lamination adhesives can be used.

  As a method for coating the anchor coating agent, a known gravure roll coating method, bar coating method, dropping method, reverse roll coating method, or the like can be used.

  As described above, the multilayer sheet (C) is composed of the inner layer (B) having gas barrier properties and the outer layer (A), and the multilayer sheet (C) is on the support layer (3) made of a synthetic resin material. Further, an inner layer (B) formed by sequentially laminating a gas barrier layer (4) and a sealant layer (5) and an outer layer (A) made of a base material layer (1) made of a synthetic resin material are combined with a partial adhesive layer ( 2), and by providing a non-adhesive part (air layer) (6) between the inner layer (B) and the outer layer (A), heat insulation, pinhole resistance, wear resistance, etc. Has excellent quality and can provide a cheaper exterior body (E) for vacuum heat insulating material.

  Next, as another example of the multilayer sheet (D), as shown in FIG. 4, for example, the inner layer (B) having gas barrier properties includes a resin layer (7) made of a thermoplastic resin, and the resin layer ( 7) The gas barrier layer (4) provided above and the sealant layer (5) provided on the gas barrier layer (4) are sequentially laminated.

  The outer layer (A) has a structure in which a base layer (1) made of a synthetic resin material is provided with a resin layer (7) made of a thermoplastic resin on one side.

  Examples of the thermoplastic resin used for the resin layer (7) include polyolefin resins such as low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), and linear low density polyethylene (L- LDPE), unstretched polypropylene (CPP), ethylene-vinyl acetate copolymer (EVA), ionomer, and the like can be used.

  The materials and lamination methods used for the other gas barrier layer (4) constituting the inner layer (B), the sealant layer (5), and the base material layer (1) constituting the outer layer (A) are shown in FIG. The same as the multilayer sheet (C) may be used.

  In the case of the multilayer sheet (D), heat applied to the resin layer (7) by applying heat to the peripheral portions of the outer layer (A) and the inner layer (B) by a heat seal method or the like. A plastic resin is melted to partially form a heat-sealing layer (8), heat-sealed, and a non-adhesive portion (air layer) (6) between the outer layer (A) and the inner layer (B). ).

  Thus, the multilayer film (D) provided with the air layer (6) has a heat insulation effect by the air layer (6), and an adhesive is applied to the entire surface of the outer layer (A), thereby laminating with the inner layer (B). Compared with the multilayer film in which the air layer (6) to be obtained is not obtained, there is no heat transfer and the heat insulating effect is excellent.

  In addition, the air layer (6) acts as a cushioning material, and the impact resistance becomes high, and even if the outer layer (A) is damaged, the outer layer (A) and the inner layer (B) are displaced to prevent the barrier layer from being damaged. can do.

  Furthermore, the lamination method of the outer layer (A) and the inner layer (B) can be easily performed only by the heat seal method, so the quality of the multilayer film (D) is stable and the yield is good, so the manufacturing cost is low and the vacuum is low. The exterior body (E) for heat insulating materials can be provided.

  The heat insulation core material (10) is enclosed in the inside of the exterior body for vacuum heat insulating material (E), the inside of the exterior body (E) is evacuated, and as shown in FIG. ) Is obtained.

  As the heat insulating core (10), a powder or foam made of an inorganic material or an organic material is generally used which is compression-molded and hardened with a binder.

  In addition, the process of manufacturing a vacuum heat insulating material (F), as shown in FIG. 2, the outer layer (A) and the inner layer (B) above and below the heat insulating core material (10), for example, as shown in FIG. After the multilayer film (C) integrated in advance is manufactured in a separate process, the peripheral portions are bent in a direction approaching each other with the multilayer film (C) sandwiched therebetween, and the peripheral portions are spread over the entire circumference. As shown in FIG. 1, a vacuum heat insulating material (F) can be manufactured by butt-bonding.

