WO2018154723A1

WO2018154723A1 - Infrared reflecting film

Info

Publication number: WO2018154723A1
Application number: PCT/JP2017/007157
Authority: WO
Inventors: 伸一岩崎; 和巳吉田
Original assignee: 株式会社麗光
Priority date: 2017-02-24
Filing date: 2017-02-24
Publication date: 2018-08-30

Abstract

[Problem] To provide an infrared reflecting film which is used for the purpose of reflecting infrared light, while transmitting visible light, and which has excellent durability that prevents the occurrence of adhesion failure and appearance defect regardless of the presence or absence of folds even after a wet heat resistance test or a salt water resistance test. [Solution] An infrared blocking film for application to windows according to the present invention is an infrared reflecting film which is obtained by laminating at least an infrared reflecting layer on one surface or both surfaces of a plastic film, and is characterized in that: the infrared reflecting layer is obtained by sequentially laminating a first thiol organic film layer, a silver alloy layer and a transparent protective layer; the silver alloy layer is laminated so as to be in direct contact with the first thiol organic film layer and the transparent protective layer; and the first thiol organic film layer contains at least a resin and a compound having a thiol group.

Description

Infrared reflective film

The present invention is an infrared reflective film that is used by being attached to a glass plate or the like used for a building or vehicle such as a building or a residential house, and has both visible light transmittance and infrared reflectance, and is excellent in durability. Related to infrared reflective film.

Conventionally, infrared reflective films are used for the purpose of reflecting infrared rays by being attached to glass plates used in vehicles, buildings, show windows, etc., and transmit visible light on transparent plastic films. Infrared reflective films in which an infrared reflective layer for reflecting infrared rays is laminated are commercially available.

Patent Document 1 discloses a metal thin film (silver alloy layer) made of silver doped with 0.5 to 10 wt% of Pd, Nd and / or Ni as an infrared reflecting layer on a transparent substrate sheet (plastic film). And a transparent heat insulating sheet (infrared reflective film) in which a ceramic thin film that is a nitride film of aluminum and / or aluminum alloy provided on each of the upper and lower sides of the metal thin film is laminated.

Further, the transparent heat insulating sheet described in Patent Document 1 is for solving the drawback that the visible light reflection is large when the infrared reflection layer is a single metal thin film (silver alloy layer), and the desired visible light transmittance cannot be obtained. The infrared reflective layer of the transparent heat insulating sheet has a three-layer structure in which a metal thin film (silver alloy layer) is sandwiched between ceramic thin films, so that the ceramic thin film becomes an optical adjustment layer that suppresses reflection of visible light of the metal thin film, and is excellent. It has visible light transmittance.

In general, an infrared reflective film has excellent infrared reflectivity when the thermal conductivity measured in accordance with the JIS R 3106 method is 5.6 W / m ² · K or less.

JP 2014-218042 A

However, although the conventional infrared reflective film represented by the transparent heat insulating sheet described in Patent Document 1 has excellent visible light transmittance and infrared reflectivity, the infrared reflective film has the following wet heat resistance test and salt resistance. When the following adhesion evaluation and appearance evaluation were carried out after carrying out the aqueous test, there was a defect that did not have durability.
In addition, having durability in the present specification means that adhesion failure cannot be confirmed in the adhesion evaluation performed after the moisture and heat resistance test and the salt water resistance test (there is no peeling), and the appearance evaluation. This means that no appearance defects can be confirmed (there is no discoloration).
Humidity and heat resistance test: Leave in an environment of temperature 60 ° C. and humidity 95% for 500 hours.
Salt water resistance test: immersed in a 5% strength by weight saline solution maintained at a temperature of 50 ° C. and left for 120 hours.
Adhesion strength evaluation: In accordance with JIS R 5600-5-6 (cross-cut method), the presence or absence of peeling of the infrared reflective layer from the plastic film is confirmed.
Appearance evaluation: Observe visually to check for discoloration (whitening).

The conventional infrared reflective film has weak adhesion between the plastic film and the infrared reflective layer. Therefore, when the adhesive strength is evaluated after the moisture and heat resistance test and after the salt water resistance test, the infrared reflective layer peels off from the plastic film. There has occurred.

In addition, the conventional infrared reflective film has the surface on which the infrared reflective layer is laminated on the inside, and is folded so that the surfaces on which the infrared reflective layer is laminated are closely attached to each other. When the salt water resistance test was performed, the bent portion was discolored (whitened), resulting in appearance defects.

Specifically, the infrared reflective layer of the conventional infrared reflective film is a metal nitride so that the ceramic thin film of the infrared reflective layer of the transparent heat insulating sheet described in Patent Document 1 is a nitride film of aluminum and / or aluminum alloy. It has a three-layer structure in which a metal thin film (silver alloy layer) is sandwiched between layers made of metal or oxide.
And since the layer made of metal nitride or oxide is not flexible, the conventional infrared reflective film in which the layer made of metal nitride or oxide is laminated, when the infrared reflective film is bent, Cracks are easily generated at the bent portions of the infrared reflective layer.

Therefore, in the conventional infrared reflecting film, water, salt water, or the like penetrates into the cracked portion of the infrared reflecting layer, and the metal of the metal thin film of the infrared reflecting layer is corroded by oxidation or chloride.
Therefore, when the conventional infrared reflective film is bent and then subjected to a moisture and heat resistance test and a salt water resistance test, the metal of the metal thin film at the portion where the crack of the infrared reflective layer of the infrared reflective film is corroded corrodes. Appearance defect that discolored (whitened) occurred.

