WO2015050217A1 - Procédé de fabrication pour un miroir en film - Google Patents

Procédé de fabrication pour un miroir en film Download PDF

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Publication number
WO2015050217A1
WO2015050217A1 PCT/JP2014/076431 JP2014076431W WO2015050217A1 WO 2015050217 A1 WO2015050217 A1 WO 2015050217A1 JP 2014076431 W JP2014076431 W JP 2014076431W WO 2015050217 A1 WO2015050217 A1 WO 2015050217A1
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Prior art keywords
layer
film mirror
film
resin
sealing
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PCT/JP2014/076431
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English (en)
Japanese (ja)
Inventor
江黒　弥生
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コニカミノルタ株式会社
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Publication of WO2015050217A1 publication Critical patent/WO2015050217A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/08—Mirrors
    • G02B5/0808—Mirrors having a single reflecting layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/416—Reflective
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/71—Resistive to light or to UV
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment

Definitions

  • the present invention relates to a method for manufacturing a film mirror for solar heat collection having a sealing structure on a side surface portion, and more specifically, for solar heat collection having excellent sealing performance and durability (delamination resistance) and a wide reflective area.
  • the present invention relates to a method for manufacturing a film mirror.
  • a solar thermal power generation method that generates power using heat obtained by reflecting and condensing sunlight with a mirror as a medium is attracting attention. Using this method, it is possible to generate electricity regardless of day and night by storing the obtained heat, and from a long-term perspective, the power generation efficiency is higher than that of solar cells, It is considered to be a method that can effectively use sunlight.
  • glass mirrors using glass as a base material are used as mirrors used in solar thermal power generation, and sunlight is collected by supporting such glass mirrors with a metal support member. Used as a reflector.
  • the glass substrate of a large format is made thin, the mirror will be damaged during installation, or the mirror may be damaged due to the impact of flying objects due to strong winds. If it is thick, it becomes very heavy, making it difficult to handle during installation and increasing the transportation cost.
  • a film mirror for solar thermal condensing As a manufacturing method of a resin film mirror, as a first step, after laminating each constituent layer on a large size resin base material to produce a large area film mirror, a film mirror for solar thermal condensing In order to apply to, it is used by cutting to any size.
  • the film mirror laminate (hereinafter also referred to as “film mirror unit”) cut in this way may have one of its constituent layers due to the stress applied to the cut surface of the film mirror laminate during cutting. Slight peeling occurs at the part, and this peeling part is the starting point, and when stored for a long period of time in various usage environments, the delamination increases and causes the quality of the film mirror to deteriorate.
  • This delamination is caused by external stress such as sliding stress or alternating load, and by decrement of interlaminar adhesion due to corrosion of the photothermal reflective layer composed of silver etc. due to intrusion of moisture etc. from the cut surface There is.
  • the functions required for the sealing means are mainly a high sealing force (barrier property) and a high adhesiveness with the cut surface of the film mirror unit.
  • a method for sealing the end portion of such a solar heat collecting film mirror for example, a method using a sealing tape made of resin or aluminum foil is known.
  • a sealing tape made of resin or aluminum foil
  • weathering tapes described in 3M company application guides and sealing tapes such as aluminum edge tapes described in Refletech company application guides have been widely put into practical use.
  • a method has been proposed in which a sealing tape is provided so as to surround the periphery of the solar panel or photovoltaic device to prevent the ingress of oxygen and moisture from the edges. (For example, refer to Patent Document 2).
  • the adhesive force of the sealing tape to the hard coat layer surface is low. It is not sufficient, and as time passes, the sealing tape peels off on the hard coat layer surface, moisture penetrates from the peeled gap, and delamination advances on the cut surface due to the penetrated moisture. Eventually, the photothermal reflection layer is corroded. In addition, there is a method for preventing corrosion by applying a wide sealing tape to the end portion, but in this method, the end portion of the film mirror becomes wide and the reflection area is lost. There is.
  • Patent Document 3 discloses a method of applying an end protection member made of silicone, polyurethane, or acrylic different from the constituent members to the end portions of the reflecting constituent members in the solar energy reflecting device having the reflecting mirrors. ing.
  • the method described in Patent Document 3 requires a step of newly providing an end protection member, which has a problem in terms of productivity, and is made of a material different from that of the reflector constituent member, and has a sealing structure. Therefore, there is a problem in terms of adhesion or compatibility with the end portion, and the durability of the sealing portion is insufficient.
  • the present invention has been made in view of the above problems, and its solution is to produce a film mirror that is excellent in sealing performance and durability (delamination resistance) at the side surface and has a small loss of reflection area due to sealing. Is to provide a method.
  • the present inventor has obtained a film mirror for producing a film mirror composed of an adhesive layer, a photothermal reflection layer, a support for forming a photothermal reflection layer, an ultraviolet absorption layer, and a hard coat layer.
  • the ultraviolet absorbing layer contains a thermoplastic resin having light permeability
  • a heating member is pressure-bonded to the end of the film mirror, heated within a temperature range of 80 to 120 ° C.
  • at least The side surface portion is produced by the method for producing a film mirror, wherein the adhesive layer and the ultraviolet absorbing layer containing a light-transmitting thermoplastic resin are softened, and a sealing portion is formed by the softened component that flows out to the end portion.
  • a film mirror manufacturing method that can manufacture a film mirror that is excellent in sealing performance and durability (delamination resistance) and has a small loss of reflection area due to sealing. Found that can bets, leading to the present invention.
  • a method for producing a film mirror comprising at least an adhesive layer, a light heat reflecting layer, a support for forming a light heat reflecting layer, an ultraviolet absorbing layer and a hard coat layer,
  • the ultraviolet absorbing layer contains a thermoplastic resin having light permeability
  • a heating member is pressure-bonded to the end of the film mirror and heated within a temperature range of 80 to 120 ° C. to soften at least the adhesive layer and the ultraviolet absorbing layer containing a light-transmitting thermoplastic resin.
  • a wide raw fabric composed of at least an adhesive layer, a light heat reflecting layer, a support for forming a light heat reflecting layer, an ultraviolet absorbing layer containing a light-transmitting thermoplastic resin, and a hard coat layer is prepared and cut into a predetermined size. Then, the sealing part is formed on the cut surface.
  • FIG. 3 is a schematic cross-sectional view showing an example of the configuration of a solar power generation reflecting mirror having a structure in which an end of a conventional method is sealed with a sealing tape.
  • the bonding area of the sealing tape 14 at the end is set. be widened is required, therefore, is considerably wider end bonding width L 1.
  • the area of the sealing tape 14 that fills the entire area of the reflecting mirror is increased, and the area of the film mirror unit FMU in the reflecting mirror 20 for solar thermal power generation is reduced.
  • the hard coat layer 9 constituting the outermost layer of the film mirror unit FMU is a layer that requires transparency, weather resistance, scratch resistance, and antifouling properties. From the viewpoint, silicone resins and acrylic resins are used. However, it was difficult to say that the adhesion between the surface of these constituent materials and the sealing tape was sufficient.
  • the manufacturing method of the film mirror of the present invention is made to solve the problems caused by the conventional sealing tape method, and without applying a new sealing member, the film mirror has an extremely small area at the end.
  • the end portion In the state where the heating member is pressed and the end portion is sandwiched, the end portion is at a specific temperature, for example, the glass transition temperature Tg or higher of the light-transmitting thermoplastic resin material constituting the adhesive layer or the ultraviolet absorbing layer.
  • Tg or higher of the light-transmitting thermoplastic resin material constituting the adhesive layer or the ultraviolet absorbing layer By heating to soften the material constituting the adhesive layer or UV absorbing layer containing a light-transmitting thermoplastic resin, and seal the side surface with the softened material that has flowed out by pressurizing the edge. It is characterized by.
  • the film mirror area is not reduced at the end of the film mirror.
  • the sealing portion formed at the end is supplied by a member constituting the film mirror. That is, the member that forms the sealing portion is made of the same material as the constituent layer of the film mirror and can be formed in a structure continuous with the constituent layer of the film mirror. It is possible to develop a difficult effect.
