JP5922312B2 - Laminated sheet - Google Patents

Description

  The present invention relates to a laminated sheet in which a metal surface treatment and a reinforcing cloth are laminated on at least one surface of a porous film containing metal particles. In particular, compared to conventional heat shield sheets, it exhibits high anti-corrosion properties and long-term durability, and the entire sheet has the characteristics of moisture permeability and waterproof and heat shield performance, and is mainly used for building materials, civil engineering, agriculture , Packaging, industrial applications, etc.

  In recent years, in buildings such as houses, various sheets have been used in which a sheet having heat insulation, moisture permeability, and waterproofing is laid on the wall surface to keep the room comfortable by blocking the physical influence from the outside. ing.

  Conventionally, the sheet | seat used for a wall base and a roof base is mainly used for the purpose of preventing the rain water etc. from an outdoor part of a house from entering inside, and preventing the corrosion of wood. Specifically, asphalt-based or rubber asphalt-based waterproof sheets or moisture-permeable waterproof sheets in which a nonwoven fabric and a film such as polyurethane are laminated are used.

  In addition, housing has evolved, and from the viewpoint of energy saving and heat shock, construction methods with increased airtightness like thermos bottles are increasing, but the above-mentioned asphalt and rubber asphalt waterproof sheets have little moisture permeability. Therefore, moisture generated inside the building, such as sweat generated from the human body, steam generated during cooking, moisture such as steam, water vapor generated by combustion of oil stoves used for heating, etc. is released outside the building. It is hard to be done. In particular, each part such as the wall, the back of the shed, and the roof base plate surface is likely to cause dew condensation, which is likely to cause mold and corrosion and deterioration of the structure, which may affect the durability of the house. Furthermore, the “Law Concerning Promotion of the Spread of Long-Term Excellent Houses” (constructed in June 2009) places more importance on durability. In order to control the generation of waste by dismantling and removing houses, it is desirable to develop countermeasures for the structure and the development of highly durable materials that do not easily deteriorate.

  Moisture permeable waterproof sheets (also called “house wrap materials”) made of polyolefin non-woven fabrics or non-woven fabrics and films are sheets that are both moisture permeable and waterproof, eliminating these problems (problems). It is now popular. However, since these sheets do not have heat shielding performance, they cannot be adequately accommodated as energy-saving houses in recent years with high airtightness and high heat insulation. Therefore, the development of a building sheet having a heat shielding performance as a next-generation moisture-permeable waterproof sheet is underway.

  For example, Patent Document 1 discloses a building sheet in which an aluminum vapor-deposited film and a breathable reinforcing material are laminated and fine holes are provided with a needle or the like. However, in these, only the penetration part of the building sheet has moisture permeability, and it is necessary to increase the area of the penetration part in order to compensate for sufficient moisture permeability performance. There is a risk.

  Patent Document 2 discloses a metallized porous film in which a metal layer is provided by depositing metal on at least one surface of a porous film containing a polyolefin-based resin. However, the heat shielding performance is imparted to the porous film only with the metal vapor deposition layer.For example, when the metal layer falls off or delamination occurs due to external friction or bending. There is a risk that sufficient heat shielding performance cannot be secured.

  Patent Document 3 discloses a molded product for a photographic photosensitive material and a photographic photosensitive material packaging material related to a photographic film that completely secures light shielding properties and is excellent in physical strength and appearance. This is a surface coating material formed of aluminum powder and a thermoplastic resin, and is not suitable for building materials because it is moisture-impermeable and air-impermeable.

  Patent Document 4 discloses a laminate formed by laminating a breathable reinforcing material on a polyethylene-based porous film kneaded with titanium oxide surface-treated with silica and / or alumina (that is, at least one of them). A sheet is disclosed. Titanium oxide surface-treated with silica and / or alumina is kneaded and a weathering agent is added to improve the weather resistance, but the heat-shielding performance is low, making it an energy-saving house that has recently been known for high airtightness and high thermal insulation. Sufficient correspondence is not possible.

Japanese Patent Publication No. 3-9259 JP 2008-105402 A Japanese Patent Application Laid-Open No. 08-022102 Japanese Patent No. 4014993

  The present invention solves the above-mentioned problems, is excellent in moisture permeability and heat shielding performance, and is at least a porous film having corrosion resistance and long-term durability that can withstand harsh environments such as high temperature and high humidity. It aims at providing the lamination sheet which performed metal surface treatment and lamination of the reinforcement cloth on the single side | surface. The term “anticorrosive” as used herein refers to the performance of preventing the brightness from being lowered, the reflectance from being lowered, and the heat shielding performance from being lowered due to the chemical change on the surface of the glittering metal particles.

Laminated sheet of the present invention, metal particles and, includes a filler for porous quality of the non-metal particles, either at least one side, the more than 10% of the area of the at least stretched uniaxially molded porous film metal printed layer or metal deposition layer provided so as to be substantially uniformly coated even at a point, a laminated sheet consisting of a fabric for reinforcement to be against wear at least on one surface of the porous film, a porous film wherein The adhesion area with the reinforcing fabric is 10 to 80% of the total area of the reinforcing fabric, and has the following performance. That is, the moisture permeability resistance is 0.04 to 0.19 m ² · s · Pa / μg, and in the initial state, the waterproofness is 10 KPa or more, the average value of the infrared reflectance at 2000 nm to 2500 nm is 50% or more, And the average value of infrared transmittance is 30% or less. Porous formation can be performed by adding a filler for this purpose so that pores are generated at the location of the filler during stretching. Moreover, the heat ray wavelength from the sun is generally referred to as infrared rays of 750 nm to 2500 nm, and in particular, shielding the wavelength of 2000 nm to 2500 nm is effective in the heat shielding effect. Thus, the infrared reflectance and transmittance at the above wavelengths are measured as indicators of the heat shielding effect. Moreover, waterproofness is evaluated by the hydrostatic pressure method of method A of JIS L 1092 (2009).

  Moreover, even after the accelerated exposure test by solar radiation specified in JIS A 1415 (2003) is performed for 200 hours and the heat treatment specified in JIS K 7212 (1999) is performed at 80 ° C. for 28 weeks, It is preferable that the waterproofness obtained by the hydrostatic pressure method of A method defined in JIS L 1092 (2009) is 8 KPa or more, and the infrared reflectance at 2000 nm to 2500 nm is 70% or more of the initial value.

Moreover, the metal printing layer is provided by applying 0.5-50 g / m < ² > of metal ink containing a metal particle and a film-forming resin to a porous film on a solid basis. The metal particles in the ink have a particle diameter of 0.5 to 50 μm, aluminum, nickel, stainless steel, chromium, silver, tin, titanium, iron, zinc, copper, silicon (metal silicon), magnesium, and these It is preferably one or any combination selected from the group consisting of alloys.

  In addition, after being left in a high temperature and high humidity of 70 ° C. × 90% RH × 72 h, the visible light reflectance by CCM (Computer Color Matching) is maintained at 70% or more from the initial value, and the infrared reflectance at 2000-2500 nm is It is preferable to maintain 70% or more from the initial value.

Further, the reinforcing fabric is made of polyester, polyamide, or polyolefin fibers having a tensile strength of 50 N / 5 cm or more and a fiber fineness of 1 to 1000 dtex in both the vertical and horizontal directions. It is preferably a woven fabric, a knitted fabric, a split fabric, or a non-woven fabric that is configured and has a mass per area of 20 to 500 g / m ² .

The metal particles contained in the porous film have a particle diameter of 0.1 to 40 μm and an aspect ratio (particle diameter / particle thickness) of 1.3 or more (N = 100 average), The filler for crystallization has a particle diameter of 0.1 to 40 μm, and 0.10 to 30 parts by mass of the metal particles and 10 to 10 parts by mass of the porous filler for 100 parts by mass of the resin base material of the film. It is preferable that 70 mass parts is contained. Here, the measurement of the particle diameters of the metal particles and the filler for making porous can be performed, for example, by image analysis in a state of being suspended on the surface of the solvent. For example, it can be evaluated with a laser diffraction / scattering particle size analyzer “Microtrack HRA (X-100) (Nikkiso Co., Ltd.)” (D ₅₀ : volume-based median diameter). Moreover, the measurement of the aspect-ratio of a metal particle can be performed by the image analysis about an electron micrograph, for example.

  Moreover, the resin base material of the porous film is an olefin resin, and pores are formed at the location of the porous filler by stretching 1.1 to 5 times in at least a uniaxial direction. It is preferable.

  Moreover, it is preferable that the laminated sheet of this invention is a heat shield sheet for building foundations.

In the method for producing a laminated sheet of the present invention, (1) the resin base of the film is mixed with metal particles and a porous filler, and then stretched in at least a uniaxial direction to make the porous sheet. A step of obtaining a porous film in which pores are formed at the filler locations, and (2) at least one surface of the porous film so that an area of 10% or more is coated almost uniformly at any location. A step of providing a printing layer or a metal vapor deposition layer; and (3) a reinforcing fabric on at least one surface of the porous film so that the adhesion area is 10 to 80% of the total area of the reinforcing fabric. Adhering.

  According to the present invention, compared to the conventional heat shield sheet, it exhibits high corrosion resistance, and the entire sheet has characteristics such as moisture permeable waterproof property, heat shield performance, and long-term durability. It is a laminated sheet having moisture permeability and water resistance and heat shielding performance, which contains metal particles suitable for packaging use, industrial use and the like.