As described above, the conventional infrared reflective film has excellent visible light transmittance and infrared reflectivity. However, when the adhesion evaluation is performed after the moisture and heat resistance test and after the salt water resistance test, the infrared reflective layer is formed. When the infrared reflective film is folded and then subjected to the moisture and heat resistance test and the salt water resistance test, the bent portion is discolored (whitened) and appearance defects occur. For this reason, there is a drawback that it does not have durability.

[1] The present invention is an infrared reflective film in which at least an infrared reflective layer is laminated on one side or both sides of a plastic film, and satisfies all the following conditions (A) to (C): It is an infrared reflective film.
(A) The infrared reflective layer is a layer in which a first thiol organic film layer, a silver alloy layer, and a transparent protective layer are sequentially laminated.
(B) The silver alloy layer is laminated so as to be in direct contact with the first thiol organic film layer and the transparent protective layer.
(C) The first thiol organic film layer is a layer containing at least a resin and a compound having a thiol group.
[2] In the present invention, the weight ratio of the resin and the thiol compound in the first thiol organic film layer is in the range of resin: compound having a thiol group = 1.0: 0.1 to 2.0. 1] The infrared reflective film according to [1].
[3] The present invention is an infrared reflecting film in which at least an infrared reflecting layer is laminated on one side or both sides of a plastic film, and satisfies all the following conditions (A) to (C). It is an infrared reflective film.
(A) The infrared reflective layer is a layer in which a first thiol organic film layer, a silver alloy layer, and a second thiol organic film layer are sequentially laminated.
(B) The silver alloy layer is laminated so as to be in direct contact with the first thiol organic film layer and the second thiol organic film layer.
(C) The first thiol organic film layer and the second thiol organic film layer are layers including at least a resin and a compound having a thiol group.
[4] The weight ratio of the resin and the thiol compound in the first thiol organic film layer and the second thiol organic film layer is in the range of resin: compound having a thiol group = 1.0: 0.1 to 2.0. The infrared reflective film according to [3] above.
[5] The infrared reflective film described in any one of [1] to [4] above, wherein a topcoat layer is laminated on the infrared reflective layer.
[6] The infrared reflective film according to [5], wherein the topcoat layer is a layer containing at least an ultraviolet curable resin and a fluorine-based compound.

The infrared reflective film of the present invention is an infrared reflective film in which at least an infrared reflective layer is laminated on one side or both sides of a plastic film, and the infrared reflective layer includes a first thiol organic film layer, a silver alloy layer, and a transparent film. The protective layer is a layer sequentially laminated, and the silver alloy layer is laminated so as to be in direct contact with the first thiol organic film layer and the transparent protective layer, and the first thiol organic film layer is made of resin and thiol. It is a layer containing at least a compound having a group.

Therefore, the infrared reflective film of the present invention has strong adhesion between the plastic film and the infrared reflective layer and between the layers constituting the infrared reflective layer laminated on the plastic film, and after the moisture and heat resistance test. And even if it is a case where adhesive strength evaluation is implemented after a salt water resistance test, an infrared reflective layer does not peel at all from a plastic film, but it is hard to generate | occur | produce an adhesion defect.

In addition, the infrared reflective film of the present invention is folded so that the surface on which the infrared reflective layer of the infrared reflective film is laminated is inside, and the surfaces on which the infrared reflective layer is laminated are in close contact with each other. Even in this case, since the first thiol organic film layer is flexible, cracks are unlikely to occur in the bent portion of the infrared reflective layer.
Therefore, even when the infrared reflective film of the present invention is folded and then subjected to a moist heat resistance test and a salt water resistance test, water, salt water, or the like hardly penetrates into the silver alloy layer of the infrared reflective film of the present invention. For this reason, the silver alloy layer at the bent portion is hardly corroded.

Moreover, since the infrared reflective film of this invention is laminated | stacked so that a silver alloy layer may contact | connect a 1st thiol organic film layer and a transparent protective layer directly, the compound which has the thiol group of a 1st thiol organic film layer is By combining with the silver of the silver alloy layer, the silver of the silver alloy layer is suppressed from being oxidized or chlorinated.

Therefore, even if the infrared reflective film of the present invention has cracks in the infrared reflective layer of the infrared reflective film of the present invention, the compound having a thiol group of the first thiol organic film layer is a silver alloy layer. Since it is combined with silver and silver in the silver alloy layer is suppressed from oxidation, chlorination, and the like, it is difficult to cause an appearance defect that the silver in the bent silver alloy layer is corroded and discolored (whitened).

As described above, the infrared reflective film of the present invention is less likely to cause an adhesion failure in which the infrared reflective layer is peeled off from the plastic film when the adhesive strength is evaluated after the moisture and heat resistance test and the salt water resistance test. When the reflective film is folded and then subjected to the moisture and heat resistance test and the salt water resistance test, the bent portion is discolored (whitened), and appearance defects are less likely to occur, so that it has excellent durability.

Furthermore, the first thiol organic film layer of the infrared reflective film of the present invention is a layer in which the weight ratio of resin to thiol compound is in the range of resin: compound having a thiol group = 1.0: 0.1 to 2.0. Then, since the infrared reflective film of this invention can exhibit the outstanding durability reliably, it is more preferable.

The infrared reflective film of the present invention has a thermal conductivity measured in accordance with the JIS R 3106 method of 4.0 W / m ² · K or less, and naturally has excellent infrared reflectivity.
As described above, the infrared reflective layer of the infrared reflective film of the present invention has a three-layer structure in which the silver alloy layer is laminated so as to be in direct contact with the first thiol organic film layer and the transparent protective layer. Since the thiol organic film layer and the transparent protective layer serve as an optical adjustment layer that suppresses reflection of visible light from the silver alloy layer, the infrared reflective film of the present invention has excellent visible light transmittance.

