JP5775349B2 - Heat ray shielding laminated glass interlayer film and heat ray shielding laminated glass - Google Patents

Description

  The present invention relates to a laminated glass having a heat ray shielding function used for windows for buildings, vehicles, railways, and the like, and more particularly, to a heat ray shielded laminated glass having a color tone adjusted.

  Conventionally, in order to reduce the air conditioning load of buildings such as office buildings and buses, passenger cars, trains, etc., railways, etc., these windows are required to have a function of shielding near infrared rays (heat rays) in sunlight. It has been. As heat shielding glass, kneaded heat ray absorbing glass in which ions such as Fe, Cr and Ti are introduced into the glass itself to give heat ray absorbing property, heat ray reflecting glass in which a metal oxide film is deposited, indium A thin film of a transparent conductive film such as tin oxide (ITO) or tin oxide (ATO) formed by dry deposition by sputtering or the like, a noble metal film / metal oxide film mainly composed of a metal oxide film / Ag film, etc. A heat ray shielding glass (Patent Document 1) on which a laminated heat ray shielding film (also referred to as Low-E film) is formed has been proposed and put into practical use.

  In addition, a coating film containing tungsten oxide and / or composite tungsten oxide fine particles and a UV-excited anti-coloring agent on a glass substrate as a heat ray shielding glass having high heat ray shielding properties and high visible light transmittance. The one formed in the above has been developed (Patent Document 2).

  On the other hand, a laminated glass having a structure in which a transparent adhesive layer such as a polyvinyl butyral (PVB) film or an ethylene-vinyl acetate copolymer (EVA) film is sandwiched between glass plates as an intermediate film is known. Laminated glass has improved penetration resistance due to the presence of an intermediate film, and even if it is destroyed for the purpose of theft or intrusion, it cannot be opened freely, so it is also useful as a security glass. . Further, glass fragments damaged by an external impact remain adhered to the intermediate film, which is useful for preventing scattering of the fragments. Such a laminated glass is used as a windshield or side glass of an aircraft, an automobile, or a window glass of a building. In general, laminated glass has excellent adhesion and penetration resistance, and is excellent in safety, but does not consider the heat ray shielding properties as described above.

  In addition, the glass or laminated glass used for the windows of the above buildings, vehicles, railways, etc. has a glass color tone from the viewpoint of functionality such as design or suppression of visible light transmission and addition of heat ray shielding. Changes may be required. In such a case, a colored glass in which the color tone of the glass itself is adjusted is generally used. Colored glass is usually colored with transition metal ions or metal oxides by adding a transition metal to a glass raw material as a coloring source (Patent Document 3). The colored glass of Patent Document 3 has relatively high visible light permeability and a heat ray shielding function.

JP 2001-226148 A JP 2007-269523 A JP-A-6-227839

  However, the colored glass as in Patent Document 3 is generally expensive, and is colored by the addition of transition metal as described above. Therefore, the environmental load is high, and glasses having different colors cannot be melted in the same melting furnace. There is a problem that it is difficult to recycle.

  Furthermore, in order to obtain high heat ray shielding in colored glass, since a considerably dark color tone is required, visible light transmittance is also greatly reduced.

  Therefore, an object of the present invention is to adjust the color tone without using colored glass, and to provide high heat ray shielding properties without greatly reducing visible light transmittance, and an intermediate film for heat ray shielding laminated glass Is to provide.

  Moreover, the objective of this invention is providing the heat ray shielding laminated glass using this intermediate film.

  The above object is an intermediate film for heat ray shielding laminated glass comprising a laminate comprising a heat ray shielding layer containing tungsten oxide and / or composite tungsten oxide, and an adhesive resin layer, wherein the adhesive resin layer and / or Another layer constituting the laminate includes a colorant and is achieved by an intermediate film for heat ray-shielding laminated glass characterized by having a total light transmittance (JISK7105 (1981)) of 40% or more. .