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

The present invention includes a porous film containing metal particles and a filler for making porous other than the metal particles, and having pores formed at portions of the filler for making porous by stretching in at least a uniaxial direction. And at least one side of the porous film, a metal printing layer or metal vapor deposition layer provided so as to cover an area of 10% or more, and at least one side of the porous film with an area of 10 to 80% A laminated sheet made of a reinforcing fabric to be bonded to each other, having a moisture permeability resistance of 0.04 to 0.19 m ² · s · Pa / μg, a waterproof property of 10 KPa or more, and an infrared reflectance at 2000 nm to 2500 nm of 50 %, And the infrared transmittance is 30% or less.

  In the porous film of the present invention, since the metal particles are kneaded into the film-forming resin base material, the metal particles do not contact the outside and receive physical force from the outside, and the surface treatment layer is damaged. Therefore, excellent anticorrosive properties can be obtained.

  Film-forming resin base materials are polyolefin (PO) resins such as homopolymers or copolymers such as ethylene, propylene, and butene, amorphous polyolefin (APO) resins such as cyclic polyolefin, polyethylene terephthalate (PET), polyethylene 2, Polyester resins such as 6-naphthalate (PEN), polyamide resins such as nylon 6, nylon 12, copolymer nylon (PA), polyvinyl alcohol (PVA) resin, polyvinyl such as ethylene-vinyl alcohol copolymer (EVOH) Alcohol-based resin, polyimide (PI) resin, polyetherimide (PEI) resin, polysulfone (PS) resin, polyethersulfone (PES) resin, polyetheretherketone (PEEK) resin, polycarbonate (PC) resin , Polyvinyl butyra (PVB) resin, polyarylate (RAR) resin, ethylene-tetrafluoroethylene copolymer (ETFE), ethylene trifluoride chloride (PFA), tetrafluoroethylene-perfluoroargyl vinyl ether copolymer ( One or two or more of fluorine resins such as FEP), vinylidene fluoride (PVF), and perfluoroethylene-perfluoropropylene-perfluorovinyl ether copolymer (EPA) can be used. In the present invention, olefins are preferred from the viewpoints of economy and productivity. More preferably, polyethylene having a melting point in the range of 100 to 140 ° C. is preferable from the viewpoint of long-term durability. Preferred olefinic resins include linear polyethylene (LLDPE), low density polyethylene (LDPE), high density polyethylene (HDPE), and polypropylene resin (PP).

  The metal particles kneaded into the film-forming resin base material are aluminum, nickel, stainless steel, chromium, silver, tin, titanium, iron, zinc, copper, silicon (“metal silicon”; almost the same light reflectivity and light as metal Since it has shielding properties, it is included in “metal” in the present application.), Magnesium and the like, and various alloys composed of these, and one or more of these can be used. Examples of the alloy include a magnesium-aluminum alloy, brass (brass), and an aluminum-tin alloy. In the present invention, aluminum is particularly preferable from the viewpoints of high reflectivity, light weight, formability, economy, and the like. Examples of the surface treatment of the metal particles include aqueous treatment, resin coating, solvent replacement, interference coating, and the like, and it is desirable that the shape of the metal particles be flat so that a leafing effect can be obtained more easily than a sphere. Therefore, it is preferable to have a flake shape, that is, a plate shape or a scale shape. By treating the flaky metal particles with a fatty acid such as stearic acid, the leafing effect can be enhanced by collecting the flaky metal particles on the surface during molding or volatilization of the solvent.

  The particle diameter of the metal particles is preferably 0.1 to 40 μm. Furthermore, 1-25 micrometers is preferable from a smoothness or a film property viewpoint. When the particle diameter is 0.1 μm or more, sufficient smoothness is obtained and the heat shielding performance is improved. Moreover, if the particle diameter is 40 μm or less, tearing during film formation can be reduced.

  In addition, in order to obtain high performance at a low cost, it is important that the thickness of the metal particles be arranged in parallel and evenly with as little gap as possible on the surface with a small addition amount. Is preferably smaller. Furthermore, the aspect ratio (particle diameter / particle thickness) is 1.3 or more, preferably 5 or more and 2000 or less. When the aspect ratio is 1.3 or more, a sufficient leafing effect can be obtained and the heat shielding performance can be improved. As used herein, “particle diameter” and “particle thickness” define the maximum dimension part of the particle as “particle diameter” and the minimum dimension part as “particle thickness”.

  In order to develop a stronger anticorrosive property even if exposed to harsh environments such as high temperature and high humidity for a long time, the metal particles to be kneaded into the film-forming resin substrate should be coated with a resin in advance. Can do. If an inorganic or organic ultra-thin transparent strong film is formed on the metal particle surface, it will not be directly exposed to oxygen or moisture in the air, so it maintains high anti-corrosion properties while maintaining its glitter. Can do. The coating layer may be one layer or two or more layers, and can be appropriately treated depending on the required performance. In general, for example, when obtaining a leafing effect, it is preferable to form a film using stearic acid or the like having a high surface tension, and when obtaining a non-leafing effect, a film is formed using oleic acid or the like having a low surface tension. It is preferable. In the present invention, the object is high luminance (high reflectance), and it is preferable to form a surface film with stearic acid or the like that provides a leafing effect. Surface treatment of metal particles to satisfy further requirements includes aqueous treatment (film formation with phosphorus compounds, molybdenum compounds, silica, etc. in aqueous solution), resin treatment (film formation with acrylate resins, etc.), solvent Substitution (replacement of mineral spirits with hydrophilic solvents such as isopropyl alcohol and glycol ether), surfactant treatment (surfactant adsorbs on the surface of metal particles), formation of interference film (plating on metal flake surface layer and metal particles) These treatments can be appropriately performed either alone or in combination. In the present invention, the above-described aqueous or oily resin treatment is preferable because metal anticorrosive properties are required.

  The resin used for coating the metal particles preferably has a melting point higher than that of the film-forming resin base material or is difficult to flow due to crosslinking. A preferred coating resin is an acrylate resin (including a methacrylate resin). The amount of the resin used for coating (coating) of the metal particles is, for example, 10% or less, particularly 5% or less of the mass of the metal particles. In blending the metal particles into the resin substrate of the film, it is preferable to mix the metal particles in a relatively small amount of the resin substrate in advance to obtain a metal-added master batch. In a preferred embodiment, the metal particles are coated with a small amount of an acrylate resin, and then kneaded into a small amount of low density polyethylene (LDPE), so that the content of the metal particles is 10 to 80% by mass. Create a master batch. And this metal internal addition masterbatch, an inorganic filler, and an additive are kneaded in the main resin base materials, for example, a low density polyethylene (LDPE). In this way, the metal-added masterbatch is substantially a resin (for example, LDPE) that becomes a part of the film base, metal particles, and a small amount of a coating resin (for example, an acrylate resin) for coating the metal particles. Consist only of. Such metal-added master batches include various types of “Metallic Compound“ Metax (trademark) ”(70% by mass of aluminum flakes, the rest being LDPE) of Toyo Aluminum Co., Ltd., various types of“ stainless flakes ”, and , Tokyo Ink Co., Ltd.'s "Silver Masterbatch" (aluminum flakes 14 to 40% by mass, the rest is LDPE). If the content of the metal particles is 10 to 80% by mass, a master batch is easily formed, and productivity is improved.

  The metal particles are preferably added in an amount of 0.1 to 30 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the film-forming resin substrate (including the resin in the metal-added master batch). In a preferred embodiment, when a metal-added master batch having a metal particle content of 70% by mass is used, it is preferably 0 with respect to 100 parts by mass of the resin base material (excluding those contained in the metal-added master batch). 5 to 40 parts by mass, more preferably 1 to 10 parts by mass of an internally added masterbatch is added. When the addition amount of the metal-added master batch is within the above range, sufficient heat shielding performance can be obtained, and tearing can be reduced during film formation.

  The filler for making porous used in the present invention is not particularly limited as long as it contributes to making it porous at the time of stretching, and is generally non-fibrous, and particularly has an aspect ratio of 1. It is preferably less than 0.5, preferably less than 1.3. If it is less than 1.5, the dispersibility with respect to a film formation resin base material will become favorable, and the uniformity of porous formation will improve. Specifically, calcium carbonate, magnesium carbonate, barium carbonate, magnesium sulfate, barium sulfate, calcium sulfate, magnesium oxide, calcium oxide, calcium carbide, titanium oxide, aluminum oxide, alumina, aluminum hydroxide, hydroxyapatite, silica, mica , Talc, clay, glass powder, zeolite, silicate clay, kaolin, silicon oxide, zinc oxide, carbon black, silicon carbide, tin oxide, crosslinked silicone resin particles, crosslinked acrylic resin particles, crosslinked polystyrene resin particles, melamine resin particles Among them, one or more of them can be used in combination. Among these, calcium carbonate is particularly preferable from the viewpoints of easy and uniform porosity formation, economic efficiency, and productivity.

  The particle diameter of the porous filler is preferably 0.1 to 40 μm. When the particle diameter is 0.1 μm or more, it is possible to efficiently obtain a porous structure and improve productivity. Moreover, if the particle diameter is 40 μm or less, it is possible to reduce tearing during film formation.

