WO2014050367A1

WO2014050367A1 - Process for producing heat-insulating laminated structure, heat-insulating laminated structure, and transparent laminated film

Info

Publication number: WO2014050367A1
Application number: PCT/JP2013/072181
Authority: WO
Inventors: 健司竹脇; 後藤　修; 徹司楢▲崎▼; 正隆犬塚; 翔一池野; 竹内　哲也
Original assignee: 東海ゴム工業株式会社
Priority date: 2012-09-25
Filing date: 2013-08-20
Publication date: 2014-04-03

Abstract

Provided is a process for producing a heat-insulating laminated structure which exhibits both excellent solar shading performance and excellent radio wave transmissivity. This process includes: a film-making step for making a transparent laminated film by forming a polymer layer (18) on the surface of a transparent polymer film (12) and then forming a laminated structure part which comprises both a metal oxide layer and a metal layer on the surface of the polymer layer (18); and a lamination step for laminating, by heating and pressing, two transparent substrates (28,28) with the transparent laminated film therebetween. In the film-making step, the metal oxide layer of the laminated structure part is formed by the sol-gel hardening of a metal oxide precursor, while a polymer that has a softening point lower than the heating temperature in the lamination step is used as the polymer constituting the polymer layer (18). In laminating the two transparent substrates (28,28), a groove is formed so as to divide the metal layer of the laminated structure part.

Description

Method for producing heat-insulating laminated structure, heat-insulating laminated structure, transparent laminated film

INDUSTRIAL APPLICABILITY The present invention is suitable for a method for manufacturing a heat-insulating laminated structure, a heat-insulating laminated structure, and a heat-insulating laminated structure suitably used for window glass of buildings such as buildings and houses, and window glass of vehicles such as automobiles. The present invention relates to a transparent laminated film.

Conventionally, a heat ray cut film is known as a film for shielding solar radiation. As a configuration of the heat ray cut film, for example, Patent Document 1 discloses a so-called multilayer film type transparent laminated film in which metal oxide layers and metal layers are alternately laminated on one side of a transparent polymer film.

For example, Patent Document 2 discloses a transparent laminate in which radio wave permeability is improved by forming a groove portion having a width of 30 μm or less in a laminated structure in which metal oxide layers and metal layers are alternately laminated on the surface of a transparent polymer film. A film has been proposed. The transparent polymer film is provided with an easy-adhesion layer on one side or both sides in advance in order to improve handling properties such as winding property. The groove portion of the laminated structure is formed by forming a laminated structure on the easy adhesion layer of the transparent polymer film.

Further, for example, in Patent Document 3, a thermoplastic resin film having a conductive film formed on an uneven surface is disposed and sandwiched between two transparent substrates, and the transparent equipment and the thermoplastic resin film are bonded. The resulting laminated structure is disclosed.

JP 2005-353656 A International Publication 2011/024756 JP 2005-104793 A

In buildings such as buildings and houses, and vehicles such as automobiles, a window glass may be formed by sandwiching a heat ray cut film between two glass substrates for the purpose of shielding solar radiation. In this case, the heat ray cut film is required to have visible light transmittance and solar shading as basic performance.

In addition, buildings such as buildings and houses may require high-frequency radio wave transmissivity of several hundred MHz or higher for the use of mobile phones and televisions. Moreover, in the automobile, with the spread of the ETC system, radio wave transmission may be required so as not to interfere with radio wave reception of the ETC on-board unit.

However, the transparent laminated film described in Patent Document 1 has a poor radio wave transmission because the metal layer is continuous. The transparent laminated film described in Patent Document 2 forms a groove portion in a laminated structure portion using an easy adhesion layer, and does not form a groove portion using an easy adhesion layer. Is different. In the laminated structure described in Patent Document 3, when the thermoplastic resin film is bonded to the transparent substrate, the uneven portions are deformed and flattened, and thus there is a possibility that desired radio wave transmission properties are difficult to obtain.

The problem to be solved by the present invention is to provide a method for manufacturing a heat-insulating laminated structure and a heat-insulating laminated structure that are excellent in solar radiation shielding properties and radio wave permeability. Moreover, it is providing the transparent laminated film which can be used suitably for such a laminated structure.

In order to solve the above problems, a method for manufacturing a heat-insulating laminated structure according to the present invention includes forming a polymer layer on the surface of a transparent polymer film, and forming a metal oxide layer and a metal layer on the surface of the polymer layer. Forming a laminated structure part to be laminated to obtain a transparent laminated film, and sandwiching the obtained transparent laminated film between two transparent substrates, and two transparent substrates under heating and pressure And in the film production process, the metal oxide layer of the laminated structure is formed by sol-gel curing of the metal oxide precursor, and the polymer of the polymer layer is combined with the polymer layer. Using a polymer having a softening temperature at a temperature lower than the heating temperature in the forming step, the gist is to form a groove part that divides the metal layer of the laminated structure part when the two transparent substrates are bonded together. .

In this case, it is preferable to use a polymer having a softening temperature of 40 to 130 ° C. as the polymer of the polymer layer. The polymer layer is preferably formed to a thickness of 0.05 to 1.0 μm. In addition, the groove for dividing the metal layer of the laminated structure is not formed in the film production process, or the width of the groove for dividing the metal layer of the laminated structure formed in the film production process is 0.6 μm or less. It is preferable to do. Further, it is preferable to use a polymer having a softening temperature of 110 to 130 ° C. as the polymer of the polymer layer and to form the polymer layer with a thickness of 0.05 to 0.5 μm.

The gist of the heat-insulating laminated structure according to the present invention is obtained by the manufacturing method according to the present invention.

In the heat-insulating laminated structure according to the present invention, a polymer layer and a laminated structure in which a metal oxide layer and a metal layer are laminated are laminated in this order on the surface of the transparent polymer film. A transparent laminated film and two transparent substrates to be bonded together, and the two transparent substrates are bonded to each other with the transparent laminated film sandwiched therebetween. The gist of the present invention is that a groove part is formed to divide the line.

In this case, the softening temperature of the polymer in the polymer layer is preferably 40 to 130 ° C. The thickness of the polymer layer is preferably 0.05 to 1.0 μm. And as a material of a polymer layer, an acrylic resin, a phenoxy resin, and a butyral resin can be mentioned as a suitable thing.

The transparent laminated film according to the present invention has a laminated structure portion in which a metal oxide layer and a metal layer are laminated on the surface of the transparent polymer film, and is softened between the transparent polymer film and the laminated structure portion. The gist is that a polymer layer having a temperature of 40 to 130 ° C. is disposed.

At this time, it is preferable that a groove for dividing the metal layer is not formed in the laminated structure. The thickness of the polymer layer is preferably 0.05 to 1.0 μm. And as a material of a polymer layer, an acrylic resin, a phenoxy resin, and a butyral resin can be mentioned as a suitable thing.

According to the method for manufacturing a heat-insulating laminated structure according to the present invention, a transparent laminated film having a laminated structure portion in which a metal oxide layer and a metal layer are laminated between two transparent substrates to be bonded is disposed. And since the groove part which divides | segments a metal layer is formed in the laminated structure part of this transparent laminated film, the heat-insulating laminated structure excellent in solar radiation shielding property and radio wave permeability is obtained.

At this time, if a polymer having a softening temperature of 40 to 130 ° C. is used as the polymer of the polymer layer, a groove for dividing the metal layer is easily formed in the laminated structure of the transparent laminated film. In addition, when the polymer layer is formed to a thickness of 0.05 to 1.0 μm, a groove part for dividing the metal layer is easily formed in the laminated structure part of the transparent laminated film.

Further, if the groove part that divides the metal layer of the laminated structure part is not formed in the film manufacturing process, it is possible to suppress the occurrence of a dent in the vicinity of the groove part of the metal layer during the aligning process. Thereby, the occurrence of irregular reflection of light near the groove is suppressed, and the appearance is also excellent. Moreover, when the width of the groove part for dividing the metal layer of the laminated structure part formed in the film production process is 0.6 μm or less, the dent generated in the vicinity of the groove part of the metal layer during the aligning process can be reduced. Thereby, the influence of the irregular reflection of the light which arises in the vicinity of a groove part can be made small, and it is excellent in an external appearance.

And according to the heat-insulating laminated structure according to the present invention, comprising a transparent laminated film having a laminated structure part in which a metal oxide layer and a metal layer are laminated between two bonded transparent substrates, Since the groove part which divides | segments a metal layer is formed in the laminated structure part of this transparent laminated film, it is excellent in solar radiation shielding property and radio wave permeability.

And according to the transparent laminated film which concerns on this invention, it has a laminated structure part by which the metal oxide layer and the metal layer were laminated | stacked on the surface of the transparent polymer film, Between a transparent polymer film and a laminated structure part Since a polymer layer with a softening temperature of 40-130 ° C is placed, when a transparent laminated film is sandwiched between two transparent substrates and the two transparent substrates are bonded together under heat and pressure In addition, a groove part for dividing the metal layer of the laminated structure part is formed. Therefore, a heat shielding laminated structure excellent in solar radiation shielding and radio wave transmission can be obtained.