In order to adjust the color tone of the laminated glass, it is considered possible by adding a colorant to the interlayer film for laminated glass. However, as in the case of using colored glass, the visible light transmittance is not significantly reduced, and is high. It is difficult to obtain heat ray shielding properties. In the present invention, the interlayer film for laminated glass is composed of a laminate including a heat ray shielding layer containing tungsten oxide and / or composite tungsten oxide (hereinafter also referred to as (composite) tungsten oxide) and an adhesive resin layer. In addition, by adding a colorant to another layer of the laminate, the color tone of the laminated glass is adjusted according to the design and other demands, and the visible light transmittance with a relatively high total light transmittance is used. Thus, it is possible to obtain an intermediate film for heat ray shielding laminated glass that imparts high heat ray shielding properties. This is because the heat ray shielding layer containing tungsten oxide and / or composite tungsten oxide has high visible light transmittance and excellent heat ray shielding properties, so that it has a great influence on the color tone adjustment by the colorant when combined with the colorant. This is considered to be because the heat ray shielding property can be improved. In addition, since the other layer contains a colorant, it is possible to make an intermediate film for heat ray-shielding laminated glass, which is easier to adjust the color tone, and the other layer is made of the transparent plastic film, By providing on the surface on the side where the heat ray shielding layer is not provided, an intermediate film for heat ray shielding laminated glass, which is easier to manufacture, can be obtained. Moreover, it can also be set as the laminated glass from which color tone differs on both surfaces as needed, and the application on a design is attained.

Preferred embodiments of the intermediate film for heat ray shielding laminated glass of the present invention are as follows.
(1) The laminate further includes a transparent plastic film, the heat ray shielding layer is provided on one surface of the transparent plastic film, and the adhesive resin layers are on both sides of the transparent plastic film. Is provided. Thereby, it can be set as the intermediate film for heat ray shielding laminated glass which is easier to manufacture and handle.
( 2 ) The colorant is an organic pigment and / or an inorganic pigment. In particular, inorganic pigments are preferred.
( 3 ) The inorganic pigment is a carbon pigment and / or a metal oxide pigment.
( 4 ) The colorant is at least one selected from the group consisting of a black pigment, a brown pigment, and a red pigment.
( 5 ) The colorant is at least one selected from the group consisting of carbon black, aniline black, and magnetite type triiron tetroxide.
( 6 ) The content of the colorant is 0.0002 to 1.0 g / m <2> based on the area of the heat ray shielding laminated glass interlayer.
( 7 ) The colorant is carbon black, and the content of the carbon black is 0.0002 to 0.02 g / m ² on the basis of the area of the heat ray shielding laminated glass interlayer.
( 8 ) The colorant is aniline black, and the content of the aniline black is 0.001 to 1.0 g / m ² on the basis of the area of the heat ray shielding laminated glass interlayer.
( 9 ) The adhesive resin layer is a layer made of an ethylene vinyl acetate copolymer.
( 10 ) Tungsten oxide is represented by the general formula WyOz (where W represents tungsten, O represents oxygen, and 2.2 ≦ z / y ≦ 2.999), and the composite tungsten oxide is General formula MxWyOz (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, 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, Hf, Os, Bi, 1 or more elements inner shell selected in I, W is tungsten, O represents oxygen, and 0.001 ≦ x / y ≦ 1,2.2 ≦ z / y ≦ 3).

  Further, the above object is achieved by a heat ray shielding laminated glass characterized in that the heat ray shielding laminated glass intermediate film of the present invention is sandwiched between two transparent substrates and these are bonded and integrated. . Thereby, without using colored glass, the color tone is adjusted according to the design and other demands, and a heat ray shielding laminated glass having a relatively high visible light permeability and a high heat ray shielding property is obtained.

  According to the present invention, the interlayer film for laminated glass has a high visible light transmittance, a heat ray shielding layer containing tungsten oxide and / or composite tungsten oxide having excellent heat ray shielding properties, and an adhesive resin layer. Since the colorant is contained in the adhesive resin layer of the laminate and / or another layer constituting the laminate, the color tone of the laminated glass is adjusted according to the design demands. In addition, it is possible to obtain an intermediate film for heat ray shielding laminated glass that maintains a relatively high visible light transmittance and gives high heat ray shielding properties without greatly affecting the color tone.

  Therefore, the heat ray-shielding laminated glass of the present invention does not use colored glass, has a color tone adjusted according to design requirements, has a relatively high visible light permeability, and has a high heat ray shielding property. It is a laminated glass, and it can be said that it is a heat ray shielding laminated glass that has a low environmental load and can reduce the air conditioning load.