Therefore, the infrared reflective film of the present invention has excellent visible light transmittance and infrared reflectivity, and has solved the disadvantages of the conventional infrared reflective film represented by the transparent heat insulating sheet described in Patent Document 1. It has excellent durability regardless of whether or not it is bent.

In addition, in the infrared reflective film of the present invention, if the transparent protective layer is a second thiol organic film layer containing at least a resin and a compound having a thiol group, the silver of the silver alloy layer is less likely to corrode and discolors. Since the appearance defect (whitening) is less likely to occur and durability is improved, the second thiol organic film layer is preferably made of a resin / thiol compound having a weight ratio of resin: thiol group = 1.0: A layer in the range of 0.1 to 2.0 is more preferable because excellent durability can be surely exhibited.
Furthermore, if the infrared reflective film of the present invention has a top coat layer laminated on the infrared reflective layer, the infrared reflective film of the present invention is imparted with hard coat properties and antifouling properties, and the infrared reflective film of the present invention. The durability of the reflective film is further improved, and it is perfectly possible to make the topcoat layer a layer containing at least an ultraviolet curable resin and a fluorine compound.

(Plastic film)
Various conventionally known plastic films such as polyethylene terephthalate film, polycarbonate film, polyethylene film, polypropylene film, and polyamide film can be used as the plastic film used in the infrared reflective film of the present invention.
The plastic film may be non-stretched, uniaxially stretched, or biaxially stretched, and may contain various additives such as an antistatic agent, a colorant, and a heat stabilizer.
The kind and thickness of the plastic film may be appropriately selected according to the desired use and purpose.

For the purpose of strengthening the adhesion between the plastic film and the first thiol organic film layer, the plastic film may be subjected to surface treatment such as easy adhesion coating or corona treatment on the plastic film. Such a plastic film is also included in the plastic film of the present specification.

The thickness of the plastic film is not particularly limited, but is preferably in the range of 12 to 250 μm.
If the thickness of the plastic film is less than 12 μm, there is a possibility that curling or wrinkling is likely to occur when the infrared reflective film of the present invention is attached to a glass plate or the like, and if it is thicker than 250 μm, When cutting the infrared reflective film of the present invention to a desired size, it is difficult to cut with a cutter knife or the like, so the workability is deteriorated, and the manufacturing cost increases when manufacturing the infrared reflective film of the present invention. It is not preferable.

(Infrared reflective layer)
The infrared reflective layer laminated on the infrared reflective film of the present invention is a layer in which a first thiol organic film layer, a silver alloy layer, and a transparent protective layer are sequentially laminated, and the silver alloy layer is a first thiol organic film. It is a layer laminated so as to be in direct contact with the layer and the transparent protective layer.
Therefore, when the compound having a thiol group contained in the first thiol organic film layer, which will be described later, is combined with the silver of the silver alloy layer, the silver of the silver alloy layer is suppressed from being corroded by oxidation, chlorination or the like. The appearance defect that the silver of the silver alloy layer corrodes and discolors (whitens) hardly occurs.
Therefore, the infrared reflective layer needs to be a layer in which the silver alloy layer is laminated so as to be in direct contact with the first thiol organic film layer and the transparent protective layer.

Further, if the second thiol organic film layer containing at least a resin and a compound having a thiol group is used instead of the transparent protective layer of the infrared reflecting layer, the silver of the silver alloy layer is corroded by oxidation, chloride, etc. This is preferable because the appearance of the silver alloy layer is corroded and discolored (whitened) is less likely to occur, and durability is improved.

In addition, as described above, the infrared reflective layer of the infrared reflective film of the present invention is laminated so that the silver alloy layer is in direct contact with the first thiol organic film layer and the transparent protective layer or the second thiol organic film layer. It is a layer structure.
And since the 1st thiol organic film layer and the transparent protective layer or the 2nd thiol organic film layer become an optical adjustment layer which suppresses reflection of visible light of a silver alloy layer, the infrared reflective film of the present invention has excellent visible Naturally, it has light transmittance.

Hereinafter, the layers constituting the infrared reflective layer will be described respectively.

(First thiol organic film layer)
The 1st thiol organic film layer laminated | stacked on the infrared reflective film of this invention is a layer which comprises the infrared reflective layer laminated | stacked on the single side | surface or both surfaces of a plastic film, and at least the compound which has resin and a thiol group is contained. Is a flexible layer.
In addition, the first thiol organic film layer is silver for the purpose of suppressing visible light reflection of a silver alloy layer, which will be described later, to obtain excellent visible light transmittance, and for the purpose of exhibiting durability of the infrared reflective film of the present invention. It is a layer laminated so as to be in direct contact with the alloy layer.

The resin used for the first thiol organic film layer can be used without any particular limitation, such as polyethylene resin, polypropylene resin, polystyrene resin, vinyl chloride resin, polyester resin, acrylic resin, urethane resin, Various known resins such as a melamine resin and an epoxy resin can be used, and any one of these or a mixture of two or more thereof may be used, and may be appropriately selected according to the purpose.

In addition, as the resin used for the first thiol organic film layer, a conventionally known ultraviolet curable resin such as an acrylic ultraviolet curable resin, a urethane ultraviolet curable resin, or an epoxy ultraviolet curable resin may be used. By using an ultraviolet curable resin, a desired hard coat property can be easily imparted to the infrared reflective film of the present invention.