  • Schematic sectional view showing an example of the configuration of the film mirror unit before sealing processing Schematic sectional view showing another example of the configuration of the film mirror unit before sealing processing
  • Schematic sectional view showing an example of a method for forming a sealing structure on the side surface Schematic sectional view showing an example of the configuration of a film mirror unit in which a sealing structure is formed on the side surface
  • the method for producing a film mirror of the present invention is a method for producing a film mirror comprising at least an adhesive layer, a light heat reflecting layer, a support for forming a light heat reflecting layer, an ultraviolet absorbing layer and a hard coat layer, and the ultraviolet absorbing layer Contains a light-transmitting thermoplastic resin, a heating member is pressure-bonded to the end of the film mirror, and is heated within a temperature range of 80 to 120 ° C., so that at least the adhesive layer and the light-transmitting heat
  • the ultraviolet absorbing layer containing the plastic resin is softened, and the sealing portion is formed by the softened component that flows out to the end portion.
  • an ultraviolet ray containing at least a pressure-sensitive adhesive layer, a photothermal reflection layer, a support for forming a photothermal reflection layer, and a light-transmitting thermoplastic resin from the viewpoint that the effects of the present invention can be further expressed.
  • the cutting process is performed. This is a preferred embodiment from the viewpoint of covering fine cracks and peeled portions generated on the side surfaces of the film and forming a strong sealing structure.
  • the reflectance at the end portion of the film mirror can be maintained by pressing the heating member to the end portion and then slowly cooling in a pressurized state to form the sealing portion.
  • the sealing portion may be formed by pressing a sealing portion molding member against the softened portion of the ultraviolet absorbing layer containing the adhesive layer and the light-transmitting thermoplastic resin that have flowed out to the end portion. From the viewpoint of preventing the occurrence of flatness and cracks in the formed sealing portion.
  • the light-transmitting thermoplastic resin contained in the ultraviolet absorbing layer is an acrylic resin from the viewpoint of being able to soften within a specified temperature range and stably forming a sealing structure. .
  • the adhesive layer is made of an acrylic resin, and when the heating member is pressure-bonded, the light-transmitting thermoplastic resin that is a constituent material of the ultraviolet absorbing layer supplied from the other, and a softening property Are approximate or the same, and the compatibility is improved when the two are combined to form a sealing structure, which is preferable from the viewpoint that a uniform and stable sealing portion can be formed.
  • the pressure condition by the heating member at the time of forming the sealing portion is preferably in the range of 0.1 to 1.0 MPa from the viewpoint of stably forming the sealing structure.
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • the film mirror of the present invention includes at least an adhesive layer, a light heat reflection layer, a support for forming a light heat reflection layer, a light-transmitting thermoplastic resin (hereinafter also simply referred to as a thermoplastic resin), and a hard layer. It is a film mirror unit composed of a coat layer, and is bonded to a metal substrate or a resin substrate via an adhesive layer of the film mirror unit to constitute a solar power generation reflecting mirror.
  • a thermoplastic resin hereinafter also simply referred to as a thermoplastic resin
  • the film mirror unit according to the present invention comprises at least an adhesive layer, a light heat reflecting layer, a support for forming a light heat reflecting layer, an ultraviolet absorbing layer containing a light-transmitting thermoplastic resin, particularly preferably an ultraviolet absorbing material containing an acrylic resin. It is comprised from a layer (henceforth an acrylic resin layer) and a hard-coat layer, You may provide another functional layer as needed.
  • the light-transmitting thermoplastic resin referred to in the present invention refers to a thermoplastic resin having a 50 ⁇ m-thick coating film and having an average light transmittance of 70% or more in the visible light region measured for the coating film. It is defined as a thermoplastic resin capable of obtaining an average light transmittance of 85% or more, preferably 80% or more.
  • the light transmittance can be measured using a commercially available spectrophotometer.
  • FIG. 1 is a schematic cross-sectional view showing an example of the configuration of the film mirror unit FMU1 before the sealing structure is formed. Such a configuration is referred to as Type A.
  • the film mirror unit FMU1 before forming the Type A sealing structure shown in FIG. 1 includes, as main constituent layers, an adhesive layer 3, a topcoat layer 4, a photothermal reflective layer 5, an anchor layer 6, and a photothermal reflective layer forming support 7.
  • the second anchor layer 6A, the ultraviolet absorbing layer 8 containing a light-transmitting thermoplastic resin, the hard coat layer 9 and the like are laminated.
  • the ultraviolet absorbing layer 8 containing the light-transmitting thermoplastic resin according to the present invention is preferably formed by a coating method.
  • the configuration from the top coat layer 4 to the anchor layer 6A is referred to as a photothermal reflection unit 2A.
  • the film mirror unit FMU1 is bonded to the back side of the adhesive layer 3 and, for example, a metal substrate surface or a resin substrate surface to constitute a solar power generation reflecting mirror.
  • FIG. 2 is a schematic cross-sectional view showing another example of the configuration of the film mirror unit FMU2 before the sealing structure is formed. Such a configuration is referred to as Type B.
  • the type B film mirror unit FMU2 has a pressure-sensitive adhesive layer 3, a photothermal reflective layer forming support 7, an anchor layer 6, a photothermal reflective layer 5, a top coat layer 4, an adhesive layer 3A, and light transparency.
  • An ultraviolet absorbing layer 8A containing a thermoplastic resin and a hard coat layer 9 are laminated.
  • the configuration between the light heat reflecting layer forming support 7 and the adhesive layer 3A is referred to as a light heat reflecting unit 2B.
  • An ultraviolet absorbing layer 8A containing a light-transmitting thermoplastic resin used in the configuration shown in FIG. 2 is an acrylic film laminated via an adhesive layer (3A), for example, an adhesive layer (3A) by a dry lamination process.
  • an acrylic film for example, Technoloy S001GU (manufactured by Sumitomo Chemical Co., Ltd., thickness: 100 ⁇ m)
  • an ultraviolet absorber in an acrylic resin layer (8A) which is a thermoplastic resin having optical transparency, as a laminating temperature.
  • a method of bonding at 60 ° C. and forming an adhesive layer (3A) and an ultraviolet absorbing layer (8A) containing a light-transmitting thermoplastic resin can also be applied.
  • FIG. 3 is a schematic cross-sectional view showing an example of the configuration of a solar power generation reflecting mirror having a structure in which a side surface portion of a conventional method is sealed with a sealing tape.
  • the Type A film unit FMU1 illustrated in FIG. 1 is shown as an example.
  • the sealing tape used in such a system is a weatherproof tape 10386-ND (tape width: 2.54 cm (1 inch), thickness: 87 ⁇ m, adhesive: acrylic resin) manufactured by 3M, Teraoka Seisakusho Aluminum foil tape No. 833, an aluminum edge tape manufactured by Reflec Tech.
  • the tape covering width L 1 in the end region is Since the width is about 5 to 12 mm, the ratio shown in the surface area of the film mirror is increased, leading to a reduction in the reflection area.
  • the hard coat layer 9 forming the outermost surface of the film mirror unit FMU is formed of, for example, a silicone resin
  • the surface characteristics of the hard coat layer 9 The adhesiveness with the sealing tape 14 cannot be sufficiently maintained, and when stored for a long period of time in a high temperature and high humidity environment, a peeling portion P is generated from the adhesive surface, and further, moisture and Oxygen penetrates and sealability is lowered. As a result, peeling or the like is caused between the constituent layers of the film mirror unit FMU.
  • a heating member is pressure-bonded to the end of the film mirror and heated within a temperature range of 80 to 120 ° C., and the adhesive layer, a light-transmitting thermoplastic resin,
  • the adhesive layer a light-transmitting thermoplastic resin
  • a sealing portion is formed on the side surface by the softened component of the eluted adhesive layer and the ultraviolet absorbing layer containing a light-transmitting thermoplastic resin. It is characterized by doing.
  • FIG. 4 shows a sealing method for a side surface portion that can be applied to the method for manufacturing a film mirror of the present invention, using the type A shown in FIG. It is.
  • the adhesive layer 3 to the hard coat layer 9 are laminated in the order shown in FIG. 4 to produce a Type A film mirror unit FMU.
  • the end of the film mirror unit FMU to cover a distance range of L 2, after placing a pair of heating members 10A and 10B, by performing the crimping and heat, among the constituent layers of the film mirror unit FMU
  • the light-transmitting thermoplastic resin material constituting the adhesive layer 3 and the ultraviolet absorbing layer 8 formed of a material having a relatively low glass transition temperature Tg is softened and eluted to the side surface, and sealed Part 11 is formed.
  • the eluted softened material is left as it is, the surface of the sealing portion becomes an uneven structure, and therefore the sealing portion molding member 12 is pressed against the side surface portion in the softened state to smooth the surface.
  • the method is preferred.