At this time, if the groove portion for dividing the metal layer is not formed in the laminated structure portion, the width of the groove portion for dividing the metal layer of the laminated structure portion formed at the time of the alignment process becomes narrower. It is possible to suppress the formation of a dent in the vicinity of the groove portion. Thereby, the occurrence of irregular reflection of light near the groove is suppressed, and the appearance is also excellent.

It is process drawing which shows the manufacturing process of the heat insulating laminated structure which concerns on this invention. It is an enlarged view of the groove part of a laminated structure part. It is the image obtained by image | photographing the surface of a transparent laminated film with a microscope. It is the image obtained by image | photographing the surface of the transparent laminated film in a laminated glass with a microscope. 3 is an image obtained by photographing a cross section of a laminated glass with an FE-SEM (field emission scanning electron microscope).

DETAILED DESCRIPTION OF THE INVENTION A method for manufacturing a heat-insulating laminated structure according to the present invention (hereinafter sometimes referred to as the present manufacturing method) will be described in detail.

This production method includes a film production process for obtaining a transparent laminated film having heat shielding properties, and a combining process performed using the obtained transparent laminated film and two transparent substrates.

The film production process includes a first process of forming a polymer layer 18 on the surface of the transparent polymer film 12 as shown in FIG. 1 (a) and a polymer layer 18 as shown in FIG. 1 (b). And a second step of forming the laminated structure portion 16 in which the metal oxide layer 22 and the metal layer 24 are laminated on the surface. The polymer layer 18 is provided for the purpose of forming the groove portion 20 in the laminated structure portion 16 in the combining step described later.

As shown in FIG. 1A, an easy-adhesion layer 14 may be formed on the surface of the transparent polymer film 12 in advance for the purpose of improving handling properties such as winding property. As shown in FIG. 1A, 18 may be formed on the surface of the transparent polymer film 12 opposite to the surface on which the easy adhesion layer 14 is formed, or may be formed on the easy adhesion layer 14. May be.

In the first step, the polymer layer 18 is formed by preparing a coating liquid containing a polymer material, coating the surface of the transparent polymer film 12, and then drying to form a coating film. it can. In preparing the coating solution, a solvent for dissolving the polymer material can be used as necessary. Examples of such solvents include alcohols such as methanol, ethanol, propanol, butanol, heptanol and isopropyl alcohol, organic acid esters such as ethyl acetate, ketones such as acetonitrile, acetone and methyl ethyl ketone, and cycloethers such as tetrahydrofuran and dioxane. Acid amides such as formamide and N, N-dimethylformamide, hydrocarbons such as hexane, aromatics such as toluene and xylene, and the like. These may be used alone or in combination.

The laminated structure portion 16 is formed by laminating a metal oxide layer 22 and a metal layer 24. The metal oxide layer 22, the metal layer 24, the metal oxide layer 22... Are alternately stacked on the surface of the polymer layer 18 in this order. In FIG. 1B, the lowermost metal oxide layer is represented by 22a, the uppermost metal oxide layer is represented by 22b, and the metal oxide layer between them is the middle metal oxide layer. Call it.

In the second step, the metal oxide layer 22 is formed by sol-gel curing of a metal oxide precursor. Specifically, a coating liquid (coating liquid) containing a metal oxide precursor is prepared, applied to the surface of the transparent polymer film 12 or the surface of the metal layer 24, and then dried to form a coating film. And sol-gel curing by a predetermined method. The coating solution may contain water as necessary from the viewpoint that hydrolysis by the sol-gel method is promoted and a high refractive index is easily achieved.

Examples of the metal oxide precursor include organometallic compounds such as metal alkoxide, metal acylate, and metal chelate. By using the organometallic compound as the metal oxide precursor, the organic component derived from the organometallic compound can remain in the metal oxide layer 22. The softness | flexibility of the transparent laminated film 10 increases because the metal oxide layer 22 contains an organic component with a metal oxide. Among organometallic compounds, metal chelates are preferable from the viewpoint of excellent stability in air.

Examples of the sol-gel curing means include irradiation with light energy such as ultraviolet rays, electron beams, and X-rays, and heating. Among these, from the viewpoint of being able to produce a metal oxide at a low temperature and in a short time, and being difficult to give a load due to heat to the transparent polymer film 12, irradiation with light energy, particularly irradiation with ultraviolet rays is preferable. In the case of ultraviolet irradiation, relatively simple equipment is sufficient.

In the combining step, as shown in FIG. 1 (c), the obtained transparent laminated film 10 is sandwiched between two

transparent substrates

28 and 28, and the two

transparent substrates

28 and 28 are heated and pressurized. Paste together. An adhesive can be used for bonding. The transparent laminated film 10 is sandwiched between two

transparent base materials

28 and 28 via an adhesive layer 26 made of an adhesive.

The transparent substrate 28 is not particularly limited as long as it is a plate-like transparent body that sufficiently transmits visible light, but preferred examples include a glass plate and a resin plate. Examples of the glass include normal float glass, semi-tempered glass, and tempered glass. Examples of the resin include an acrylic resin and a polycarbonate resin. The thickness of the transparent substrate 28 may be determined as appropriate according to the application.

Examples of the main material of the adhesive include polyvinyl butyral (PVB), ethylene vinyl acetate (EVA), acrylic resin, silicone resin, and urethane resin. The adhesive may be a liquid or a solid one. Examples of the solid material include a film material.

Here, as the polymer of the polymer layer 18, a polymer having a softening temperature lower than the heating temperature in the combining step is used. If it does so, the softness | flexibility of the polymer layer 18 will increase with the heat | fever of a matching process, and the freedom degree of the in-plane direction of the laminated structure part 16 will become high. If pressure is applied in this situation and the two

transparent base materials

28 and 28 are bonded together, the pressure causes a crack in the laminated structure portion 16 and the metal layer 24 is divided. That is, the groove part 20 which divides the metal layer 24 of the laminated structure part 16 when the two

transparent base materials

28 and 28 are bonded together is formed. Since the cracks are randomly formed, the groove part 20 formed of the cracks tends to be a groove part 20 having no directionality. For this reason, the directivity of the surface resistance is difficult to be obtained, and the surface resistance is easily made uniform. The softening temperature is a glass transition temperature (Tg) in the case of an amorphous polymer, and a melting point (Tm) in the case of a crystalline polymer, and can be measured by differential scanning calorimetry (DSC). .

The heating temperature in the mating step is set to a temperature at which the adhesive used is softened. When, for example, polyvinyl butyral is used as the adhesive, the heating temperature in the combining step is set to, for example, about 130 to 135 ° C. in consideration of the softening temperature. Therefore, in consideration of the softening temperature of the adhesive used, it is preferable to use a polymer having a softening temperature of 40 to 130 ° C. as the polymer of the polymer layer 18.

When a polymer having a softening temperature at a temperature lower than the heating temperature in the polymerizing process is used in accordance with the polymer of the polymer layer 18, the softening temperature may be lower than the sol-gel curing temperature in the film manufacturing process.

When a polymer having a softening temperature at a temperature lower than the temperature at the time of sol-gel curing in the film production process is used as the polymer of the polymer layer 18, the flexibility of the polymer layer 18 by heat at the time of sol-gel curing. Increases, and the degree of freedom in the in-plane direction of the laminated structure portion 16 increases. At the time of sol-gel curing, stress accumulates in the laminated structure portion 16 due to curing shrinkage of the metal oxide precursor. However, when the degree of freedom in the in-plane direction of the laminated structure portion 16 increases, the accumulated stress in the laminated structure portion 16 is released. As a result, a crack may occur in the laminated structure portion 16. This crack becomes the groove 20. That is, when the sol-gel is cured, the groove 20 may be formed in the laminated structure portion 16 due to the stress generated by the sol-gel curing on the polymer layer 18.

The lower the softening temperature of the polymer in the polymer layer 18 is, the higher the degree of freedom of the laminated structure portion 16 is during sol-gel curing, and stress is less likely to be accumulated (easily released) in the laminated structure portion 16. Then, cracks occur in the metal oxide precursor layer at an early stage of sol-gel curing, forming islands of the metal oxide precursor in the middle of curing, and the metal oxide precursor in the middle of curing divided by the cracks. Since the island cures and shrinks in the in-plane direction, the width of the groove 20 tends to be relatively large. Further, cracks are likely to occur during the sol-gel curing of the middle or lowest metal oxide layer 22 instead of the uppermost layer of the laminated structure portion 16.

On the other hand, when the softening temperature of the polymer in the polymer layer 18 is increased, the degree of freedom of the laminated structure portion 16 is reduced during sol-gel curing, and stress is easily accumulated in the laminated structure portion 16. Then, since the stress is dispersed when the stress is released, many narrower cracks are formed. Further, cracks are likely to occur during the sol-gel curing of the upper metal oxide layer 22 of the laminated structure portion 16. When the softening temperature of the polymer in the polymer layer 18 is further increased, cracks are not generated in the laminated structure portion 16 during sol-gel curing.

