JP6409885B2 - Infrared absorbing film for exterior - Google Patents

Description

  The present invention relates to an infrared absorbing film for exterior use, and more specifically, a laminated film provided with a primer layer and a surface protective layer on a substrate, having infrared absorbing ability, and having both weather resistance and interlayer adhesion. Infrared absorbing film for exteriors used for window films such as window glass regardless of plan, inorganic glass, organic glass, and infrared absorbing film used for the outside surface of indoor glass in double glazing and double windows It is about.

  The sunlight that enters the room through the window glass contains not only visible rays but also infrared rays and ultraviolet rays. Ultraviolet rays contained in sunlight cause sunburn, and adverse effects on the human body have been pointed out. It is also well known that the contents are altered due to deterioration of the packaging material due to ultraviolet rays. On the other hand, infrared rays contained in sunlight also have problems such as causing an increase in indoor temperature due to direct sunlight and reducing the cooling effect in summer.

Conventionally, such problems have been dealt with by, for example, attaching a colored film, a metal vapor-deposited film or the like to a window glass (for example, see Patent Document 1).
However, although the above-mentioned colored film cuts ultraviolet rays to some extent, it hardly cuts infrared rays and cuts visible rays, so that there is a problem that transparency is impaired when pasted on a window glass or the like.

  In addition, although the above-mentioned metal vapor-deposited film cuts ultraviolet rays and infrared rays, it has poor transparency because it does not transmit visible light, and it reflects rather than absorbs visible light. As a result, there is a problem that the applications that can be used are very limited. Therefore, in recent years, films using fine particles of inorganic infrared absorbers have been used.

The film attached to the window glass is usually an active energy ray curable resin such as polyester acrylate, epoxy acrylate, urethane acrylate, polyol acrylate resin for imparting scratch resistance to the surface. Etc., and a hard coat layer formed by curing.
Examples of the film using fine particles of the inorganic infrared absorber include (1) a heat ray in which antimony-doped tin oxide (ATO) fine particles or tin-doped indium oxide (ITO) fine particles are contained in a hard coat layer or an adhesive layer. Shielding film (for example, see Patent Document 2), (2) Curing heat ray shielding resin composition containing ATO or ITO fine particles and active energy ray polymerizable polyfunctional (meth) acrylate having (meth) acryloyl group A film having a hard coat layer (see, for example, Patent Document 3), (3) an infrared shielding material having an infrared shielding hard coat layer comprising a cured product of a coating film containing an ionizing radiation curable resin and a rare earth metal-based infrared shielding agent Film (see, for example, Patent Document 4), (4) Tungsten oxide fine particles with better infrared shielding performance than ATO and ITO A film (for example, see Patent Document 5) is disclosed in which a coating solution formed by mixing an ultraviolet curable resin for hard coat is applied on a polyethylene terephthalate film and cured to form an infrared shielding film.

  In addition to the use of the above film, for example, organic dyes such as amino compounds are known as materials that transmit visible light but absorb infrared rays, but these organic dyes are light-resistant over time, There is a problem that heat resistance is poor and the infrared shielding effect does not last long.

JP-A-57-59749 JP-A-8-281860 JP-A-9-108621 JP 2000-318090 A WO2005-037932 pamphlet

In the techniques described in Patent Documents 2 to 5, all of them are techniques for containing inorganic infrared absorbent particles in the hard coat layer. In this case, the hard coat layer contains an ultraviolet absorber or a light stabilizer. Even if it is intended to improve the weather resistance, there arises a problem that the deterioration of the weather resistance cannot be avoided.
Moreover, when the infrared absorption layer which consists only of infrared absorbers is formed between a base material and a primer layer, or between a primer layer and a hard-coat layer, the problem that the adhesiveness between each layer cannot be obtained arises.
The present invention has been made under such circumstances, and provides an infrared absorbing film for exterior use that is used as a window film or the like while having infrared absorbing ability and achieving both weather resistance and interlayer adhesion. It is intended.

As a result of intensive studies to achieve the above object, the present inventors have obtained the following knowledge.
That is, a laminated film having a surface protective layer on a substrate via a primer layer, the surface protective layer is made of a weather-resistant resin cured product, and the primer layer contains an infrared absorber As a result, it was found that an infrared absorbing film for exterior use that has an infrared absorbing ability and can achieve both weather resistance and interlayer adhesion can be obtained.
The present invention has been completed based on such findings.

  That is, the present invention has, on a base material, a primer layer, a surface protective layer made of a resin cured material in this order, and the primer layer contains an infrared absorber, A glass made of an inorganic or organic material provided with an infrared absorbing film for exterior use is provided.

  ADVANTAGE OF THE INVENTION According to this invention, while having infrared absorption ability, it can aim at coexistence with a weather resistance and interlayer adhesiveness, and can provide the infrared absorption film for exteriors used for window films etc.

It is a cross-sectional schematic diagram which shows an example of the structure in the infrared rays absorption film for exterior | packing of this invention. The example which used the infrared rays absorption film (for exterior) of the present invention for double glazing, (a) When arranged on the outer glass of double glazing, (b) Section which shows the case where it arranges on the outdoor side of inner glass It is a schematic diagram. The example which used the infrared rays absorption film (for exterior) of this invention for a double window, (a) When arrange | positioning to the outer window of a double window, (b) Section which shows the case where it arrange | positions to the outdoor side of an inner window It is a schematic diagram.

First, the infrared absorbing film for exterior use according to the present invention will be described.
[Infrared absorbing film for exterior]
FIG. 1 is a schematic cross-sectional view showing an example of the configuration of the infrared absorbing film for exterior use according to the present invention. Hereinafter, the infrared absorbing film for exterior use will be described with reference to FIG.
The exterior infrared absorbing film 10 has a surface protective layer 3 on one surface of the substrate 1 with a primer layer 2 interposed therebetween, and is attached to an adherend such as a window glass on the other surface of the substrate 1. In order to affix the infrared absorbing film, a pressure-sensitive adhesive layer 4 is provided as necessary, and a release sheet 5 for protecting the pressure-sensitive adhesive layer 4 is further affixed.
In addition, when the infrared absorbing film is disposed on the multilayer glass as shown in FIG. 2, it is stuck on the outer glass as shown in FIG. 2 (a) and on the outer side of the inner glass as shown in FIG. 2 (b). In some cases, the infrared absorbing film is included in the “infrared absorbing film for exterior” of the present invention.
Furthermore, as shown in FIG. 3, when the infrared absorbing film is disposed on a double window having an outer window and an inner window, the infrared absorbing film is pasted on the outer window as shown in FIG. 3 (a), and FIG. 3 (b). In some cases, the infrared absorbing film is included in the “infrared absorbing film for exterior” of the present invention.