  • the slow cooling referred to in the present invention means that the film mirror unit end is softened by a heating member to form a sealing portion, and then each component member (heating members 10A and 10B, sealing portion molding member 12). 4) while maintaining the pressurized state shown in FIG. 4, heating is stopped, natural cooling is performed, and in some cases forced cooling is performed, and a predetermined time is required, and the softened sealed portion is kept at a room temperature of about 25 ° C. The temperature is gradually lowered until solidification.
  • the specific device provided with the heating members 10A and 10B used for the crimping step and heating of the end portion there are no particular limitations on the specific device provided with the heating members 10A and 10B used for the crimping step and heating of the end portion, but typical devices include a heat sealer, pulse Examples thereof include a heating device and an electromagnetic induction heating bonding device. Among these, it is preferable to use a heat sealer from the viewpoint of easy operation.
  • heat sealers applicable to the present invention include thicker gusset bag sealers T-130K and T-230K (both of which are heated up and down), such as policy impulser P-200 (one side lower heating method) manufactured by Fuji Impulse. Method), AZ-200W, AZ-300W (all up and down heating methods), heating temperature control auto sealer OPL series (one side lower heating method, up and down heating method), Fi-WA series (one side lower heating method and up and down heating method) ), CA series, CV series ((one side lower heating method, upper and lower heating method), etc.
  • the seal width (L 2 + L 3 in FIG. 4) of these heat sealers is in the range of 2 to 10 mm.
  • Other examples include heat sealers HS-300, HS-400, HS-400 manufactured by Taiyo Electric Industry Co., Ltd.
  • the end of the film mirror is sandwiched between the heating members 10 ⁇ / b> A and 10 ⁇ / b> B, and the thermocompression treatment is performed, but the heating is performed by one or both of the heating members 10 ⁇ / b> A and 10 ⁇ / b> B. Heating may be performed.
  • the sealing portion 11 is formed on the side surface portion by heating and pressurizing the end portion.
  • the heating temperature is mainly used. , Pressure conditions and processing time thereof.
  • the heating temperature which is the first control factor is characterized in that it is carried out in a temperature range of 80 to 120 ° C., preferably in the temperature range of 100 to 120 ° C.
  • the end portion is heated to a temperature range of 80 to 120 ° C. by the heating member to soften the adhesive layer and the ultraviolet absorbing layer, and the resin component is oozed out on the side surface portion to It is characterized by forming. Therefore, in the pressure-sensitive adhesive layer and the ultraviolet absorbing layer constituting the sealing portion, as a guideline for satisfying the conditions for softening, the light transmission with the softening temperature or the glass transition temperature Tg within the range of 80 to 120 ° C. It is important to select a thermoplastic resin material having properties.
  • the heating condition of the end portion within the temperature range specified above, as a material constituting the adhesive layer and the ultraviolet absorbing layer, for example, an acrylic resin is remolded without thermal deterioration. It is preferable in that it can be softened and a desired sealing shape can be formed. Accordingly, it is preferable to heat at a temperature not lower than the glass transition temperature Tg of the applied resin material and not causing coloring, foaming, baking, or the like.
  • the pressurizing condition as the second control factor is not particularly limited, but is preferably in the range of 0.1 to 1.0 MPa, more preferably in the range of 0.2 to 0.5 MPa. More preferably, it is in the range of 0.2 to 0.4 MPa.
  • the heating and pressurizing time which is the third control factor, varies depending on the heating temperature to be set, but is generally within the range of 0.1 to 30 seconds, preferably within the range of 1 to 20 seconds. In consideration of efficiency and the like, it is more preferably in the range of 1 to 10 seconds.
  • the width (L 2 + L 3 ) of the heating members 10A and 10B is approximately in the range of 2 to 10 mm.
  • Such heating member the end heating area L 2 in the case of contacting the end portion of the film mirror unit FMU, preferably in the range of 0.1 ⁇ 5 mm, more preferably 0.5 ⁇ 3 mm And particularly preferably within the range of 0.5 to 1.5 mm.
  • the constituent material of the softened adhesive layer 3 and the ultraviolet absorbing layer 8 is eluted in the space V from the end of the film mirror unit FMU to the sealing portion molding member 12 to form the sealing portion 11.
  • the thickness L 3 of the sealing portion 11 is preferably in the range of 0.5 to 5 mm, more preferably in the range of 0.5 to 3 mm, and particularly preferably 1.0. Within 3 mm.
  • the thickness L 3 of the sealing portion 11, the width of the heating member 10A and 10B and the end heating area L 2, is determined by the thickness hd1 and thickness hd2 acrylic resin layer 8 of adhesive layer 3.
  • FIG. 5 shows a film mirror in which the sealing portion 11 is formed on the side surface portion after the heating members 10A and 10B and the sealing portion molding member 12 are removed after the sealing portion 11 is formed and cooled in FIG. shows the form of a unit FMU, L 3 is a thickness of the sealing portion.
  • FIG. 6 is a schematic diagram showing an example of the process of the method for producing a film mirror of the present invention in which a sealing structure is formed on the side surface.
  • the edge of the TypeA film mirror unit FMU which consists of the adhesion layer 3, the photothermal reflection unit 2A, the ultraviolet absorption layer 8 containing the thermoplastic resin which has a light transmittance, and the hard-coat layer 9
  • a pair of heating members 10 ⁇ / b > A and 10 ⁇ / b > B are disposed at a predetermined end width (L 2 ) position.
  • the end portion of the film mirror unit FMU is sandwiched between a pair of heating members 10A and 10B and heated in a pressurized state to heat the pressure-sensitive adhesive layer 3 and light transmissive.
  • the end softening component of the ultraviolet absorbing layer 8 containing a plastic resin is extruded in the direction of the arrow to form the sealing portion 11.
  • FIG. 6 although it divided
  • extruding the softening component as shown in c of FIG. 6, it may be performed in a state where the sealing portion forming member 12 is provided in advance.
  • FIG. 7 shows a state in which the sealing portion 11 is formed on the Type B film mirror unit FMU shown in FIG. 2.
  • the method for forming the sealing portion 11 includes the method described in FIGS. It is the same.
  • the film mirror unit according to the present invention includes at least an adhesive layer, a light heat reflecting layer, a support for forming a light heat reflecting layer, a light transmitting thermoplastic resin, preferably an ultraviolet absorbing layer and a hard coat layer containing an acrylic resin.
  • the thickness of the film mirror unit is preferably in the range of 50 to 500 ⁇ m, more preferably in the range of 80 to 300 ⁇ m, and still more preferably in the range of 80 to 170 ⁇ m.
  • the thickness of the film mirror unit is preferably in the range of 50 to 500 ⁇ m, more preferably in the range of 80 to 300 ⁇ m, and still more preferably in the range of 80 to 170 ⁇ m.
  • the film mirror unit can be said to be very lightweight because the material used and the thickness are in the range of 50 to 500 ⁇ m. Further, unlike the glass, the film mirror unit does not have a problem such as cracking and has flexibility. That is, the film mirror unit has the characteristics that it is lightweight and flexible, and can be manufactured with a large area and mass production while suppressing manufacturing costs.
  • the film mirror unit may have a layer other than an adhesive layer, a light heat reflecting layer, a support for forming a light heat reflecting layer, an ultraviolet absorbing layer containing a light-transmitting thermoplastic resin, and a hard coat layer. .
  • the surface roughness Ra of the film mirror unit is preferably in the range of 0.01 to 0.1 ⁇ m, more preferably in the range of 0.02 to 0.07 ⁇ m. If the surface roughness of the film mirror unit is 0.01 ⁇ m or more, even if the surface is accidentally touched with a finger during transportation or when assembling or adjusting the solar reflective mirror, fingerprints will adhere. It is possible to prevent the reflection efficiency from being lowered. Further, it is assumed that the film mirror unit is used in a concave shape. In that case, even if the surface roughness Ra is rough, the reflection shape can be prevented from being lowered by the concave shape. In addition, the roughness of the surface of the film mirror unit and the mirror for sunlight reflection and the roughness of each layer constituting the film mirror unit include not only the roughness of the layer but also the influence of the layer separated from the adjacent layer. It depends on the overall influence.
  • the shape of the film mirror unit viewed from the direction perpendicular to the center is not particularly limited, but is preferably a circle, an ellipse, a quadrangle such as a square or a rectangle, or a regular hexagon.
