JP2013218261A - Heat ray control film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat ray control film including a light transmissive part that transmits sunlight and an absorption part group made of a light absorption material including nano fine particles that absorb sunlight, the heat ray control film being a kind of light control sheet allowing cost-effective formation while satisfying scratch resistance, adhesion to a surface of the absorption part group, and entire light transmittance.SOLUTION: A heat ray control film includes, in a surface direction: a light transmission part that transmits sunlight; and an absorption part group made of a light absorption material including nano fine particles that absorb sunlight. The absorption part group includes: a plurality of absorption parts aligned in the surface direction of the film and having thickness in a cross sectional direction of the film; and a surface protective layer made of a cured product of a curable resin composition and having at least a hard coat function on a surface on which the absorption part group is provided.

Description

  The present invention is provided on window glass or the like regardless of whether it is inorganic glass or organic glass, blocks most of the heat rays contained in the sunlight taken into the room in the summer, and can take in sunlight including the heat rays in the winter. In a heat ray control film, which is a kind of light control sheet, a surface protective layer is provided to provide the surface physical properties required for windowed films and prevent the appearance and performance of the heat ray control film from being damaged by scratches etc. The present invention relates to a heat ray control film that is a kind of light control sheet that can be used.

  Patent Document 1 includes a light transmissive part that transmits sunlight and a light shielding part group that absorbs sunlight, and a plurality of light shielding part groups are arranged at a predetermined pitch in one direction in the sheet, There has been proposed a light control sheet that blocks the intake of sunlight into the room in summer and allows the intake of sunlight in winter (Patent Document 1). By using such a sheet, it is possible to suppress an increase in room temperature in summer and to capture light that increases the room temperature in winter without changing the film.

In Patent Document 1, the shape of the light shielding part is defined as follows.
θ ₂₀ ≦ tan− ¹ ((Pa− (Wa / 2)) / Ta) <θ ₁₀
Pa: Pitch, Wa: Bottom width, Ta: Height,
θ ₂₀ : Refraction angle when light at south mid altitude θ _{1 in} the summer solstice enters the light-transmitting part θ ₁₀ : Refraction angle when light at autumn mid-sun altitude θ ₂ enters the light-transmitting part

JP 2010-259406 A

On the other hand, when the film for light control is actually attached to a window or the like, the hard coat function is indispensable because it rubs the surface during construction and is exposed to rain and wind in later use. . For this reason, Patent Document 1 proposes a configuration in which a transparent sheet (film) is arranged on the surface, but even in this case, the surface of the film needs to be further hard-coated. In addition, when a film is arranged, since an adhesive for bonding the film and the base film layer is usually required, a three-layer structure of a hard coat layer, an adhesive layer, and a base film layer is formed. There are disadvantages such as an increase in the number of processes, an increase in cost, a decrease in workability due to an increase in film thickness due to an increase in layers, and a decrease in transmittance due to reflection loss due to an increase in the interface of each layer.
Therefore, in the present invention, the heat ray control film including a light-transmitting part that transmits sunlight and an absorbing part group made of a light-absorbing material containing nanoparticles that absorbs sunlight, the scratch resistance, the surface of the absorbing part group, etc. The object of the present invention is to provide a heat ray control film that can be formed in a cost-effective manner while satisfying the adhesiveness and the total light transmittance.

As a result of diligent examination in view of the above-mentioned purpose, when a hard coat layer is formed with a cured product obtained by coating the surface of the light transmission part and the absorption part with a curable resin composition, the scratch resistance, adhesion with the surface of the absorption part group, etc., Knowing that the total light transmittance can be improved, the present invention was completed.
That is, the present invention provides the following [1] to [5].
[1] A heat ray control film provided with a light transmission part that transmits sunlight and an absorption part group made of a light-absorbing material containing nano-particles that absorb sunlight, each in a plane direction, the absorption part group A plurality of the absorbers arranged in the plane direction of the film and having a thickness in the cross-sectional direction of the film, and a cured product of the curable resin composition on the surface on which the absorber portion group is provided And a heat ray control film provided with a surface protective layer having at least a hard coat function.
[2] The heat ray control film according to [1], wherein the change in haze value before and after the Taber abrasion test in accordance with JIS K5400 of the surface protective layer is 3 or less.
[3] The heat ray control film according to [1] or [2], wherein the surface protective layer is further provided with a weather resistance function.
[4] The heat ray control film according to any one of [1] to [3], wherein the surface protective layer is provided with a hydrophilic function.
[5] The heat ray control film according to any one of [1] to [4], wherein the surface protective layer is a cured product of an ionizing radiation curable resin composition.
[6] A glass made of an inorganic or organic material, comprising the heat ray control film according to any one of [1] to [5].