  The vacuum heat insulating material (F) is composed of, for example, a vacuum heat insulating material exterior body (E) made of two multilayer films (C) and filled with a heat insulating core material (10), as shown in FIG. After vacuum evacuation, the four sides may be sealed finally to form a vacuum heat insulating material (F).

  Or it consists of the exterior body (E) for vacuum heat insulating materials which consists of one multilayer film (C), and after filling with a heat insulating core material (10) and evacuating, the three sides are finally sealed and the vacuum heat insulating material (F ).

  Specific examples of the present invention will be described below.

As the inner layer (B) of the multilayer film (C) that constitutes the vacuum insulator exterior body (E) according to the present invention, as shown in FIG. 3, the support layer (3) has a biaxial thickness of 12 μm. A stretched polyethylene terephthalate film (hereinafter referred to as PET film) is used, a 7 μm thick aluminum foil (Al foil) is used for the gas barrier layer (4), and a 50 μm thick linear chain is used for the sealant layer (5). Dry lamination method through an adhesive layer coated with ² g / m ² (solid content) of a polyurethane adhesive (A525 manufactured by Mitsui Takeda Chemical Co., Ltd.) sequentially using a low-density polyethylene film (L-LDPE) Laminated.

Thus, PET film 12 μm (support layer) (3) / polyurethane adhesive 2 g / m ² (solid content) (adhesive layer) / Al foil 7 μm (gas barrier layer) (4) / polyurethane adhesive An inner layer (B) having a 5-layer structure of ² g / m ² (solid content) (adhesive layer) / L-LDPE 50 μm (sealant layer) (5) was obtained.

  Next, as the outer layer (A), a biaxially stretched polyamide film (ON film) having a thickness of 25 μm was used for the base material layer (1).

Next, an adhesive layer (2) composed of ² g / m ² (solid content) of a polyurethane-based adhesive (A525 manufactured by Mitsui Takeda Chemical Co., Ltd.) is formed on the base layer (1) which is the outer layer (A). A multilayer film (C) having a non-adhesive part (air layer) (6) was obtained by applying a pattern only to the film and laminating the inner layer (B) with a dry lamination method.

  Next, as shown in FIG. 1, a pair of sealant layers (5) of the multilayer film (C) were faced to each other and the periphery was heat-sealed to obtain a vacuum heat insulating material exterior body (E).

  As described above, the vacuum insulator outer body (E) thus obtained is non-adhered between the inner layer (B) and the outer layer (A) of the multilayer film (C) constituting the outer body (E). Since it has the part (air layer) (6), it has excellent heat insulation, pinhole resistance, wear resistance and the like, and can be manufactured at a low cost.

  Therefore, the vacuum heat insulating material obtained by vacuum-sealing the powdered silica molded body as the heat insulating core material (10) using the vacuum heat insulating material outer body (E) is maintained in a vacuum state for a long time. Insulation performance was maintained.

  As the inner layer (B) of the multilayer film (C) that constitutes the vacuum insulator exterior body (E) according to the present invention, as shown in FIG. 3, the support layer (3) has a biaxial thickness of 12 μm. A stretched polyethylene terephthalate film (hereinafter referred to as PET film) is used, and the gas barrier layer (4) is provided with a gas barrier layer (4) having a three-layer structure of a first vapor deposition layer / intermediate layer / second vapor deposition layer. did.

  As the first vapor deposition layer, an aluminum oxide first vapor deposition layer having a thickness of 300 mm was provided on one side of the support layer (3) by a winding electron beam vacuum vapor deposition method.

  Next, as an intermediate layer, PVA [Nippon Gosei Chemical Co., Ltd. PVA, N300: complete saponification type product, saponification, having a gas barrier property on the first vapor deposition layer and having a solid content thickness of 0.01 μm] Degree 98.0-99.0 mol%; diluted in a mixed solvent of water / isopropyl alcohol = 8/2 (weight ratio))] by a gravure roll coating method, and dried at 80 ° C. for 1 minute.