  • the central portion of the film mirror unit is preferably near the center of the circle in the case of a circle, near the intersection of diagonal lines in the case of a square shape, and near the intersection of diagonal lines in the case of a regular hexagon.
  • Photothermal reflection layer forming support 7 As the photothermal reflective layer forming support 7 used in the film mirror unit FMU, conventionally known supports having various flexibility can be used.
  • polyester films such as polyethylene terephthalate, norbornene resin films, cellulose ester films, and acrylic films are preferable.
  • a polyester film such as polyethylene terephthalate or an acrylic film, and it may be a film manufactured by melt casting film formation or a film manufactured by solution casting film formation.
  • the surface of the support may be subjected to corona discharge treatment, plasma treatment or the like in order to improve adhesion with a layer or the like provided on the surface.
  • the support preferably contains any one of benzotriazole, benzophenone, triazine, cyanoacrylate, and polymer type ultraviolet absorbers.
  • the ultraviolet absorber which can also use the ultraviolet absorption layer mentioned later can be mentioned.
  • the thickness of the photothermal reflective layer forming support 7 is an appropriate thickness depending on the type and purpose of the resin. For example, it is generally in the range of 10 to 250 ⁇ m. The thickness is preferably 20 to 200 ⁇ m.
  • the photothermal reflection layer (hereinafter also simply referred to as “reflection layer”) according to the present invention is a layer composed of a metal or the like having a function of reflecting sunlight.
  • the surface reflectance of the photothermal reflection layer is preferably 80% or more, more preferably 90% or more.
  • the light heat reflecting layer is preferably disposed on the light incident side for the purpose of preventing the resin base material from being deteriorated by sunlight.
  • the thickness of the photothermal reflection layer is preferably in the range of 10 to 200 nm, more preferably in the range of 30 to 150 nm, from the viewpoint of reflectivity and the like. It is preferable that the thickness of the reflective layer be 10 nm or more because the film thickness is sufficient, so that light is not transmitted and sufficient reflectivity in the visible light region of the film mirror unit can be secured. Further, the reflectance increases in proportion to the film thickness up to about 200 nm. However, when the thickness exceeds 200 nm, the reflectance does not depend on the film thickness.
  • the surface roughness Ra of the reflective layer is preferably in the range of 0.01 to 0.1 ⁇ m, more preferably in the range of 0.02 to 0.07 ⁇ m.
  • the surface of the film mirror unit also becomes rough due to the roughness. Even when the roll method is used, sticking such as blocking in the reflective layer of the film mirror unit and the adjacent layer on the incident light side can be prevented. Further, when the surface becomes rough, the reflected light may be scattered.
  • the film mirror unit having the reflective layer has a concave shape, the film mirror unit has a surface roughness Ra of 0.1 ⁇ m or less. By making the surface into a concave shape, it is possible to prevent a reduction in reflection efficiency.
  • the reflective layer is formed as a material containing any element selected from the group consisting of aluminum, silver, chromium, nickel, titanium, magnesium, rhodium, platinum, palladium, tin, gallium, indium, bismuth and gold. It is preferable.
  • aluminum or silver is preferably the main component from the viewpoint of reflectance and corrosion resistance, and two or more such metal thin films may be formed. By doing so, the reflectance from the infrared region to the visible light region of the film mirror unit can be increased, and the dependency of the reflectance on the incident angle can be reduced. From the infrared region to the visible light region means a wavelength region of 2500 to 400 nm.
  • the incident angle means an angle with respect to a line (normal line) perpendicular to the film surface. Among these, it is particularly preferable to use a silver reflective layer mainly composed of silver.
  • a wet method or a dry method can be used as a method for forming the reflective layer.
  • the wet method is a general term for a plating method, and is a method of forming a film by depositing a metal from a solution. Specific examples include silver mirror reaction.
  • the dry method is a general term for a vacuum film forming method, and specifically includes a resistance heating vacuum deposition method, an electron beam heating vacuum deposition method, an ion plating method, an ion beam assisted vacuum deposition method, and a sputtering method. and so on.
  • a vapor deposition method capable of a roll-to-roll method for continuously forming a film is preferably used.
  • the manufacturing method of the film mirror unit for sunlight reflection it is preferable that it is a manufacturing method which forms a reflection layer by vapor deposition.
  • two or more metals may be selected from the above element group and used as an alloy.
  • silver is 90 to 99.8 atomic% in the total (100 atomic%) of silver and other metals in the reflective layer. It is preferable to be within the range.
  • the other metal is preferably 0.2 to 10 atomic% from the viewpoint of durability.
  • gold is particularly preferable from the viewpoint of high temperature humidity resistance and reflectance.
  • a silver reflective layer as the photothermal reflective layer according to the present invention.
  • anchor layer When the anchor layers 6 and 6A are each made of a resin material and are provided adjacent to the photothermal reflection layer 5, for example, the adhesion between the photothermal reflection layer forming support 7 and the photothermal reflection layer 5 is improved. Can do. Moreover, the adhesiveness at the time of closely_contact
  • the resin material used for the anchor layers 6 and 6A is not particularly limited as long as it satisfies the above adhesiveness, heat resistance, and smoothness conditions.
  • the polyester resin, acrylic resin, melamine resin, epoxy Resins, polyamide resins, vinyl chloride resins, vinyl chloride vinyl acetate copolymer resins, or the like, or a mixture thereof can be used.
  • a mixed resin of a polyester resin and a melamine resin is preferable, and a thermosetting resin in which a curing agent such as isocyanate is further mixed is more preferable.
  • the anchor layers 6 and 6A can be formed by a conventionally known coating method such as a gravure coating method, a reverse coating method, a die coating method, or the like in which a predetermined resin material is applied and applied.
  • the thickness of the anchor layers 6 and 6A is preferably 0.01 to 3 ⁇ m, more preferably 0.1 to 1 ⁇ m.
  • the thickness 0.01 ⁇ m or more adhesion can be maintained, and by covering up the unevenness on the surface of the photothermal reflection layer forming support 7, smoothness is improved, and as a result, the photothermal reflection layer 5 The reflectance can be increased.
  • the thickness is 3 ⁇ m or less, sufficient adhesion can be exhibited, delamination does not easily occur, and deterioration of smoothness due to occurrence of coating unevenness can be prevented.
  • the ultraviolet absorbing layer 8 is a layer containing an ultraviolet absorber for the purpose of preventing deterioration of the film mirror due to sunlight or ultraviolet rays, and further containing a light-transmitting thermoplastic resin as a constituent component, and preferably an acrylic type It is a layer containing a resin.
  • the ultraviolet absorbing layer 8 is preferably provided on the light incident side with respect to the photothermal reflection layer forming support 6, and is preferably provided on the light incident side with respect to the photothermal reflection layer 5.
  • the ultraviolet absorber layer may contain fine particles of a plasticizer in order to obtain an ultraviolet absorber layer that is difficult to block.
  • the plasticizer fine particles include butyl rubber and butyl acrylate fine particles.
  • the thickness of the ultraviolet absorbing layer is preferably 20 to 150 ⁇ m because it can provide an appropriate transmittance to the incident light and a suitable surface roughness to the film mirror. More preferably, it is 20 to 100 ⁇ m.
  • an antioxidant or the like may be added to the ultraviolet absorbing layer.
  • thermoplastic resin applicable to the present invention is not particularly limited, and various conventionally known synthetic resins that can maintain transparency when a thin film is formed can be used.
  • polyesters such as polyethylene terephthalate (abbreviation: PET), polyethylene naphthalate (abbreviation: PEN), polyethylene, polypropylene, cellophane, and cellulose diacetate, cellulose triacetate (abbreviation: TAC), cellulose acetate butyrate, cellulose acetate propio Nate (abbreviation: CAP), cellulose esters such as cellulose acetate phthalate, cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, poly Ether ketone, polyimide, polyethersulfone (abbreviation: PES), polysulfones, polyetherke N'imido,
  • the ultraviolet absorbing layer according to the present invention preferably contains an acrylic resin as the light-transmitting thermoplastic resin, and more specifically, methacrylic resin as the main constituent resin is the interface reflection due to the refractive index. It is preferable from the viewpoint of reducing loss, ensuring transmittance, and suppressing light deterioration.
  • the methacrylic resin is a polymer mainly composed of methacrylic acid ester, and may be a homopolymer of methacrylic acid ester, 50% by mass or more of methacrylic acid ester, and 50% by mass or less of other monomers.
  • the copolymer may be used.
  • the methacrylic acid ester an alkyl ester of methacrylic acid is usually used.