  As for the addition amount of the filler for porous formation with respect to 100 mass parts of film forming resin base materials, 10-70 mass parts is preferable. More preferably, 40-60 mass parts is preferable from a viewpoint of a moisture-permeable effect, waterproofness, and film forming property. When the addition amount is 10 parts by mass or more with respect to 100 parts by mass of the resin substrate, the film is sufficiently made porous when the film is stretched and the moisture permeability is improved. Moreover, if it is 70 mass parts or less, the tear at the time of film forming, etc. can be reduced. Moreover, in order to make it contain in a film, it is preferable to use the thing surface-treated with aluminum, silicon, and zinc from a viewpoint of a dispersibility and a stability improvement as a filler for porous formation. Thus, the filler for making porous may contain a relatively small amount of metal in a part of the surface layer or the like.

  The thickness of the porous film in the present invention (mean thickness (* N = 10 average)) is preferably 5 to 150 μm. Furthermore, 20-40 micrometers is preferable from a viewpoint of production efficiency. Moreover, if it is 5 micrometers or more, at the time of extending | stretching, the tearing of a film and an intensity | strength insufficient can be reduced. Moreover, if it is 150 micrometers or less, glossiness will improve if a metal particle is arranged in parallel and uniformly without the space | gap near the surface in a film.

  If necessary, the porous film may be used in combination of one or two or more additives such as an ultraviolet absorber, a light stabilizer, and an antioxidant as long as the object of the present invention is not impaired. You can also

  Examples of the ultraviolet absorber include benzophenone, salicylate, cyanoacrylate, benzoate, benzotriazole, triazine, nickel, and the like. Examples of the light stabilizer include benzotriazole, triazine, benzophenone, organic nickel, hindered piperidine, and hindered amine. In addition to the above, examples of the antioxidant include phenol-based, phosphorus-based, sulfur-based, blend-based, and phosphite-based agents. Moreover, the ultraviolet absorber, the light stabilizer, and the antioxidant to be used are not particularly limited in kind. Other additives include flame retardants, thermal stabilizers, rust inhibitors, copper damage stabilizers, antistatic agents, pigments, colorants, plasticizers, unblocking agents, lubricants, organic lubricants, and chlorine scavengers. You may add an agent, a blocking agent, a viscosity modifier, etc. as needed.

  The preferred production method of the porous film uses the above-mentioned resin base masterbatch, metal-added masterbatch, and filler for porous formation as raw materials, and if necessary, UV absorber, light stabilizer, antioxidant An agent and / or other additives are added and mixed using a Henschel mixer, a super mixer, a tumbler type mixer, or the like, and then kneaded using a single screw or twin screw extruder to be pelletized. Then, these pellets are subjected to a known molding machine such as a T-die molding machine, an inflation molding machine, a calendar method, a multilayer molding method, a comma coater, a knife coater in the temperature range of the melting point of the resin substrate + 20 ° C. or more and less than the decomposition temperature. Used to form a melt. In some cases, the film can be formed directly with an extruder without being pelletized.

  The formed film is stretched at least in a uniaxial direction from a room temperature to a resin softening point (value measured by a method defined in JIS K 6760) by a known method such as a roll method or a tenter method, A porous film is produced by causing interfacial peeling from the inorganic filler. Stretching may be performed in multiple stages.

  The draw ratio of the porous film is 1.1 to 5 times in at least a uniaxial direction, and preferably 1.5 to 3.5 times from the viewpoint of moldability and moisture permeability effect. If it is 1.1 times or more, it is made sufficiently porous and moisture permeability is improved. Moreover, if it is 5 times or less, generation | occurrence | production of a tear etc. can be suppressed in the case of extending | stretching of a film. Moreover, in order to stabilize the shape of the obtained opening as necessary after stretching, a heat setting treatment may be performed, and the heat setting treatment is performed at a temperature not lower than the softening point of the resin substrate and lower than the melting point. And a method of heat treatment for 0.1 to 300 seconds.

  Excellent heat-shielding performance and long-term durability by providing a metal printing layer or metal vapor deposition layer on at least one surface of the porous film obtained as described above so as to cover the porous film with an area of 10% or more. The ability to show off. A metal printing layer is preferably used in that it has superior durability and productivity. Hereinafter, the ratio of the metal printing layer or the metal vapor deposition layer to the surface area (including the hole) of the porous film is referred to as “cover ratio”.

  By having the metal printing layer or the metal vapor deposition layer on the surface of the porous film, the reflectance of ultraviolet rays and infrared rays is improved, and deterioration of the porous film due to ultraviolet rays and heat can be suppressed. In addition, in the case of a porous film without a metal printing layer or a metal vapor deposition layer, the metal easily absorbs heat, so the metal particles kneaded in the porous film absorb heat, and the metal particles surround the resin. Since it is covered and hardly dissipates heat, there is a concern that the deterioration of the resin is promoted and the durability of the porous film is affected. However, by providing a metal printing layer or metal vapor deposition layer on the porous film surface, the heat accumulated in the resin and metal particles in the porous film can be dissipated through the metal printing layer or metal vapor deposition layer, Deterioration promotion can be suppressed. By the above action, the deterioration of the porous film is remarkably improved, and long-term durability can be realized.

  In the case of a metal printing layer, a metal ink (metallic ink) used in metal printing contains a film-forming resin composition and metal particles, and contains at least one of water and an organic solvent. The film-forming resin composition is preferably thermosetting or photocurable. That is, it is preferably cured by a heat treatment at a temperature lower than the thermal softening point of the film, or can be cured by irradiation with ultraviolet rays or blue light. The film-forming resin composition is, for example, an emulsion or a solution containing, as a main component, a synthetic resin such as a polyurethane resin, a polyester resin, a polyamide resin, a polyolefin resin, or an epoxy resin, and is usually water or an organic solvent. Or a mixture of water and an organic solvent. The metal ink is obtained, for example, by mixing a metal paste in which metal particles are dispersed at a high concentration in a medium composed of an organic solvent or water and a film-forming resin composition. Alternatively, an organic solvent or water is appropriately added and mixed together with the metal paste and the resin composition. In a preferred embodiment, the film-forming resin is a one-component urethane resin composed of a urethane prepolymer, and preferably forms a porous or non-porous moisture-permeable waterproof membrane by curing. is there. In a preferred embodiment, the film-forming resin is a curable resin that can be dispersed in an aqueous solvent such as an aqueous urethane resin. For example, the “Hydran” series of DIC Corporation or the “Hymlen” series of Dainichi Seika Kogyo Co., Ltd. can be used as appropriate. On the other hand, when the metal particles dispersed at a high concentration in the solvent in the form of a metal paste or the like are non-corrosion resistant metal, a corrosion resistance treatment such as coating is performed in advance. In particular, in the case of aluminum particles, a treatment for preventing whitening or the like is performed. As such a metal paste, for example, those in each series of “Aqueous Al Paste” manufactured by Toyo Aluminum Co., Ltd., in which aluminum particles are dispersed at a high concentration in an organic solvent, can be used. “Aqueous Alpaste” includes (1) “EMR series” (“aluminum flake surface coated with high-density silica”, solvent is propylene glycol monomethyl ether), (2) “WL series” (“aluminum And (3) "WXM series" ("Aluminum surface treated with phosphorus compound (antirust)")) . In addition, as a metal paste in which corrosion-resistant metal particles are dispersed at a high concentration, Toyo Aluminum Co., Ltd.'s "RFA series" ("high quality stainless steel (SUS316L) is flaked" and dispersed in a solvent) Etc. can be used.

  Examples of metal particles disposed on the surface layer such as a metal printing layer include aluminum, nickel, stainless steel, chromium, silver, tin, titanium, iron, zinc, copper, silicon (“metal silicon”), magnesium, which are infrared reflective metals. As well as various alloys made of these, a printed layer mainly composed of aluminum, which is most excellent in infrared reflectivity and economy, is preferable. Examples of the alloy include a magnesium-aluminum alloy, brass (brass), and an aluminum-tin alloy. Although the metal particle diameter of the metal ink used for printing is not particularly limited, an average particle diameter (the above-mentioned volume-based median diameter) of 0.5 to 50 μm is preferable as a general-purpose range. The aspect ratio of the metal particles used in the metal ink is not particularly limited, but the leafing effect can be obtained by setting the same as the aspect ratio of the metal particles kneaded into the film-forming resin base material. . However, an aspect ratio close to 1, that is, close to a perfect sphere may be used. In the present application, a pearl pigment having light reflectance substantially equivalent to that of metal particles and a required degree of light shielding is also included in the metal particles for convenience, and ink and printing made of such pearl pigments are also included. It will be called metal ink and metal printing. The above-mentioned “true” metal particles containing a metal as a main component and a pearl pigment not containing a metal as a main component may be included. Here, the pearl pigment to be included in the metal particles is 40% or more or 50% or more when the reflectance with respect to infrared rays contained in sunlight is contained in a resin film having a thickness of 10 μm at 25% by weight, for example. Can be. The pearl pigments here are not only typical pearl pigments (natural mica (silicate mineral) coated with metal oxides such as titanium oxide and iron oxide), but also synthetic mica. A coated one can be used, and in some cases, a glass-based one, a bismuth oxychloride-based one, a titanium oxide polycrystalline flake, or the like may be used.

  The method for forming the metal printing layer is not particularly limited, but a coating method such as a comma coater, a knife coater or a gravure coater, or a method using flexographic printing or the like is preferable. In addition, methods using (flat) screen printing, rotary (screen) printing, ink jet, spraying, T-die, and the like are also included.