  Further, as the second vapor-deposited layer, an inorganic oxide vapor-deposited film having a gas barrier property is provided by providing a second vapor-deposited layer of aluminum oxide having a thickness of 300 mm on the intermediate layer by a winding electron beam vacuum vapor deposition method. Produced.

A polyurethane adhesive (A525 manufactured by Mitsui Takeda Chemical Co., Ltd.) was applied at ² g / m ² (solid content) on the second vapor deposition layer of the vapor deposition film thus produced.

  A 50 μm-thick linear low density polyethylene film (L-LDPE) formed by the T-die method was used for the sealant layer (5) to be dry-laminated by the dry lamination method.

Thus, PET film 12 μm (support layer) (3) / aluminum oxide 300 mm / PVA 0.01 μm (solid content thickness) / aluminum oxide 300 mm (gas barrier layer) (4) / polyurethane adhesive 2 g / m ² (solid Min) (adhesive layer) / L-LDPE 50 μm (sealant layer) (5) 6-layer inner layer (B) was obtained.

  Next, as the outer layer (A), a biaxially stretched polyamide film (ON film) having a thickness of 25 μm was used for the base material layer (1).

The adhesive layer (2) composed of ² g / m ² (solid content) of a polyurethane-based adhesive (A525 manufactured by Mitsui Takeda Chemical Co., Ltd.) is patterned only on the peripheral portion on the base material layer (1) which is the outer layer (A). It was applied and laminated with the inner layer (B) by a dry lamination method to obtain a multilayer film (C) having a non-adhesive part (air layer) (6).

  Next, as shown in FIG. 1, a pair of sealant layers (5) of the multilayer film (C) were faced to each other and the periphery was heat-sealed to obtain a vacuum heat insulating material exterior body (E).

  As described above, the vacuum insulator outer body (E) thus obtained is non-adhered between the inner layer (B) and the outer layer (A) of the multilayer film (C) constituting the outer body (E). Since it has the part (air layer) (6), it has excellent heat insulation, pinhole resistance, wear resistance and the like, and can be manufactured at a low cost.

Therefore, the vacuum heat insulating material obtained by vacuum-sealing the powdered silica molded body as the heat insulating core material (10) using the vacuum heat insulating material outer body (E) is maintained in a vacuum state for a long time. Insulation performance was maintained.

As the inner layer (B) of the multilayer film (D) that constitutes the vacuum insulator outer body (E) according to the present invention, as shown in FIG. 4, the resin layer (7) has a low-density polyethylene having a thickness of 30 μm. A film (LDPE) is used, a 7 μm thick aluminum foil (Al foil) is used for the gas barrier layer (4), and a 30 μm thick linear low density polyethylene film (L-) is used for the sealant layer (5). (LDPE) were sequentially laminated by a dry lamination method through an adhesive layer coated with ² g / m ² (solid content) of a polyurethane adhesive (A525 manufactured by Mitsui Takeda Chemical Co., Ltd.).

Thus, LDPE film 30 μm (resin layer) (7) / polyurethane adhesive 2 g / m ² (solid content) (adhesive layer) / Al foil 7 μm (gas barrier layer) (4) / polyurethane adhesive 2 g / An inner layer (B) having a 5-layer structure of m ² (solid content) (adhesive layer) / L-LDPE 30 μm (sealant layer) (5) was obtained.

Next, as the outer layer (A), a biaxially stretched polyamide film (ON film) having a thickness of 15 μm is used for the base material layer (1), and a polyurethane-based adhesive (Takeshi Mitsui) is formed on the base material layer (1). Laminate by dry lamination using a low-density polyethylene film (LDPE) with a thickness of 30 μm on the resin layer (7) through an adhesive layer coated with 2g / m ² (solid content) manufactured by Chemical Co., Ltd. did.