As described above, when the softening temperature of the polymer of the polymer layer 18 changes, the flexibility of the polymer layer 18 during sol-gel curing or the combining process changes, and the groove portion 20 is formed in the laminated structure portion 16. The timing, the size of the width of the groove 20 to be formed, the divided shape of the laminated structure 16 and the like are changed. Therefore, the flexibility of the polymer layer 18 at the time of sol-gel curing or the combining process can be controlled by selecting the polymer of the polymer layer 18, the timing at which the groove 20 is formed in the laminated structure 16, and the groove to be formed It is possible to adjust the size of the width of 20, the divided shape of the laminated structure portion 16, and the like. In addition, even when a crack does not occur in the laminated structure portion 16 during sol-gel curing, the groove portion 20 that divides the metal layer 24 of the laminated structure portion 16 can be formed before the alignment process. For example, after the metal oxide layer 22 is formed by sol-gel curing of a metal oxide precursor, the polymer of the polymer layer 18 is heated to the softening temperature or higher before the combining step, whereby the polymer layer It is also possible to soften the polymer 18 and release the stress generated in the metal oxide layer 22, thereby forming the groove 20 that divides the metal layer 24 of the laminated structure 16.

The timing at which the groove 20 is formed in the laminated structure 16 can be adjusted by the softening temperature of the polymer in the polymer layer 18. It can also be adjusted by the thickness of the polymer layer 18 and the temperature during sol-gel curing. As an example in the case of adjusting by the softening temperature, when the softening temperature of the polymer layer 18 is less than 40 ° C., the groove 20 (crack) is formed when the first metal oxide layer 22a of the laminated structure 16 is formed. Is done. When the softening temperature is not lower than 40 ° C. and lower than 60 ° C., the groove 20 (crack) is generated for the first time when the third metal oxide layer 22 of the laminated structure 16 is formed. In this case, the groove 20 (crack) is formed when the uppermost metal oxide layer 22 is formed in the three-layer laminated structure, but the middle metal oxide layer 22 is formed in the five-layer laminated structure or the seven-layer laminated structure. Sometimes grooves 20 (cracks) are formed. When the softening temperature is not less than 60 ° C. and less than 70 ° C., the groove 20 (crack) is generated for the first time when the fifth metal oxide layer 22 of the laminated structure 16 is formed. When the softening temperature is 70 ° C. or higher and 130 ° C. or lower, since the softening temperature is relatively high, the groove 20 (crack) is generated for the first time when the seventh metal oxide layer 22b of the laminated structure 16 is formed. In this case, even in the seven-layer stacked structure, the groove 20 (crack) can be formed when the uppermost metal oxide layer 22b is formed.

As the polymer layer 18 is thicker, the degree of freedom of the laminated structure portion 16 can be increased when the sol-gel is cured, and the groove portion 20 (crack) is easily generated in the laminated structure portion 16. However, as shown in FIG. 2, as the thickness increases, the sinking toward the polymer layer 18 side becomes larger at the end portion constituting the groove portion 20 and causes irregular reflection. Therefore, from the viewpoint of suppressing irregular reflection at the groove 20, the thickness of the polymer layer 18 is preferably 1.0 μm or less. Further, from the viewpoint of suppressing the generation of the groove 20 before the alignment step, the thickness of the polymer layer 18 is preferably 0.5 μm or less. On the other hand, the lower limit of the thickness is not particularly limited, but is preferably 0.05 μm or more from the viewpoint of manufacturing.

When the groove 20 is formed in the transparent laminated film 10 itself before the combining step, the flexibility of the polymer layer 18 is increased by the heat of the combining step, and the degree of freedom in the in-plane direction of the laminated structure portion 16 is increased. As a result, the stacked structure portion 16 is further cracked starting from the groove portion 20 formed in advance, and the metal layer 24 divided by the groove portion 20 is further divided. Moreover, the width | variety of the already formed groove part 20 may spread with progress of the fragmentation of the groove part 20. FIG.

When the width of the groove portion 20 is too wide, a dent is generated in the vicinity of the groove portion 20 of the metal layer 24 due to the pressure during the alignment process. Due to this dent, irregular reflection of light occurs in the vicinity of the groove portion 20, and the appearance may be poor.

Therefore, from the viewpoint of suppressing the occurrence of irregular reflection of light due to the occurrence of a dent in the vicinity of the groove 20, the groove 20 is not formed in the transparent laminated film 10 itself before the alignment process, or the groove Even if 20 is formed, it is preferable that the groove 20 has a narrow width. When the groove 20 is formed in the transparent laminated film 10 itself before the combining step, the width of the groove 20 is 0.6 μm or less from the viewpoint of suppressing the occurrence of irregular reflection of light. preferable. More preferably, it is 0.3 μm or less. The width of the groove part 20 is an average value of the widths measured at three places (15 places in total) of the groove part 20 by photographing five surfaces of the laminated structure with an optical microscope.

In order to prevent the groove 20 from being formed in the transparent laminated film 10 itself before the combining step, or to reduce the width of the groove 20 to 0.6 μm or less even if it is formed, the polymer layer 18 It is preferable to increase the softening temperature and reduce the thickness of the polymer layer 18. In order to prevent the groove 20 from being formed in the transparent laminated film 10 itself before the combining step, the polymer softening temperature of the polymer layer 18 is 110 ° C. or more and the thickness of the polymer layer 18 is 0.5 μm or less. It is preferable to set to. Further, in order to make the width of the groove portion 20 0.6 μm or less, it is preferable to set the polymer softening temperature of the polymer layer 18 to 40 ° C. or more and the thickness of the polymer layer 18 to 0.5 μm or less. .

Specific examples of the material for the polymer layer 18 include acrylic resin, phenoxy resin, and butyral resin. Of these, acrylic resins and butyral resins are preferred from the viewpoints of excellent optical properties (transparency) and excellent coating properties.

This manufacturing method makes it possible to obtain a heat shielding laminated structure 30 having excellent solar radiation shielding properties and radio wave transmission properties. As shown in FIG. 1 (c), the heat shielding laminated structure 30 has two

transparent base materials

28 and 28 bonded together with the transparent laminated film 10 sandwiched therebetween, and the laminated structure portion 16 of the transparent laminated film 10 is attached. A groove 20 for dividing the metal layer 24 is formed.

Since the obtained heat shielding laminated structure 30 includes the transparent laminated film 10, it is excellent in solar shading. Moreover, since the groove part 20 which divides | segments the metal layer 24 is formed in the laminated structure part 16, it is excellent also in radio wave permeability. The heat shielding laminated structure 30 can be set to a desired surface resistance value by adjusting the pressure and temperature conditions when the two

transparent substrates

28 and 28 are bonded together. The surface resistance value of the heat-insulating laminated structure 30 is preferably 100Ω / □ or more from the viewpoint of radio wave transmission.

As shown in FIG. 1B, the transparent laminated film 10 has a transparent polymer film 12, an easy adhesion layer 14, a laminated structure portion 16, and a polymer layer 18. The easy adhesion layer 14 is provided on one surface of the transparent polymer film 12. The laminated structure portion 16 is provided on a surface opposite to the surface on which the easy adhesion layer 14 of the transparent polymer film 12 is formed. The polymer layer 18 is provided between the transparent polymer film 12 and the laminated structure portion 16.

The transparent polymer film 12 is a base material serving as a base for forming the laminated structure portion 16. The material of the transparent polymer film 12 is not particularly limited as long as it has transparency in the visible light region and can form a thin film on the surface without hindrance.

Specific examples of the material of the transparent polymer film 12 include polyethylene terephthalate, polycarbonate, polymethyl methacrylate, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polystyrene, polyimide, polyamide, polybutylene terephthalate, polyethylene naphthalate. , Polymer materials such as polysulfone, polyethersulfone, polyetheretherketone, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, triacetyl cellulose, polyurethane, and cycloolefin polymer. These may be used alone or in combination of two or more. Among these, polyethylene terephthalate, polycarbonate, polymethyl methacrylate, and cycloolefin polymer are more preferable materials from the viewpoint of excellent transparency, durability, and processability.

The easy-adhesion layer 14 is provided in advance on the transparent polymer film 12 in order to improve handling properties such as winding property of the transparent polymer film 12. The easy adhesion layer 14 is often formed on the surface of the transparent polymer film 12 for optical applications. This is because it is difficult for the transparent polymer film 12 for optical applications to improve handling properties by blending silica particles or the like into the film.