  By forming a surface protective layer having a hard coat function that is coated at least on the surface, when applying the heat ray control film to a window or the like, the surface is rubbed to prevent scratches from occurring and haze reduction. Compared to the case where a hard coat layer is formed by laminating a film having a hard coat layer, the number of processes, cost reduction, transmittance improvement, adhesion improvement, film thickness reduction, etc. The advantageous effect of can be produced.

FIG. 1A is a schematic cross-sectional view for explaining an example of an embodiment of a heat ray control film of the present invention and control of irradiation light of sunlight, and FIG. 1B is an example shown in FIG. FIG. 1C is a diagram showing a usage pattern of the heat ray control film of the example shown in FIG. 1A. It is explanatory drawing of the layer structure of the heat ray | wire control film shown in FIG. Description of the modification in the case where the cross-sectional shape when cut in the thickness direction of the film perpendicular to the arrangement direction is substantially rectangular in the solar light absorber arranged in a predetermined direction in the heat ray control film of the present invention FIG.

A heat ray control film provided with a light transmission part for transmitting sunlight according to the present invention and an absorption part group made of a light absorption material containing nano-particles that absorb sunlight, respectively, in the plane direction, the absorption part group A plurality of the absorbers arranged in the plane direction of the film and having a thickness in the cross-sectional direction of the film, and a cured product of the curable resin composition on the surface on which the absorber portion group is provided And a surface protective layer having at least a hard coat function is provided.
In the following description, the absorbent unit will be described centering on the case where a plurality of linear absorbent unit groups are arranged at a predetermined pitch in the plane direction, but the absorbent unit of the present invention is not limited to this. For example, the absorbing portion group may be wavy or zigzag when the individual absorbing portions constituting the absorbing portion group are viewed from the film plane direction, or may be a figure that is not continuous in a certain direction such as a circle or a square. There may be. Further, the pitch between the absorbing portions is not necessarily constant.

  An example of the heat ray control film of the present invention will be described based on FIG. In the heat ray control film 100 shown in the figure, a plurality of substantially rectangular shaped grooves 12a are formed on a light-transmitted shaped film 11f supported by a base film 10, and the shaped grooves 12a are formed. After being filled with a nanoparticle-containing light absorbing material that absorbs sunlight, this is cured to form the absorbing portion 12. The light transmission part 11 is between the adjacent absorption parts 12 and 12. The surface protective layer 13 is provided on the surface S1 side on the side filled with the light absorbing material.

Moreover, the absorption part of the heat ray | wire control film of this invention is demonstrated based on FIGS. 1-3. As shown in FIGS. 1A, 1 </ b> B, and 2, a plurality of absorbers are arranged in the plane direction. Moreover, as shown to Fig.1 (a), FIG.2 and FIG.3, an absorption part has thickness in a cross-sectional direction. These absorption parts gather and it becomes an absorption part group. In addition, although the absorption part of FIG.1 (b) is linear and is formed with a fixed pitch, as above-mentioned, the shape of a light absorption part is not restricted to a linear form, and a pitch may not be constant. .
In addition, the light transmission part 11 becomes a structure connected between absorption parts, as shown to Fig.1 (a), (b), and FIG.

(Base film)
As the base film that can be used for the heat ray control film of the present invention, it is preferable to use a film of polyethylene terephthalate (PET) or polycarbonate (PC) because transparency and strength as a window pasting film are required.
The thickness of the base film may be appropriately selected according to the purpose of use, but is usually in the range of 5 to 200 μm, preferably 10 to 150 μm. Moreover, this base 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 shaped film 11f or the pressure-sensitive adhesive layer 14 provided for pasting the window, the surface S2 and the surface S3 may be subjected to an oxidation method or an unevenness method on one or both sides as necessary. Surface treatment can be performed by such as. 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.