(Base material)
As the base material 1 used for the infrared absorbing film 10 for an exterior, a transparent plastic film is preferable. The transparent plastic film is not particularly limited, and may be appropriately selected from various transparent plastic films according to the situation. Can do. Examples of the transparent plastic film include polyolefin resins such as polyethylene, polypropylene, poly-4-methylpentene-1 and polybutene-1, polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate, polycarbonate resins, and polychlorinated resins. Vinyl resins, polyphenylene sulfide resins, polyether sulfone resins, polyethylene sulfide resins, polyphenylene ether resins, styrene resins, acrylic resins, polyamide resins, polyimide resins, cellulose resins such as cellulose acetate, etc. Or a laminated film of these. Among these, a polyethylene terephthalate film is particularly preferable.

There is no restriction | limiting in particular as thickness of this transparent plastic film, Although what is necessary is just to select suitably according to the intended purpose, Usually, it is 5-200 micrometers, Preferably it is the range of 10-150 micrometers. Moreover, this transparent plastic film may be colored or vapor-deposited as desired, and may contain an antioxidant, an ultraviolet absorber, or the like. Furthermore, for the purpose of improving the adhesion with the layer provided on the surface, one or both surfaces can be subjected to a surface treatment by an oxidation method, a concavo-convex method or the like as necessary. Examples of the oxidation method include corona discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone ultraviolet irradiation treatment, and the like. Examples of the unevenness method include a sand blast method and a solvent treatment method. Can be mentioned. These surface treatment methods are appropriately selected according to the type of the base film, but generally, a corona discharge treatment method is preferably used from the viewpoints of effects and operability.
In the present invention, an easy adhesion coating treatment can be suitably performed as the chemical surface treatment. The easy adhesion coating treatment is to improve the adhesiveness by coating a resin layer or the like on the base material. For example, there is a method of providing a polyester resin layer.
As thickness of a resin layer, it is about 0.005-0.2 micrometer normally, Preferably it is 0.01-0.1 micrometer.
The polyester-based resin layer is preferably crosslinked, and examples of the crosslinking agent include melamine-based crosslinking agents and epoxy-based crosslinking agents.

(Primer layer)
(1) Thermosetting type Primer layer 2 in exterior infrared absorbing film 10 is formed using a binder resin comprising polycarbonate urethane acrylate, polyester urethane acrylate, or polycarbonate urethane acrylate and acrylic polyol. Is preferred.
The polycarbonate-based urethane acrylate described above as a binder resin is a resin obtained by radically polymerizing an acrylic monomer using a polycarbonate-based polyurethane polymer obtained by reacting a polycarbonate diol and diisocyanate using a radical polymerization initiator.
Here, examples of the diisocyanate include aromatic isocyanates, aliphatic isocyanates, alicyclic isocyanates, or adducts and multimers thereof. These may be used alone or in combination of two or more. Can do. Of these, aliphatic isocyanates such as hexamethylene diisocyanate, and alicyclic isocyanates such as isophorone diisocyanate and hydrogen-converted xylylene diisocyanate are preferable.
Preferred examples of the acrylic monomer include (meth) acrylic acid and (meth) acrylic acid alkyl esters having about 1 to 6 carbon atoms in the alkyl group, and these can be used alone or in combination of two or more. .

  The mass ratio between the acrylic component and the urethane component of the polycarbonate-based urethane acrylate is not particularly limited, but the mass ratio of urethane component: acrylic component is in the range of 80:20 to 20:80 in terms of weather resistance and solvent resistance. It is preferable to set it in the range of 70:30 to 30:70. In addition, when the content of the acrylic and urethane components is within the above range, the coating film is not excessively hard and sufficient processing suitability is obtained, and white streaks (whitening) occur on the resin surface during the bending process. Such a problem is unlikely to occur.

  Polyester urethane acrylate is a resin obtained by radical polymerization of an acrylic monomer using a polyester polyurethane polymer obtained by reacting polyester diol and diisocyanate as a radical polymerization initiator. The diisocyanate and the acrylic monomer are appropriately selected from those used for the polymerization of the polycarbonate urethane acrylate.

  An acrylic polyol is a polymer of an acrylic monomer having a hydroxyl group. For example, it can be synthesized by copolymerizing the acrylic monomer with a hydroxy acrylate such as 2-hydroxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate. These acrylic polyols function as a crosslinking agent.

  The mass ratio of the polycarbonate urethane acrylate and the acrylic polyol is preferably in the range of 100: 0 to 10:90 of the polycarbonate urethane acrylate alone, more preferably in the range of 100: 0 to 30:70. In this range, sufficient weather resistance can be obtained. In addition, when it is only an acrylic polyol, not only a weather resistance will fall, but since this will react with an isocyanate, adhesiveness with a surface protective layer changes with time, and the stable performance may not express.

  The primer layer may be formed from a thermosetting resin composition other than the above. Other thermosetting resin compositions include, for example, epoxy resins, phenol resins, urea resins, unsaturated polyester resins, melamine resins, alkyd resins, polyimide resins, silicone resins, hydroxyl functional acrylic resins, carboxyl functional acrylic resins. , A curable resin such as an amide functional copolymer and a urethane resin, and a curing agent or a crosslinking agent added as necessary.