FIG. 1 is a schematic sectional view showing a typical example of the intermediate film for heat ray shielding laminated glass of the present invention. FIG. 2 is a schematic cross-sectional view showing another example of the intermediate film for heat ray shielding laminated glass of the present invention. FIG. 3 is a schematic cross-sectional view showing a typical example of the heat ray shielding laminated glass of the present invention.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. FIG. 1 is a schematic sectional view showing a typical example of the intermediate film for heat ray shielding laminated glass of the present invention, and FIG. 2 is a schematic sectional view showing another example of the intermediate film for heat ray shielding laminated glass of the present invention. . The interlayer film for heat ray shielding laminated glass of the present invention comprises a laminate comprising a heat ray shielding layer containing tungsten oxide and / or composite tungsten oxide and an adhesive resin layer, and the adhesive resin layer and / or the laminate thereof. The colorant is contained in another layer that constitutes. The fine particles of tungsten oxide and / or composite tungsten oxide do not substantially block visible light, and are excellent in the blocking function of near infrared rays (particularly, near infrared rays in the vicinity of 850 to 1150 nm where the amount of radiation from sunlight is large). Excellent heat shielding properties. As a result, the color tone of the laminated glass is adjusted according to the demands of the design and the like, and the total light transmittance (JISK 7105 (1981)) is relatively high visible with 40% or more without affecting the color tone adjustment. An intermediate film for heat ray-shielding laminated glass that maintains light transmittance and imparts high heat ray shielding properties can be obtained. In the present invention, the total light transmittance of the interlayer film for laminated glass is obtained by preparing a laminated glass using the interlayer film for laminated glass and a transparent glass plate, and measuring the total light transmittance of the laminated glass. To do.

  The intermediate film 20 for heat ray shielding laminated glass of the present invention in FIG. 1 includes an adhesive resin layer 12A, a heat ray shielding layer 14 containing tungsten oxide and / or composite tungsten oxide, a transparent plastic film 13, a colorant layer 15, and an adhesive resin. The layer 12B is a laminated body that is laminated and integrated in this order. Usually, the heat ray shielding layer 14 is first formed on the surface of the rectangular transparent plastic film 13, and the colorant layer 15 is formed on the other surface. Thereafter, the transparent plastic film 13 provided with the heat ray shielding layer 14 and the colorant layer 15 is sandwiched from both sides by the adhesive resin layers 12A and 12B and bonded and integrated.

  The colorant layer 15 is not formed on the surface of the transparent plastic film 13 on which the heat ray shielding layer 14 is formed, but on the surface on which the heat ray shielding layer 14 is formed, on the upper layer or the lower layer of the heat ray shielding layer 14. Also good. As a design application of the heat ray shielding laminated glass, the colorant layer 15 is formed on the surface of the transparent plastic film 13 on the side where the heat ray shielding layer 14 is not formed in that it can be adjusted to different colors on the front and back as necessary. Preferably it is formed. In this case, if necessary, another colorant layer may be formed on the upper layer or the lower layer of the heat ray shielding layer 14.

  In the present invention, the transparent plastic film 13 may be omitted. For example, the heat ray shielding layer 14 is directly formed on the surface of the adhesive resin layer 12A, and the colorant layer 15 and the adhesive resin layer 12B are formed thereon. good. Moreover, the colorant layer 15 and the adhesive resin layer 12B may be formed on the adhesive resin layer 12A as a heat ray shielding layer by containing tungsten oxide and / or composite tungsten oxide. The heat ray shielding layer 14 can be easily manufactured by applying a binder resin composition-containing coating solution containing tungsten oxide and / or composite tungsten oxide to a plastic film, and can form a uniform layer. It is preferable to include the transparent plastic film 13.

  Further, the intermediate film 30 for heat-shielding laminated glass in FIG. 2 includes an adhesive resin layer 22A, a heat ray shielding layer 24 containing tungsten oxide and / or composite tungsten oxide, a transparent plastic film 23, and an adhesive resin containing a colorant. The layer 22B is a stacked body that is stacked and integrated in this order. In FIG. 1, the colorant layer 15 is provided as another layer containing the colorant. However, as shown in FIG. 2, the colorant can also be contained in the adhesive resin layer. If necessary, an adhesive resin layer containing a colorant and a colorant layer as another layer containing a colorant can be used in combination.

  In the example of FIG. 2, the transparent plastic film 23 may be omitted. For example, the heat ray shielding layer 24 is directly formed on the surface of the adhesive resin layer 22A, and the adhesive resin layer 22B containing a colorant is formed thereon. May be. Alternatively, the adhesive resin layer 22A may contain tungsten oxide and / or composite tungsten oxide to form a heat ray shielding layer, and the adhesive resin layer 22B containing a colorant may be formed thereon. Since the heat ray shielding layer 24 is easy to manufacture by applying a binder resin composition-containing coating solution containing tungsten oxide and / or composite tungsten oxide to a plastic film and curing it, a uniform layer can be formed. It is preferable to include the transparent plastic film 23.