(Shaped film)
The shaped film that can be used for the heat ray control film of the present invention is formed by extruding a solventless resin such as an ionizing radiation curable epoxy acrylate from an extrusion roll, curing it, and denting it in the thickness direction of the film. It is obtained by producing a film having a molded groove (recess). If necessary, heat and pressure are applied and extrusion is performed, and ionizing radiation is applied to cure.
From the viewpoint of visibility that a plurality of shaped grooves are arranged at a predetermined pitch in one direction in the film and the shape does not impair the parallelism of light, when cut in the thickness direction of the film perpendicular to one direction It is preferable that the cross-sectional shape becomes substantially rectangular.
Here, as shown in FIGS. 3A to 3E, the substantially rectangular shape includes a square, a rectangle (FIG. 3A), a trapezoid (FIG. 3B), and a top portion in the thickness direction (FIG. 3). 3 (c)) or the bottom (FIG. 3 (d)) may be rounded, and the tangent line connecting each corner may be a straight line or a curved line ((FIG. 3 (e)).
In addition, the (colored) absorbing portion preferably has a width of 50 μm or less because stripes are visible and the appearance is impaired when the width Wa is wide. Moreover, the pitch Pa and height Ta of an absorption part can be set according to the absorption performance, transparency, and productivity which are calculated | required, and it is preferable that pitch Pa shall be 0.1-500 micrometers and height 0.1-750 micrometers.
The light-absorbing composition filled in the molded groove part conveys the molded film 11f having the molded groove part 12a supported by the base film 10 along the roll and absorbs sunlight. As a nanoparticle to be applied, for example, an ionizing radiation-curable solvent-free resin composition containing fine particles such as ATO or ITO is applied by die coating or the like, and the groove portion 12a of the light transmissive film 11f (a film having a shaped groove portion) is applied. To fill. In the case of a material having a high viscosity and is difficult to fill, the groove portion 12a may be appropriately embedded with a squeegee or the like, or a plurality of times may be applied.

As the binder of the ionizing radiation-curable resin-free resin composition constituting the light-absorbing composition, that is, the resin composition containing fine particles such as ATO or ITO, for example, a transparent resin having a predetermined refractive index is used. An ultraviolet curable resin or an electron beam curable resin having an ionizing radiation curing action is used. Some of them are directly cured by ionizing radiation, but the curing reaction is generally caused through a substance called a catalyst or an initiator that excites the reaction.
In order to cause a curing action with ultraviolet rays having a wavelength of 300 to 400 nm, it is common to mix several percent of a substance called a photoinitiator that excites a reaction in the ultraviolet region. Photoinitiators include those based on ketones and acetophenones, such as Sandley 1000, Darocur 1163, Darocur 1173, Irgacure 183, Irgacure 651, and the like, and are appropriately selected according to the type (wavelength characteristics) of ionizing radiation for curing. it can. Examples of ionizing radiation curable resins include reactive oligomers (epoxy acrylate, urethane acrylate, polyether acrylate, polyester acrylate, polythiol, etc.) and reactive monomers (vinyl pyrrolidone, 2-ethylhexyl acrylate, β-hydroxy). Acrylate, tetrahydrofurfuryl acrylate, etc.) are appropriately selected. In order to adjust the fluidity of the ionizing radiation curable light absorber before curing, the kind of reactive oligomer and the composition ratio of the low molecular weight reactive monomer having a low viscosity may be appropriately changed.

Nanoparticles that absorb sunlight that can be used in the heat ray control film of the present invention are metal oxide infrared absorbers, such as titanium oxide, zinc oxide, and indium oxide, for the purpose of absorbing sunlight heat rays (infrared rays). , Tin-doped indium oxide (ITO), tin oxide, antimony-doped tin oxide (ATO), and at least one nanoparticle selected from the group consisting of zinc sulfide. Among these, antimony-doped tin oxide ( ATO) or tin-doped indium oxide (ITO) nanoparticles are preferred. From the viewpoint of suppressing haze, the average particle size of the added nanoparticles, particularly ATO and ITO nanoparticles, is preferably 1 to 300 nm, and more preferably 1 to 100 nm.
In the present invention, from the viewpoint of efficiently absorbing infrared rays, the metal oxide infrared absorber is preferably contained in the absorbent composition in an amount of 1 to 50% by mass, and preferably 5 to 45% by mass. More preferably, it is more preferably 10 to 40% by mass, and particularly preferably 15 to 35% by mass. Moreover, when using ATO, it is preferable to contain 3-30 mass% from a transparency viewpoint.