(2) Ionizing radiation curable type Furthermore, the primer layer may be formed from an ionizing radiation curable resin composition. An ionizing radiation curable resin composition is one having an energy quantum capable of crosslinking and polymerizing molecules in an electromagnetic wave or charged particle beam, that is, a resin composition that is crosslinked and cured by irradiation with ultraviolet rays or electron beams. Point to. Specifically, it can be appropriately selected from polymerizable monomers, polymerizable oligomers, or prepolymers conventionally used as ionizing radiation curable resins.
As the polymerizable monomer, a (meth) acrylate-based monomer having a radical polymerizable unsaturated group in the molecule is preferable, and among them, a polyfunctional (meth) acrylate is preferable. Here, “(meth) acrylate” means “acrylate or methacrylate”, and other similar ones have the same meaning.
In the ionizing radiation curable resin composition, in addition to the polyfunctional (meth) acrylate, a monofunctional (meth) acrylate is used for the purpose of reducing the viscosity thereof, and the scope of the present invention is not impaired. Can be used together as appropriate.
Examples of the polymerizable oligomer include oligomers having a radical polymerizable unsaturated group in the molecule, such as epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate. Can be mentioned.

<Lamination of primer layer>
The primer layer may be a laminate of two or more layers. When two or more primer layers are laminated, two or more of thermosetting type or ionizing radiation curable type may be laminated, or a combination of thermosetting type and ionizing radiation curable type may be laminated.

<Infrared absorber>
In the said infrared absorption film for exterior | packing, in order to provide an infrared absorption function, without deteriorating the weather resistance of the surface protective layer 3 mentioned later, it is required to contain an infrared absorber in the above-mentioned primer layer 2. FIG.
In addition, when the primer layer is formed by laminating two or more layers, it is sufficient that at least one primer layer contains an infrared absorber.

<Formation of primer layer>
In forming the primer layer, first, a resin composition for forming a primer layer is prepared. Specifically, in the case of the thermosetting type, 1 to 50% by mass of an infrared absorber in terms of solid content, if necessary, with respect to the total amount of the resin composition containing the polycarbonate-based urethane acrylate described above, and ultraviolet rays as necessary. A resin composition for forming a primer layer containing 0.1 to 40% by mass of an absorber, 0.05 to 20% by mass of a hindered amine light stabilizer and 1 to 30% by mass of a diisocyanate curing agent is prepared.
Moreover, in the case of ionizing radiation curable type, 1-50 mass% of infrared absorbers are converted into solid content as necessary with respect to the total amount of the above-mentioned ionizing radiation curable resin composition, and 0% of ultraviolet absorber is necessary. A primer layer-forming resin composition containing 1 to 40% by mass and 0.05 to 20% by mass of a hindered amine light stabilizer is prepared.
In addition, in this invention, it is preferable to contain 1-50 mass% in the primer layer of the below-mentioned metal oxide type infrared absorber from a viewpoint which absorbs infrared rays efficiently, and 5-45 mass% is contained. Is more preferable, it is more preferable to contain 10-40 mass%, and it is still more preferable to contain 15-35 mass%.

The primer layer 2 can be formed by a known printing method, coating method or the like using the resin composition as it is or dissolved or dispersed in a solvent.
The primer layer 2 is preferably applied so that the weight after curing is 0.5 to 20 g / m ² , more preferably 1 to 10 g / m ² . Adhesiveness with a surface protective layer improves that the weight after hardening is in the said range.

≪Infrared absorber≫
The infrared absorber is not particularly limited as long as it has a property of effectively absorbing infrared light, particularly light having a wavelength in the near infrared region, and both inorganic and organic can be used. From the viewpoint of durability, inorganic materials are preferred.
Examples of the inorganic infrared absorber include at least one selected from titanium oxide, zinc oxide, indium oxide, tin-doped indium oxide (ITO), tin oxide, antimony-doped tin oxide (ATO), and zinc sulfide. Of these, antimony-doped tin oxide (ATO) is preferred because of the balance between cost and infrared absorption performance and supply stability.

In addition, as the inorganic infrared absorber, tungsten oxide is preferable and composite tungsten oxide is more preferable from the viewpoints of weather resistance, near infrared absorption performance, visible light transmittance, and the like.
As the composite tungsten oxide, the general formula (I)
M _m WO _n (I)
(In the formula, M element is H, He, alkali metal, alkaline earth metal, rare earth element, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, One or more elements selected from Hf, Os, Bi, and I are shown, and m and n are numbers satisfying 0.001 ≦ m ≦ 1.0 and 2.2 ≦ n ≦ 3.0. .)
The compound represented by these can be mentioned.

The composite tungsten oxide represented by the general formula (I) is excellent in durability when it has a hexagonal, tetragonal, or cubic crystal structure, and is therefore selected from the hexagonal, tetragonal, and cubic crystals. Preferably it contains more than one crystal structure. Of these, hexagonal crystals are particularly preferred because they have the least absorption in the visible light region. For example, as a composite tungsten oxide having a hexagonal crystal structure, one type selected from each element of Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn as preferable M elements. A composite tungsten oxide containing the above elements can be given.
The addition amount m of the M element in the composite tungsten oxide is preferably 0.001 or more and 1.0 or less, and more preferably about 0.33. This is because the value of m theoretically calculated from the hexagonal crystal structure is 0.33, and preferable optical characteristics as an infrared absorber can be obtained with the addition amount before and after this. On the other hand, the amount n of oxygen is preferably 2.2 or more and 3.0 or less. Typical examples include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _{3 and the} like, and m and n fall within the above ranges. If it is a thing, a useful near-infrared absorption characteristic can be acquired.

In the present invention, as the composite tungsten oxide, a cesium-containing composite tungsten oxide is preferable from the viewpoints of optical properties and weather resistance as an infrared absorber, and the cesium-containing composite tungsten oxide is represented by the formula (Ia )
Cs _{0.2 to 0.4} WO _{2.5 to 3.0} (Ia)
The compound represented by these can be mentioned.
Compared to fluorine-containing phthalocyanine compounds that are known to be particularly excellent in weather resistance, the composite tungsten oxide is particularly excellent in weather resistance and has high visible light transmittance among organic infrared absorbers.
The composite tungsten oxide is preferably used in the form of fine particles, and the average particle size is preferably 800 nm or less, and more preferably 100 nm or less, from the viewpoints of dispersibility and optical characteristics.
In the present invention, one type of the composite tungsten oxide may be used, or two or more types may be used in combination.

Further, as an inorganic infrared _{absorber, LaB 6, CeB 6, PrB} 6, NdB 6, GdB 6, TbB 6, DyB 6, HoB 6, YB 6, SmB 6, EuB 6, ErB 6, TmB 6, YbB 6 And hexaboride such as LuB ₆ , SrB ₆ , CaB ₆ and (La, Ce) B ₆ .