The coating amount of metal ink (solid content including metal particles and resin) forming the metal printing layer is preferably 0.5 to 50 g / m ² . More preferably, it is ² to 25 g / m ² , and in this case, the film thickness of the metal printing layer is 1.6 to 20 μm when the density of the coating film is assumed to be, for example, 1.25. The coating amount is more preferably at 3 to 15 g / ^{m 2,} more preferably a 4~10g / ^{m 2.} If it is 0.5 g / m ² or more, the heat shielding performance is improved, and if it is 50 g / m ² or less, sufficient flexibility is obtained and the workability is improved. In addition, the application amount here is the amount of solid content per area covered with the metal printing layer, that is, the area where the application is actually performed.

  The coverage of the metal print layer is preferably 10 to 80%, more preferably 20 to 80%, still more preferably 30 to 80%, and particularly preferably 40 to 70%. If the cover rate is 10% or more, the heat shielding performance can be improved. Moreover, if it is 80% or less, moisture permeability can be improved. Metal printing is performed so that the coverage is almost uniform at any location. That is, for example, the printing layer pattern such as a dot shape, a stripe shape, or a lattice shape is distributed almost evenly. In one specific example, a dot pattern such as a rectangle with rounded corners, a circle, or an ellipse is evenly distributed, and the width of each dot pattern (minimum diameter) or the width of a linear portion of a stripe or grid For example, it is 50 micrometers-0.5 cm. However, in this printing, the pattern (garb; the shape and arrangement pattern of the printed layer pattern) is not particularly limited. Even when printing is performed using a comma coater or a knife coater, a desired coverage can be obtained by applying the adhesive tape to the coater at a predetermined interval in a streak-like manner. In addition, for example, by including bubbles with a substantially constant diameter in the metal ink, the dot-like non-printing portions can be provided substantially uniformly. In addition, even if it is a location covered with the metal printing layer, if the thickness of the coating film forming the metal printing layer is sufficiently smaller than the diameter of the opening, for example, 60% or less, the opening is blocked. Absent. Therefore, moisture permeability can be sufficiently contributed even in the region of the metal print layer. In addition, the content (% by weight) of the metal particles in the metal printing layer is preferably 5 to 35%.

  In the case of a metal vapor deposition layer, the metal used for metal vapor deposition is an infrared reflective metal such as aluminum, nickel, stainless steel, tin, silver, chromium, etc. Among them, aluminum that is most excellent in infrared reflectivity and economy. The metal vapor deposition layer which has as a main component is preferable.

  The metal deposition layer preferably has a film thickness of 10 to 100 nm. More preferably, it is 20-80 nm. If it is 10 nm or more, infrared rays can be sufficiently reflected, and the heat shielding performance is improved. If it is 100 nm or less, sufficient moisture permeability is obtained, and further productivity is improved. If the thickness of the metal vapor deposition layer is within the above range, it is considered that the pores formed in a size corresponding to the particle diameter of the porous filler are retained in the porous film without being buried. .

  The metal deposition layer can be formed by a normal vacuum deposition method, but other thin film formation methods such as sputtering, ion plating, and plasma vapor deposition (CVD) are used. You can also. However, in consideration of productivity, the vacuum deposition method is the best. As the heating means of the vacuum evaporation apparatus by the vacuum evaporation method, an electron beam heating method, a resistance heating method, or an induction heating method is preferable. In order to improve the adhesion between the thin film and the substrate and the denseness of the thin film, plasma assist It is also possible to use an ion beam assist method.

In order to prevent the peeling or falling off due to the deterioration of the above-mentioned metal printing layer or metal deposition layer, the metal printing layer or metal deposition layer is synthesized with polyurethane, polyamide, polyester, polyolefin, acrylic, epoxy, etc. It is preferable to coat with a protective layer made of a resin, and to add a water-repellent agent such as fluorine, silicone or paraffin. Synthetic resin amount constituting the protective layer is preferably from 0.05-5 g / ^{m 2} in solid content is more preferably a 0.1 to 1 g / ^{m 2.} If it is 0.05 g / m < ² > or more, the intensity | strength as a protective layer will improve. Moreover, if it is 5 g / m < ² > or less, sufficient moisture permeability can be obtained. In order to increase the durability of the protective layer, corrosion inhibitors (surfactants, etc.) and antioxidants (phenolic, amine-based primary antioxidants, phosphorus-based, sulfur-based secondary antioxidants, etc.) Is preferably used. Further, it is more preferable to use an ultraviolet absorber (octyl methoxycinnamate, oxybenzone, etc.), a light stabilizer (hindered amine type, etc.) and a crosslinking agent (isocyanate type, epoxy type) in combination. The method for applying the protective layer is not particularly limited as long as a thin film can be formed and can be uniformly coated, but a coating method such as a comma coater, a knife coater or a gravure coater, or a method using flexographic printing is preferable. In addition, methods using padding (dip / nip), screen printing, rotary printing, ink jet, spraying, T-die, and the like are also included.

  In addition, for the purpose of improving the adhesion of the metal printing layer or the metal vapor deposition layer in advance to the porous film on which the metal printing layer or the metal vapor deposition described above is laminated, the primer treatment or the film surface modification treatment is performed. May be performed. For example, the primer coating treatment may be performed by using a resin composition mainly composed of a polyurethane resin, a polyester resin, a polyamide resin, a polyolefin resin, an epoxy resin, or the like, such as a solvent type, an aqueous type, or an emulsion type. A coating method such as a comma coater, a knife coater, a gravure coater, or a method using flexo printing is preferably used. In addition, padding (dip / nip), kiss coater, screen print, rotary print, inkjet, It can also be applied using a spray, T-die or the like. Examples of the surface modification method include corona discharge treatment, ozone treatment, plasma treatment using argon gas, oxygen gas, or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, and the like. . By performing such a treatment, the adhesion and surface smoothness of the metal layer can be improved, and the drop-off preventing property can be improved.

  In order to obtain the required physical properties (strength) on at least one side of the porous film on which the metal printing layer or metal vapor deposition layer obtained as described above is laminated, one or two or more layers of reinforcing cloth and laminate processing are performed. It is effective that the laminated product is implemented.

Examples of the reinforcing fabric include woven fabrics, knitted fabrics, split fabrics, and nonwoven fabrics, and may be known ones. Among these, from the viewpoint of securing strength, it is preferable to be composed of fibers of polyester, polyamide, polyolefin and the like. The fineness of the fiber is preferably 1 to 1000 dtex. If it is 1 dtex or more, the strength is improved, and if it is 1000 dtex or less, sufficient flexibility is obtained and the workability is improved. Moreover, 20-500 g / m < ² > is preferable for the mass (area weight) per area. If it is 20 g / m ² or more, sufficient strength can be obtained. Moreover, since it is lightweight if it is 500 g / m < ² > or less, the workability | operativity at the time of construction improves. Furthermore, it is preferable that the tensile strength is 50 N / 5 cm or more for both vertical and horizontal. If it is 50 N / 5 cm or more, tearing, tearing, etc. during construction can be reduced.

  When the reinforcing fabric is a non-woven fabric, a known method such as chemical bond, spun lace, spun bond, melt blow, or the like is used as the manufacturing method. Further, the lamination is not limited to two layers, and may be a multilayer having a plurality of structures from the viewpoints of strength and tension according to the purpose and application. For example, a reinforcing fabric can be attached to both sides of a porous film provided with a metal printing layer or a metal vapor deposition layer, respectively, or can be attached to one side of the porous film. At this time, two reinforcing fabrics can be pasted so that their vertical directions intersect.

  As a method for laminating the film and the reinforcing cloth of the present invention, a general method such as dry lamination, wet lamination, thermal lamination, hot lamination, etc. can be used, and it is laminated so that it is difficult to peel off during construction and use. The adhesive used for lamination may be a solvent-based, water-based, or emulsion-based adhesive, but is not particularly limited and is not limited. For example, organic solvent-based, one-component moisture-curable or two-component curable dry laminate adhesives for food packaging films (for example, “Yunoflex” series manufactured by Sanyo Chemical Industries, Ltd.) or urethane-based reactive curing Type, solvent-free laminate adhesive for food packaging film (for example, “Dick Dry” series manufactured by DIC Graphics Co., Ltd.) or hot-melt type dry laminate adhesive for food packaging film (for example, Asahi Chemical) “Asahi Melt” series (ethylene-vinyl acetate) manufactured by Synthetic Co., Ltd. can be used. Moreover, the total area of the adhesion location between the film at the time of lamination | stacking and a reinforcement cloth is 10 to 80% of the total area overlapped and bonded. If it is less than 10%, sufficient adhesiveness may not be obtained, and there is a risk of peeling between the layers, and if it exceeds 80%, the opening may be filled with an adhesive and air permeability may be impaired. For example, if a dry laminate adhesive for food packaging film as described above is applied to a reinforcing cloth with a roller to a moderately thin thickness and then superposed on a porous film, the area ratio of the bonded portions can be easily reduced to 30 to 70%. It can be. Moreover, if the adhesive is spray-applied to the reinforcing cloth, it can be applied in a fine dot shape (for example, the diameter is 10 μm to 0.1 cm), and the area ratio of the bonded portion is, for example, 10 to 50%. In particular, it may be 10 to 30%.