In the laminated structure portion 16, the metal oxide layer 22, the metal layer 24, the metal oxide layer 22,... Are alternately laminated in this order from the transparent polymer film 12 side. Further, it has a seven-layer laminated structure. A metal oxide layer 22 is disposed on the innermost layer (22a) on the transparent polymer film 12 side and the outermost layer (22b) on the opposite side of the transparent polymer film 12. The metal oxide layer 22 and the metal layer 24 are made of a thin film. A barrier layer may be further formed on one surface or both surfaces of the metal layer 24. The barrier layer is a thin film layer attached to the metal layer 24 and is counted as one layer together with the metal layer 24. The barrier layer suppresses diffusion of elements constituting the metal layer 24 into the metal oxide layer 22.

The metal oxide layer 22 exhibits functions such as enhancing transparency (excelling in the visible light region) by being laminated together with the metal layer 24, and can function mainly as a high refractive index layer. It is. High refractive index means a case where the refractive index for light of 633 nm is 1.7 or more. The metal layer 24 can mainly function as a solar radiation shielding layer. Such a laminated structure 16 has good visible light transparency (transparency) and solar shading.

In addition, the number of layers of the laminated structure portion 16 may be appropriately set according to the optical characteristics such as visible light transparency (transparency) and solar shading, and the electrical characteristics such as the surface resistance of the entire film. The number of layers can be other than seven. The number of layers of the laminated structure portion 16 is preferably in the range of 2 to 10 layers in consideration of the material, film thickness, manufacturing cost, etc. of each thin film. In consideration of optical characteristics, odd-numbered layers are more preferable, and 3 layers, 5 layers, and 7 layers are particularly preferable.

Hereinafter, the metal oxide layer 22, the metal layer 24, and the barrier layer of the laminated structure portion 16 will be described in detail.

Examples of the metal oxide of the metal oxide layer 22 of the multilayer structure portion 16 include titanium oxide, zinc oxide, indium oxide, tin oxide, indium and tin oxide, magnesium oxide, Examples thereof include aluminum oxide, zirconium oxide, niobium oxide, and cerium oxide. These may be contained alone or in combination of two or more. These metal oxides may be composite oxides in which two or more metal oxides are combined. Among these, titanium oxide, indium and tin oxide, zinc oxide, tin oxide, and the like are preferable from the viewpoint of relatively high refractive index with respect to visible light.

The lower limit of the content of the organic component contained in the metal oxide layer 22 is preferably 3% by mass or more, more preferably 5% by mass or more, and still more preferably, from the viewpoint of easily imparting flexibility. 7 mass% or more. On the other hand, the upper limit of the content of the organic component contained in the metal oxide layer 22 is preferably 30% by mass or less from the viewpoint of easily ensuring a high refractive index and easily ensuring solvent resistance. More preferably, it is 25% by mass or less, and further preferably 20% by mass or less. The organic content can be examined using X-ray photoelectron spectroscopy (XPS) or the like. Moreover, the kind of said organic content can be investigated using infrared spectroscopy (IR) (infrared absorption analysis) etc.

The metal oxide layer 22 is formed by sol-gel curing of a metal oxide precursor. When light energy irradiation is selected as the sol-gel curing means, the organometallic compound is light-absorbing (for example, UV-absorbing). It is preferable to have a ligand that forms a chelate. By providing the light-absorbing chelate ligand, the metal oxide layer 22 can be formed at a relatively low temperature.

Such chelate ligands include β diketones, alkoxy alcohols, alkanolamines and the like. Examples of β diketones include acetylacetone, benzoylacetone, ethyl acetoacetate, methyl acetoacetate, diethyl malonate, and the like. Examples of alkoxy alcohols include 2-methoxyethanol, 2-ethoxyethanol, 2-methoxy-2-propanol and the like. Examples of alkanolamines include monoethanolamine, diethanolamine, and triethanolamine. Of these, β diketones are preferred, and among them, acetylacetone can be most suitably used.

The content of the metal oxide precursor in the coating liquid is preferably 1 to 20% by mass, more preferably, from the viewpoint of the film thickness uniformity of the coating film and the film thickness that can be applied at one time. It is good that it is in the range of 3 to 15% by mass, more preferably 5 to 10% by mass.

The amount of the solvent is preferably from 5 to 100 times, more preferably from the viewpoint of the film thickness uniformity of the coating film and the film thickness that can be applied at one time with respect to the solid weight of the metal oxide precursor. 7 to 30 times, more preferably 10 to 20 times. When the amount of the solvent is more than 100 times, the film thickness that can be formed by one coating becomes thin, and a tendency to require many coatings to obtain a desired film thickness is observed. On the other hand, if the amount is less than 5 times, the film thickness becomes too thick and the hydrolysis / condensation reaction of the metal oxide precursor does not proceed sufficiently. Therefore, the amount of solvent should be selected in consideration of these.

Specific examples of the solvent for dissolving the metal oxide precursor include alcohols such as methanol, ethanol, propanol, butanol, heptanol, and isopropyl alcohol, organic acid esters such as ethyl acetate, acetonitrile, acetone, and methyl ethyl ketone. Ketones, cycloethers such as tetrahydrofuran and dioxane, acid amides such as formamide and N, N-dimethylformamide, hydrocarbons such as hexane, aromatics such as toluene, and the like. These may be used alone or in combination.

The preparation of the coating liquid is performed by, for example, stirring the metal oxide precursor weighed so as to have a predetermined ratio, an appropriate amount of solvent, and other components added as necessary, with stirring means such as a stirrer. It can be prepared by a method such as stirring and mixing for a predetermined time. In this case, the components may be mixed at a time or may be mixed in a plurality of times.

As the coating method of the coating liquid, from the viewpoint of easy uniform coating, microgravure method, gravure method, reverse roll coating method, die coating method, knife coating method, dip coating method, spin coating method, bar coating Various wet coating methods such as the method can be exemplified as suitable ones. These may be appropriately selected and used, and one or more may be used in combination. When the applied coating liquid is dried, it may be dried using a known drying device. Specific examples of the drying conditions include a temperature range of 80 ° C. to 120 ° C., Examples include a drying time of 0.5 minute to 5 minutes.

The sol-gel curing of the metal oxide precursor can be performed by irradiation with light energy such as ultraviolet rays, electron beams, X-rays or heating.

When performing light energy irradiation, the amount of light energy to be irradiated can be variously adjusted in consideration of the type of metal oxide precursor, the thickness of the layer, and the like. However, if the amount of light energy to be irradiated is too small, it is difficult to increase the refractive index of the metal oxide layer 22. On the other hand, if the amount of light energy to be irradiated is excessively large, the transparent polymer film 12 may be deformed by the heat generated during the light energy irradiation. Therefore, these should be noted.

When the light energy to be irradiated is ultraviolet light, the amount of light is preferably from 300 to 8000 mJ at a measurement wavelength of 300 to 390 nm from the viewpoint of the refractive index of the metal oxide layer 22 and damage to the transparent polymer film 12. / Cm ² , more preferably in the range of 500 to 5000 mJ / cm ² . In this case, specific examples of the ultraviolet irradiator to be used include a mercury lamp, a xenon lamp, a deuterium lamp, an excimer lamp, a metal halide lamp, and the like. These may be used alone or in combination of two or more.

The film thickness of the metal oxide layer 22 can be adjusted in consideration of solar shading, visibility, reflection color, and the like. The lower limit of the film thickness of the metal oxide layer 22 is preferably 10 nm or more, more preferably, from the viewpoints of easily suppressing red and yellow coloring of the reflected color, and easily obtaining high transparency. It is good that it is 15 nm or more, more preferably 20 nm or more. On the other hand, the upper limit value of the film thickness of the metal oxide layer 22 is preferably 90 nm or less, more preferably, from the viewpoint of easily suppressing the green color of the reflected color and obtaining high transparency. 85 nm or less, more preferably 80 nm or less.

Examples of the metal of the metal layer 24 include metals such as silver, gold, platinum, copper, aluminum, chromium, titanium, zinc, tin, nickel, cobalt, niobium, tantalum, tungsten, zirconium, lead, palladium, and indium. And alloys thereof. These may be contained alone or in combination of two or more.

As the metal of the metal layer 24, silver or a silver alloy is preferable from the viewpoint of being excellent in visible light transmittance, heat ray reflectivity, conductivity, and the like when laminated. More preferably, from the viewpoint of improving durability against environment such as heat, light, and water vapor, the main component is silver, and at least one metal element such as copper, bismuth, gold, palladium, platinum, and titanium is included. It should be a silver alloy. More preferably, a silver alloy containing copper (Ag—Cu alloy), a silver alloy containing bismuth (Ag—Bi alloy), a silver alloy containing titanium (Ag—Ti alloy), or the like is preferable. This is because there are advantages such as a large silver diffusion suppression effect and cost advantage.

When using a silver alloy containing copper, other elements and inevitable impurities may be contained in addition to silver and copper, for example, within a range that does not adversely affect the aggregation / diffusion suppression effect of silver.