  • a particularly preferred methacrylic resin is polymethyl methacrylate resin (PMMA).
  • the preferred monomer composition of the methacrylic resin is 50 to 100% by weight of methacrylic acid ester, 0 to 50% by weight of acrylic acid ester, and 0 to 49% by weight of other monomers based on the total monomers. More preferably, methacrylic acid ester is 50 to 99.9% by mass, acrylic acid ester is 0.1 to 50% by mass, and other monomers are 0 to 49% by mass.
  • examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate and the like, and the alkyl group usually has 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. It is. Of these, methyl methacrylate is preferably used.
  • alkyl acrylates include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and the like.
  • the alkyl group usually has 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. is there.
  • the monomer other than alkyl methacrylate and alkyl acrylate may be a monofunctional monomer, that is, a compound having one polymerizable carbon-carbon double bond in the molecule, or a polyfunctional monofunctional monomer. Although it may be a monomer, that is, a compound having at least two polymerizable carbon-carbon double bonds in the molecule, a monofunctional monomer is preferably used.
  • the monofunctional monomer include aromatic alkenyl compounds such as styrene, ⁇ -methylstyrene, and vinyl toluene, and alkenyl cyan compounds such as acrylonitrile and methacrylonitrile.
  • polyfunctional monomers examples include polyunsaturated carboxylic acid esters of polyhydric alcohols such as ethylene glycol dimethacrylate, butanediol dimethacrylate, trimethylolpropane triacrylate, allyl acrylate, allyl methacrylate, and cinnamon.
  • Alkenyl esters of unsaturated carboxylic acids such as allyl acids
  • polyalkenyl esters of polybasic acids such as diallyl phthalate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate
  • aromatic polyalkenyl compounds such as divinylbenzene, etc.
  • alkyl methacrylate alkyl methacrylate
  • alkyl acrylate and monomers other than these, respectively, you may use those 2 or more types as needed.
  • the glass transition temperature of the methacrylic resin is preferably 40 ° C. or higher, more preferably 60 ° C. or higher, from the viewpoint of heat resistance of the film mirror. This glass transition temperature can be appropriately set by adjusting the type of monomer and the ratio thereof.
  • the methacrylic resin can be prepared by polymerizing the monomer component by a method such as suspension polymerization, emulsion polymerization, or bulk polymerization. At that time, in order to obtain a suitable glass transition temperature or to obtain a viscosity showing a formability to a suitable film, it is preferable to use a chain transfer agent during the polymerization.
  • the amount of the chain transfer agent may be appropriately determined according to the type of monomer and the ratio thereof.
  • the ultraviolet absorber added to the ultraviolet absorbing layer is not particularly limited, but examples of the organic type include benzophenone type, benzotriazole type, phenyl salicylate type, triazine type, benzoate type, and inorganic type. Examples include titanium, zinc oxide, cerium oxide, and iron oxide.
  • a polymeric ultraviolet absorber having a molecular weight of 1000 or more. Preferably, the molecular weight is in the range of 1000 to 3000.
  • benzophenone ultraviolet absorber examples include 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxy-benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone, 2- Hydroxy-4-octadecyloxy-benzophenone, 2,2'-dihydroxy-4-methoxy-benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone, 2,2 ', 4,4'-tetra And hydroxy-benzophenone.
  • benzotriazole ultraviolet absorbers examples include 2- (2'-hydroxy-5-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) benzotriazole, 2,2'-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1, 1,3,3-tetramethylbutyl) phenol] (molecular weight 659; examples of commercially available products are LA31 manufactured by ADEKA), 2- (2H-benzotriazol-2-yl) -4,6-bis (1 -Methyl-1-phenylethyl) phenol (molecular weight 447.6; an example of a commercially available product is Tinuvin 234 manufactured by BASF Japan Ltd.).
  • phenyl salicylate ultraviolet absorber examples include phenylsalicylate, 2-4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, and the like.
  • hindered amine ultraviolet absorber examples include bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate.
  • triazine ultraviolet absorbers examples include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-). Ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-) Butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2- Hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-tria 2,4-diphenyl-6- (2-hydroxy-4-dodecyloxy
  • benzoate-based ultraviolet absorber examples include 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate (molecular weight 438.7; examples of commercially available products) Sumisorb 400) manufactured by Sumitomo Chemical Co., Ltd.
  • the ultraviolet absorber a compound having a function of converting the energy held by ultraviolet rays into vibrational energy in the molecule and releasing the vibrational energy as heat energy or the like can be used. Furthermore, those that exhibit an effect when used in combination with an antioxidant or a colorant, or light stabilizers that act as light energy conversion agents, called quenchers, can be used in combination.
  • quenchers light stabilizers that act as light energy conversion agents
  • the said ultraviolet absorber can also use those 2 or more types as needed, respectively.
  • an ultraviolet absorber other than the above-described ultraviolet absorber for example, a salicylic acid derivative, a substituted acrylonitrile, a nickel complex, a benzophenone-based ultraviolet absorber, a triazine-based ultraviolet absorber, or the like can be contained.
  • the addition amount of the ultraviolet absorber to the ultraviolet absorbing layer is preferably within a range of 0.1 to 20% by mass, more preferably within a range of 1 to 15% by mass with respect to the total mass of the ultraviolet absorbing layer. More preferably, it is in the range of 3 to 10% by mass.
  • the addition amount of the ultraviolet absorber to the ultraviolet absorption layer is preferably in the range of 0.17 to 2.28 g / m 2 , more preferably 0.4 to 2 per film unit area. Within the range of .28 g / m 2 .
  • the antioxidant added to the ultraviolet absorbing layer the antioxidants described in the hard coat layer described later, including the description of the light stabilizer, can be used in the same manner.
  • an antioxidant it is possible to prevent deterioration of the acrylic resin layer during melt film formation.
  • the hard coat layer 9 is mainly a transparent layer which is disposed at the outermost surface position of the film mirror unit and is provided for the purpose of adding scratch resistance, antifouling property and the like on the surface of the film mirror unit.
  • the hard coat layer reduces the metal used in the photothermal reflective layer, especially corrosion of silver film by oxygen, water vapor, hydrogen sulfide, etc., deterioration of the resin layer by ultraviolet rays, discoloration of the film mirror unit and film peeling. Can do.
  • the hard coat layer can reduce scratches on the surface of the film mirror unit caused by washing away dirt adhering to the film mirror unit with a brush or the like, and as a result, a reduction in reflection efficiency can also be prevented.
  • the position of the hard coat layer is preferably provided on the outermost surface portion on the sunlight incident side of the film mirror unit.
  • Another thin layer (preferably a thickness of 1 ⁇ m or less) may be provided on the hard coat layer.
  • the layer thickness of the hard coat layer is preferably in the range of 0.05 to 10 ⁇ m, more preferably in the range of 1.0 to 4 ⁇ m, and still more preferably in the range of 1.5 to 3.0 ⁇ m. Is within the range.
  • the thickness of the hard coat layer is 0.05 ⁇ m or more, sufficient scratch resistance can be obtained. Moreover, if the layer thickness of a hard-coat layer is 10 micrometers or less, it can prevent that a stress becomes too strong and a hard-coat layer cracks. Furthermore, from the viewpoint of preventing electrostatic adhesion of dirt such as dust, the thickness is preferably 10 ⁇ m or less in order to reduce the electric resistance value.
  • the pencil hardness is in a range of H to 5H, and the number of scratches in a steel wool test with a load of 500 g / cm 2 is 30 or less.
  • the electric resistance value of the outermost surface of the film mirror unit is 1.0 ⁇ 10 ⁇ 3 to 1.0 ⁇ 10 12 ⁇ / ⁇ . More preferably, it is 3.0 ⁇ 10 9 to 2.0 ⁇ 10 11 ⁇ / ⁇ .
  • the falling angle of the hard coat layer is larger than 0 ° and not larger than 30 ° because water droplets adhering to the surface of the film mirror unit are likely to fall due to rain or condensation.
  • the falling angle refers to a value obtained by dropping a water drop on a horizontal mirror, and then gradually increasing the tilt angle of the mirror, and measuring the minimum angle at which a stationary water drop of a predetermined mass falls. Say. It can be said that the smaller the tumbling angle, the easier it is for the water droplets to roll off the surface and the hydrophobic surface to which the water droplets are less likely to adhere.
  • the material for forming the hard coat layer is preferably a material that can form a layer that can provide transparency, weather resistance, scratch resistance, and antifouling properties.