Furthermore, 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, etc., but if m and n fall within the above ranges, they are useful. Infrared absorption characteristics can be obtained.

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.

<Surface protective layer>
The surface protective layer is provided by applying a curable resin composition having a hard coat function to the surface on the surface side where the absorbing portion group is provided and curing the composition. Application of the curable resin composition is a known method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, etc., preferably so that the weight after curing is usually about 1 to ²⁰ g / m ^2. Perform by gravure 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 thickness of the surface protective layer is preferably 3 to 10 μm, and if it is less than 3 μm, the role as the protective layer may be insufficient. If it exceeds 10 μm, the cost increases.
The surface protective layer does not have to be solvent-free, but at least a hard coat function is required to protect the lower layer and satisfy physical properties such as scratch resistance required for window pasting films, etc., and is a taber in accordance with JIS K5400. The change in haze before and after the wear test is preferably 3 or less. When the haze value exceeds 3, the function as the surface protective layer is insufficient, the construction is damaged, the appearance is impaired, and the visibility may be deteriorated.
In the present invention, the “surface on the side where the absorbing portion group is provided” means the surface on the side where the absorbing portion is exposed, for example, the surface of S1 in FIG. 2, before the surface protective layer is provided. The surface intended to be protected by providing a surface protective layer having a hard coat function shall be pointed out.

(Curable resin)
There is no restriction | limiting in particular as curable resin used for a surface protective layer, A thermosetting resin, an ionizing radiation curable resin, etc. are mentioned.
Thermosetting resins include epoxy resin, phenol resin, urea resin, unsaturated polyester resin, melamine resin, alkyd resin, polyimide resin, silicone resin, hydroxyl functional acrylic resin, carboxyl functional acrylic resin, amide functional copolymer Examples include coalescence and urethane resin.
The mode of crosslinking and curing of these resins is not particularly limited, and includes the following modes. Epoxy resin is reaction with amine, acid catalyst, carboxylic acid, acid anhydride, hydroxyl group, dicyandiamide or ketimine, phenol resin is reaction between base catalyst and excess aldehyde, urea resin is polycondensation under alkaline or acidic conditions Reaction, unsaturated polyester resin is a co-condensation reaction of maleic anhydride and diol, melamine resin is a heat polycondensation reaction of methylol melamine, alkyd resin is a reaction by air oxidation of unsaturated groups introduced into side chains, The polyimide resin is a reaction in the presence of an acid or a weak alkali catalyst, or a reaction with an isocyanate compound (in the case of a two-component type), the silicone resin is a condensation reaction in the presence of an acid catalyst of a silanol group, hydroxyl group functionality Acrylic resin is a reaction between hydroxyl group and amino resin of its own (in the case of 1-pack type), carboxyl functional acrylic resin is Reactions with carboxylic acids such as acrylic acid or methacrylic acid and epoxy compounds, amide functional copolymers react with hydroxyl groups or self-condensation reactions, urethane resins include hydroxyl group-containing polyester resins, polyether resins, acrylic resins, etc. Crosslinking and curing are promoted by reaction of the resin with an isocyanate compound or a modified product thereof. A crosslinking agent or a curing agent utilizing these reactions is usually used.
In the present invention, an ionizing radiation curable resin is more preferable from the viewpoint of curability, and an electron beam curable resin is particularly preferable because it is not necessary to use a solvent.

(Ionizing radiation curable resin)
The ionizing radiation curable resin refers to a resin having an energy quantum capable of crosslinking and polymerizing molecules in an electromagnetic wave or a charged particle beam, that is, a resin that is crosslinked and cured by irradiation with ultraviolet rays or electron beams. Specifically, it can be appropriately selected from polymerizable monomers, polymerizable oligomers, or prepolymers conventionally used as ionizing radiation curable resins.

  Typically, a (meth) acrylate monomer having a radical polymerizable unsaturated group in the molecule is suitable as the polymerizable monomer, and among them, a polyfunctional (meth) acrylate is preferable. Here, “(meth) acrylate” means “acrylate or methacrylate”, and other similar ones have the same meaning. The polyfunctional (meth) acrylate is not particularly limited as long as it is a (meth) acrylate having two or more ethylenically unsaturated bonds in the molecule. Specifically, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified diphosphate ( (Meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylo Propane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris ( Acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. Is mentioned. These polyfunctional (meth) acrylates may be used singly or in combination of two or more.