Specific examples of the other elements include elements that can be dissolved in Ag such as Mg, Pd, Pt, Au, Zn, Al, Ga, In, Sn, Sb, Li, Cd, Hg, and As. In Ag-Cu alloys such as Be, Ru, Rh, Os, Ir, Bi, Ge, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Si, Tl, Pb, etc. Element which can be precipitated as a single phase in Y; La, Ce, Nd, Sm, Gd, Tb, Dy, Ti, Zr, Hf, Na, Ca, Sr, Ba, Sc, Pr, Eu, Ho, Er, Tm Examples include elements capable of precipitating intermetallic compounds with Ag such as Yb, Lu, S, Se, and Te. These may be contained alone or in combination of two or more.

When using a silver alloy containing copper, the lower limit of the copper content is preferably 1 atomic% or more, more preferably 2 atomic% or more, and even more preferably 3 atomic% or more, from the viewpoint of obtaining the effect of addition. Good to be. On the other hand, the upper limit of the copper content is preferably 20 atomic% or less, more preferably 10 atomic%, from the viewpoint of manufacturability such as easy to ensure high transparency and easy production of a sputtering target. Hereinafter, it is more preferable that it is 5 atomic% or less.

Further, when using a silver alloy containing bismuth, in addition to silver and bismuth, for example, other elements and inevitable impurities may be included as long as they do not adversely affect the aggregation / diffusion suppression effect of silver. good.

Specific examples of the other elements include elements that can be dissolved in Ag such as Mg, Pd, Pt, Au, Zn, Al, Ga, In, Sn, Sb, Li, Cd, Hg, and As. ; Be, Ru, Rh, Os, Ir, Cu, Ge, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Si, Tl, Pb, etc. in Ag-Bi alloys Element which can be precipitated as a single phase in Y; La, Ce, Nd, Sm, Gd, Tb, Dy, Ti, Zr, Hf, Na, Ca, Sr, Ba, Sc, Pr, Eu, Ho, Er, Tm Examples include elements capable of precipitating intermetallic compounds with Ag such as Yb, Lu, S, Se, and Te. These may be contained alone or in combination of two or more.

When using a silver alloy containing bismuth, the lower limit of the bismuth content is preferably 0.01 atomic% or more, more preferably 0.05 atomic% or more, and still more preferably, from the viewpoint of obtaining the effect of addition. It may be 0.1 atomic% or more. On the other hand, the upper limit of the bismuth content is preferably 5 atomic% or less, more preferably 2 atomic% or less, and still more preferably 1 atomic% from the viewpoint of manufacturability such as easy production of a sputtering target. It is good to be below.

In addition, when using a silver alloy containing titanium, other than silver and titanium, for example, other elements and inevitable impurities may be included as long as they do not adversely affect the aggregation / diffusion suppression effect of silver. good.

Specific examples of the other elements include elements that can be dissolved in Ag such as Mg, Pd, Pt, Au, Zn, Al, Ga, In, Sn, Sb, Li, Cd, Hg, and As. ; Be-Ru, Rh, Os, Ir, Cu, Ge, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Si, Tl, Pb, Bi, etc., Ag-Ti system Elements that can be precipitated as a single phase in the alloy; Y, La, Ce, Nd, Sm, Gd, Tb, Dy, Zr, Hf, Na, Ca, Sr, Ba, Sc, Pr, Eu, Ho, Er, Tm Examples include elements capable of precipitating intermetallic compounds with Ag such as Yb, Lu, S, Se, and Te. These may be contained alone or in combination of two or more.

When using a silver alloy containing titanium, the lower limit value of the titanium content is preferably 0.01 atomic% or more, more preferably 0.05 atomic% or more, and still more preferably, from the viewpoint of obtaining an addition effect. It may be 0.1 atomic% or more. On the other hand, the upper limit of the content of titanium is preferably 2 atomic% or less, more preferably 1.75 atomic% or less, and still more preferably, from the viewpoint that a complete solid solution is easily obtained when it is formed into a film. Is preferably 1.5 atomic% or less.

It should be noted that the ratio of subelements such as copper, bismuth and titanium can be measured using ICP analysis. Further, the metal (including alloy) constituting the metal layer 24 may be partially oxidized.

The lower limit of the film thickness of the metal layer 24 is preferably 3 nm or more, more preferably 5 nm or more, and even more preferably 7 nm or more from the viewpoints of stability, heat ray reflectivity, and the like. On the other hand, the upper limit of the film thickness of the metal layer 24 is preferably 30 nm or less, more preferably 20 nm or less, and even more preferably 15 nm or less, from the viewpoints of transparency of visible light, economy, and the like.

Here, as a method of forming the metal layer 24, specifically, for example, a physical vapor deposition method (PVD) such as a vacuum deposition method, a sputtering method, an ion plating method, an MBE method, a laser ablation, a thermal method, etc. Examples thereof include a vapor phase method such as a chemical vapor deposition method (CVD) such as a CVD method and a plasma CVD method. The metal layer 24 may be formed using any one of these methods, or may be formed using two or more methods.

Among these methods, sputtering methods such as DC magnetron sputtering method and RF magnetron sputtering method can be preferably used from the viewpoint of obtaining a dense film quality and relatively easy film thickness control.

Note that the metal layer 24 may be oxidized within a range that does not impair the function of the metal layer 24 by receiving post-oxidation or the like to be described later.

The barrier layer associated with the metal layer 24 mainly has a barrier function that suppresses the diffusion of elements constituting the metal layer 24 into the metal oxide layer 22. Further, by interposing between the metal oxide layer 22 and the metal layer 24, it is possible to contribute to improvement in adhesion between the two. The barrier layer may have discontinuous portions such as floating islands as long as the diffusion can be suppressed.

Specific examples of the metal oxide constituting the barrier layer include, for example, titanium oxide, zinc oxide, indium oxide, tin oxide, indium and tin oxide, and magnesium oxide. And aluminum oxide, zirconium oxide, niobium oxide, cerium oxide, and the like. These may be contained alone or in combination of two or more. Further, these metal oxides may be double oxides in which two or more metal oxides are combined. Note that the barrier layer may contain inevitable impurities in addition to the metal oxide.

Here, as a barrier layer, it is mainly comprised from the oxide of the metal contained in the metal oxide layer 22 from a viewpoint of being excellent in the diffusion inhibitory effect of the metal which comprises the metal layer 24, and being excellent in adhesiveness. Good to be.

More specifically, for example, when a TiO ₂ layer is selected as the metal oxide layer 22, the barrier layer is a titanium oxide layer mainly composed of an oxide of Ti that is a metal contained in the TiO ₂ layer. Good to be.

When the barrier layer is a titanium oxide layer, the barrier layer may be a thin film layer formed as titanium oxide from the beginning, or a thin film layer formed by post-oxidation of a metal Ti layer, Alternatively, it may be a thin film layer formed by post-oxidizing a partially oxidized titanium oxide layer.

The barrier layer is mainly composed of a metal oxide in the same manner as the metal oxide layer 22, but is set to be thinner than the metal oxide layer 22. This is because the diffusion of the metal constituting the metal layer 24 occurs at the atomic level, so that it is not necessary to increase the film thickness to a level necessary to ensure a sufficient refractive index. Moreover, by forming it thinly, the film-forming cost is reduced correspondingly, and it can contribute to the reduction of the manufacturing cost of the transparent laminated film 10.

The lower limit value of the film thickness of the barrier layer is preferably 1 nm or more, more preferably 1.5 nm or more, and further preferably 2 nm or more from the viewpoint of easily ensuring barrier properties. On the other hand, the upper limit value of the thickness of the barrier layer is preferably 15 nm or less, more preferably 10 nm or less, and still more preferably 8 nm or less, from the viewpoint of economy and the like.

When the barrier layer is mainly composed of titanium oxide, the lower limit value of the atomic molar ratio Ti / O of titanium to oxygen in the titanium oxide is 1.0 / 4.0 or more from the viewpoint of barrier properties and the like. Preferably, 1.0 / 3.8 or higher, more preferably 1.0 / 3.5 or higher, even more preferably 1.0 / 3.0 or higher, most preferably 1.0 / 2.8. It is good to be above.

When the barrier layer is mainly composed of titanium oxide, the upper limit of the atomic molar ratio Ti / O of titanium to oxygen in the titanium oxide is preferably 1.0 / 0.5 or less, more preferably 1.0 / 0.7 or less, more preferably 1.0 / 1.0 or less, even more preferably 1.0 / 1.2 or less, most preferably 1 0.0 / 1.5 or less is preferable.

The Ti / O ratio can be calculated from the composition of the layer. As a composition analysis method of the layer, energy dispersive X-ray fluorescence analysis (EDX) can be preferably used from the viewpoint of enabling comparatively accurate analysis of the composition of an extremely thin thin film layer.