  • Examples of materials applicable to the formation of the hard coat layer include acrylic resins, urethane resins, melamine resins, epoxy resins, organic silicate compounds, and silicone resins.
  • acrylic resins urethane resins, melamine resins, epoxy resins, organic silicate compounds, and silicone resins.
  • silicone resins and acrylic resins are preferable.
  • an active energy ray-curable acrylic resin or a thermosetting acrylic resin is also preferable in terms of curability, flexibility, and productivity.
  • thermosetting resin composed of a partially hydrolyzed oligomer of an alkoxysilane compound, a heat A hard coat made of a curable polysiloxane resin, an ultraviolet curable acrylic hard coat made of an acrylic compound having an unsaturated group, and a thermosetting inorganic material are preferable.
  • materials that can be used for the hard coat layer include aqueous colloidal silica-containing acrylic resins (for example, compounds described in JP-A-2005-66824), polyurethane-based resin compositions (for example, JP-A-2005-110918).
  • a resin film using an aqueous silicone compound as a binder for example, a compound described in JP-A-2004-142161
  • a photocatalytic oxide-containing silica film such as titanium oxide or alumina
  • a high aspect ratio Photocatalyst film such as titanium oxide or niobium oxide (for example, compounds described in JP-A-2009-62216), photocatalyst-containing fluororesin coating (for example, manufactured by Pyrex Technologies), organic / inorganic polysilazane film, organic / inorganic Polysilazane and hydrophilization promoter (for example, Z Electronics Co.) membrane was used, and the like can also be mentioned.
  • thermosetting silicone hard coat layer a partially hydrolyzed oligomer of an alkoxysilane compound synthesized by a known method can be used.
  • An example of the synthesis method is as follows. First, tetramethoxysilane or tetraethoxysilane is used as an alkoxysilane compound, and a predetermined amount of water is added to the alkoxysilane compound in the presence of an acid catalyst such as hydrochloric acid or nitric acid to remove by-produced alcohol from room temperature to 80 ° C. React with.
  • an acid catalyst such as hydrochloric acid or nitric acid
  • the alkoxysilane is hydrolyzed, and further, a partially hydrolyzed oligomer of the alkoxysilane compound having an average polymerization degree of 4 to 8 having two or more silanol groups or alkoxy groups in one molecule is obtained by the condensation reaction.
  • a curing catalyst such as acetic acid or maleic acid is added to this and dissolved in an alcohol or glycol ether organic solvent to obtain a thermosetting silicone hard coat liquid.
  • a hard coat layer can be formed by applying this to the outer surface of a film mirror unit or the like by a coating method using a normal paint, followed by heat curing at a temperature of 80 to 140 ° C.
  • a polysiloxane hard coat layer can be produced in the same manner by using di (alkyl or aryl) dialkoxysilane or mono (alkyl or aryl) trialkoxysilane instead of tetraalkoxysilane. It is.
  • the ultraviolet curable acrylic hard coat layer as an acrylic compound having an unsaturated group, for example, pentaerythritol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylol
  • a polyfunctional (meth) acrylate mixture such as tetra (meth) acrylate or the like can be used, and a photopolymerization initiator such as benzoin, benzoin methyl ether, or benzophenone is blended and used. And this is apply
  • a hydrophilic property by subjecting the hard coat layer to a surface treatment.
  • a surface treatment for example, corona treatment (for example, the method described in JP-A-11-172028), plasma surface treatment, ultraviolet ray / ozone treatment, surface projection formation (for example, the method described in JP-A-2009-226613), A surface fine processing treatment can be exemplified.
  • wet coating methods such as a gravure coating method, a reverse coating method, and a die coating method can be used.
  • the hard coat layer may contain various additives such as conventionally known ultraviolet absorbers and antioxidants.
  • UV absorber applicable to the hard coat layer
  • examples of the ultraviolet absorber applicable to the hard coat layer include the same ultraviolet absorbers listed in the above-described ultraviolet absorbing layer.
  • the UV compound 1 exemplified below in the hard coat layer.
  • the amount of the UV absorber used in the hard coat layer is preferably in the range of 0.1 to 20% by mass in order to improve the weather resistance while maintaining good adhesion. More preferably, it is in the range of 0.25 to 15% by mass, more preferably 0.5 to 10% by mass.
  • antioxidant it is preferable to use organic antioxidants such as phenolic antioxidants, hindered amine antioxidants, thiol antioxidants, and phosphite antioxidants. Further, an antioxidant and a light stabilizer may be used in combination.
  • antioxidant and the light stabilizer for example, compounds described in paragraphs (0063) to (0070) of International Publication No. 2013/103139 can be used.
  • the hard coat layer particularly the hard coat layer containing a polyfunctional acrylic monomer and a silicone resin, preferably contains a polymerization initiator for initiating polymerization.
  • a polymerization initiator for initiating polymerization.
  • a photopolymerization initiator of an active energy ray-curable resin such as ultraviolet rays is preferably used. Examples include benzoin and derivatives thereof, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, ⁇ -amyloxime ester, thioxanthone, and the like.
  • various additives can be further blended as necessary.
  • a surfactant, a leveling agent, an antistatic agent, and the like can be used.
  • each constituent layer described below can be formed on the outer surface side of the photothermal reflection layer 5.
  • the topcoat layer 4 constituting the film mirror unit according to the present invention is a resin layer containing a corrosion inhibitor and is also referred to as a corrosion prevention layer, and in particular, may be provided adjacent to the photothermal reflection layer 5. preferable.
  • the top coat layer 4 may be composed of only one layer, or may be composed of a plurality of layers.
  • the layer thickness of the top coat layer 4 is preferably in the range of 1 to 10 ⁇ m, more preferably in the range of 2 to 8 ⁇ m.
  • Examples of the resin used for forming the top coat layer 4 include cellulose ester, polyester, polycarbonate, polyarylate, polysulfone (including polyethersulfone), polyester such as polyethylene terephthalate and polyethylene naphthalate, polyethylene, polypropylene, cellophane, Cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, polyvinylidene chloride, polyvinyl alcohol, ethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene, polymethylpentene, polyetherketone, polyether Ketone imide, polyamide, fluororesin, nylon, polymethyl methacrylate, acrylic It can be exemplified Le resins. Of these, acrylic resins are preferred.
  • the top coat layer 4 can be formed by applying these resin materials (binders) adjacent to the photothermal reflection layer 5.
  • the corrosion inhibitor contained in the top coat layer 4 preferably has an adsorptive group for silver.
  • corrosion refers to a phenomenon in which metal (silver) is chemically or electrochemically eroded or deteriorated by the environmental material surrounding it (see JIS Z0103-2004).
  • the optimum content of the corrosion inhibitor varies depending on the compound used, but is generally preferably in the range of 0.1 to 1.0 / m 2 .
  • Corrosion inhibitors having an adsorptive group for silver include amines and derivatives thereof, compounds having a pyrrole ring, compounds having a triazole ring such as benzotriazole, compounds having a pyrazole ring, compounds having a thiazole ring, and having an imidazole ring It is desirable to be selected from a compound, a compound having an indazole ring, a copper chelate compound, a thiourea, a compound having a mercapto group, a naphthalene-based compound, or a mixture thereof.
  • the ultraviolet absorber may also serve as a corrosion inhibitor.
  • a silicone-modified resin It does not specifically limit as a silicone modified resin. As these compounds, for example, compounds described in paragraphs (0057) to (0062) of International Publication No. 2013/103139 can be used.
  • the adhesive layer 3 of the film mirror unit FMU is a layer for joining the film mirror unit FMU to the base material by the adhesive layer 3 to form a sunlight reflecting mirror.
  • the film mirror unit FMU may have a layer made of a release sheet on the side opposite to the sunlight incident side of the adhesive layer 3.
  • the adhesive layer 3 is not particularly limited, and for example, any of a dry laminating agent, a wet laminating agent, an adhesive, a heat seal agent, a hot melt agent, and the like is used.
  • a dry laminating agent for example, polyester resins, urethane resins, polyvinyl acetate resins, acrylic resins, silicone resins, nitrile rubbers, and the like are used, and acrylic resins are particularly preferable.
  • the laminating method for joining the adhesive layer and the substrate is not particularly limited. For example, it is preferable to carry out the roll method continuously from the viewpoint of economy and productivity.