[Colorant]
In the present invention, the colorant is not particularly limited as long as it can correct the color tone of the laminated glass. Examples of the colorant include dyes, inorganic pigments, and organic pigments. The dye is preferably an inorganic pigment or an organic pigment because it may sublime when mixed in a colorant layer or an adhesive resin layer, or may fade when used for a long time. Furthermore, inorganic pigments are preferred because they are excellent in stability such as light resistance. Examples of the organic pigment include black pigments such as aniline black and red pigments such as alizarin lake. As the inorganic pigment, a carbon pigment and / or a metal oxide pigment is preferable. For example, black pigments such as carbon black, ivory black, mars black, peach black, lamp black, magnetite type triiron tetroxide, brown pigments such as amber, burton amber, yellow walker, van dyke brown, senna, burton senna, bengara, Red pigments such as molybdenum red and cadmium red, orange pigments such as reddish yellow lead and chrome vermilion, blue pigments such as ultramarine, bitumen, cobalt blue and cerulean blue, and green pigments such as chrome oxide, pyridian, emerald green and cobalt green Yellow pigments such as yellow lead, cadmium yellow, yellow iron oxide and titanium yellow, and purple pigments such as manganese violet and mineral violet. It is preferable that it is at least one selected from the group consisting of a black pigment, a brown pigment, and a red pigment in terms of being effective in adjusting the color tone. In particular, it is preferably at least one selected from the group consisting of carbon black, aniline black, and magnetite-type triiron tetroxide because it is stable, can be adjusted in color with a small amount, and is easy to use. In the present invention, these colorants can be used alone or in combination of two or more.

As shown in FIG. 1, the colorant may be contained in the colorant layer as a layer separate from the adhesive resin layer, or may be contained in the adhesive layer as shown in FIG. The content of the colorant is not particularly limited in any case as long as the visible light transmittance with a total light transmittance of 40% or more of the interlayer film is obtained, and can be appropriately adjusted depending on the type of the colorant. Considering the conditioning effect and the visible light transmittance of the color, based on the area of the heat ray shielding laminated glass intermediate film, preferably 0.0002~1.0g / m ^2, more 0.001~0.02g / m ² preferable. In particular, when the colorant is carbon black, it is preferably 0.0002 to 0.02 g / m ² on the basis of the area of the heat ray-shielding laminated glass interlayer, and when it is aniline black, the heat ray-shielding laminated glass. It is preferable that it is 0.001-1.0 g / m < ² > on the basis of the area of an intermediate film.

[Colorant layer]
As shown in FIG. 1, when the colorant is contained in the colorant layer as a separate layer, the colorant layer preferably contains the above-mentioned colorant, binder resin, and, if necessary, a resin composition containing an organic solvent. It is a hardened layer. As the binder resin contained in the resin composition, known thermoplastic resins, ultraviolet curable resins, and thermosetting resins can be used. For example, silicone resin, fluorine resin, olefin resin, acrylic resin, polyester resin, epoxy resin, urethane resin, phenol resin, resorcinol resin, urea resin, melamine resin, furan resin, ethylene vinyl acetate copolymer (EVA), and polyvinyl Examples include butyral resin (PVB). Silicone resin, fluororesin, olefin resin, and acrylic resin are preferable in terms of weather resistance.

  Examples of silicone resins include straight silicone varnish and modified silicone varnish. Straight silicone varnish is usually produced by hydrolysis polymerization of phenyltrichlorosilane, diphenyldichlorosilane, methyltrichlorosilane, and dimethyldichlorosilane (when used, it is generally cured at 100 ° C. or higher after application). The modified silicone varnish is obtained by reacting a silicone varnish with a resin such as alkyd, polyester, acrylic, or epoxy.

Examples of fluororesins include polytetrafluoroethylene (PTFE), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), and polyvinylidene fluoride (PVDF). ), Polychlorotrifluoroethylene (PCTFE), tetrafluoroethylene / ethylene copolymer (ETFE), fluoroethylene vinyl ether (FEVE), ethylene chlorotrifluoroethylene copolymer (ECTFE), and the like.
Examples of the olefin resin monomer include polyethylene, polypropylene, and chlorinated polyethylene.