Examples of organic infrared absorbers include cyanine compounds, squarylium compounds, thiol nickel complex compounds, naphthalocyanine compounds, phthalocyanine compounds, triallylmethane compounds, naphthoquinone compounds, anthraquinone compounds, N, N, N ′, N′-tetrakis (p-di-n-butylaminophenyl) -p-phenylenediaminium perchlorate, phenylenediaminium chloride, phenylenediaminium hexafluoroantimonate , Amino compounds such as phenylene diaminium fluoride boronate, phenylene diaminium fluoride salt, phenylene diaminium perchlorate, copper compound and bisthiourea compound, phosphorus compound and copper compound, phosphate compound and copper Phosphoric acid obtained by reaction with a compound A steal copper compound etc. are mentioned.
Among these, thiol nickel complex salt compounds (Japanese Patent Laid-Open No. 9-230134 etc.) and phthalocyanine compounds are preferable. In particular, fluorine-containing phthalocyanine compounds disclosed in Japanese Patent Laid-Open No. 2000-26748 are organic compounds. Among infrared absorbers, it has high visible light transmittance and is excellent in properties such as heat resistance, light resistance, and weather resistance. Therefore, it is suitable when used in combination with an inorganic system.

≪Ultraviolet absorber, light stabilizer≫
As the ultraviolet absorber and hindered amine light stabilizer contained in the primer layer 2 as necessary, a triazine ultraviolet absorber described in the description of the surface protective layer 3 described later, and a hindered amine having a reactive functional group A The same thing as a system light stabilizer can be mentioned. Moreover, what does not have the reactive functional group A can also be used for a hindered amine light stabilizer.
Further, when the primer layer is two or more layers, the ultraviolet absorber may be blended in any layer, but blending in the sun side (or outdoor side) layer is an ultraviolet absorbing effect on the infrared absorbing film for exterior use. From the viewpoint of

(Surface protective layer)
The surface protective layer 3 in the infrared absorbing film for exterior 10 is a layer made of a resin cured product provided on the primer layer 2 containing the infrared absorber described above, and is a cured product of an ionizing radiation curable resin composition. Preferably there is. The ionizing radiation curable resin composition used for forming this surface protective layer is a coating agent composition comprising a caprolactone urethane (meth) acrylate, a triazine ultraviolet absorber, and a hindered amine light stabilizer having a reactive functional group A. It is preferable that it is a thing.

<Caprolactone urethane (meth) acrylate>
The caprolactone-based urethane (meth) acrylate used in the present invention is a resin having ionizing radiation curability, and is usually obtained by a reaction of a caprolactone-based polyol, an organic isocyanate, and a hydroxy (meth) acrylate. Here, the ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. Electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams can also be used.

Here, as a caprolactone-type polyol, what is marketed can be used, Preferably it has two hydroxyl groups, The weight average molecular weight becomes like this. Preferably it is 500-3000, More preferably, the thing of 750-2000 is mentioned. It is done. Moreover, polyols other than caprolactone, for example, polyols such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, etc., can be used by mixing one kind or plural kinds at an arbitrary ratio.
As the organic polyisocyanate, a diisocyanate having two isocyanate groups is preferable, and from the viewpoint of suppressing yellowing, isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, trimethylhexamethylene diisocyanate and the like are preferable. . Moreover, as a hydroxy (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, caprolactone modified | denatured 2-hydroxyethyl (meth) acrylate, etc. are mentioned preferably.

  Caprolactone-based urethane (meth) acrylate can be synthesized by reaction of these polycaprolactone-based polyols, organic polyisocyanate, and hydroxy (meth) acrylate. As a synthesis method, a polycaprolactone-based polyol and an organic polyisocyanate are reacted to form a polyurethane prepolymer containing -NCO groups (isocyanate groups) at both ends, and then reacted with hydroxy (meth) acrylate. The method is preferred. The reaction conditions and the like may be in accordance with conventional methods.

  The caprolactone-based urethane (meth) acrylate used in the present invention preferably has a weight average molecular weight (polystyrene equivalent weight average molecular weight measured by GPC method) of 1000 to 12000, more preferably 1000 to 10,000. That is, the caprolactone urethane (meth) acrylate is preferably an oligomer. If the weight average molecular weight is within the above range (oligomer), the processability is excellent, and the coating agent composition has an appropriate thixotropy, so that the surface protective layer can be easily formed.

<Triazine UV absorber>
As the triazine-based UV absorber used in the present invention, a hydroxyphenyl triazine-based UV absorber is preferable. Examples of such an ultraviolet absorber include 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine. 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2 , 4-Bis [2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyl) Oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3- (2 ′) -Ethyl) Xyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and the like are preferable, and these are used alone or in combination. be able to.

  1-10 mass parts is preferable with respect to 100 mass parts of caprolactone type urethane (meth) acrylates, as for content of a triazine type ultraviolet absorber, 3-10 mass parts is more preferable, and 5-10 mass parts is still more preferable. If the content of the triazine-based ultraviolet absorber is within the above range, the absorber does not bleed out and sufficient ultraviolet absorbing ability can be obtained, so that excellent weather resistance can be obtained. In general, when adding 1 part by mass or more of the UV absorber to 100 parts by mass of the binder resin, the absorber may bleed out. I couldn't. However, according to the present invention, even if a large amount of ultraviolet absorber of 1 part by mass or more is added by combining a triazine ultraviolet absorber, caprolactone urethane (meth) acrylate, and a predetermined light stabilizer, It became possible to obtain excellent weather resistance without bleeding out.

<Hindered amine light stabilizer having reactive functional group A>
In the hindered amine light stabilizer used in the present invention, the reactive functional group A is not particularly limited as long as it has reactivity with a caprolactone urethane (meth) acrylate. For example, a (meth) acryloyl group, a vinyl group Preferred examples include functional groups having an ethylenic double bond such as an allyl group, and at least one selected from these is preferred. Of these, a (meth) acryloyl group is preferable.
Examples of such a light stabilizer include 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4- (Meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,6- Examples thereof include tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate and the like, but are not particularly limited. These light stabilizers can be used alone or in combination.