  In the present invention, a monofunctional (meth) acrylate can be used in combination with the polyfunctional (meth) acrylate as long as the object of the present invention is not impaired, for the purpose of lowering the viscosity. Examples of monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl ( Examples include meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isobornyl (meth) acrylate. These monofunctional (meth) acrylates may be used alone or in combination of two or more.

Next, as the polymerizable oligomer, an oligomer having a radical polymerizable unsaturated group in the molecule, for example, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate The system etc. are mentioned.
Here, the epoxy (meth) acrylate oligomer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. . Further, a carboxyl-modified epoxy (meth) acrylate oligomer obtained by partially modifying this epoxy (meth) acrylate oligomer with a dibasic carboxylic acid anhydride can also be used. The urethane (meth) acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. Examples of polyester (meth) acrylate oligomers include esterification of hydroxyl groups of polyester oligomers having hydroxyl groups at both ends obtained by condensation of polycarboxylic acid and polyhydric alcohol with (meth) acrylic acid, It can be obtained by esterifying the hydroxyl group at the end of the oligomer obtained by adding alkylene oxide to a monovalent carboxylic acid with (meth) acrylic acid. The polyether (meth) acrylate oligomer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid.

  Furthermore, other polymerizable oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity that have (meth) acrylate groups in the side chain of polybutadiene oligomers, and silicone (meth) acrylate oligomers that have polysiloxane bonds in the main chain. In a molecule such as an aminoplast resin (meth) acrylate oligomer modified with an aminoplast resin having many reactive groups in a small molecule, or a novolak epoxy resin, bisphenol epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. There are oligomers having a cationic polymerizable functional group.

When an ultraviolet curable resin is used as the ionizing radiation curable resin, it is desirable to add about 0.1 to 5 parts by mass of the photopolymerization initiator with respect to 100 parts by mass of the resin. The initiator for photopolymerization can be appropriately selected from those conventionally used and is not particularly limited. For example, for a polymerizable monomer or polymerizable oligomer having a radically polymerizable unsaturated group in the molecule. Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2 -Phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1 - 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4′-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2 -Tertiary butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal It is done.
Examples of the polymerizable oligomer having a cationic polymerizable functional group in the molecule include aromatic sulfonium salts, aromatic diazonium salts, aromatic iodonium salts, metallocene compounds, and benzoin sulfonic acid esters.
Moreover, as a photosensitizer, p-dimethylbenzoic acid ester, tertiary amines, a thiol type sensitizer, etc. can be used, for example.

  In the present invention, it is preferable to use an electron beam curable resin as the ionizing radiation curable resin. This is because the electron beam curable resin can be made solvent-free, is more preferable from the viewpoint of environment and health, and does not require a photopolymerization initiator, and can provide stable curing characteristics.

In addition, various additives such as a filler for improving scratch resistance and silicone for providing slipperiness may be added to the surface protective layer.
Moreover, when using by external pasting, weathering agents, such as a ultraviolet absorber (UVA) and a hindered amine light stabilizer (HALS), can also be added to a surface protective layer.

(Filler)
In the present invention, the filler used in the hard coat layer as desired includes inorganic and organic fillers. Examples of inorganic substances include spherical particles such as α-alumina, silica, kaolinite, iron oxide, diamond, and silicon carbide. Particles. Examples of the particle shape include a sphere, an ellipsoid, a polyhedron, a scale shape, and the like. Although there is no particular limitation, a spherical shape is preferable.

  Of these inorganic fillers, silica is one of the preferred ones. Silica improves friction resistance and does not hinder the transparency of the surface protective layer as a hard coat functional layer. As the silica, it is possible to appropriately select and use conventionally known silica, and for example, colloidal silica can be preferably mentioned. Colloidal silica is preferable because it hardly affects the transparency even when the amount added is increased. As the particle diameter of silica, those having a primary particle diameter of 5 to 1000 nm are preferably used, more preferably 10 to 50 nm, and particularly preferably 10 to 30 nm. When silica having a primary particle diameter of 1000 nm or less is used, transparency is secured. Moreover, the primary particle diameter of the silica used does not need to be one kind, and it is also possible to mix and use silica having different primary particle diameters. As a compounding quantity of a silica, it is preferable that it is a ratio of 1-20 mass parts with respect to 100 mass parts of electron beam curable resins. Spherical α-alumina or colloidal alumina is also preferable because of its high hardness, a large effect on improving wear resistance, and relatively easy to obtain spherical particles.