Describing a specific composition analysis method, first, a test piece having a thickness of 100 nm or less in the cross-sectional direction of the laminated structure including the layer to be analyzed is prepared using an ultrathin section method (microtome) or the like. Next, the laminated structure and the position of the layer are confirmed by a transmission electron microscope (TEM) from the cross-sectional direction. Next, an electron beam is emitted from the electron gun of the EDX apparatus and is incident on the vicinity of the center of the film thickness of the layer to be analyzed. Electrons incident from the surface of the test specimen enter to a certain depth and generate various electron beams and X-rays. By detecting and analyzing characteristic X-rays at this time, the constituent elements of the layer can be analyzed.

As the barrier layer, a vapor phase method can be suitably used from the viewpoint that a dense film can be formed and a thin film layer of about several nm to several tens of nm can be formed with a uniform film thickness.

Specific examples of the vapor phase method include physical vapor deposition methods (PVD) such as vacuum deposition, sputtering, ion plating, MBE, and laser ablation, thermal CVD, and plasma CVD. Examples thereof include chemical vapor deposition (CVD) and the like. As the vapor phase method, a sputtering method such as a DC magnetron sputtering method or an RF magnetron sputtering method is preferable from the viewpoint of excellent adhesion at the film interface as compared with a vacuum deposition method and the like and easy control of the film thickness. Can be used.

Each barrier layer that can be included in the laminated structure may be formed using any one of these vapor phase methods, or formed using two or more methods. May be.

The barrier layer may be formed as the metal oxide layer 22 from the beginning using the above-described vapor phase method, or the metal layer 24 or the partially oxidized metal oxide layer 22 may be temporarily formed. It is also possible to form the film by oxidizing it after the film has been formed. The partially oxidized metal oxide layer 22 refers to a metal oxide layer 22 that has room for further oxidation.

In the case where the metal oxide layer 22 is formed from the beginning, specifically, for example, a gas containing oxygen as a reactive gas is mixed with an inert gas such as argon or neon as a sputtering gas, and the metal and oxygen are mixed. A thin film may be formed while reacting with (reactive sputtering method). For example, when a titanium oxide layer having the Ti / O ratio is obtained by using the reactive sputtering method, the oxygen concentration in the atmosphere (the volume ratio of the gas containing oxygen to the inert gas) is the film thickness range described above. The optimum ratio may be appropriately selected in consideration of the above.

On the other hand, when the metal layer 24 or the partially oxidized metal oxide layer 22 is formed and then post-oxidized later, specifically, the above-described laminated structure is formed on the transparent polymer film 12. Thereafter, the metal layer 24 or the partially oxidized metal oxide layer 22 in the laminated structure may be post-oxidized. A sputtering method or the like may be used for forming the metal layer 24, and the reactive sputtering method or the like described above may be used for forming the partially oxidized metal oxide layer 22.

Also, examples of the post-oxidation method include heat treatment, pressure treatment, chemical treatment, and natural oxidation. Of these post-oxidation techniques, heat treatment is preferable from the viewpoint of enabling post-oxidation relatively easily and reliably. Examples of the heat treatment include a method of causing the transparent polymer film 12 having the above-described laminated structure to exist in a heating atmosphere such as a heating furnace, a method of immersing in warm water, a method of microwave heating, A method of energizing and heating the metal layer 24, the partially oxidized metal oxide layer 22, and the like can be exemplified. These may be performed in combination of one or two or more.

Specifically, the heating conditions at the time of the heat treatment are, for example, preferably 30 ° C. to 60 ° C., more preferably 32 ° C. to 57 ° C., and still more preferably 35 ° C. to 55 ° C. When present in the atmosphere, the heating time is preferably selected from 5 days or longer, more preferably 10 days or longer, and even more preferably 15 days or longer. This is because the post-oxidation effect, the thermal deformation / fusion suppression of the transparent polymer film 12 and the like are good within the above heating condition range.

Further, the heating atmosphere at the time of the heat treatment is preferably an atmosphere containing oxygen or moisture, such as the air, a high oxygen atmosphere, or a high humidity atmosphere. Particularly preferably, it is in the air from the viewpoint of manufacturability and cost reduction.

When the above-described post-oxidation thin film is included in the laminated structure, the moisture and oxygen contained in the metal oxide layer 22 are consumed during the post-oxidation. The physical layer 22 becomes difficult to chemically react. Specifically, for example, when the metal oxide layer 22 is formed by a sol-gel method, moisture and oxygen contained in the metal oxide layer 22 are consumed at the time of post-oxidation. The starting material (metal alkoxide or the like) by the sol-gel method remaining in the oxide layer 22 and moisture (adsorbed water or the like), oxygen, or the like hardly undergo a sol-gel curing reaction by sunlight. Therefore, it is possible to relieve internal stress caused by volume change such as curing shrinkage, and it is easy to suppress interfacial peeling of the laminated structure, and to improve durability against sunlight.

The transparent laminated film 10 is not limited to the configuration of the above embodiment, and may have a configuration in which the easy adhesion layer 14 is not provided in FIG. Moreover, the structure by which the easily bonding layer 14 is provided between the transparent polymer film 12 and the polymer body layer 18 in FIG.1 (b) may be sufficient. The laminated structure portion 16 and the polymer layer 18 may be provided on both surfaces of the transparent polymer film 12, respectively. When the polymer layer 18 is formed on the easy-adhesion layer 14, adhesion to the transparent polymer film 12 is ensured via the easy-adhesion layer 14. There is an advantage that the range of selection of the resin is widened.

Hereinafter, the present invention will be described in detail using examples.

(Example 1)
Acrylic resin (softening temperature = 40 ° C., “FS-3022” manufactured by Nippon Kako Paint Co., Ltd.) was diluted with a solvent to prepare a coating liquid <1>. This coating liquid <1> is opposite to the easy adhesive layer of a 50 μm thick polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., “Cosmo Shine (registered trademark) A4100”) having an easy adhesive layer formed on one side. The polymer layer (thickness 0.5 μm) made of an acrylic resin was formed by coating on the surface and drying at 100 ° C. for 2 minutes. Next, a three-layer laminated structure composed of metal oxide layer / metal layer / metal oxide layer was formed on the formed polymer layer. The method for forming the three-layer laminated structure is as follows.

On the formed polymer layer, using a micro gravure coater, the following coating solution for TiO ₂ layer was continuously applied with a gravure roll having a predetermined groove volume. Subsequently, the coating film was dried at 100 ° C. for 80 seconds using an in-line drying furnace to form a precursor layer of TiO ₂ layer. Then, using an in-line ultraviolet irradiator [high pressure mercury lamp (160 W / cm)], the precursor layer was continuously irradiated with ultraviolet rays for 1.5 seconds at the same linear velocity as that during the coating. Thus, a TiO ₂ layer (first layer) was formed by a sol-gel method using ultraviolet energy during sol-gel curing (hereinafter sometimes abbreviated as “(sol-gel + UV)”).

<Coating solution for TiO ₂ layer>
As titanium alkoxide, tetra-n-butoxytitanium tetramer (“B4” manufactured by Nippon Soda Co., Ltd.), acetylacetone as an additive that forms an ultraviolet-absorbing chelate, n-butanol and isopropyl alcohol The resulting mixture was mixed for 10 minutes using a stirrer to prepare a TiO ₂ layer coating solution. At this time, the composition of tetra-n-butoxy titanium tetramer / acetylacetone / n-butanol / isopropyl alcohol was 6.75 mass% / 3.38 mass% / 59.87 mass% / 30.00 mass%, respectively. did.

Next, each thin film constituting the second layer was formed on the formed first layer. That is, a lower metal Ti layer was formed by sputtering on the first TiO ₂ layer using a DC magnetron sputtering apparatus. Next, an Ag—Cu alloy layer was formed on the lower metal Ti layer by sputtering. Next, an upper metal Ti layer was formed on this Ag—Cu alloy layer by sputtering. At this time, the film formation conditions of the upper and lower metal Ti layers were as follows: Ti target (purity 4N), vacuum ultimate pressure: 5 × 10 ⁻⁶ (Torr), inert gas: Ar, gas pressure: 2.5 × 10 ⁻³ (Torr), input power: 1.5 (kW), and film formation time: 1.1 seconds. The film formation conditions of the Ag—Cu alloy thin film are as follows: Ag—Cu alloy target (Cu content: 4 atomic%), vacuum ultimate pressure: 5 × 10 ⁻⁶ (Torr), inert gas: Ar, gas pressure: 2.5 × 10 ⁻³ (Torr), input power: 1.5 (kW), and film formation time: 1.1 seconds.

Next, a TiO ₂ layer by (sol gel + UV) was formed as a third layer on the formed second layer. Here, the film forming procedure according to the first layer is performed twice to obtain a predetermined film thickness.

Next, the film after the formation of the third layer is heat-treated in a heating furnace at 40 ° C. for 300 hours to thereby form the second layer (metal Ti layer / Ag—Cu alloy layer / metal Ti layer) of metal Ti. The layer was post-oxidized. The transparent laminated film of Example 1 which has a 3 layer laminated structure part was produced by the above.