The moisture permeability resistance of the laminated sheet obtained from the above is 0.04 to 0.19 m ² · s · Pa / μg, and in the initial state, according to JIS L 1092 (2009) The waterproof property obtained by the hydrostatic pressure method is 10 KPa or more. If the moisture permeability resistance is less than 0.04 m ² · s · Pa / μg, the waterproof property may be impaired. In addition, if it exceeds 0.19 m ² · s · Pa / μg, the humidity in the room is difficult to escape to the outside in actual use, and there is a risk of mold on wood and building materials such as pillars. It may be damaged and is not preferable. If the waterproof property is less than 10 kPa, it is difficult to say that it is waterproof in actual use. And in 2000-2500 nm which is a heat ray wavelength range of sunlight, the average value of infrared reflectance is 50% or more, and the average value of infrared transmittance is 30% or less. If the average value of the infrared reflectance is less than 50% and / or the average value of the infrared transmittance is more than 30%, it is difficult to say that there is a heat shielding effect in actual use.

  In addition, after the accelerated exposure test by solar radiation specified in JIS A 1415 (2003) was performed for 200 hours and the heat treatment specified in JIS K 7212 (1999) was performed at 80 ° C. for 28 weeks, JIS L 1092 It is preferable that the waterproofness obtained by the hydrostatic pressure method of method A defined in (2009) is 8 KPa or more and that the infrared reflectance at 2000 nm to 2500 nm is maintained at 70% or more of the initial value. If the retention rate is 70% or more, the heat shielding performance can be improved even in long-term construction.

Hereinafter, although an example is given and explained about the present invention concretely, the present invention is not necessarily limited to the example. In addition, each physical property in an Example and a comparative example was measured with the following method.
(1) Formability The film forming state was visually confirmed and evaluated as follows.
○: Moldable without defects ×: Breakage and cracks occur, and molding is impossible (2) Moisture permeability resistance The evaluation machine uses DH-400 manufactured by Daiei Kagaku Seisakusho Co., Ltd. and conforms to JIS A 6111 (2004). Measurements were performed according to the above. The smaller the numerical value obtained, the more moisture is released outdoors.
(3) Waterproofness The evaluation machine used WP-100K made by Daiei Kagaku Seiki Seisakusho Co., Ltd., and measured according to the A method prescribed in JIS L 1092 (2009). It was determined that there was no problem in actual use as long as the initial evaluation criteria for waterproofness were 10 KPa or more.

(4) Infrared reflectivity and transmittance Infrared reflectivity and transmittance are measured using an ultraviolet / visible / near-infrared spectrophotometer (UV-3600, manufactured by Shimadzu Corporation). Infrared reflectance and transmittance were measured under the measurement wavelength of 2000 to 2600 nm.
(5) Infrared reflectance retention after corrosion treatment (high-temperature and high-humidity treatment) The test piece is left for 72 hours in a constant-temperature dryer (FC-612, manufactured by ADVANTEC) at 70 ° C. × 90% RH. Then, using an ultraviolet / visible / near-infrared spectrophotometer (UV-3600, manufactured by Shimadzu Corporation), the surface reflectance of the test piece (the outer wall surface during construction) was measured under the conditions of a measurement wavelength of 2000 to 2600 nm. Was measured, and the retention rate was calculated by the following formula.
Infrared reflectance retention rate = (infrared reflectance after endurance treatment / initial infrared reflectance) × 100
(6) Discoloration judgment after corrosion treatment (high temperature and high humidity treatment) The test piece is left in a constant temperature dryer (FC-612 manufactured by ADVANTEC) in an environment of 70 ° C. × 90% RH for 72 hours. Then, using CCM (CM-3700A, CM-S100W, manufactured by Konica Minolta Sensing Co., Ltd.), the reflectance of visible light (400 to 700 nm) was measured, and the integrated value was obtained. The values were evaluated as follows based on the values.
○: Value after corrosion treatment is 70% or more of initial value ×: Value after corrosion treatment is less than 70% of initial value

(7) Waterproofness after endurance treatment (accelerated exposure treatment equivalent to 20 years) JIS A 6111 (2004) Based on the treatment content in the durability of moisture permeable waterproof sheet, according to accelerated exposure test JIS A 1415 (2013) Then, a sunshine weather meter ((SWM): WEL-SUN-MCH, B type manufactured by Suga Test Instruments Co., Ltd.) was used for the test piece, and irradiated for 2 hours / cycle at 100 cycles, and then JIS K 7212 (1999), heat treatment was performed. The treatment temperature and time were 80 ± 2 ° C. for 28 weeks. Thus, after performing the accelerated exposure process equivalent to 20 years, waterproof evaluation was performed by the hydrostatic pressure method of the A method prescribed | regulated to JISL1092 (2009). However, the pressure surface of the water pressure was the surface of the test piece (outer wall surface during construction). The evaluation criteria for waterproofness after the durability treatment was judged to be durable without being a problem in actual use as long as it was maintained at 8 KPa or more.

(8) Retention rate of infrared reflectance after endurance treatment (accelerated exposure treatment equivalent to 20 years) After performing accelerated exposure treatment equivalent to 20 years in the same manner as (7) above, ultraviolet / visible / near infrared rays Using a spectrophotometer (UV-3600, manufactured by Shimadzu Corporation), the infrared reflectance was measured under the conditions of a measurement wavelength of 2000 to 2500 nm on the front side surface (surface on the outer wall side during construction) of the test piece, The retention rate was calculated by the following formula.
Infrared reflectance retention rate = (infrared reflectance after endurance treatment / initial infrared reflectance) × 100
And it confirms that this average value is 70% or more before a test.
(9) Tensile strength and elongation The tensile strength and tensile elongation of the laminated sheet were measured by a tensile test based on JIS L 1906, and the polyester spunbond nonwoven fabric (Toyobo Co., Ltd.) used for the backing in all Examples and Comparative Examples. It was confirmed that it was almost the same as that of 3701A). That is, in the vertical direction of the nonwoven fabric (the direction of feeding the belt-like sheet at the time of manufacturing the nonwoven fabric), both the strength of around 269 N / 5 cm and the elongation of around 27% are observed. In the width direction, it was confirmed that an intensity of around 104 N / 5 cm and an elongation of around 33% were observed. These results are not shown in the table.
(10) Coverage ratio and adhesion area ratio It was confirmed by image analysis after taking an image at a magnification of 300 times using a scanning electron microscope that a predetermined coverage ratio was obtained. Also, the adhesion area ratio at the time of dry lamination is the total of the places where the nonwoven fabric fibers are adhered and the places where the fibers are peeled off on the porous film after the nonwoven fabric is peeled off from the porous film. The ratio of the area to the total area is determined in units of 10% by observing with a stereomicroscope. These results are also not shown in the table.

[Example 1]
The particle diameter is 1 μm with respect to 100 parts by mass of resin-based polyethylene (Nippon Polyethylene Co., Ltd., Novatec HD, HF560; high-density polyethylene resin for film, melting point 128 ° C., density 0.963, melt flow rate 7.0). An aluminum masterbatch having a particle thickness of 0.05 μm and an aspect ratio of 20 (manufactured by Tokyo Ink Co., Ltd., PEX496Silver AL; 32% by mass of aluminum particles, the rest being a low density polyethylene resin (LDPE), and a small amount of coating material 25 parts by mass of an acrylate resin), 25 parts by mass of an inorganic filler (heavy calcium carbonate; manufactured by Shiraishi Calcium Co., Ltd., BF-400) having a particle diameter of 40 μm, and an ultraviolet absorber (TINUVIN 120 manufactured by Ciba Japan Co., Ltd.) 2 parts by weight, light stabilizer (Ciba Japan 2 parts by mass of CHIMASSORB 2020 FDL manufactured by Co., Ltd. and 2 parts by mass of antioxidant (manufactured by Ciba Japan Co., Ltd., IRGANOX 1098) were added and melted and kneaded at a temperature of 210 ° C. with a co-rotating twin screw extruder. Homogenized. Next, a film having a thickness of 30 μm was extruded by a T die. Thereafter, the film was stretched 1.1 times in the film formation (length) direction to obtain a porous film having a thickness of 27 μm. Further, the aluminum printing of Formula 1 was applied to one side (surface) of this film by a gravure coating method so that the solid content was 5 g / m ² (dot pattern with a diameter of 0.3 cm circle, covering rate 65%), and air blowing Heat treatment was performed at 80 ° C. for 30 seconds in a constant temperature dryer. In addition, a polyester spunbonded nonwoven fabric having a basis weight of 70 g / m ² (3701A manufactured by Toyobo Co., Ltd., tensile strength (elongation) warp 269 N / 5 cm (27%), width 104 N / 5 cm ( 33%)) was adhered by a dry laminating method to obtain a house wrap material. For bonding nonwoven fabric to polyethylene moisture permeable waterproof film, hot melt dry laminate adhesive for food packaging film (Asahimelt K1217 manufactured by Asahi Chemical Synthetic Co., Ltd.) is dissolved at 230 degrees and applied by spray method. The amount of dry laminate adhesive applied to the nonwoven fabric was 5 g / m ^{2 in} terms of solid content, and the adhesion area was 50% of the total area of the nonwoven fabric. And it clamped between a pair of rollers. The evaluation results are shown in Table 1.
[Prescription 1]
50 parts by mass of Hydran HW-201 (ether polyurethane resin, solid content 35%, manufactured by DIC Corporation)
Isopropyl alcohol 15 parts by mass Water 100 parts by mass EMR-D3422 10 parts by mass (aluminum paste, metal content 60%, average particle size 22 μm, manufactured by Toyo Aluminum Co., Ltd.)