  • the thickness of the pressure-sensitive adhesive layer 3 is preferably in the range of usually about 1 to 100 ⁇ m from the viewpoint of the pressure-sensitive adhesive effect, the drying speed, and the like. When the thickness is larger than 1 ⁇ m, it is preferable because a sufficient adhesive effect can be obtained. On the other hand, when the thickness is smaller than 100 ⁇ m, the pressure-sensitive adhesive layer is not too thick and the drying speed is not slowed, which is efficient. In addition, the original adhesive strength can be obtained, and no adverse effects such as residual solvent can occur.
  • Adhesive layer In this invention, as shown in FIG. 2, it can be set as the structure which adhere
  • the adhesive layer 3A is not particularly limited as long as it has a function of improving the adhesion between the layers.
  • Adhesive layer has adhesion to adhere the layers, heat resistance that can withstand heat when the silver reflective layer is formed by vacuum deposition, etc., and smoothness to bring out the high reflective performance that the silver reflective layer originally has. It is preferable to have.
  • the adhesive layer may be composed of only one layer, or may be composed of a plurality of layers.
  • the layer thickness of the adhesive layer is preferably in the range of 1 to 10 ⁇ m, more preferably in the range of 3 to 8 ⁇ m, from the viewpoints of adhesion, smoothness, reflectance of the reflector, and the like.
  • the resin for forming the adhesive layer is not particularly limited as long as it satisfies the above conditions of adhesion, heat resistance, and smoothness.
  • polyester resin, urethane resin, acrylic resin, melamine resin , Epoxy resins, polyamide resins, vinyl chloride resins, vinyl chloride vinyl acetate copolymer resins, etc., or a mixture of these resins can be used.
  • polyester resins and melamine resins or polyester resins And a urethane-based resin mixed resin are preferable, and a thermosetting resin in which a curing agent such as isocyanate is mixed such that an isocyanate is mixed with an acrylic resin is more preferable.
  • a method for forming the adhesive layer conventionally known coating methods such as a gravure coating method, a reverse coating method, and a die coating method can be used.
  • a gas barrier layer may be provided on the sunlight incident side of the photothermal reflection layer. It is preferable to provide a gas barrier layer between the hard coat layer or the ultraviolet absorbing layer containing a light-transmitting thermoplastic resin and the light-heat reflecting layer.
  • the gas barrier layer is intended to prevent deterioration of humidity, in particular, deterioration of the photothermal reflection layer forming support 7 and each component layer supported by the photothermal reflection layer forming support 7 due to high humidity.
  • the gas barrier layer may be provided with a function and an application, and various types of gas barrier layers can be provided as long as it has the above-described deterioration preventing function.
  • the water vapor permeability at 40 ° C. and 90% RH is preferably 1 g / m 2 ⁇ day or less, more preferably 0.5 g / m 2 ⁇ day or less, still more preferably It is 0.2 g / m 2 ⁇ day or less.
  • the oxygen permeability of the gas barrier layer is preferably 0.6 ml / m 2 ⁇ day ⁇ atm or less under the conditions of a measurement temperature of 23 ° C. and a humidity of 90% RH.
  • the gas barrier layer may be composed of only one layer or may be composed of a plurality of layers.
  • the thickness of the gas barrier layer is preferably in the range of 10 to 500 nm, more preferably in the range of 50 to 200 nm.
  • Examples of the method for forming the gas barrier layer include a method of forming an inorganic oxide by a method such as vacuum deposition, sputtering, ion beam assist, chemical vapor deposition, etc., but a precursor of an inorganic oxide by a sol-gel method
  • a method of forming an inorganic oxide film by applying a heat treatment and / or a modification treatment by ultraviolet irradiation to the coating film after coating is preferably used.
  • the resin coat layer is preferably provided between the ultraviolet absorption layer and the photothermal reflection layer.
  • a corrosion inhibitor is preferably added so that the resin coat layer prevents corrosion of the light heat reflective layer.
  • the resin coat layer may have an ultraviolet absorbing ability.
  • the resin coat layer may be composed of only one layer or may be composed of a plurality of layers.
  • the layer thickness of the resin coat layer is preferably in the range of 0.1 to 10 ⁇ m, more preferably in the range of 2 to 8 ⁇ m.
  • the binder of the resin coat layer for example, the resins mentioned as the resin used for forming the top coat layer 4 described above can be used.
  • an antistatic layer can be provided as necessary.
  • the film mirror unit has a support made of a resin film or the like as compared with a glass mirror or the like, and since the surface is often formed of a resin, the film mirror unit is easily charged, and sand or dust. It is easy to attract dirt. Therefore, sand, dust, etc. adhere and it is mentioned as a problem that reflection efficiency falls.
  • the antistatic layer is preferably present through an extremely thin layer between the outermost layer adjacent to the outermost layer of the film mirror unit.
  • Example 1 ⁇ Production of film mirror unit> [Production of Film Mirror Unit 1 Having Sealing Section] (Production of film mirror unit) A film mirror unit having the structure of Type A shown in FIG. 1 was produced according to the following procedure.
  • a polyester resin (Polyester SP-181 manufactured by Nippon Synthetic Chemical), a melamine resin (manufactured by Superbeccamin J-820 DIC), a TDI-based isocyanate is formed on one side of the prepared support for forming a light heat reflective layer (7).
  • (2,4-tolylene diisocyanate) and HMDI isocyanate (1,6-hexamethylene diisocyanate) were mixed in toluene at a resin solid content ratio of 20: 1: 1: 2 and a solid content concentration of 10%.
  • the obtained resin was coated by a gravure coating method to form an anchor layer (6) having a thickness of 100 nm.
  • topcoat layer (4) Formation of topcoat layer (4)>
  • the sample on which the photothermal reflection layer (5) was formed was taken out from the vacuum deposition apparatus, and a polyester resin and TDI (tolylene diisocyanate) isocyanate were mixed at a resin solid content ratio of 10: 2 on the photothermal reflection layer (5).
  • 2-mercaptobenzothiazole as a silver corrosion inhibitor was added so as to be 10% by mass with respect to the resin, and a coating solution in which the solid content was adjusted to 5% by mass with methyl ethyl ketone was obtained by a gravure coating method. Coating was performed to form a topcoat layer (4) having a thickness of 4.0 ⁇ m.
  • a polyester resin (polyester) is formed on the surface opposite to the surface on which the anchor layer (6), the light heat reflection layer (5) and the top coat layer (4) of the prepared support (7) for light heat reflection layer formation are formed.
  • a UV curable functional hard coat agent LIODURAS TYZ series (filler component: ZrO 2 , solvent: ketone / alcohol / glycol system) manufactured by Toyo Ink Co., Ltd. is used on the ultraviolet absorbing layer (8) using an extrusion coater. Application and drying were performed to form a hard coat layer (9) having a dry film thickness of 3.0 ⁇ m.
  • an adhesive layer (3) composed of an acrylic resin adhesive (SZ-7543, manufactured by Nippon Carbide Industries Co., Ltd.) having a thickness of 25 ⁇ m is formed on the top coat layer (4), and a Type A film mirror is formed. A unit was made.
  • heating members 10A and 2mm ends the heating width L 2 by 10B, the left end portion of the heating member 10A and 10B
  • the pressure-sensitive adhesive layer (3) and the ultraviolet absorbing layer (with the holding pressure of the film mirror unit of 0.35 MPa and the heating temperature of 130 ° C.)
  • the softening component of 8) was softened and extruded, and the sealing part 11 having a thickness of 3 mm was formed while the side part of the sealing part 11 was regulated by the sealing part molding member 12.
  • the cooling member 11 was slowly cooled in a state where the sealing member 11 was held by the heating members 10A and 10B and the sealing member forming member 12 for 30 minutes.
  • a polyester resin (Polyester SP-181 manufactured by Nippon Synthetic Chemical), a melamine resin (manufactured by Superbeccamin J-820 DIC), a TDI-based isocyanate is formed on one side of the prepared support for forming a light heat reflective layer (7).
  • the resin mixed in toluene was coated by a gravure coating method to form an anchor layer (6) having a thickness of 100 nm.
  • topcoat layer (4) Formation of topcoat layer (4)>
  • the sample on which the photothermal reflection layer (5) was formed was taken out from the vacuum deposition apparatus, and a polyester resin and TDI (tolylene diisocyanate) isocyanate were mixed at a resin solid content ratio of 10: 2 on the photothermal reflection layer (5).