Thus, the outer layer (A) having a three-layer structure of ON film 15 μm (base layer) (1) / polyurethane adhesive 2 g / m ² (solid content) (adhesive layer) / LDPE 30 μm (resin layer) (7) Got.

  Next, the resin layer (7) of the outer layer (A) and the resin layer (7) of the inner layer (B) are patterned with a heat-sealing layer (8) only at the peripheral portion with a two-stage bag making machine. And heat sealing was performed to obtain a multilayer film (D) having a non-adhesive part (air layer) (6).

  Next, the pair of sealant layers (5) of the multilayer film (D) were faced to each other and the periphery was heat-sealed to obtain a vacuum heat insulating material exterior body (E).

  As described above, the outer package (E) thus obtained is non-adhered between the inner layer (B) and the outer layer (A) of the multilayer film (D) constituting the outer package (E). Since it has the part (air layer) (6), it has excellent heat insulation, pinhole resistance, wear resistance and the like, and can be manufactured at a low cost.

  Therefore, the vacuum heat insulating material obtained by vacuum-sealing the powdered silica molded body as the heat insulating core material (10) using the vacuum heat insulating material outer body (E) is maintained in a vacuum state for a long time. Insulation performance was maintained.

  As the inner layer (B) of the multilayer film (D) that constitutes the vacuum insulator outer body (E) according to the present invention, as shown in FIG. 4, the resin layer (3) has a low-density polyethylene having a thickness of 30 μm. A film (LDPE) was used, and the gas barrier layer (4) was a gas barrier layer (4) having a three-layer structure of first vapor deposition layer / intermediate layer / second vapor deposition layer.

  As the first vapor deposition layer, an aluminum oxide first vapor deposition layer having a thickness of 300 mm was provided on one surface of the resin layer (7) by a winding electron beam vacuum vapor deposition method.

  Next, as the intermediate layer, PVA (Nippon Gosei Kagaku Kogyo Co., Ltd., P300, complete saponification type product, saponification) has a gas barrier property on the first vapor deposition layer and a solid content thickness of 0.01 μm. Degree 98.0-99.0 mol%; diluted in a mixed solvent of water / isopropyl alcohol = 8/2 (weight ratio)) was coated by a gravure roll coating method and dried at 80 ° C. for 1 minute.

  Further, as the second vapor-deposited layer, a vapor-deposited film having a gas barrier property is prepared by providing a second vapor-deposited layer of aluminum oxide having a thickness of 300 mm on the first intermediate layer by a winding electron beam vacuum vapor deposition method. did.

2 g / m ² (solid content) of a polyurethane adhesive (A525 manufactured by Mitsui Takeda Chemical Co., Ltd.) was applied as an adhesive layer on the second vapor deposition layer of the inorganic oxide vapor deposition film thus produced.

  A 30 μm thick linear low density polyethylene film (L-LDPE) formed by the T-die method was used for the sealant layer (5) to be dry-laminated by the dry lamination method.

Thus, LDPE film 30 μm (resin layer) (7) / aluminum oxide 300 μm / PVA 0.01 μm (solid content thickness) / aluminum oxide 300 μm (gas barrier layer) (4) / polyurethane adhesive 2 g / m ² (solid content ) (Adhesive layer) / L-LDPE 30 [mu] m (sealant layer) (5), an inner layer (B) having a 6-layer structure was obtained.

Next, as the outer layer (A), a biaxially stretched polyamide film (ON film) having a thickness of 15 μm is used for the base material layer (1), and a polyurethane-based adhesive (Takeshi Mitsui) is formed on the base material layer (1). Laminate by dry lamination using a low-density polyethylene film (LDPE) with a thickness of 30 μm on the resin layer (7) through an adhesive layer coated with 2g / m ² (solid content) manufactured by Chemical Co., Ltd. did.

In this way, an outer layer of a three-layer structure of ON film 15 μm (base layer) (1) / polyurethane adhesive 2 g / m ² (solid content) (adhesive layer) / LDPE 30 μm (resin layer) (7) A) was obtained.