[Example 2]
The particle size is 0 with respect to 100 parts by mass of resin-based polyethylene (Nippon Polyethylene Co., Ltd., Novatec HD, HF560; high-density polyethylene resin for film, melting point 128 ° C., density 0.963, melt flow rate 7.0). .1 μm, particle thickness of 0.01 μm, aspect ratio of 10 aluminum masterbatch (manufactured by Tokyo Ink Co., PEX526Silver; 40% by mass of aluminum particles, the rest being low density polyethylene resin, and a small amount of acrylate resin as a coating material ) 10 parts by mass of inorganic filler (synthetic calcium carbonate; manufactured by Shiraishi Calcium Co., Ltd., Softon 23000) and 2 UV absorbers (TINVAIN 120, manufactured by Ciba Japan Co., Ltd.). Parts by weight, light stabilizer (Ciba Japan Ltd. 2 parts by mass of CHIMASSORB 2020 FDL (made by company) and 2 parts by mass of antioxidant (Ciba Japan Co., Ltd., IRGANOX 1098) were added and melted and kneaded uniformly at a temperature of 210 ° C. in a co-rotating twin screw extruder. Turned into. Next, a film having a thickness of 7.5 μm was formed by a T die. Thereafter, the film was stretched 1.5 times in the film formation (length) direction to obtain a porous film having a thickness of 5 μm. Further, in the same manner as in Example 1, aluminum printing was performed on one side of the film, and a non-woven fabric was laminated on the other side. The evaluation results are shown in Table 1.

[Example 3]
The particle diameter is 10 μm with respect to 100 parts by mass of resin-based polyethylene (Nippon Polyethylene Co., Ltd., Novatec HD, HF560; high-density polyethylene resin for film, melting point 128 ° C., density 0.963, melt flow rate 7.0). An aluminum masterbatch having a particle thickness of 7.6 μm and an aspect ratio of 1.32. (Toyo Aluminum Co., Ltd., NME010T6B; 70% by mass of aluminum particles, the rest being a low density polyethylene resin and polyethylene wax, as a small amount of coating material Acrylate resin) and 20 parts by mass of inorganic filler (heavy calcium carbonate; manufactured by Shiraishi Calcium Co., Ltd., BF-200) having a particle diameter of 5 μm, UV absorber (manufactured by Ciba Japan Co., Ltd., TINUVIN 120). ) 2 parts by weight, light stabilizer (Ciba 2 parts by mass of CHIMASSORB 2020 FDL manufactured by Japan Co., Ltd. and 2 parts by mass of antioxidant (IRGANOX 1098 manufactured by Ciba Japan Co., Ltd.) were added and dissolved and kneaded at a temperature of 210 ° C. with a co-rotating twin screw extruder. And homogenized. Next, a film having a thickness of 135 μm was formed by a T die. Thereafter, the film was stretched 5 times in the film formation (length) direction to obtain a porous film having a thickness of 27 μm. Further, in the same manner as in Example 1, aluminum printing was performed on one side of the film, and a non-woven fabric was laminated on the other side. The evaluation results are shown in Table 1.

[Example 4]
The particle diameter is 10 μm with respect to 100 parts by mass of resin-based polyethylene (Nippon Polyethylene Co., Ltd., Novatec HD, HF560; high-density polyethylene resin for film, melting point 128 ° C., density 0.963, melt flow rate 7.0). An aluminum masterbatch having a particle thickness of 0.5 μm and an aspect ratio of 20 (Toyo Aluminum Co., Ltd., NME010T6; 70% by mass of aluminum particles, the rest being low-density polyethylene resin, polyethylene wax, and a small amount of acrylate as a coating material 20 parts by mass of resin), 70 parts by mass of inorganic filler (heavy calcium carbonate; manufactured by Shiraishi Calcium Co., Ltd., BF-200) having a particle size of 5 μm, and UV absorber (TINUVIN 120 manufactured by Ciba Japan Co., Ltd.). 2 parts by weight, light stabilizer (Ciba Ja 2 parts by mass of CHIMASSORB 2020 FDL) and 2 parts by mass of antioxidant (Ciba Japan Co., Ltd., IRGANOX 1098) are added and melted and kneaded at a temperature of 210 ° C. with a co-rotating twin screw extruder. And homogenized. Next, a film having a thickness of 60 μm was formed by a T die. Thereafter, the film was stretched 5 times in the film formation (length) direction to obtain a porous film having a thickness of 12 μm. Further, in the same manner as in Example 1, aluminum printing was performed on one side of the film, and a non-woven fabric was laminated on the other side. The evaluation results are shown in Table 1.

[Example 5]
The particle diameter is 20 μm with respect to 100 parts by mass of resin-based polyethylene (Nippon Polyethylene Co., Ltd., Novatec HD, HF560; high-density polyethylene resin for film, melting point 128 ° C., density 0.963, melt flow rate 7.0). An aluminum masterbatch having a particle thickness of 0.05 μm and an aspect ratio of 400 (Toyo Aluminum Co., Ltd., NME020T2; 70% by mass of aluminum particles, the rest being a low-density polyethylene resin, polyethylene wax, and a small amount of acrylate as a coating material 1 part by mass of resin), 60 parts by mass of inorganic filler (heavy calcium carbonate; manufactured by Shiraishi Calcium Co., Ltd., BF-300) having a particle diameter of 8 μm, and UV absorber (TINUVIN 120 manufactured by Ciba Japan Co., Ltd.). 2 parts by weight, light stabilizer (Ciba 2 parts by mass of CHIMASSORB 2020 FDL manufactured by Bread Co., Ltd. and 2 parts by mass of antioxidant (manufactured by Ciba Japan Co., Ltd., IRGANOX 1098) are added and melted and kneaded at a temperature of 210 ° C. with a co-rotating twin screw extruder. And homogenized. Next, a film having a thickness of 60 μm was formed by a T die. Thereafter, the film was stretched 1.5 times in the film formation (length) direction to obtain a porous film having a thickness of 40 μm. Further, in the same manner as in Example 1, aluminum printing was performed on one side of the film, and a non-woven fabric was laminated on the other side. The evaluation results are shown in Table 1.

[Example 6]
Resin base polyethylene (Nippon Polyethylene Co., Ltd., Novatec HD, HF560; High-density polyethylene resin for film, melting point 128 ° C., density 0.963, melt flow rate 7.0) SUS masterbatch with a particle thickness of 0.04 μm and aspect ratio of 1000 (Toyo Aluminum Co., Ltd., RFA-3000; 70% by mass of stainless steel (SUS316L) particles, the rest being low density polyethylene resin and polyethylene wax, a small amount 1 part by mass of an acrylate resin as a coating material, 50 parts by mass of an inorganic filler (heavy calcium carbonate; manufactured by Shiraishi Calcium Co., Ltd., BF-200) having a particle size of 5 μm, an ultraviolet absorber (manufactured by Ciba Japan Co., Ltd.) TINUVIN 120), 2 parts by weight, light stable (Ciba Japan Co., Ltd., CHIMASSORB 2020 FDL) 2 parts by mass, antioxidant (Ciba Japan Co., Ltd., IRGANOX 1098) was added 2 parts by mass, and the temperature was 210 ° C. in a co-rotating twin screw extruder at high speed. And kneaded to make uniform. Next, a film having a thickness of 450 μm was formed by a T die. Thereafter, the film was stretched 3 times in the film formation (length) direction to obtain a porous film having a thickness of 150 μm. Further, in the same manner as in Example 1, aluminum printing was performed on one side of the film, and a non-woven fabric was laminated on the other side. The evaluation results are shown in Table 1.

[Example 7]
The particle diameter is 10 μm with respect to 100 parts by mass of polyethylene as a resin base (Nippon Polyethylene Co., Ltd., Novatec HD, HF560; high-density polyethylene resin for film, melting point 128 ° C., density 0.963, melt flow rate 7.0) Aluminum masterbatch with particle thickness of 1 μm and aspect ratio of 10 (Toyo Aluminum Co., Ltd., NME010T6; 70% by mass aluminum particles, the rest being low density polyethylene resin, polyethylene wax, and acrylate resin as a small amount of coating material) 5 parts by mass, an inorganic filler (heavy calcium carbonate; BF-200, manufactured by Shiraishi Calcium Co., Ltd., BF-200) having a particle size of 5 μm, and a masterbatch ultraviolet absorber (Ciba Japan Co., Ltd., TINUVIN 120) 2 parts by weight, light stable (Ciba Japan Co., Ltd., CHIMASSORB 2020 FDL) 2 parts by mass, antioxidant (Ciba Japan Co., Ltd., IRGANOX 1098) was added 2 parts by mass, and the temperature was 210 ° C. in a co-rotating twin screw extruder at high speed. And kneaded to make uniform. Next, a film having a thickness of 60 μm was formed by a T die. Thereafter, the film was stretched twice in the film formation (length) direction to form a 30 μm porous film. Further, stainless steel printing of Formula 2 was applied to one side (surface) of this film by a gravure coating method so that the solid content was 0.5 g / m ² (dot pattern with a diameter of 2.5 cm circle, covering rate 80%). And heat treatment at 80 ° C. for 30 seconds. In addition, the lamination process of the nonwoven fabric was performed on the opposite surface of the printing surface in the same manner as in Example 1. The evaluation results are shown in Table 1.
[Prescription 2]
Heimlen T-21-1 100 parts by mass (ether polyurethane resin, solid content 25%, manufactured by Dainichi Seika Kogyo Co., Ltd.)
IPA 15 parts by mass RFA-4000 10 parts by mass (SUS flakes, metal content 60%, average particle size 30 μm, manufactured by Toyo Aluminum Co., Ltd.)