  • 2-mercaptobenzothiazole as a silver corrosion inhibitor was added so as to be 10% by mass with respect to the resin, and a coating solution in which the solid content was adjusted to 5% by mass with methyl ethyl ketone was obtained by a gravure coating method. Coating was performed to form a topcoat layer (4) having a thickness of 3.0 ⁇ m.
  • an adhesive layer (3) composed of an acrylic resin adhesive (SZ-7543, manufactured by Nippon Carbide Industries Co., Ltd.) having a thickness of 25 ⁇ m is formed on the back side of the support for forming a light heat reflective layer (7).
  • SZ-7543 acrylic resin adhesive
  • a Type B film mirror unit was produced.
  • heating members 10A and 2mm ends the heating width L 2 by 10B, the left end portion of the heating member 10A and 10B
  • the pressure-sensitive adhesive layer (3) and the ultraviolet absorbing layer (with the holding pressure of the film mirror unit of 0.35 MPa and the heating temperature of 130 ° C.)
  • the softened material of 8A) was extruded, and the sealing portion 11 having a thickness of 3 mm was formed while the side portion of the sealing portion 11 was regulated by the sealing portion molding member 12.
  • the cooling member 11 was slowly cooled in a state where the sealing member 11 was held by the heating members 10A and 10B and the sealing member forming member 12 for 30 minutes.
  • a weather-resistant tape 10386-ND (tape width: 24.5 mm (1 inch)) manufactured by 3M was cut in half and a tape having a width of 12.3 mm was used. It bonded by the pressure and sealed with the structure which surrounds each edge part of the film mirror unit FMU in a U shape as shown in FIG. Incidentally, it is shown in FIG. 3, the tape width L 1 at the end was 6 mm.
  • sealing tape aluminum foil tape No. Using 833 (tape width: 12.3 mm (1/2 inch)), bonding is performed at a pressure of 0.35 MPa, and each end of the film mirror unit FMU is formed into a U shape as shown in FIG. Sealed with a surrounding structure. Incidentally, FIG. 3, the tape width L 1 at the end was 6 mm.
  • Table 1 shows a typical configuration of each film mirror unit produced as described above.
  • the acrylic resin (Dainar ENB457 manufactured by Mitsubishi Rayon Co., Ltd.) and the ultraviolet absorber-containing acrylic film (Technoloy S001GU) constituting Type A and Type B used for the production of the film mirror units 1 to 33 have a layer thickness.
  • Samples having a thickness of 50 ⁇ m were prepared, and the light transmittance in the visible light region (400 to 700 nm) of each sample was measured with a commercially available spectrophotometer, and the average value was obtained. It was within the range of 94%.
  • ⁇ The formed sealing part is in a good state with no non-adhered part or coloration.
  • ⁇ Very weak peeling or coloring is observed at the end of the sealing part, but acceptable quality in practical use.
  • X The sealing part is not completely bonded to the film mirror unit, and peeling occurs [Evaluation of reflection area loss of film mirror] The reflection area of each produced film mirror unit after sealing was measured, and the reflection area loss was evaluated according to the following criteria.
  • ⁇ The loss rate of the reflection mirror area with respect to the total film mirror unit area (10000 mm 2 ) is less than 5%.
  • ⁇ The loss rate of the reflection mirror area with respect to the entire film mirror unit area (10000 mm 2 ) is 5% or more and less than 15%.
  • X The loss rate of the reflection mirror area with respect to the total film mirror unit area (10000 mm 2 ) is 15% or more [Evaluation of Barrier Properties]
  • Each film mirror unit with its end sealed is immersed in 25 ° C., 3% by weight saline solution for 5 days, and then the corrosion state of the photothermal reflective layer (silver reflective layer) is visually observed, according to the following criteria: The barrier property was evaluated.
  • ⁇ No occurrence of corrosion area is observed.
  • ⁇ The rate of occurrence of the corroded area is 1% or more and less than 5% of the total area.
  • ⁇ The rate of occurrence of the corroded area is Although it is 5% or more and less than 15% of the total area, it is within a practically acceptable range.
  • X The rate of occurrence of the corroded area is 15% or more of the total area, which is a practical problem.
  • Table 2 shows the results obtained as described above.
  • the film mirror of the present invention having the sealing part produced by the production method defined in the present invention on the side part is superior to the comparative example in the formation state of the sealing part. It can be seen that the reflection area loss as a film mirror is small, and the barrier property, the peel resistance after the friction treatment, and the durability are excellent.
  • Example 2 In the production of the film mirror units 2 to 17, 22, 24 to 28, and 31 described in Example 1, acrylic resin (Mitsubishi Rayon) was used as the light-transmitting thermoplastic resin used to form the ultraviolet absorbing layer (8).
  • ABS resin styrene / butadiene / acrylonitrile copolymer
  • PS polystyrene resin
  • Example 1 the same evaluation was performed for the formation state of the sealing portion, the presence or absence of a reflection area loss as a film mirror, barrier properties, peeling resistance after friction treatment, and durability. As a result, the same result as in Example 1 could be obtained, but the effect was slightly less than the level to which the acrylic resin was applied.
  • the film mirror manufactured by the method for manufacturing a film mirror of the present invention has a small reflection area loss, has characteristics of excellent barrier properties, peeling resistance after friction treatment, and durability, and is applied to, for example, a reflector for solar power generation. It can be suitably used as a film mirror for concentrating solar heat.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Optical Elements Other Than Lenses (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention vise à proposer un procédé de fabrication pour un miroir en film qui a une excellente aptitude au scellement et une excellente durée de vie (résistance à la déstratification) d'une partie de surface latérale, et pour lequel la perte de surface réfléchissante due au scellement est faible. A cet effet, l'invention porte sur un procédé de fabrication pour un miroir en film, lequel procédé sert à fabriquer un miroir en film comprenant au moins une couche adhésive, une couche réfléchissant la lumière et la chaleur, un support pour la formation de la couche réfléchissant la lumière et la chaleur, une couche absorbant les ultraviolets, et une couche de revêtement dur, lequel procédé de fabrication est caractérisé par ce qui suit : la couche absorbant les ultraviolets contient une résine thermoplastique ayant des propriétés d'émission de la lumière, un élément chauffant est lié par pression à une extrémité du miroir en film, le miroir en film est chauffé à l'intérieur d'une plage de température de 80 à 120° C pour ramollir la couche adhésive et la couche absorbant les ultraviolets contenant une résine acrylique, et une partie de scellement est formée par un composant ramolli qui s'est écoulé vers l'extérieur jusqu'à la partie d'extrémité.
PCT/JP2014/076431 2013-10-04 2014-10-02 Procédé de fabrication pour un miroir en film WO2015050217A1 (fr)

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JP2013208729A JP2016203376A (ja) 2013-10-04 2013-10-04 フィルムミラーの製造方法

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KR102116375B1 (ko) * 2018-04-10 2020-05-29 이창석 내구성 및 시공성이 우수한 유리코팅용 필름
JP2022144910A (ja) * 2021-03-19 2022-10-03 昭和電工パッケージング株式会社 熱交換器

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5515833A (en) * 1978-07-20 1980-02-04 Toppan Printing Co Ltd Laminatetube manufacturing method
JP2010113325A (ja) * 2008-10-09 2010-05-20 Hitachi Cable Ltd ミラー付き光伝送体及びその製造方法
WO2011096284A1 (fr) * 2010-02-02 2011-08-11 コニカミノルタオプト株式会社 Miroir sous forme de film permettant une production d'énergie solaire thermique, procédé de fabrication du miroir sous forme de film et dispositif de réflexion permettant une génération d'énergie solaire thermique
JP2011158751A (ja) * 2010-02-02 2011-08-18 Konica Minolta Opto Inc フィルムミラー、その製造方法、それを用いた太陽熱発電用反射装置

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5515833A (en) * 1978-07-20 1980-02-04 Toppan Printing Co Ltd Laminatetube manufacturing method
JP2010113325A (ja) * 2008-10-09 2010-05-20 Hitachi Cable Ltd ミラー付き光伝送体及びその製造方法
WO2011096284A1 (fr) * 2010-02-02 2011-08-11 コニカミノルタオプト株式会社 Miroir sous forme de film permettant une production d'énergie solaire thermique, procédé de fabrication du miroir sous forme de film et dispositif de réflexion permettant une génération d'énergie solaire thermique
JP2011158751A (ja) * 2010-02-02 2011-08-18 Konica Minolta Opto Inc フィルムミラー、その製造方法、それを用いた太陽熱発電用反射装置

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