Compounds having a thiol group used for the first thiol organic film layer are trimethylolpropane tris (3-mercaptopropionate) (TMMP), pentaerythritol tetrakis (3-mercaptopropionate) (PEMP), tris- [ (3-mercaptopropionyloxy) -ethyl] -isocyanurate (TEMPIC), tetraethylene glycol bis (3-mercaptopropionate) (EGMP-4), dipentaerythritol hexakis (3-mercaptopropionate) (DPMP) ) And other compounds having a thiol group, and pentaerythritol tetrakis (3-mercaptopropionate) (PEMP) is used because it contains a large amount of thiol groups in the structure of the compound having a thiol group. Is preferred.

The weight ratio of the resin of the first thiol organic film layer to the compound having a thiol group is preferably in the range of resin: compound having a thiol group = 1.0: 0.1 to 2.0. If the weight ratio of the resin and the compound having a thiol group is not the above weight ratio, the infrared reflective film of the present invention may not be able to exhibit the desired durability. This is not preferable because there is a possibility that the desired adhesive strength cannot be obtained.

The thickness of the first thiol organic film layer is preferably in the range of 0.005 to 2 μm. If the thickness of the first thiol organic film layer is thinner than 0.005 μm, it will not be possible to exert the effect of suppressing silver corrosion of the silver alloy layer, and the silver of the silver alloy layer is likely to corrode. It is not preferable, and if the thickness of the first thiol organic film layer is greater than 2 μm, the infrared reflection film of the present invention may not be able to obtain the desired visible light transmittance. This is not preferable because the manufacturing cost increases when the reflective film is manufactured.

If necessary, the first thiol organic film layer may be added to the first thiol organic film layer within the range that does not impair the durability effect of the infrared reflective film of the present invention, and the antistatic agent, ultraviolet absorber, light stabilizer, heat One or more kinds of various additives such as a stabilizer, an antioxidant, a polymerization initiator, and a curing agent may be added. The kind and amount of various additives to be added are appropriately selected according to the desired purpose. That's fine.

The first thiol organic film layer may contain inorganic fine particles for the purpose of adjusting the refractive index of the first thiol organic film layer and further improving the visible light transmittance of the infrared reflective film of the present invention. Absent.

The inorganic fine particles used in the first thiol organic film layer are not particularly limited, and metal oxide fine particles such as silicon oxide fine particles, aluminum oxide fine particles, zinc oxide fine particles, titanium oxide fine particles, zirconium oxide fine particles, indium oxide fine particles, and calcium carbonate fine particles. Conventional inorganic fine particles such as calcium sulfate fine particles and calcium silicate fine particles can be used and may be appropriately selected according to the purpose. In particular, it is more preferable to use silicon oxide fine particles from the viewpoint of visible light transmittance, and hollow silicon oxide fine particles are used from the viewpoint that the visible light transmittance of the infrared reflective film of the present invention can be improved with certainty. It is particularly preferred.
The amount of inorganic fine particles added may be appropriately selected according to the purpose.

The size (particle size) of the inorganic fine particles is preferably 2.0 μm or less.
If the size of the inorganic fine particles is larger than 2.0 μm, irregularities are likely to occur in the first thiol organic film layer, and the visible light transmittance of the infrared reflective film of the present invention is lowered, and the desired visible light transmittance is obtained. This is not preferable because there is a risk that it may not be possible.

Further, the shape of the inorganic fine particles is not particularly limited, but may be appropriately selected according to the purpose such as a spherical shape, a needle shape, and an elliptic shape. The size (particle size) of the inorganic fine particles refers to the length of the inorganic fine particles if the shape is needle-shaped, and the longest value of the fine particles such as the long diameter of the inorganic fine particles if the shape is elliptical. Say.

As a method of laminating the first thiol organic film layer, conventionally known coating methods such as a gravure coating method, a reverse coating method, a die coating method, a micro gravure coating (reverse gravure coating) method and a bar coating method can be used. To choose as appropriate

As described above, since the first thiol organic film layer of the infrared reflective film of the present invention is a flexible layer containing at least a resin and a compound having a thiol group, the infrared reflective film of the present invention is folded. Even so, cracks are less likely to occur in the infrared reflective layer.
Therefore, the infrared reflective film of the present invention is less susceptible to cracking in the infrared reflective layer even when the heat and moisture resistance test and the salt water resistance test are performed after the infrared reflective film is bent, and the silver alloy layer Difficult to penetrate water and salt water.
Moreover, since the 1st thiol organic film layer of the infrared reflective film of this invention contains the compound which has a thiol group, when the thiol group of the compound which has a thiol group couple | bonds with silver of a silver alloy layer, silver Corrosion of silver in the alloy layer due to oxidation, chlorination or the like is suppressed.
Therefore, in the infrared reflective film of the present invention, the silver in the silver alloy layer is hardly corroded and appearance defects such as discoloration (whitening) are unlikely to occur.

(Silver alloy layer)
The silver alloy layer laminated on the infrared reflective film of the present invention is a layer laminated mainly for the purpose of reflecting infrared rays, and is made of a silver alloy that is an alloy of silver and other metals mainly composed of silver, It is a layer laminated | stacked so that it may contact | connect the said 1st thiol organic film layer and the transparent protective layer mentioned later, or the 2nd thiol organic film layer mentioned later.
The silver alloy used for the silver alloy layer is preferably a silver alloy having a silver content of 90% by weight or more and less than 99% by weight.
If the silver content of the silver alloy used in the silver alloy layer is not within the above range, the infrared reflection film of the present invention may not be desired infrared reflectivity and desired durability, which is not preferable.