  The content of the hindered amine light stabilizer having the reactive functional group A is preferably 1 to 10 parts by mass, more preferably 3 to 10 parts by mass, with respect to 100 parts by mass of the caprolactone urethane (meth) acrylate. 10 parts by mass is more preferable. If the content of the hindered amine light stabilizer is within the above range, the light stabilizer does not bleed out and sufficient light stability is obtained, so that excellent weather resistance is obtained.

<Silicate compound having reactive functional group B>
The silicate compound used in the present invention is used as desired to impart self-cleaning properties to the surface protective layer. The silicate compound used in the present invention is not particularly limited as long as it is a silicate compound having a reactive functional group B reactive with caprolactone-based urethane (meth) acrylate. Preferred examples of the reactive functional group B include a functional group having an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, and an allyl group, and is preferably at least one selected from these. Of these, a (meth) acryloyl group is preferable.
The silicate compound having the reactive functional group B is preferably a compound represented by the following general formula (1).

Wherein ^(1), R 1 to R ³ each independently represent a hydrogen atom or an organic group having 1 to 10 carbon atoms, more of ^{R 1} and ^{R 2} may be the same or different. R ⁴ is a functional group containing a reactive functional group B.
Preferred examples of the organic group having 1 to 10 carbon atoms include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an aralkyl group. These groups may be substituted or unsubstituted, and the alkyl group and alkenyl group may be linear or branched. Of these, an alkyl group having 1 to 4 carbon atoms is more preferable.

Further, _{n 1} is preferably 1 to 30, 1 to 10 is more preferable. That is, the silicate compound having the reactive functional group B is preferably a silicate compound represented by the general formula (1) or a condensate thereof, and the condensate is preferably a 2-30 mer, preferably a 2-10 mer. More preferably. In addition, when the hydrophilizing agent is a condensate of a silicate compound, the above preferable 2 to 30 mer or more preferable 2 to 10 mer includes the case of an average value.

  More specifically, a compound represented by the following general formula (2) is preferable.

In formula (2), R ^{5 to} R ⁷ are the same as R ^{1 to} R ³ , respectively. R ¹¹ is the same as R ¹ , and particularly preferably a hydrogen atom or a methyl group. R ⁸ and R ¹⁰ represent a single bond or a divalent organic group. R ⁹ is a single bond, a carbonyl group (—CO—), an ether bond (—O—), an ester bond (—COO—), a thioether bond (—S—), an amide bond (—CONH—), an imino. A bond (—NH—), a carbonate bond (—OCOO—), and a group in which a plurality of these are linked are shown. Preferred examples of the divalent organic group include an alkanediyl group, an alkenediyl group, an arylene group, and an arylenealkanediyl group. These groups may be substituted or unsubstituted, and the alkanediyl group and alkenediyl group may be linear or branched. Among these, a C1-C4 alkanediyl group is more preferable. R ⁹ is more preferably an ester bond (—COO—).
N ₂ is the same as n ₁ described above.

  The content of the silicate compound having the reactive functional group B is preferably 1 to 15 parts by mass, more preferably 3 to 15 parts by mass, and more preferably 5 to 15 parts by mass with respect to 100 parts by mass of the caprolactone urethane (meth) acrylate. Is more preferable. If content of a silicate compound is in the said range, the favorable crosslinked state of a caprolactone type | system | group urethane (meth) acrylate will be obtained. Moreover, since the surface protective layer formed using the coating agent composition in this invention has moderate hydrophilicity, the wettability of water increases and it can have the outstanding self-cleaning property.

<Alkyl silicate>
The alkyl silicate is used as desired in order to impart self-cleaning properties to the surface protective layer in the present invention. The alkyl silicate may be any one having at least one alkoxyl group bonded to the Si atom, and is preferably a tetraalkyl silicate represented by the following general formula (3).

In formula (3), R ^{12 to} R ¹⁵ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, and a plurality of R ¹² and R ¹⁵ may be the same or different. It may be. Moreover, all R < ¹² > -R < ¹⁵ > does not become a hydrogen atom simultaneously. As R < ¹² > -R < ¹⁵ >, a C1-C4 alkyl group is preferable from a viewpoint of improving self-cleaning performance and visible light transmittance, and a C1-C2 alkyl group is more preferable.

n ₃ from the viewpoint of improving the self-cleaning, 1-40, more preferably from 10 to 30, more preferably 10 to 20. That is, the alkyl silicate is preferably an alkyl silicate represented by the general formula (3) or a condensate thereof, and the condensate is preferably a 2 to 40-mer, more preferably a 10 to 30-mer. A 10-20 mer is preferable. In the present invention, when the hydrophilizing agent is a condensate of a silicate compound, the above preferable 2 to 40 mer, more preferable 10 to 30 mer, or more preferable 10 to 20 mer is an average value. Including some cases. Therefore, for example, even if a mixture of 15-45 mer and an average 20-mer alkyl silicate that is larger than the 40-mer is included, the average 40-mer or less is preferable in the present invention. It is contained in the condensate of the 2-40 mer alkyl silicate used.
Moreover, 150-4000 are preferable, as for a weight average molecular weight, 1000-3000 are more preferable, and 1000-2000 are more preferable.

<Various additives>
The coating agent in this invention can contain various additives in the range which does not inhibit the performance. Examples of various additives include polymerization inhibitors, crosslinking agents, antistatic agents, adhesion improvers, antioxidants, leveling agents, thixotropic agents, coupling agents, plasticizers, antifoaming agents, fillers, and solvents. Etc.

<Formation of surface protective layer>
The surface protective layer 3 in the infrared absorbing film 10 for exterior use of the present invention is obtained by applying the coating agent composition on the primer layer 2 described above to provide a layer of ionizing radiation curable resin composition, and this is provided with ionizing radiation. Can be formed by crosslinking and curing.
Application of the coating composition is a known method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, preferably gravure so that the weight after curing is usually about 1 to ²⁰ g / m ^2. Perform by coating. Moreover, from the viewpoint of obtaining excellent weather resistance and its durability, and further transparency and antifouling properties, it is preferably ² to ²⁰ g / m ² .

  The layer of the uncured resin composition formed by application of the coating agent composition becomes a surface protective layer by irradiating with ionizing radiation such as an electron beam and ultraviolet rays and crosslinking and curing. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the resin used and the thickness of the layer, but the layer of the uncured resin composition is usually cured at an acceleration voltage of about 70 to 300 kV. It is preferable to make it.