[Example 8]
Resin base polyethylene (Nippon Polyethylene Co., Ltd., Novatec HD, HF560; High-density polyethylene resin for film, melting point 128 ° C., density 0.963, melt flow rate 7.0) SUS masterbatch with a particle thickness of 0.04 μm and aspect ratio of 1000 (Toyo Aluminum Co., Ltd., RFA-3000; 70% by mass of stainless steel (SUS316L) particles, the rest being low density polyethylene resin and polyethylene wax, a small amount 1 part by mass of an acrylate resin as a coating material, 50 parts by mass of an inorganic filler (heavy calcium carbonate; manufactured by Shiraishi Calcium Co., Ltd., BF-200) having a particle size of 5 μm, and a masterbatch UV absorber (Ciba TINUVIN 120 manufactured by Japan Co., Ltd. 2 parts by weight, 2 parts by weight of a light stabilizer (CibaSSO 2020 FDL) and 2 parts by weight of an antioxidant (Ciba Japan, IRGANOX 1098) are added and rotated in the same direction at high speed. The mixture was melted and kneaded with a twin screw extruder at a temperature of 210 ° C. to make it uniform. Next, a film having a thickness of 450 μm was formed by a T die. Thereafter, the film was stretched 3 times in the film formation (length) direction to form a 150 μm porous film. Furthermore, stainless steel printing of Formula 2 was applied to one side (surface) of this film by a gravure coating method so that the solid content was 50 g / m ² (dot pattern with a diameter of 0.5 cm circle, coverage rate 10%), 90 Heat treatment was carried out at 30 ° C. for 30 seconds. In addition, the lamination process of the nonwoven fabric was performed on the opposite surface of the printing surface in the same manner as in Example 1. The evaluation results are shown in Table 1.

[Example 9]
A film was formed in the same manner as in Example 7. Further, in the same manner as in Example 1, aluminum printing was performed on one side of the film, and a non-woven fabric was laminated on the other side. The evaluation results are shown in Table 1.

[Example 10]
A film was formed in the same manner as in Example 7, and further, stainless steel printing of Formula 2 was applied to one side (surface) of this film by a gravure coating method so that the solid content was 5 g / m ² (diameter 0.3 cm yen). (The cover rate was 65%) and heat treatment was performed at 80 ° C. for 30 seconds. In addition, the lamination process of the nonwoven fabric was performed on the opposite surface of the printing surface in the same manner as in Example 1. The evaluation results are shown in Table 1.

[Example 11]
A film was formed in the same manner as in Example 7, and further, stainless steel printing of Formula 2 was applied to one side (surface) of this film by a gravure coating method so that the solid content was 2 g / m ² (diameter of 0.5 cm). A dot pattern of 15%) and heat treated at 80 ° C. for 30 seconds. In addition, the lamination process of the nonwoven fabric was performed on the opposite surface of the printing surface in the same manner as in Example 1. The evaluation results are shown in Table 2.

[Example 12]
A film was formed in the same manner as in Example 7, and further, stainless steel printing of Formula 2 was applied to one side (surface) of this film by a gravure coating method so that the solid content was 8 g / m ² (diameter of 0.5 cm). A dot pattern of 73% covering rate) and heat treated at 80 ° C. for 30 seconds. In addition, the lamination process of the nonwoven fabric was performed on the opposite surface of the printing surface in the same manner as in Example 1. The evaluation results are shown in Table 2.

[Example 13]
A film was formed in the same manner as in Example 7, and further, stainless steel printing treatment was performed on one side of the film in the same manner as in Example 10. In addition, a polyester spunbonded nonwoven fabric having a basis weight of 70 g / m ² (3701A manufactured by Toyobo Co., Ltd., tensile strength (elongation) length 269 N / 5 cm (27%), width 104 N / 5 cm (33%)) )) Was bonded by a dry laminating method to obtain a house wrap material. For bonding nonwoven fabric to polyethylene moisture permeable waterproof film, hot melt dry laminate adhesive for food packaging film (Asahimelt K1217 manufactured by Asahi Chemical Synthetic Co., Ltd.) is dissolved at 230 degrees and applied by spray method. The amount of the dry laminate adhesive applied to the nonwoven fabric was 4 g / m ^{2 in} terms of solid content, and the adhesion area was 17% of the total area of the nonwoven fabric. And it clamped between a pair of rollers. The evaluation results are shown in Table 2.

[Example 14]
A film was formed in the same manner as in Example 7, and further, stainless steel printing treatment was performed on one side of the film in the same manner as in Example 10. In addition, a polyester spunbonded nonwoven fabric having a basis weight of 70 g / m ² (3701A manufactured by Toyobo Co., Ltd., tensile strength (elongation) length 269 N / 5 cm (27%), width 104 N / 5 cm (33%)) )) Was bonded by a dry laminating method to obtain a house wrap material. For bonding nonwoven fabric to polyethylene moisture permeable waterproof film, hot melt dry laminate adhesive for food packaging film (Asahimelt K1217 manufactured by Asahi Chemical Synthetic Co., Ltd.) is dissolved at 230 degrees and applied by spray method. The amount of dry laminate adhesive applied to the nonwoven fabric was 8 g / m ^{2 in} terms of solid content, and the adhesion area was 76% of the total area of the nonwoven fabric. And it clamped between a pair of rollers. The evaluation results are shown in Table 2.

[Example 15]
A film was formed in the same manner as in Example 7. Further, the primer treatment solution of Formula 3 was applied to one side of this film by a gravure coating method so that the dry solid content was 0.5 g / m ^2, and at 80 ° C. Heat-treated for 30 seconds. Next, aluminum vapor deposition was performed on the primer-treated surface of the film so as to have a film thickness of 450 ± 50 mm (coverage rate 98%). Further, an aqueous solution of the following formulation 4 was applied to this vapor deposition surface by a knife coating method so as to have a dry solid content of 1.0 g / m ^2, and heat-treated at 80 ° C. for 30 seconds to form a protective layer having a thickness of 1.0 μm. Formed. In addition, a polyester spunbonded nonwoven fabric having a basis weight of 70 g / m ² (3701A manufactured by Toyobo Co., Ltd., tensile strength (elongation) length 269 N / 5 cm (27%), horizontal 104 N / 5 cm) (33%)) was bonded by a dry laminating method to obtain a house wrap material. For bonding nonwoven fabric to polyethylene moisture permeable waterproof film, hot melt dry laminate adhesive for food packaging film (Asahimelt K1217 manufactured by Asahi Chemical Synthetic Co., Ltd.) is dissolved at 230 degrees and applied by spray method. The amount of the dry laminate adhesive applied to the nonwoven fabric was 4.5 g / m ^{2 in} terms of solid content, and the adhesion area was 30% of the total area of the nonwoven fabric. And it clamped between a pair of rollers. The evaluation results are shown in Table 2.
[Prescription 3]
Permarin UA-99 10 parts by weight (ether polyurethane resin, solid content 20%, manufactured by Sanyo Chemical Industries, Ltd.)
100 parts by weight of water [Prescription 4]
Hydran HW-201 100 parts by weight (ether polyurethane resin, solid content 35%, manufactured by DIC Corporation)
Colomine W 1 part by weight (polyoxyethylene alkyl ether solid content 10%, manufactured by Kao Corporation)
Shineguard F-70 1 part by weight (aliphatic amine derivative solid content 10%, manufactured by Senka Corporation)
Drypon 600E 2 parts by weight (silicone activator solid content 54% manufactured by Nikka Chemical Co., Ltd.)
IPA 30 parts by weight Water 100 parts by weight

[Comparative Example 1]
50 parts by mass of an inorganic filler (heavy calcium carbonate; BF-200, manufactured by Shiraishi Calcium Co., Ltd.) having a particle size of 5 parts by mass with respect to 100 parts by mass of polyethylene (Nippon Polyethylene Co., Ltd., Novatec HD, HF560) as a resin base material. , 2 parts by mass of a masterbatch UV absorber (manufactured by Ciba Japan Co., Ltd., TINUVIN 120), 2 parts by mass of light stabilizer (manufactured by Ciba Japan Co., Ltd., CHIMASSORB 2020 FDL), and antioxidant (Ciba 2 parts by mass of IRGANOX 1098) manufactured by Japan Co., Ltd. was added, and the mixture was melted and kneaded at a temperature of 210 ° C. with a same-direction rotating twin screw extruder. Next, a film having a thickness of 135 μm was formed by a T die. Thereafter, the film was stretched 5 times in the film formation (length) direction to form a 27 μm porous film. Further, as in Example 10, aluminum printing was performed on one side of the film, and a nonwoven fabric was laminated on the other side in the same manner as in Example 1. The evaluation results are shown in Table 2.

[Comparative Example 2]
Aluminum masterbatch (Toyo Aluminum Co., Ltd.) having a particle diameter of 10 μm, a particle thickness of 6.5 μm, and an aspect ratio of 1.54 with respect to 100 parts by mass of resin-based polyethylene (Nippon Polyethylene Co., Ltd., Novatec HD, HF560) NME010T6; 70% by weight of aluminum particles, the rest being low-density polyethylene resin, polyethylene wax, and a small amount of acrylate resin as a coating material), 20 parts by weight, UV absorber (TINUVIN 120, manufactured by Ciba Japan Co., Ltd.) 2 parts by weight, 2 parts by weight of light stabilizer (CibaSSO 2020 FDL), 2 parts by weight of antioxidant (Ciba Japan Co., Ltd., IRGANOX 1098) are added, and the same direction rotating biaxial Dissolved at a temperature of 210 ° C in an extruder And homogenized by kneading. Next, a film having a thickness of 135 μm was formed by a T die. Thereafter, the film was stretched 5 times in the film formation (length) direction to form a 27 μm porous film. Further, as in Example 10, aluminum printing was performed on one side of the film, and a nonwoven fabric was laminated on the other side in the same manner as in Example 1. The evaluation results are shown in Table 2.