The metal other than silver used for the silver alloy is one or a combination of two or more conventionally known metals such as palladium, neodymium, nickel, copper, gold, platinum, germanium, cerium, gallium, and bismuth. However, it may be appropriately selected depending on the purpose. In particular, it is preferable to use palladium from the viewpoint of durability.

The thickness of the silver alloy layer is preferably in the range of 3 to 30 nm.
If the thickness of the silver alloy layer is less than 3 nm, the infrared reflective film of the present invention may not be able to obtain the desired infrared reflectivity, so this is not preferred. The thickness of the silver alloy layer is greater than 30 nm. And the infrared reflective film of the present invention may not be able to obtain the desired visible light transmittance, which is not preferable.

(Transparent protective layer)
The transparent protective layer laminated on the infrared reflective film of the present invention is laminated on one or both sides of the plastic film, protects the silver alloy layer, suppresses reflection of visible light of the silver reflective layer, and has excellent visible light transmission. It is a transparent layer laminated on the silver alloy layer for the purpose of obtaining properties.

The thickness of the transparent protective layer is preferably in the range of 0.005 to 2 μm. If the thickness of the transparent protective layer is not within the above range, the above-mentioned purpose of laminating the transparent protective layer may not be achieved, and the infrared reflective film of the present invention may not be able to obtain excellent visible light transmittance. Because there is, it is not preferable.

The transparent protective layer may be at least an organic film layer made of a resin or a dielectric layer made of a dielectric as long as it can achieve the above object, and may be appropriately selected according to the purpose.

First, the case where the transparent protective layer laminated | stacked on the infrared reflective film of this invention is made into an organic film layer is described.

In the infrared reflective film of the present invention, the transparent protective layer may be an organic film layer made of at least a resin.
If the transparent protective layer of the infrared reflective film of the present invention is an organic film layer, the first thiol organic film layer and the organic film layer of the infrared reflective film of the present invention are both layers composed of at least a resin. Even when the infrared reflective film of the present invention is folded, cracks are less likely to occur in the infrared reflective layer, which is more preferable.

The infrared reflective film of the present invention having the transparent protective layer as an organic film layer is cracked more in the infrared reflective layer even when the infrared reflective film is folded and then subjected to a moisture and heat resistance test and a salt water resistance test. It is difficult for water and salt water to penetrate into the silver alloy layer.

The resin used for the organic film layer can be the same resin as the first thiol organic film layer, and the method of laminating the organic film layers is the same as that of the first thiol organic film layer.

The organic film layer may contain inorganic fine particles in order to adjust the refractive index of the organic film layer and further improve the visible light transmittance of the infrared reflective film of the present invention.
In addition, the kind, size (particle shape), and addition amount of the inorganic fine particles used in the organic film layer can be the same as those in the first thiol organic film layer, and can be appropriately selected according to the purpose. That's fine.

In addition, the organic film layer may be added to the organic film layer as necessary within a range that does not impair the durability effect of the infrared reflective film of the present invention, and an antistatic agent, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an oxidation agent. One or more various additives such as an inhibitor, a polymerization initiator, and a curing agent may be added, and the type and amount of various additives to be added may be appropriately selected according to the desired purpose.

The organic film layer is provided with polytetrafluoroethylene (PTFE) or tetrafluoroethylene / hexafluoropropylene copolymer for the purpose of imparting antifouling properties to prevent water and dirt from adhering to the infrared reflective film of the present invention. Fluorine compounds such as (FEP) and modified perfluoropolyether (PFPE) may be contained, and the type and amount of the fluorine compound to be used may be appropriately selected according to the desired purpose.

Next, the case where the transparent protective layer laminated | stacked on the infrared reflective film of this invention is made into a dielectric material layer is described.

In the infrared reflective film of the present invention, the transparent protective layer may be a dielectric layer made of a dielectric.
If the transparent protective layer of the infrared reflective film of the present invention is a dielectric layer, the step of laminating the silver alloy layer and the step of laminating the dielectric layer can be sequentially performed as a series of operations using one manufacturing apparatus. Therefore, when producing the infrared reflective film of the present invention, the infrared reflective film of the present invention can be obtained efficiently.

Dielectrics used for the dielectric layer are oxides or nitrides of titanium, zirconium, hafnium, niobium, zinc, aluminum, gallium, indium, thallium, tin, etc. Conventional dielectrics such as complex oxides such as indium (ITO), antimony-doped tin oxide (ATO), tin-doped zinc oxide (ZTO), and zinc-doped indium oxide (IZO) are used. It can be used and may be appropriately selected according to the purpose.

The thickness of the dielectric layer is preferably in the range of 0.005 to 2 μm, and if it is in the range of 0.005 to 0.1 μm, the infrared reflective film of the present invention can surely obtain excellent visible light transmittance. Since it can do, it is more preferable.

As a method for laminating the dielectric layers, a conventionally known laminating method such as a vacuum vapor deposition method, a sputtering method, a chemical vapor deposition method (CVD method) or the like can be used, and may be appropriately selected according to the purpose.

In addition, assuming that the infrared reflective film of the present invention is used, the first thiol organic film layer and the transparent protective layer of the infrared reflective layer are both organic film layers made of resin, and the infrared reflective layer is sandwiched between the organic film layers and the silver alloy layer. When the three-layer structure is used, the desired visible light transmittance and infrared reflectivity can be obtained, but the silver alloy layer cannot be prevented from corroding due to oxidation, chlorination, etc. It becomes a thing which cannot demonstrate durability irrespective of the presence or absence.