(Examples 2 to 4)
As in Example 1, except that an acrylic resin (softening temperature = 58 ° C., “UV ink EXP100119 medium” manufactured by DIC) was used as the material of the polymer layer, and the thickness of the polymer layer was set to a predetermined thickness, 3 Transparent laminated films of Examples 2 to 4 having a layer laminated structure were produced.

(Comparative Example 1)
It has a three-layer laminated structure in the same manner as in Example 1 except that phenoxy resin (softening temperature = 30 ° C., “Phenotote YPS-007 A30” manufactured by Nippon Steel Chemical Co., Ltd.) was used as the polymer layer material. A transparent laminated film of Comparative Example 1 was produced.

(Example 5)
Acrylic resin (softening temperature = 73 ° C., “Thermolac M-45C” manufactured by Soken Chemical Co., Ltd.) is used as a material for the polymer layer, and a metal oxide layer / metal layer / metal oxide layer / metal on the polymer layer A seven-layer laminated structure composed of layer / metal oxide layer / metal layer / metal oxide layer was formed. The method for forming the seven-layer laminated structure is as follows. The same procedure as in Example 1 was performed until the formation of the third layer. The third layer had a predetermined thickness by performing the film formation procedure according to the first layer three times.

Each thin film constituting the fourth layer was formed on the formed third layer. Here, a film forming procedure according to the second layer was performed. However, when forming the Ag—Cu alloy thin film, the above-mentioned film formation conditions are as follows: Ag—Cu alloy target (Cu content: 4 atom%), vacuum ultimate pressure: 5 × 10 ⁻⁶ (Torr), inert gas The film thickness was changed by changing: Ar, gas pressure: 2.5 × 10 ⁻³ (Torr), input power: 1.8 (kW), and film formation time: 1.1 seconds.

Next, a TiO ₂ layer having the same configuration as that of the third layer (sol gel + UV) was formed as a fifth layer on the formed fourth layer. Moreover, each thin film having the same configuration as the second layer was formed as the sixth layer on the formed fifth layer. In addition, a TiO ₂ layer by (sol gel + UV) was formed as a seventh layer on the formed sixth layer. Here, a predetermined film thickness is obtained by performing the film formation procedure according to the first layer once.

Next, the film after forming the seventh layer is heat-treated in a heating furnace at 40 ° C. for 300 hours, whereby the second, fourth, and sixth layers (metal Ti layer / Ag—Cu alloy layer / metal Ti layer). The metal Ti layer was post-oxidized. Thus, a transparent laminated film of Example 5 having a 7-layer laminated structure was produced.

(Example 6)
Phenoxy resin (softening temperature = 120 ° C., “Phenotote ERF-001 M30” manufactured by Nippon Steel Chemical Co., Ltd.) was used as the material of the polymer layer, and the thickness of the polymer layer was changed to a predetermined thickness. Thus, a transparent laminated film of Example 6 having a 7-layer laminated structure was produced.

(Example 7)
Example 5 except that the polymer layer was formed on the easy-adhesion layer of the polyethylene terephthalate film and the seven-layer laminated structure was formed on the formed polymer layer instead of the surface opposite to the easy-adhesion layer. Similarly, the transparent laminated film of Example 7 which has a 7-layer laminated structure part was produced. In addition, the acrylic resin of the polymer layer used in Example 7 has the same softening temperature as in Example 5 = 73 ° C.

(Example 8)
A transparent laminated film of Example 8 having a 7-layer laminated structure was produced in the same manner as in Example 5 except that the polyethylene terephthalate film having a thickness of 50 μm was changed to a polyethylene terephthalate film having a thickness of 125 μm.

(Comparative Example 2)
The 7-layer laminated structure was formed in the same manner as in Example 5 except that the 7-layer laminated structure was formed directly on the easy-adhesive layer of the polyethylene terephthalate film and the polymer layer corresponding to Example 1 was not formed. A transparent laminated film of Comparative Example 2 was prepared.

Table 1 shows the detailed layer structure of the transparent laminated films of Examples 1 to 4 and Comparative Example 1 (transparent laminated film having a three-layer laminated structure). Table 2 shows the detailed layer structure of the transparent laminated films of Examples 5 to 8 and Comparative Example 2 (transparent laminated film having a 7-layer laminated structure).

About each produced transparent laminated film, the surface resistance value of the film single-piece | unit was measured using the eddy current meter (made by DELCOM company), and the groove width was measured. Furthermore, optical characteristics, radio wave permeability, and appearance were evaluated by the evaluation methods shown below. To the measurement sample, a 22 μm thick acrylic adhesive sheet (“N-CLE”, manufactured by Toyo Packaging Co., Ltd.) was attached to the thin film laminated surface of the transparent laminated film, and the adhesive layer of this adhesive sheet was What was affixed on the single side | surface of 3 mm float glass was used. Moreover, the measurement light at the time of optical characteristic evaluation was entered from the glass surface side. These results are shown in Table 3. Also, in FIG. 3, as an example, the surface of the transparent laminated film alone was obtained with each of Examples 2, 4 to 6, and Comparative Example 2 by photographing with a microscope (“Digital Fine Scope VCR800” manufactured by OMRON). The displayed image is shown. (FIG. 3 (a): Comparative example 2, FIG. 3 (b): Example 2, FIG. 3 (c): Example 4, FIG. 3 (d): Example 5, FIG. 3 (e): Example 6 )

(Groove width)
This was performed by cross-sectional observation with an SEM (scanning electron microscope). Five SEM photographs were taken for each sample, and the average value of the maximum values of each groove width was calculated.

(Visible light transmittance, visible light reflectance)
In accordance with JIS A5759, by using a spectrophotometer (manufactured by Shimadzu Corporation, “UV3100”), a transmission spectrum with a wavelength of 300 to 1000 nm is measured, and a visible light transmittance and a visible light reflectance are calculated. Asked.

(Solar radiation transmittance)
In accordance with JIS A5759, a transmission spectrum at a wavelength of 300 to 2500 nm was measured using a spectrophotometer (manufactured by Shimadzu Corporation, “UV3100”), and the solar transmittance was calculated.

(Radio wave transmission)
An electromagnetic shielding characteristic tester (“MA8602B” manufactured by Anritsu Co., Ltd.) and a spectrum analyzer (“MS2661C” manufactured by Anritsu Co., Ltd.) are used to comply with the Kansai Electronics Industry Promotion Center (KEC) method. The transmission attenuation at 1 GHz was measured.

(appearance)
The thin film layer forming surface side of the transparent laminated film was attached with water using a window glass. It was confirmed whether a groove part was visually recognized from the position 30 cm away. The appearance was good when the groove was not visually recognized, and the appearance was poor when the groove was visible.

The refractive index of the TiO ₂ layer (measurement wavelength was 633 nm) was measured by FilmTek 3000 (manufactured by Scientific Computing International). Moreover, content of the organic component contained in the TiO ₂ layer was measured by X-ray photoelectron spectroscopy (XPS).

Further, EDX analysis was performed on the titanium oxide thin film formed by post-oxidizing the metal Ti layer, and the Ti / O ratio was determined as follows. That is, a transparent laminated film is cut out with a microtome (“Lultrome V2088” manufactured by LKB Co., Ltd.), and a test piece having a thickness in a cross-sectional direction of a laminated structure portion including a titanium oxide layer (barrier layer) to be analyzed is 100 nm or less. Was made. The cross section of the produced test piece was confirmed with a field emission electron microscope (HRTEM) (manufactured by JEOL Ltd., “JEM2001F”). Then, using an EDX device (resolution of 133 eV or less) (“JED-2300T” manufactured by JEOL Ltd.), an electron beam is emitted from the electron gun of this device, and a titanium oxide layer (barrier layer) to be analyzed The elemental component of the titanium oxide layer (barrier layer) was analyzed by making it incident near the center of the film thickness and detecting and analyzing the generated characteristic X-rays.

Further, the content of the sub-element Cu in the alloy layer was determined as follows. That is, under each film forming condition, a test piece in which an Ag—Cu alloy layer was separately formed on a glass substrate was prepared, and this test piece was immersed in a 6% HNO ₃ solution and eluted with ultrasonic waves for 20 minutes. Then, it measured by the concentration method of ICP analysis method using the obtained sample solution.

Moreover, the film thickness of each layer was measured from the cross-sectional observation of the test piece by the field emission electron microscope (HRTEM) (manufactured by JEOL Ltd., “JEM2001F”). Further, the width of the groove formed in the metal layer was measured from the surface observation of the test piece by the field emission electron microscope (HRTEM) (manufactured by JEOL Ltd., “JEM2001F”).

In Comparative Example 1, the polymer softening temperature of the polymer layer is less than 40 ° C. In Comparative Example 1, a crack was generated in the laminated structure portion when the first layer of sol-gel was cured, and a groove portion was formed. Since the formed groove was visually recognized, the appearance was poor. In Comparative Example 2, the 7-layer laminated structure is formed directly on the easy-adhesion layer without providing a polymer layer. In Comparative Example 2, as shown in FIG. 3A, no crack was formed in the laminated structure portion and no groove portion was formed even when the seventh layer of sol-gel was cured. For this reason, the radio wave permeability was inferior.