The irradiation dose is preferably such that the crosslinking density of the caprolactone urethane (meth) acrylate is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).
The electron beam source is not particularly limited, and for example, various electron beam accelerators such as a cockroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type are used. be able to.
When ultraviolet rays are used as ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are irradiated. There is no restriction | limiting in particular as an ultraviolet-ray source, For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, etc. are used. In this case, it is preferable that a conventionally known photopolymerization initiator is contained in the coating agent composition.

(Adhesive layer)
In the infrared absorbing film for exterior use, an adhesive layer 4 is provided as necessary in order to adhere the opposite surface of the substrate 1 on the side where the primer layer 2 is provided to an adherend such as a window glass. The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 4 is not particularly limited and can be appropriately selected and used depending on the situation from various conventionally known pressure-sensitive adhesives, particularly from the viewpoint of weather resistance and the like. Acrylic, urethane and silicone adhesives are preferred. The pressure-sensitive adhesive layer has a thickness of usually 1 to 100 μm, preferably 2 to 50 μm.
The pressure-sensitive adhesive layer can contain a weathering agent such as an ultraviolet absorber, a light stabilizer, and an antioxidant, if necessary.
A release sheet 5 can be attached to the pressure-sensitive adhesive layer 4 in order to protect the pressure-sensitive adhesive layer 4. Examples of the release sheet 5 include a polyester film such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and a plastic film such as a polyolefin film such as polypropylene and polyethylene coated with a release agent. As the release agent, silicone-based, fluorine-based, long-chain alkyl-based, and the like can be used, and among these, a silicone-based material that is inexpensive and provides stable performance is preferable. Although there is no restriction | limiting in particular about the thickness of this peeling sheet, Usually, about 20-250 micrometers and 20-50 micrometers are preferable when performing thermoforming.
Thus, when sticking a release sheet to an adhesive layer, after apply | coating an adhesive to the release agent layer surface of this release sheet and providing the adhesive layer of predetermined thickness, this is used as the primer of a base material The pressure-sensitive adhesive layer may be transferred to the surface opposite to the side where the layer is provided, and the release sheet may be left as it is.
In addition, the application amount of the pressure-sensitive adhesive is preferably in the range of 10 to 30 g / m ² by dry weight. If it is 10 g / m ² or more, sufficient adhesive strength is obtained, and if it is 30 g / m ² or less, the pressure-sensitive adhesive does not protrude during processing.
The pressure-sensitive adhesive is applied by a method in which the pressure-sensitive adhesive is diluted with a solvent such as ethyl acetate or toluene to prepare a coating solution having a solid content of 20 to 60% by mass and this coating solution is applied to a release sheet. Can do. Examples of the application device for the pressure-sensitive adhesive include known coating devices such as a knife coater, a comma coater, a gravure coater, and a roll coater.

  The thus obtained infrared absorbing film for exterior use of the present invention (hereinafter sometimes simply referred to as “infrared absorbing film”) is a laminated film having a surface protective layer on a base material via a primer layer. In addition, it has excellent infrared absorption ability and transparency, and the surface protective layer is excellent in weather resistance and self-cleaning property, and has good interlayer adhesion, and can be used for the following applications.

《Glass》
The infrared absorbing film for exterior use of the present invention is preferably a glass made of an inorganic material such as silicate glass or quartz glass generally containing silicon dioxide as a main component (hereinafter referred to as “inorganic glass”) or. It is used by being placed on glass made of an organic material (hereinafter referred to as “organic glass”).
Organic glass refers to glass composed of resin and is used as a substitute for inorganic glass. Examples of the inorganic glass and organic glass include transparent glass, colored transparent glass, frosted glass, tempered glass, and multilayer glass.

(Organic glass)
Various resins can be used as the resin constituting the organic glass, but a resin that can be melted is preferable from the viewpoint of moldability such as injection molding or extrusion molding.
Examples of the resin that can be melted include vinyl polymers such as polyvinyl chloride and polyvinylidene chloride; styrene resins such as polystyrene, acrylonitrile-styrene copolymer, and ABS resin (acrylonitrile-butadiene-styrene copolymer resin). Resins: Acrylic resins such as polymethyl (meth) acrylate, polyethyl (meth) acrylate, polyacrylonitrile, polyolefin resins such as polyethylene, polypropylene, polybutene, polyethylene terephthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymer, polybutylene Examples thereof include polyester resins such as terephthalate; polycarbonate resins. Among these, acrylic resins or polycarbonate resins are preferable from the viewpoints of transparency and impact resistance.

  In addition to the above resins, various additives such as antioxidants, heat stabilizers, UV absorbers, light stabilizers, flame retardants, plasticizers, silica, alumina, carbonic acid are added to the organic glass. Inorganic powders such as calcium and aluminum hydroxide, fillers such as wood powder and glass fiber, lubricants, mold release agents, antistatic agents, colorants and the like can be added.

There is no restriction | limiting in particular about the thickness of organic glass, Although it selects according to the use of the said functional organic glass, 1-20 mm is preferable normally and 2-10 mm is more preferable. When the thickness of the substrate is 1 mm or more, practical strength such as surface rigidity is sufficient, and when it is 20 mm or less, workability is improved.
In the present invention, as means for “distributing” the infrared absorbing film for exterior to inorganic glass or organic glass, the above-mentioned adhesive layer is used for sticking, the base sheet is thermally fused, and the organic glass is thermally fused. Can be mentioned.

(Use of infrared absorbing film)
The infrared absorbing film for exterior use of the present invention is suitably used by attaching inorganic glass or organic glass as described above. More specifically, it is attached to a building or vehicle, or a window of a refrigerated / frozen showcase. In addition, it is possible to reduce the temperature rise in the room and save energy, and it is particularly suitable for sticking curved glass such as a window of a vehicle, for example, a window glass of an automobile.
Further, since the infrared absorbing film of the present invention is excellent in transparency, infrared absorbing ability, weather resistance, self-cleaning property, etc., the infrared absorbing film of the present invention is used as it is or has a hydrophilic function for preventing water droplets from falling on plants. The film for agriculture having a light scattering function for uniformly irradiating light to a plant and the infrared absorbing film of the present invention, or a film having a self-cleaning property added to the weather resistant surface protective layer of the infrared absorbing film of the present invention Also, it can be used as an agricultural covering material used in the cultivation of houses and tunnels for agricultural crops.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In addition, the following evaluation was performed about the laminated | multilayer film obtained by the comparative example 1, and the infrared rays absorption film obtained by Example 1 and Comparative Examples 2-4.