  Next, the resin layer (7) of the outer layer (A) and the resin layer (7) of the inner layer (B) are patterned with a heat-sealing layer (8) only at the peripheral portion with a two-stage bag making machine. And heat sealing was performed to obtain a multilayer film (D) having a non-adhesive part (air layer) (6).

  Next, as shown in FIG. 1, the pair of sealant layers (5) of the multilayer film (D) face each other and the periphery was heat-sealed to obtain a vacuum heat insulating material exterior body (E).

  As described above, the outer package (E) thus obtained is non-adhered between the inner layer (B) and the outer layer (A) of the multilayer film (D) constituting the outer package (E). Since it has the part (air layer) (6), it has excellent heat insulation, pinhole resistance, wear resistance and the like, and can be manufactured at a low cost.

  Therefore, the vacuum heat insulating material obtained by vacuum-sealing the powdered silica molded body as the heat insulating core material (10) using the vacuum heat insulating material outer body (E) is maintained in a vacuum state for a long time. Insulation performance was maintained.

It is a sectional side view which shows one Example of the vacuum heat insulating material which uses the multilayer sheet which comprises the exterior body for vacuum heat insulating materials which concerns on this invention shown in FIG. It is an exploded view before assembling a vacuum heat insulating material. It is a sectional side view which shows one Example of the laminated constitution of the multilayer sheet which comprises the exterior body for vacuum heat insulating materials which concerns on this invention. It is a sectional side view which shows the other Example of the laminated constitution of the multilayer sheet which comprises the exterior body for vacuum heat insulating materials which concerns on this invention.

Explanation of symbols

A ... Outer layer B ... Inner layer C ... Multilayer film D ... Multilayer film E ... Exterior body for vacuum heat insulating material 1 ... Base material layer 2 ... Adhesive layer 3 ... Support layer 4 ... Gas barrier layer 5 ... Sealant layer 6 ... Non-adhesive layer (air layer)
7 ... Resin layer 8 ... Thermal fusion layer 10 ... Heat insulation core material

Claims (3)

An exterior body composed of a multilayer sheet composed of an inner layer and an outer layer having gas barrier properties, and the inner layer and the outer layer are laminated before assembling the vacuum heat insulating material, and the vacuum heat insulating material is provided on the inner layer side of the outer body. In a vacuum insulation material exterior body that is used by laminating exterior bodies on the front and back surfaces of the vacuum insulation material so as to be placed and vacuum packed ,
The multilayer sheet comprises an inner layer formed by sequentially laminating a gas barrier layer and a sealant layer on a support layer made of a synthetic resin material, and an outer layer made of a base layer of the synthetic resin material. An exterior body for a vacuum heat insulating material, wherein an outer layer is provided between the inner layer and the outer layer. An exterior body composed of a multilayer sheet composed of an inner layer and an outer layer having gas barrier properties, and the inner layer and the outer layer are laminated before assembling the vacuum heat insulating material, and the vacuum heat insulating material is provided on the inner layer side of the outer body. In a vacuum insulation material exterior body that is used by laminating exterior bodies on the front and back surfaces of the vacuum insulation material so as to be placed and vacuum packed ,
The multilayer sheet comprises an inner layer formed by sequentially laminating a gas barrier layer and a sealant layer on a support layer made of a synthetic resin material, and an outer layer made of a base layer of the synthetic resin material. An exterior body for a vacuum heat insulating material, wherein the outer layer is laminated through a partially formed heat-sealing layer, and an air layer is provided between the inner layer and the outer layer.   A heat insulating core material is disposed on the inner layer side of the multilayer sheet constituting the exterior body for a vacuum heat insulating material according to claim 1 or 2, and the inner layers are bonded to each other by heat sealing around the vacuum exhaust. Vacuum insulation material.

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