(Second thiol organic film layer)
The infrared reflective film of the present invention is a second thiol organic film layer containing at least a resin and a compound having a thiol group, instead of the transparent protective layer, and is laminated on the infrared reflective film of the present invention. The first thiol organic film layer, the silver alloy layer, and the second thiol organic film layer may be sequentially stacked.
Then, the infrared reflecting layer is a layer laminated so that the silver alloy layer is in direct contact with the first thiol organic film layer and the second thiol organic film layer, so that the silver of the silver alloy layer is oxidized, chlorinated. It is preferable because corrosion of the silver alloy layer is further suppressed, and appearance defects such as corrosion and discoloration (whitening) of the silver alloy layer are less likely to occur and durability is improved.

As the resin used for the second thiol organic film layer and the compound having a thiol group, the same resin as the first thiol organic film layer and a compound having a thiol group can be used.
Further, the weight ratio of the resin of the second thiol organic film layer and the compound having a thiol group, the thickness of the second thiol organic film layer, and the method of laminating the second thiol organic film layer are also the first thiol organic film. Same as layer.

When laminating the second thiol organic film layer, the weight ratio between the resin of the first thiol organic film layer and the second thiol organic film layer and the compound having a thiol group is the same weight ratio as long as it is within the above range. Or different weight ratios, and the thickness of each of the first thiol organic film layer and the second thiol organic film layer is different even if the thickness is within the above range. It does not matter.

For the purpose of adjusting the refractive index of the second thiol organic film layer and further improving the visible light transmittance of the infrared reflective film of the present invention, the second thiol organic film layer contains inorganic fine particles in the second thiol organic film layer. It may be contained, and a fluorine-based compound may be contained for the purpose of imparting antifouling property to prevent water and dirt from adhering to the infrared reflective film of the present invention.
Further, the kind, size (particle shape), and addition amount of the inorganic fine particles used for the second thiol organic film layer can be the same as the inorganic fine particles of the first thiol organic film layer, The kind and amount of the fluorine-based compound used for the second thiol organic film layer can be the same as the fluorine-based compound used for the organic film layer (transparent protective layer). Just choose.

In addition, the second thiol organic film layer may be added to the second thiol organic film layer as necessary within the range that does not impair the durability effect of the infrared reflective film of the present invention. In addition, one or more kinds of various additives such as a heat stabilizer, an antioxidant, a polymerization initiator, and a curing agent may be added, and the kinds and amounts of various additives to be added are appropriately determined according to the desired purpose. Just choose.

(Topcoat layer)
The infrared reflective film of the present invention has a hard coat property that prevents the infrared reflective layer from being scratched, and an antifouling property that prevents water and dirt from adhering to the surface of the infrared reflective film of the present invention. A top coat layer may be laminated on the infrared reflective layer.

If the infrared reflective film of the present invention is formed by laminating a top coat layer, the infrared reflective film of the present invention is provided with hard coat properties and antifouling properties, and water or dirt is deposited on the surface of the infrared reflective film of the present invention. As a result, the silver in the silver alloy layer is less likely to corrode, and the appearance defect of whitening is less likely to occur, leading to improved durability.

The top coat layer is preferably a layer made of a resin such as an ultraviolet curable resin, a thermosetting resin, and the like, and is capable of easily obtaining desired hard coat properties by preventing the infrared reflective layer from being scratched. It is more preferable to use a curable resin.

Further, the top coat layer may be a layer further containing a fluorine-based compound in that the desired antifouling property can be easily imparted to the infrared reflective film of the present invention.

If the topcoat layer is a layer containing at least an ultraviolet curable resin and a fluorine-based compound, it is possible to easily impart both the desired hard coat property and the desired antifouling property to the infrared reflective film of the present invention. It is perfect.

As the UV curable resin used for the top coat layer, conventionally known UV curable resins such as acrylic UV curable resin, urethane UV curable resin, epoxy UV curable resin and the like can be used. As the thermosetting resin used in the coating layer, a conventionally known thermosetting resin such as a melamine thermosetting resin, an epoxy thermosetting resin, or a urethane thermosetting resin can be used. May be selected as appropriate.

The fluorine-based compound used for the topcoat layer can achieve the above-mentioned purpose, such as polytetrafluoroethylene (PTFE), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), and modified perfluoropolyether (PFPE). Any fluorine compound that can be used can be used without particular limitation, and may be appropriately selected depending on the purpose.

The weight ratio of the UV curable resin and the fluorine compound in the topcoat layer is preferably in the range of UV curable resin: fluorine compound = 1.0: 0.1 to 5.0.
If the weight ratio of the ultraviolet curable resin to the fluorine-based compound is not the above weight ratio, the hard coat property and antifouling property obtained by laminating the topcoat layer should be the desired hard coat property and antifouling property. This is not preferable because there is a risk that it will not be possible.

The top coat layer may contain inorganic fine particles for the purpose of further improving the visible light transmittance of the infrared reflective film of the present invention.
The kind, size (particle shape), and addition amount of the inorganic fine particles used for the top coat layer can be the same as those used for the first thiol organic film layer.

The thickness of the top coat layer is preferably in the range of 0.005 to 2.0 μm.
If the thickness of the top coat layer is not in the above range, the hard coat properties and antifouling properties obtained by laminating the top coat layer may not be able to be the desired hard coat properties and antifouling properties. It is not preferable.

In addition, the topcoat layer is added with one or more kinds of various additives such as an antistatic agent, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antioxidant, a polymerization initiator, and a curing agent as necessary. However, the type and amount of various additives to be added may be appropriately selected according to the purpose.