(1) Evaluation of weather resistance The film obtained in each example was set in an eye super UV tester (manufactured by Iwasaki Electric Co., Ltd.) and light conditions (illuminance: 60 mW / cm ² , black panel temperature: 63 ° C., humidity: 50 % RH) for 20 hours, condensation conditions (illuminance: 0 mW / cm ² , black panel temperature: 30 ° C., humidity: 98% RH) for 4 hours, water spraying conditions (30 seconds before and after the condensation conditions), and film The time until yellowing, cracking, and whitening were observed was measured and evaluated according to the following criteria.
◎: No change in appearance until 800 hours of test time ○: No change in appearance until 500 hours of test time ×: Yellowing, cracks, and whitening occurred within 200 hours of test time

(2) Evaluation of interlayer adhesion The film obtained in each example was tested according to JIS K 5600-5-6 (cut interval: 1 mm, tape: Nichiban cello tape (registered trademark)), and film ( The peeled state of the layer) was evaluated according to the following criteria.
○: No peeling is observed ×: Peeling is observed

(3) Infrared absorption performance The transmittance of infrared rays (wavelength region 780 to 2100 nm: measurement interval 1 nm) is measured with a spectrophotometer (manufactured by Hitachi High-Technologies Corporation "model number: U-4000") for the film obtained in each example. And the average value was calculated | required and it evaluated with the following criteria as infrared absorption performance.
○: Infrared transmittance 80% or less ×: Infrared transmittance greater than 80%

Comparative Example 1
A PET (thickness: 50 μm) film was prepared as a substrate. A primer layer forming composition having the following composition was applied to the surface of the PET film to form a primer layer (5 g / m ² ).
Next, an ionizing radiation curable resin composition having the following composition is prepared, a coating film is formed by a gravure coating method, and the coating film is crosslinked and cured by irradiation with an electron beam under the conditions of 175 keV and 5 Mrad (50 kGy). Thus, a surface protective layer (5 g / m ² ) was formed to obtain a laminated film. Said evaluation was performed about the obtained laminated | multilayer film. In addition, the lamination | stacking order of the film of the comparative example 1 is a base material, a primer layer, and a surface protective layer, and a surface protective layer is a layer which consists of hardened | cured material of an ionizing radiation curable resin composition. The evaluation results are shown in Table 1.

<Composition of primer layer forming composition>
It is a composition obtained by mixing the following resin composition and curing agent in a ratio of 100: 5 (mass ratio).
Composition of resin composition:
Polycarbonate urethane acrylate: 100 parts by mass (urethane component in polycarbonate urethane acrylate: mass ratio of acrylic component 70:30)
Hydroxyphenyltriazine-based UV absorber: 15 parts by mass (“Tinuvin 400 (trade name)”, manufactured by BASF Japan Ltd.)
Hydroxyphenyltriazine-based ultraviolet absorber: 5 parts by mass (“Tinuvin 479 (trade name)”, manufactured by BASF Japan Ltd.)
Hindered amine light stabilizer: 6 parts by mass (“Tinuvin 123 (trade name)”, manufactured by BASF Japan Ltd.)
Curing agent: hexanemethylene diisocyanate <Composition of ionizing radiation curable resin composition for forming surface protective layer>
Caprolactone-based urethane acrylate oligomer: 100 parts by mass (trifunctional, molecular weight: about 1200)
Triazine-based UV absorber: 2 parts by mass (“Tinuvin 479 (trade name)”, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl- 1,3,5-triazine, manufactured by BASF Japan Ltd.)
Light stabilizer having a reactive functional group: 6 parts by mass (“Sanol LS-3410 (trade name)”, 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, manufactured by BASF Japan Ltd.)

Example 1
An infrared absorbing film was produced in the same manner as in Comparative Example 1 except that the following infrared absorber was added to the total amount of the primer layer forming composition so as to be 30% by mass in terms of solid content. Said evaluation was performed about the obtained infrared rays absorption film. In addition, the lamination | stacking order of the film of Example 1 is a base material, a primer layer (infrared absorber containing), and a surface protective layer. The evaluation results are shown in Table 1.
<Infrared absorber>
30% by mass methyl ethyl ketone (MEK) dispersion of antimony-doped tin oxide (ATO) (“SNS-10M (trade name)”, manufactured by Ishihara Sangyo Co., Ltd.)

Comparative Example 2
The infrared absorber was added to the surface protective layer in the same manner as in Comparative Example 1 except that the infrared absorber was further added to 30% by mass in terms of solid content with respect to the total amount of the ionizing radiation curable resin composition. An infrared-absorbing film containing was prepared. Said evaluation was performed about the obtained infrared rays absorption film. In addition, the lamination | stacking order of the film of the comparative example 2 is a base material, a primer layer, and a surface protective layer (infrared absorber containing). The evaluation results are shown in Table 1.

Comparative Example 3
A primer layer forming composition having the composition shown in Comparative Example 1 was applied to the surface of the PET film to form a primer layer (5 g / m ² ).
Next, a 30% by mass methyl ethyl ketone (MEK) dispersion of antimony-doped tin oxide (ATO) (“SNS-10M (trade name)”, manufactured by Ishihara Sangyo Co., Ltd.) was applied, and an infrared absorption layer (1.5 g / m ² ). Formed.
Next, an ionizing radiation curable resin composition having the composition shown in Comparative Example 1 was prepared, a coating film was formed by a gravure coating method, and the above coating was performed by irradiating an electron beam under the conditions of 175 keV and 5 Mrad (50 kGy). By crosslinking and curing the film, a surface protective layer (5 g / m ² ) was formed to obtain an infrared absorbing film. Said evaluation was performed about the obtained infrared rays absorption film. In addition, the lamination order of the film of the comparative example 3 is a layer which consists of a base material, a primer layer, an infrared absorber, and a surface protective layer. The evaluation results are shown in Table 1.