[Comparative Example 3]
A film was formed in the same manner as in Example 7, and the aluminum printing of Formula 1 was applied to one side (surface) of this film by a gravure coating method so that the solid content was 20 g / m ² (diameter of 1.5 cm). The heat treatment was carried out at 80 ° C. for 30 seconds. In addition, the lamination process of the nonwoven fabric was performed on the opposite surface of the printing surface in the same manner as in Example 1. The evaluation results are shown in Table 2.

[Comparative Example 4]
A film was formed in the same manner as in Example 7, and further, stainless steel printing treatment was performed on one side of the film in the same manner as in Example 10. In addition, a polyester spunbonded nonwoven fabric having a basis weight of 70 g / m ² (3701A manufactured by Toyobo Co., Ltd., tensile strength (elongation) length 269 N / 5 cm (27%), width 104 N / 5 cm (33%)) )) Was bonded by a dry laminating method to obtain a house wrap material. For bonding nonwoven fabric to polyethylene moisture permeable waterproof film, hot melt dry laminate adhesive for food packaging film (Asahimelt K1217 manufactured by Asahi Chemical Synthetic Co., Ltd.) is dissolved at 230 degrees and applied by spray method. The amount of dry laminate adhesive applied to the nonwoven fabric was 2.5 g / m ^{2 in} terms of solid content, and the adhesion area was 8% of the total area of the nonwoven fabric. And it clamped between a pair of rollers. The evaluation results are shown in Table 2.

[Comparative Example 5]
A film was formed in the same manner as in Example 7, and further, stainless steel printing treatment was performed on one side of the film in the same manner as in Example 10. In addition, a polyester spunbonded nonwoven fabric having a basis weight of 70 g / m ² (3701A manufactured by Toyobo Co., Ltd., tensile strength (elongation) length 269 N / 5 cm (27%), width 104 N / 5 cm (33%)) )) Was bonded by a dry laminating method to obtain a house wrap material. For bonding nonwoven fabric to polyethylene moisture permeable waterproof film, hot melt dry laminate adhesive for food packaging film (Asahimelt K1217 manufactured by Asahi Chemical Synthetic Co., Ltd.) is dissolved at 230 degrees and applied by spray method. The amount of the dry laminate adhesive applied to the nonwoven fabric was 11 g / m ^{2 in} terms of solid content, and the adhesion area was 83% of the total area of the nonwoven fabric. And it clamped between a pair of rollers. The evaluation results are shown in Table 2.

  As known from the results of Tables 1 and 2, Examples 1 to 15 provided excellent moisture permeability and waterproofness, excellent infrared shielding properties, and long-term durability thereof. In particular, in Example 5, particularly excellent infrared shielding ability and durability were obtained by adding a small amount of metal particles. In Example 5, although a small amount was added, the particle size and the aspect ratio were within suitable ranges, so it is considered that a good leafing effect was obtained. On the other hand, Examples 9 to 10 and 12 to 14 whose results are shown in Table 2 are particularly preferable conditions, the initial infrared reflectance is 85% or more, and the retention rate is any durability. Even in the test, the value exceeded 90%. In Example 11, since the coating amount (film thickness) and the coverage of metal printing were both small, the initial infrared reflectance and transmittance were slightly inferior. Further, as is known from a comparison between Example 9 and Example 10, in Example 10 in which stainless steel particles and a moisture permeable waterproof film were used for the metal printing layer, aluminum particles and a moisture permeable urethane film were used. The moisture permeability was higher than that of Example 9, and the durability was excellent. However, the initial infrared reflectance was higher in Example 9 using aluminum. In addition, although the Example which used the aluminum particle and the moisture-permeable waterproof film for the metal printing layer is not shown, it is almost equivalent to Example 10 in moisture permeability and durability, and in the initial infrared reflectance, the Example It is confirmed by preliminary experiments that it is almost equivalent to 9.

  In Example 12, in which the coating amount (film thickness) and the coverage of metal printing were both increased under the same conditions as in Example 10, the moisture permeability decreased, but the initial infrared reflectance and transmittance, and 2 The durability of the two tests was very good. Further, in Example 13 in which the adhesion area ratio with the reinforcing fabric was reduced to 17% under substantially the same conditions as in Example 10, the moisture permeability was slightly improved as compared with Example 10, but the other performance was affected. I couldn't see it. From this, it was considered that the adhesion area ratio is preferably small, for example, 10 to 30% is preferable. On the other hand, in Example 14 in which the adhesion area ratio with the reinforcing cloth was increased to 73%, the transmittance of infrared rays was slightly improved, but the moisture permeability decreased. However, there were no other effects in other respects. In Example 15, when the metal vapor deposition layer was provided, the durability was lowered, but the initial infrared reflectance and transmittance and moisture permeability were all excellent. Although detailed results are omitted, if any of the conditions deviates from the preferred range, any of moldability, moisture-permeable waterproof property, infrared shielding property, and durability thereof is inferior.

Claims (9)

A porous film containing metal particles and a filler for porous formation other than metal particles, and having pores formed in the porous filler portions by stretching in at least a uniaxial direction, and this porous on at least one surface quality film, a generally uniform coating to so provided metal printed layer or metal deposition layer, porous reinforcement being against wear at least on one side of the film at any point the area of the more than 10% A laminated sheet made of the fabric of
The adhesive area between the porous film and the reinforcing fabric is 10 to 80% of the total area of the reinforcing fabric,
The moisture permeability resistance is 0.04 to 0.19 m ² · s · Pa / μg, and in the initial state, the waterproofness by the hydrostatic pressure method of A method of JIS L 1092 (2009) is 10 KPa or more, 2000 nm to 2500 nm A laminated sheet having heat shielding performance and moisture permeability waterproofing, characterized in that the infrared reflectance in the glass is 50% or more and the infrared transmittance is 30% or less.   Even after the accelerated exposure test by solar radiation specified in JIS A 1415 (2003) is performed for 200 hours and the heat treatment specified in JIS K 7212 (1999) is performed at 80 ° C. for 28 weeks, the waterproofing is performed. The laminated sheet according to claim 1, wherein the laminated sheet has a heat shielding performance and a moisture permeable and waterproof property, wherein the property is 8 KPa or more and the infrared reflectance at 2000 nm to 2500 nm is 70% or more of the initial value. A metal printing layer is provided by applying a metal ink containing metal particles and a film-forming resin to a porous film on a solid basis in an amount of 0.5 to 50 g / m ^2. The metal particles have a particle diameter of 0.5 to 50 μm and are made of aluminum, nickel, stainless steel, chromium, silver, tin, titanium, iron, zinc, copper, silicon (metal silicon), magnesium, and alloys thereof. It is 1 type chosen from the group which consists of, or arbitrary combinations, The lamination sheet of Claim 1 or 2 characterized by the above-mentioned.   After being left in a high temperature and high humidity of 70 ° C. × 90% RH × 72 h, the visible light reflectance by CCM (Computer Color Matching) is maintained at 70% or more from the initial value, and the infrared reflectance at 2000-2500 nm is the initial value. The laminated sheet according to any one of claims 1 to 3, wherein the laminated sheet is retained by 70% or more. The reinforcing fabric is composed of polyester-based, polyamide-based, and polyolefin-based fibers having a tensile strength of 50 N / 5 cm or more and a fiber fineness of 1 to 1000 dtex in both the vertical and horizontal directions. and, laminated sheet according to any one of claims 1 to 4, characterized in that the mass per unit area of a textile is 20 to 500 g / m ^2, knit, split cloth or nonwoven fabric.   The metal particles contained in the porous film have a particle diameter of 0.1 to 40 μm, an aspect ratio (particle diameter / particle thickness) of 1.3 or more, and the porous filler has a particle diameter of 0.1 to 40 μm, and 100 parts by mass of the resin base material of the film includes 0.10 to 30 parts by mass of the metal particles and 10 to 70 parts by mass of the filler for making porous. The laminated sheet according to any one of claims 1 to 5.   The resin base material of the porous film is an olefin resin, and pores are formed at the location of the porous filler by stretching at least uniaxially 1.1 to 5 times. The laminated sheet according to any one of 1 to 6.   A heat insulating sheet for building foundations comprising the laminated sheet according to any one of claims 1 to 7. After blending metal particles and a porous filler other than metal particles into the resin base of the film, pores are formed in the porous filler by stretching in at least a uniaxial direction. Obtaining a porous film,
Providing at least one surface of the porous film with a metal printing layer or a metal vapor deposition layer so that an area of 10% or more thereof is almost uniformly covered at any location ;
Bonding the reinforcing fabric to at least one surface of the porous film so that the bonding area is 10 to 80% of the total area of the reinforcing fabric;
And the resulting laminated sheet has a moisture permeability resistance of 0.04 to 0.19 m ² · s · Pa / μg, and a waterproof property by hydrostatic pressure method of A method of JIS L 1092 (2009) is 10 KPa or more, 2000 nm to An infrared reflectance at 2500 nm is 50% or more, and an infrared transmittance is 30% or less.