Conventionally known coating methods such as gravure coating method, reverse coating method, die coating method, micro gravure coating (reverse gravure coating) method, bar coating method, etc. can be used as the method of laminating the top coat layer, and it is appropriately selected according to the purpose. do it

In the infrared reflective film of the present invention, the infrared reflective layer of the infrared reflective film of the present invention on the glass plate (the top coat layer when the infrared reflective film of the present invention is laminated with a top coat layer) is the outermost surface. And can be used for applications such as vehicles, buildings, and show windows that require both visible light transmission and infrared reflection.

The method of sticking the infrared reflective film of the present invention to a glass plate or the like can be used without any particular limitation, and an adhesive layer comprising an adhesive or a pressure sensitive adhesive between the infrared reflective film of the present invention and the glass plate or the like can be used. What is necessary is just to select suitably according to the objectives, such as the method of sticking through an adhesion layer. *

As described above, the infrared reflective film of the present invention is an infrared reflective film in which at least an infrared reflective layer is laminated on one side or both sides of a plastic film, and the infrared reflective layer is a first thiol organic film layer, silver An alloy layer and a transparent protective layer are sequentially laminated, and a silver alloy layer is laminated so as to be in direct contact with the first thiol organic film layer and the transparent protective layer, and the first thiol organic film layer Is a layer containing at least a resin and a compound having a thiol group.

In addition, the infrared reflective film of the present invention is subjected to a moisture and heat resistance test after being bent so that the surface on which the infrared reflective layer is laminated is inward and the surfaces on which the infrared reflective layer is laminated are in close contact with each other. Even when the salt water resistance test is carried out, cracks are unlikely to occur in the infrared reflecting layer, so that the appearance defect that the silver of the bent silver alloy layer corrodes and discolors (whitens) hardly occurs.

As a result, the infrared reflective film of the present invention has excellent visible light transmittance and infrared reflectivity, and excellent durability.

In addition, in the infrared reflective film of the present invention, if the transparent protective layer is a second thiol organic film layer containing at least a resin and a compound having a thiol group, the silver of the silver alloy layer is less likely to corrode and discolors. It is preferable because the appearance defect (whitening) is less likely to occur and the durability is improved.
Furthermore, if the infrared reflective film of the present invention has a top coat layer laminated on the infrared reflective layer, the infrared reflective film of the present invention is imparted with hard coat properties and antifouling properties, and the infrared reflective film of the present invention. The durability of the reflective film is further improved, and it is perfectly possible to make the topcoat layer a layer containing at least an ultraviolet curable resin and a fluorine compound.

Hereinafter, “parts by weight” used herein refers to parts by weight of solid content [Example 1].
The following (Step 1) to (Step 4) are carried out in order, and an infrared reflecting layer comprising a first thiol organic film layer, a silver alloy layer, and a second thiol organic film layer, and a topcoat layer on one side of the plastic film As a result, the infrared reflective film of the present invention of Example 1 in which the layers were sequentially laminated was obtained.

(Step 1) Acrylic ultraviolet light is applied to one side of the 50 μm thick polyethylene terephthalate film (trade name: Cosmo Shine A4100 manufactured by Toyobo Co., Ltd.) on which the easy adhesion layer is laminated. Curable resin (trade name: V-620, manufactured by KS Corporation) and pentaerythritol tetrakis (3-mercaptopropionate) (PEMP) (product of SC Organic Chemical Co., Ltd.) as a compound having 100 parts by weight and a thiol group ) A mixed paint mixed with 100 parts by weight was coated by a gravure coating method, and a first thiol organic film layer having a thickness of 0.05 μm was laminated.
(Step 2) On the first thiol organic film layer, an alloy of silver and palladium (silver content: 98% by weight, palladium content: 2% by weight) is used as a silver alloy and is thickened by sputtering. A 7 nm thick silver alloy layer was laminated.
(Step 3) A second thiol organic film layer having a thickness of 0.05 μm was laminated on the silver alloy layer by the gravure coating method using the mixed paint used in (Step 1).
(Step 4) On the second thiol organic film layer, 100 parts by weight of an acrylic ultraviolet curable resin (trade name: V-620, manufactured by KS Corporation) as an ultraviolet curable resin and a modified perfluoropolyether as a fluorine compound. (PFPE) (trade name: Optool DAC-HP, manufactured by Daikin Industries, Ltd.) A mixed paint mixed with 30 parts by weight was coated by a gravure coating method, and a top coat layer having a thickness of 0.07 μm was laminated.

[Example 2]
In place of the mixed paint used in (Process 3) of Example 1, 30 parts by weight of a fluorine-based compound (trade name: OPTOOL DAC-HP, manufactured by Daikin Industries, Ltd.) was further added to the mixed paint used in the same process. An infrared reflecting film of the present invention of Example 2 was obtained in the same manner as Example 1 except that the paint was used and that (Step 4) was not performed.

[Example 3]
In place of the second thiol organic film layer in (Step 3) of Example 1, zinc-doped indium oxide (IZO) was used as a dielectric, and a 0.04 μm thick dielectric layer (transparent by sputtering) The first thiol organic film layer, the silver alloy layer, and the zinc-doped indium oxide (IZO) layer except that the protective layer was doped with an indium oxide (IZO) layer doped with zinc. An infrared reflective film of Example 3 in which an infrared reflective layer composed of an (IZO) layer was laminated was obtained.