  On the other hand, organic fillers include synthetic resin beads such as cross-linked acrylic resin and polycarbonate resin. The particle size is preferably about 30 to 200% of the normal film thickness. It is preferable that a compounding quantity is a ratio of about 1-20 mass parts with respect to 100 mass parts of resin which forms a surface protective layer as a hard-coat functional layer.

(Weatherproof function)
In order to impart a weathering function to the surface protective layer of the present invention, a weathering agent may be added to the surface protective layer. Examples of the ultraviolet absorber (UVA) that can be added include benzotriazole ultraviolet absorbers, triazine ultraviolet absorbers, benzophenone ultraviolet absorbers, salicylate ultraviolet absorbers, and acrylonitrile ultraviolet absorbers.
Examples of the hindered amine light stabilizer (HALS) may include Tinuvin 123 ”,“ Tinuvin 144 ”,“ Tinuvin 292 ”, and“ Tinuvin 111FDL ”manufactured by BASF.

(Hydrophilic function)
Further, by adding a hydrophilic agent such as an alkyl silicate to the surface protective layer and making it hydrophilic, it is possible to impart a hydrophilic function such as antifouling property and antifogging property.
In order to impart a hydrophilic function, the ionizing radiation curable resin composition forming the coating layer as the surface protective layer may contain a hydrophilizing agent having excellent self-cleaning performance and visible light permeability. . As the hydrophilizing agent used in the present invention, a silicate compound or an alkyl silicate having a reactive functional group is preferable.

<Silicate compound having a reactive functional group>
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 particularly preferably a silicate compound having a reactive functional group having reactivity with the ionizing radiation curable resin forming the coating layer. Preferred examples of the reactive functional group include a functional group having an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, and an allyl group, and at least one selected from these is preferable. Of these, a (meth) acryloyl group is preferable.
The silicate compound having a reactive functional group 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.
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 a reactive functional group is preferably a silicate compound represented by the general formula (1) or a condensate thereof, and the condensate is preferably a 2-30 mer, and a 2-10 mer. It is more preferable. 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, carbonyl group (—CO—), ether bond (—O—), ester bond (—COO—), thioether bond (—S—), amide bond (—CONH—), 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 a reactive functional group is preferably 1 to 15 parts by mass, more preferably 3 to 15 parts by mass, and still more preferably 5 to 15 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin. . When the content of the silicate compound is within the above range, a good cross-linked state with the ionizing radiation curable resin can 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.

From the viewpoint of improving self-cleaning properties, n ₃ is preferably 1 to 40, more preferably 10 to 30, and still 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.

  Further, in the heat ray control film of the present invention, from the viewpoint of suppressing the reflection / refraction of light at the interface and improving the visibility, the refractive index n1 of the light transmitting portion and the light absorbing material composition constituting the absorbing portion group The difference from the refractive index n2 of the object is preferably 0.03 or less, and more preferably the same.

《Glass》
The heat ray control film of the present invention is generally a glass made of an inorganic material such as silicate glass containing silica dioxide as a main component, quartz glass (hereinafter referred to as “inorganic glass”) or a 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 inorganic glass and organic glass include transparent glass, colored transparent glass, frosted glass, tempered glass, and multilayer glass.
In the present invention, as means for “distributing” the heat ray control sheet to inorganic glass or organic glass, application by an adhesive layer described later, thermal fusion by a base sheet, thermal adhesion with an organic glass, or the like Etc.

(Organic glass)
Although various resins can be used as the resin constituting the organic glass, a resin that can be melted is preferable from the viewpoint of molding such as injection molding and 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.