Comparative Example 4
An antimony-doped tin oxide (ATO) 30 mass% methyl ethyl ketone (MEK) dispersion (“SNS-10M (trade name)”, manufactured by Ishihara Sangyo Co., Ltd.) was applied to the PET film surface, and an infrared absorption layer (1.5 g / m ² ) was formed.
Subsequently, the primer layer forming composition having the composition shown in Comparative Example 1 was applied to form a primer layer (5 g / m ² ).
Next, an ionizing radiation curable resin composition having the composition shown in Comparative Example 1 was prepared, a coating film was formed by a gravure coating method, and the above coating was performed by irradiating an electron beam under the conditions of 175 keV and 5 Mrad (50 kGy). By crosslinking and curing the film, a surface protective layer (5 g / m ² ) was formed to obtain an infrared absorbing film. Said evaluation was performed about the obtained infrared rays absorption film. In addition, the lamination order of the film of the comparative example 4 is a base material, the layer which consists of infrared absorbers, a primer layer, and a surface protective layer. The evaluation results are shown in Table 1.

Example 2
In Example 1, as the first primer layer-forming resin composition on the PET film surface, the same infrared absorber as that used in Example 1 with respect to the total amount of the ultraviolet (UV) curable resin composition, The primer layer forming composition added so as to be 30% by mass in terms of solid content is applied to form the first primer layer (5 g / m ² ), and then the primer layer forming composition of Comparative Example 1 The same procedure as in Example 1 (Comparative Example 1) was carried out except that a primer layer forming composition having the same composition as the product was applied to form a second primer layer (5 g / m ² ). Was made.
<Composition of the first primer layer forming resin composition>
The following ultraviolet curable resin is obtained by adding the infrared absorbent and ultraviolet absorbent used in Example 1.
Composition of resin composition:
・ Transparent acrylic UV curable prepolymer (trade name: Aronix M-305, chemical name: pentaerythritol triacrylate: PETA, manufactured by Toagosei Co., Ltd.)
: 100 parts by mass / infrared absorber: 30% by mass of an antimony-doped tin oxide (ATO) having an average particle diameter of 100 nm in a methyl ethyl ketone (MEK) dispersion (“SNS-10M (trade name)” manufactured by Ishihara Sangyo Co., Ltd.): 150 Part by mass / photopolymerization initiator: 1-hydroxy-cyclohexyl-phenyl-ketone
(Trade name: Irgacure 184, manufactured by BASF): 2 parts by mass, UV absorber: hydroxyphenyl triazine UV absorber (trade name: TINUVIN 479, manufactured by BASF Japan Ltd.): 0.25 part by mass The order of film lamination is: base material, primer layer (first primer layer) made of UV curable resin containing infrared absorber, two-component curable weatherable primer layer (second primer layer), and surface protective layer. . The evaluation results are shown in Table 1.

Example 3
In Example 2, except that the addition amount of hydroxyphenyltriazine-based ultraviolet absorber (trade name: TINUVIN 479, manufactured by BASF) in the first primer layer-forming resin composition was 0.5 parts by mass. The same operation as 2 was performed to produce an infrared absorbing film. The order of lamination of the film of Example 3 is the same as that of Example 2. The evaluation results are shown in Table 1.

  The infrared absorbing film for exterior use according to the present invention has excellent infrared absorbing ability and transparency, and the surface protective layer is excellent in weather resistance and self-cleaning property, and has good interlayer adhesion, and can be used in buildings, vehicles, refrigeration / freezing shows. It can be affixed to a case window or the like to reduce the temperature rise in the room and save energy, and is particularly suitable for affixing curved glass such as a vehicle window, for example, an automobile window glass. Furthermore, it can also be used as an agricultural covering material used in house cultivation and tunnel cultivation of agricultural products.

DESCRIPTION OF SYMBOLS 1 Base material 2 Primer layer 3 Surface protective layer 4 Adhesive layer 5 Release sheet 10 Infrared absorbing film for exterior

Claims (10)

On the base material, it has a primer layer and a surface protective layer made of a cured resin in this order,
The primer layer is composed of two or more layers including a polycarbonate urethane acrylate as a binder resin, or a thermosetting resin and / or an ionizing radiation curable resin composed of a polycarbonate urethane acrylate and an acrylic polyol. At least one layer contains 15 to 35% by mass of an infrared absorber, and the infrared absorber is a tungsten oxide.   The two or more primer layers are those in which at least one layer uses an ionizing radiation curable resin as a binder resin, and at least another layer uses a thermosetting resin as a binder resin, and 2. The infrared absorbing film for exterior use according to claim 1, wherein the ionizing radiation curable resin is a transparent acrylic ultraviolet curable prepolymer. The infrared absorbing film for exterior use according to claim 1 or 2 , wherein the tungsten oxide is at least one selected from composite tungsten oxides represented by the following general formula (I).
Formula (I)
M _m WO _n (I)
(In the formula, M element is H, He, alkali metal, alkaline earth metal, rare earth element, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, One or more elements selected from Hf, Os, Bi, and I are shown, and m and n are numbers satisfying 0.001 ≦ m ≦ 1.0 and 2.2 ≦ n ≦ 3.0. .)   The composite tungsten oxide described in the general formula (I) has a hexagonal crystal structure, and the M element is each of Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn. The infrared absorbing film for exterior use according to claim 3, which is one or more selected from elements. The infrared absorbing film for exterior use according to claim 3, wherein the composite tungsten oxide is a cesium-containing composite tungsten oxide represented by the following formula (Ia).
Formula (Ia)
Cs _0.2-0.4 WO _2.5-3.0 (Ia)   The infrared absorbing film for exterior use according to any one of claims 1 to 5, wherein the surface protective layer is a cured product of an ionizing radiation curable resin composition.   The infrared absorbing film for exterior use according to claim 6, wherein the ionizing radiation curable resin composition comprises a caprolactone (meth) urethane acrylate, a triazine UV absorber, and a hindered amine light stabilizer having a reactive functional group A. .   The infrared absorbing film for exterior use according to claim 7, wherein the reactive functional group A is a functional group having an ethylenic double bond.   The infrared absorption film for exterior | packing in any one of Claims 1-8 which has an adhesive layer in the surface on the opposite side to the primer layer of a base material.   A glass made of an inorganic or organic material, wherein the exterior infrared absorbing film according to any one of claims 1 to 9 is arranged.