[Comparative Example 1]
Instead of the first thiol organic film layer in (Step 1) of Example 1, aluminum nitride was used and an aluminum nitride layer having a thickness of 0.04 μm was laminated by sputtering, and the second in (Step 3). An aluminum nitride layer, a silver alloy layer, and an oxidation layer were formed in the same manner as in Example 1 except that niobium oxide was used instead of the thiol organic film layer and a niobium oxide layer having a thickness of 0.025 μm was laminated by sputtering. An infrared reflective film of Comparative Example 1 in which an infrared reflective layer made of a niobium layer was laminated was obtained.

[Comparative Example 2]
Instead of the first thiol organic film layer in (Process 1) of Example 1 and the second thiol organic film layer in (Process 3), a paint composed only of the acrylic UV curable resin used in the same process was used. The infrared reflective film of Comparative Example 2 was obtained in the same manner as in Example 1 except that an organic film layer, a silver alloy layer, and an infrared reflective layer composed of an organic film layer were laminated.

[Test sample]
After the infrared reflecting film of the present invention obtained in Examples 1 to 3 and the infrared reflecting film obtained in Comparative Examples 1 and 2 were cut out into 5 cm × 10 cm squares, two of them were tested as they were. The remaining two sheets were bent so that the surface on which the infrared reflecting layer was laminated was inside, and the surfaces on which the infrared reflecting layer was laminated were in close contact with each other to obtain test samples.

[Moisture and heat resistance test]
(contents of the test)
Each test sample (one unfolded test sample and one folded test sample) was left in an environment at a temperature of 60 ° C. and a humidity of 95% for 500 hours, and then each test sample was evaluated for adhesion by the following method. The appearance was evaluated.

(Adhesion evaluation)
Using each test sample after the test, in accordance with JIS R 5600-5-6 (cross-cut method), the presence or absence of peeling of the infrared reflecting layer from the plastic film was confirmed, and the infrared reflecting layer was peeled from the plastic film. The case where there was no peeling of some or all of the layers was marked with ◯, and the case where peeling of some or all of the infrared reflective layer was confirmed was marked with x.
(Appearance evaluation)
Each test sample after the test is visually observed to confirm the presence or absence of discoloration (whitening) of the test sample. The case where discoloration (whitening) cannot be confirmed is marked with ◯, and the case where discoloration (whitening) is confirmed is marked with ×. .

(Evaluation results)
Shown in Table 1

[Salt water resistance test]

(contents of the test)
Each test sample (one unfolded test sample and one folded test sample) was immersed in a 5 wt% saline solution maintained at a temperature of 50 ° C. and allowed to stand for 120 hours. Force evaluation and appearance evaluation were carried out.

(Adhesion evaluation and appearance evaluation)
Evaluation was performed in the same manner as in the heat and humidity resistance test.

(Evaluation results)
Shown in Table 1

As shown in Table 1, each of the infrared reflective films of the present invention obtained in Examples 1 to 3 has an infrared reflective layer made of plastic regardless of whether it is bent or not when the moisture and heat resistance test and the salt water resistance test are performed. There was no problem of adhesion that peeled off from the film, and there was no appearance problem that the silver of the silver alloy layer was corroded and discolored (whitened), and it had excellent durability.
On the other hand, the infrared reflective film obtained in Comparative Example 1 did not cause a discoloration (whitening) appearance defect when the moisture and heat resistance test and the salt water resistance test were performed without being bent. In the case of the above, an adhesion defect and an appearance defect occurred. In addition, the infrared reflective film obtained in Comparative Example 2 had an adhesion defect and an appearance defect regardless of the presence or absence of bending when the moisture and heat resistance test and the salt water resistance test were performed.
Therefore, none of the infrared reflective films obtained in Comparative Examples 1 and 2 had durability.

The infrared reflective films of the present invention obtained in Examples 1 to 3 and the infrared reflective films obtained in Comparative Examples 1 and 2 all had a thermal conductivity of 4.0 W / measured according to the JIS R 3106 method. m ² · K or less and excellent infrared reflectivity.

Claims

1. An infrared reflecting film, which is an infrared reflecting film in which at least an infrared reflecting layer is laminated on one side or both sides of a plastic film, and satisfies all the following conditions (A) to (C).
(A) The infrared reflective layer is a layer in which a first thiol organic film layer, a silver alloy layer, and a transparent protective layer are sequentially laminated.
(B) The silver alloy layer is laminated so as to be in direct contact with the first thiol organic film layer and the transparent protective layer.
(C) The first thiol organic film layer is a layer containing at least a resin and a compound having a thiol group.
2. The infrared reflective film according to claim 1, wherein a weight ratio of the resin and the thiol compound in the first thiol organic film layer is in a range of resin: compound having a thiol group = 1.0: 0.1 to 2.0.
1. An infrared reflecting film, which is an infrared reflecting film in which at least an infrared reflecting layer is laminated on one side or both sides of a plastic film, and satisfies all the following conditions (A) to (C).
(A) The infrared reflective layer is a layer in which a first thiol organic film layer, a silver alloy layer, and a second thiol organic film layer are sequentially laminated.
(B) The silver alloy layer is laminated so as to be in direct contact with the first thiol organic film layer and the second thiol organic film layer.
(C) The first thiol organic film layer and the second thiol organic film layer are layers including at least a resin and a compound having a thiol group.
The weight ratio of the resin and the thiol compound in the first thiol organic film layer and the second thiol organic film layer is in the range of resin: compound having a thiol group = 1.0: 0.1 to 2.0. Item 4. The infrared reflecting film according to Item 3.
The infrared reflective film according to any one of claims 1 to 4, wherein a topcoat layer is laminated on the infrared reflective layer.
6. The infrared reflective film according to claim 5, wherein the top coat layer is a layer containing at least an ultraviolet curable resin and a fluorine-based compound.