(Adhesive layer)
The heat ray absorbing film of the present invention preferably has an adhesive layer on the surface opposite to the surface protective layer. For example, as shown in FIG. 2, in order to adhere the opposite surface S3 of the side S2 to be bonded to the molded film 11f of the base film 10 to an adherend such as a window glass, a pressure-sensitive adhesive layer 14 is necessary. Is provided. The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 14 is not particularly limited, and can be appropriately selected and used depending on the situation from various conventionally known pressure-sensitive adhesives. System, 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.
Further, a release sheet (not shown) can be attached to the pressure-sensitive adhesive layer 14 in order to protect the pressure-sensitive adhesive layer 14. Examples of the release sheet 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 on 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 made into the base film 10 The adhesive layer 14 may be transferred to the surface S3 opposite to the side S2 to be bonded to the molded film 11f, and the release sheet may be adhered as it is.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In addition, the various characteristics of the heat ray | wire control film which has the surface protective layer obtained in each example were evaluated according to the following procedure.

(Scratch resistance)
Taber abrasion hardness was measured according to JISK5400. The abrasion resistance test was performed under the following conditions, and the difference in haze values (conforming to JISK6714) before and after the test was measured to obtain the Taber abrasion hardness.
(Condition): Wear wheel: CS-10F, load: 250 g, rotation speed: 100 times

(Adhesion of surface protective layer (weather resistance))
A heat ray control film (weather-resistant hard coat film) having a surface protective layer obtained in Examples and Comparative Examples was set on a metal weather manufactured by Daipura Wintes Co., Ltd., and light conditions (illuminance: 60 mW / cm ² , black panel temperature) 63 hours at a temperature of 63 ° C. and a humidity of 50% RH for 20 hours, 4 hours under conditions of condensation (illuminance: 0 mW / cm ² , a black panel temperature of 30 ° C., a humidity of 98% RH) 10 Second) was conducted for 100 hours.
About the weather-resistant hard coat film which performed the said weather resistance test, operation which affixed the Nichiban cello tape (trademark) on the surface and peeled rapidly was performed. At this time, whether or not each layer provided on the substrate sheet peeled was confirmed by visual observation, and the presence or absence of peeling was evaluated.
○: No peeling is observed in any of the layers.
X: Peeling is observed in any layer.

(Total light transmittance)
It measured with the haze meter based on JISK6714.

Production Example A liquid urethane acrylate-based prepolymer and dipentaerythritol hexaacrylate monomer on one surface S2 of the base film 10 as a transparent support made of a transparent biaxially stretched PET film having a thickness of 188 μm and a continuous belt shape And a liquid UV curable resin comprising a mixed solution of benzophenone photoinitiator was applied so that the film thickness after curing was 155 μm.
Next, it is continuous in the circumferential direction along the surface direction of the roll mold surface, the main cut surface is a rectangle having a height of 150 μm, a width on the plate surface side of 30 μm, and a width on the side far from the plate of 30 μm. UV curable resin applied between a roll mold and a PET film formed with a ridge group (same shape and reverse concavo-convex shape as the absorbing section group) in which a plurality of ridges are arranged in parallel with each other at a period of 60 μm. The ultraviolet curable resin is irradiated with ultraviolet rays from a mercury lamp in a state where the transparent resin layer is sandwiched, whereby the ultraviolet curable resin is cross-linked and cured to form a transparent resin layer, and then the roll mold is released to form the transparent resin layer on the surface. The main cut surface is a rectangle with a height of 150 μm, a transparent resin layer surface side length of 30 μm, and a PET film side length of 30 μm. Groove portion 12a composed of groove groups The embossing has been film 11f having a surface formed on one surface S2 of the substrate film 10. In 100 parts by mass of a transparent acrylic UV curable prepolymer, 10 parts by mass of ATO nanoparticles (average particle diameter 100 nm), 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: Irgacure 184) as a photopolymerization initiator 2 parts by mass) (manufactured by Ciba Specialty Chemicals) was mixed to prepare a liquid light-absorbing material composition.
The liquid composition is applied to the groove 12a of the shaped film 11f, and then the coating film is squeezed with an iron doctor blade to scrape and remove only the liquid composition outside the (concave) groove, The light-absorbing material composition was filled only in the concave groove 12a to form a heat ray control film in which the absorbing portion groups 11 and 11 were not cured.