In contrast, in the examples, the softening temperature of the polymer in the polymer layer is within a desired range. In Examples 1 to 5 and 7 to 8, cracks were formed in the laminated structure portion when the metal oxide layer was formed. The manner in which cracks are formed in the laminated structure is shown in FIGS. 3B to 3D as an example. The groove width was 0.3 to 0.6 μm. On the other hand, in Example 6, no crack was generated in the laminated structure portion and no groove portion was formed even when the seventh layer of sol-gel was cured. This situation is shown in FIG. In Examples 1 to 5 and 7 to 8, the surface resistance of the film alone was high (100Ω / □ or more), and it was confirmed that the film alone was excellent in radio wave transmission. On the other hand, in Example 6, the surface resistance of the film alone was slightly low (less than 100Ω / □). And in all of the Examples, the solar shading was excellent and the appearance was also good.

In addition, according to Examples 5 and 7 to 8, the softening temperature of the polymer in the polymer layer is 70 ° C. or higher, and cracks are formed in the laminated structure for the first time when the seventh layer of sol-gel is cured to form a groove. It was. On the other hand, in Examples 1 to 4, the softening temperature of the polymer in the polymer layer was less than 60 ° C., and cracks were formed in the laminated structure for the first time when the third layer of sol-gel was cured to form a groove. From these results, it was shown that by adjusting the softening temperature of the polymer in the polymer layer, it is possible to control the timing of generating cracks in the laminated structure.

Next, laminated glass was made using each of the produced transparent laminated films, and the obtained laminated glass was evaluated.

(Production of laminated glass)
Each of the produced transparent laminated films is sandwiched between two polyvinyl butyral membranes (thickness: 380 μm), and further, a laminate obtained by sandwiching between two glass plates (thickness: 2 mm) from the outside of the polyvinyl butyral membrane is placed in an autoclave. Laminated vitrification was performed by processing under the conditions of ° C. × 13 kgf / cm ² × 20 minutes.

About each produced laminated glass, the surface resistance value was measured using the eddy current meter (made by DELCOM company), and also the optical characteristic, the radio wave permeability, and the external appearance were evaluated by the evaluation method shown below. These results are shown in Table 4. Also, in FIG. 4, as an example, the surface of the transparent laminated film in the laminated glass for each of Examples 2, 4 to 6, and Comparative Example 2 is a laser microscope (3D measurement laser microscope LEXT “OLS 4000” manufactured by Olympus). ) Shows an image obtained by shooting. (FIG. 4 (a): Comparative example 2, FIG. 4 (b): Example 2, FIG. 4 (c): Example 4, FIG. 4 (d): Example 5, FIG. 4 (e): Example 6 ). Also, in FIG. 5, as an example, for each of Examples 2, 4 to 6, a cross section of the laminated glass was taken with a field emission scanning electron microscope (FE-SEM, “S-4800” manufactured by Hitachi High-Technologies Corporation). The obtained image is shown. (FIG. 5 (a): Example 2, FIG. 5 (b): Example 4, FIG. 5 (c): Example 5, FIG. 5 (d): Example 6).

(Visible light transmittance, visible light reflectance)
Based on JIS R3212, the visible light transmittance and visible light reflectance of the laminated glass were determined.

(Direct sunlight transmittance)
Based on ISO 13837, a transmission spectrum at a wavelength of 300 to 2500 nm was measured using a spectrophotometer (manufactured by Shimadzu Corporation, “UV3100”), and the direct sunlight transmittance was calculated.

(appearance)
It was confirmed whether a groove part was visually recognized from the position 30 cm away. The appearance was good when the groove was not visually recognized, and the appearance was poor when the groove was visible.

In Comparative Example 1, the appearance of the film alone was poor, the width of the groove was further expanded by vitrification, and the appearance of the laminated glass was also poor. In Comparative Example 2, no crack was formed in the laminated structure portion in the film alone, but no crack was formed in the laminated structure portion even by vitrification. For this reason, the laminated glass was inferior in radio wave transmission.

On the other hand, in Examples 1 to 5 and 7 to 8 in which the groove portion was formed in the laminated structure portion by a single film, the laminated structure portion (metal layer) was divided due to the laminated glass. An example of the progress of the segmentation of the laminated structure portion (metal layer) is shown in FIGS. 4B to 4D. On the other hand, in Example 6 in which the groove portion was not formed in the laminated structure portion with a single film, cracks (groove portions) were formed in the laminated structure portion (metal layer) due to the laminated glass. This is shown in FIG. In Example 6, the surface resistance value of the film alone was less than 100 Ω / □, but the surface resistance value greatly increased as a result of the laminated glass, and the laminated glass was 100 Ω / □ or more, and was excellent in radio wave transmission. Was confirmed. In all of the examples, the solar shading was excellent and the appearance was also good.

In Example 6, since the groove portion was not formed in the laminated structure portion in the film alone, no dent was formed in the vicinity of the groove portion formed at the time of forming the laminated glass, and the occurrence of irregular reflection of light near the groove portion was suppressed. It can be seen that it has the best appearance as a laminated glass. On the other hand, in Examples 1 to 5 and 7 to 8, since a groove was formed in the laminated structure portion of the film alone, it was found that a recess was formed in the vicinity of the groove portion when the laminated glass was formed. However, the smaller the width of the groove is, the smaller the recess is formed, and the less the influence on the appearance is. In Examples 1 to 5 and 7 to 8, the width of the groove was 0.3 to 0.6 μm, the influence on the appearance was small, and the appearance was good. Of the groove widths of 0.6 μm or less, those having a groove width of 0.3 μm or less were particularly good in appearance.

Although the embodiments and examples of the present invention have been described above, the present invention is not limited to the above-described embodiments and examples, and various modifications can be made without departing from the spirit of the present invention. .

Claims

Film production process of forming a polymer layer on the surface of a transparent polymer film and forming a laminated structure in which a metal oxide layer and a metal layer are laminated on the surface of the polymer layer to obtain a transparent laminate film When,
The obtained transparent laminated film is sandwiched between two transparent base materials, and has a bonding step of bonding the two transparent base materials together under heating and pressure,
In the film production process, the metal oxide layer of the laminated structure is formed by sol-gel curing of the metal oxide precursor, and the polymer of the polymer layer has a softening temperature lower than the heating temperature of the laminating process. A method for producing a heat-insulating laminated structure, comprising: forming a groove part that divides a metal layer of a laminated structure part when two transparent substrates are bonded together.
The method for producing a heat-insulating laminated structure according to claim 1, wherein a polymer having a softening temperature of 40 to 130 ° C is used as the polymer of the polymer layer.
3. The method for producing a heat shielding laminated structure according to claim 1, wherein the polymer layer is formed to a thickness of 0.05 to 1.0 μm.
Do not form a groove that divides the metal layer of the laminated structure in the film production process, or make the width of the groove that divides the metal layer of the laminated structure formed in the film production process 0.6 μm or less. The manufacturing method of the heat insulation laminated structure of any one of Claim 1 to 3 characterized by these.
5. The polymer according to claim 4, wherein a polymer having a softening temperature of 110 to 130 ° C. is used as the polymer of the polymer layer, and the polymer layer is formed to a thickness of 0.05 to 0.5 μm. Of manufacturing a heat-insulating laminated structure.
A heat-insulating laminated structure obtained by the production method according to any one of claims 1 to 5.
On the surface of the transparent polymer film, a polymer layer, a laminated structure in which a metal oxide layer and a metal layer are laminated, and a transparent laminated film laminated in this order;
Two transparent substrates to be bonded together,
Two transparent base materials are bonded together with a transparent laminated film in between.
The laminated structure part of a transparent laminated film has the groove part which divides | segments a metal layer, The heat insulating laminated structure characterized by the above-mentioned.
The heat insulating laminated structure according to claim 7, wherein the polymer softening temperature of the polymer layer is 40 to 130 ° C.
9. The heat shielding laminated structure according to claim 7, wherein the polymer layer has a thickness of 0.05 to 1.0 μm.
The heat insulating laminated structure according to any one of claims 7 to 9, wherein the material of the polymer layer is an acrylic resin, a phenoxy resin, or a butyral resin.
A polymer layer having a laminated structure in which a metal oxide layer and a metal layer are laminated on the surface of the transparent polymer film, and a softening temperature of 40 to 130 ° C. between the transparent polymer film and the laminated structure part The transparent laminated film characterized by the above-mentioned.
The transparent laminated film according to claim 11, wherein a groove part for dividing the metal layer is not formed in the laminated structure part.
The transparent laminated film according to claim 11 or 12, wherein the polymer layer has a thickness of 0.05 to 1.0 µm.
The transparent laminated film according to any one of claims 11 to 13, wherein a material of the polymer layer is an acrylic resin, a phenoxy resin, or a butyral resin.