Example 1
The following surface protective layer resin composition is applied by die coating at a coating amount of 5 g / m ² on the surface S1 side filled with the light-absorbing material composition of the uncured heat ray control film. Finally, the electron beam was irradiated under conditions of 165 keV and 5 Mrad (50 kGy) to crosslink and cure the electron beam curable resin composition to obtain a heat ray control film having a surface protective layer 13 having a thickness of 5 μm.
The resin composition for the surface protective layer is as follows.
・ Urethane acrylate: 100 parts by mass Product name “Unidic V-4005” manufactured by DIC ・ Hydroxyphenyltriazine-based UV absorber: 3 parts by mass Product name “Tinuvin 479”, manufactured by BASF Japan Ltd. ・ Reactive functional group Light stabilizer (reactive HALS): 3 parts by mass 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate,
Product name “Sanol LS-3410”, manufactured by Nippon Emulsifier Co., Ltd. ・ Methyl silicate Product name “MS-56S”, manufactured by Mitsubishi Chemical Corporation About the surface protective layer of the heat ray control film having the obtained surface protective layer, the above method is used. Scratch resistance (HAZE value), adhesion of the surface protective layer (weather resistance), and total light transmittance were measured. The results are shown in Table 1.

Example 2
A heat ray control film having a surface protective layer was produced in the same manner as in Example 1 except that in Example 1, urethane acrylate was replaced with epoxy acrylate (Arakawa Chemical Industries, Ltd., beam set 1200). The performance evaluation results are shown in Table 1.

Comparative Example 1
The absorbing part group was cured by irradiating ultraviolet rays onto the surface of the heat ray control film in which the absorbing part group was uncured and filled with the light absorbing material composition. A PET film (A4100, manufactured by Toyobo Co., Ltd.) having a thickness of 100 μm was attached to the absorbent portion group side through a transparent adhesive layer having a thickness of 100 μm to form a surface protective layer. Table 1 shows the evaluation results of the performance of the obtained heat ray control film.

Comparative Example 2
The absorbing part group was cured by irradiating ultraviolet rays onto the surface of the heat ray control film in which the absorbing part group was uncured and filled with the light absorbing material composition. A hard coat treated PET film obtained by coating a PET film (thickness: 100 μm, manufactured by Toyobo Co., Ltd., A4100) with 5 g / m ² of caprolactone urethane acrylate (molecular weight: 2000 to 5000) on this absorbing portion group side, and adhesive A surface protective layer was obtained by pasting through the layers. Table 1 shows the evaluation results of the performance of the obtained heat ray control film.

The heat ray control film of the present invention is more advantageous than applying a hard coat film to the film in terms of the number of steps, cost, transmittance, adhesion, film thickness, etc. by forming the surface protective layer by coating, light control A heat ray control film that is economically highly practical as one type of sheet can be provided.
In addition, since the heat ray control film of the present invention has a scratch-resistant (scratch-resistant) surface protective layer, there is little surface damage in the application to a glass window or the like. It can be effectively used as a heat ray control film that suppresses heat ray uptake resulting in an increase in temperature and can prevent a decrease in room temperature without inhibiting heat ray uptake in winter.

10. Base film 11. Light transmissive part 11f. Shaped film (light transmission film)
12 Absorber 12a. Molding groove 13. Surface protective layer (hard coat layer, UV absorption layer, hydrophilic agent layer)
14 Adhesive layer 20. Building 21. Side wall 22. Window 100. Heat ray control film

Claims (6)

A heat ray control film comprising a light transmission part that transmits sunlight and an absorption part group made of a light-absorbing material containing nanoparticles that absorb sunlight, each in a plane direction,
The absorbent portion group is composed of an absorbent portion that is arranged in the surface direction of the film and has a thickness in the cross-sectional direction of the film,
And the heat ray | wire control film which provides the surface protective layer which consists of hardened | cured material of a curable resin composition on the surface in which this absorption part group was provided, and has a hard-coat function at least.   The heat ray control film according to claim 1, wherein the haze value of the surface protective layer before and after the Taber abrasion test in accordance with JIS K5400 is 3 or less.   The heat ray | wire control film of Claim 1 or 2 formed by further providing a weather resistance function to the said surface protective layer.   The heat ray control film according to any one of claims 1 to 3, wherein the surface protective layer is provided with a hydrophilic function.   The heat ray control film according to any one of claims 1 to 4, wherein the surface protective layer is a cured product of an ionizing radiation curable resin composition.   The glass which consists of an inorganic or organic material characterized by having arranged the heat ray | wire control film of any one of Claims 1-5.