  Examples of acrylic resin monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth) acrylate. , Pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, ethylhexyl (meth) acrylate, nonyl (Meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylic , Alkyl (meth) acrylates such as stearyl (meth) acrylate and isostearyl (meth) acrylate; hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3- Hydroxyalkyl (meth) acrylates such as hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate; phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl ( Phenoxyalkyl (meth) acrylates such as (meth) acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, -Alkoxyalkyl (meth) acrylates such as butoxyethyl (meth) acrylate and 2-methoxybutyl (meth) acrylate; polyethylene glycol mono (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene Polyglycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, etc. Alkylene glycol (meth) acrylate; Pentaerythri Examples include tall tri (meth) acrylate, pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and glycerin di (meth) acrylate. Examples of the acrylic resin include homopolymers of these monomers, copolymers of two or more kinds, and copolymers of the monomers and other copolymerizable monomers.

  These resins may be used alone or in combination of two or more. A thermoplastic resin and an ultraviolet curable resin are preferable, and an ultraviolet curable resin is particularly preferable. The ultraviolet curable resin is preferable because it can be cured in a short time and has excellent productivity. The resin composition contains a thermal polymerization initiator and a photopolymerization initiator depending on the curing method.

  Thermal polymerization initiators include t-butyl hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, dimyristyl peroxydicarbonate, t-butyl peroxyacetate, t-butyl peroxy (2 -Ethyl hexanoate), organic peroxides such as cumyl peroxy octoate, and azo compounds such as azobisisobutyronitrile and azobiscyclohexanenitrile.

  As the photopolymerization initiator, any compound suitable for the properties of the resin can be used. For example, acetophenone such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1 Benzoin series such as benzyl dimethyl ketal, benzophenone, 4-phenylbenzophenone, benzophenone series such as hydroxybenzophenone, thioxanthone series such as isopropylthioxanthone, 2-4-diethylthioxanthone, and other special types include methylphenyl glyoxylate Etc. can be used. Particularly preferably, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1, Examples include benzophenone. These photopolymerization initiators may be optionally selected from one or more known photopolymerization accelerators such as benzoic acid type or tertiary amine type such as 4-dimethylaminobenzoic acid. It can be used by mixing at a ratio. Moreover, a photoinitiator can be used individually by 1 type or in mixture of 2 or more types. In particular, 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF Japan, Irgacure (registered trademark) 184) is preferable. Generally the quantity of a photoinitiator is 0.1-10 mass% with respect to a resin composition, Preferably it is 0.1-5 mass%.

  When forming a colorant layer, a transparent plastic using a suitable coating machine such as a bar coater, a resin composition containing a colorant, a binder resin, a polymerization initiator if necessary, and an organic solvent if necessary A method of coating on a film and drying, followed by heating or curing by irradiation with light such as ultraviolet rays, X-rays, γ-rays or electron beams is preferably used as necessary. Drying is preferably performed by heating the resin composition coated on the plastic film at 60 to 150 ° C, particularly 70 to 110 ° C. The drying time may be about 1 to 10 minutes. The light irradiation can be performed by irradiating ultraviolet rays emitted from light rays such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp.

  Examples of the organic solvent used in the resin composition include aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and butyl acetate, and alcohols such as isopropyl alcohol. Can do.

  The content of the colorant is generally 0.00005 to 0.25 parts by mass, preferably 0.00025 to 0.1 parts by mass with respect to 100 parts by mass of the binder resin. The thickness of the colorant layer is generally 0.1 to 50 μm, preferably 0.5 to 5 μm.

[Adhesive resin layer]
As the adhesive resin used for the adhesive resin layer, fluorine resin, silicone resin, olefin resin, acrylic resin, ethylene vinyl acetate copolymer (EVA), and polyvinyl butyral resin (PVB) are preferable, EVA and PVB are more preferable, EVA is particularly preferred. By using EVA, it is possible to ensure excellent adhesion between each layer and the glass surface of the laminated glass. The vinyl acetate content in EVA is 23 to 38 parts by mass, particularly preferably 23 to 28 parts by mass with respect to 100 parts by mass of EVA. If the vinyl acetate content is less than 23 parts by mass, the transparency of the resin obtained when crosslinking and curing at a high temperature is not sufficient. Conversely, if it exceeds 38 parts by mass, the moldability may decrease. Moreover, it is preferable that EVA has a melt flow index (MFR) of 1.0 to 30.0 g / 10 min, particularly 1.5 to 5.0 g / 10 min.

  When forming an adhesive resin layer with the resin composition (EVA resin composition) containing EVA, it is preferable that an EVA resin composition contains an organic peroxide as a crosslinking agent. Furthermore, various additives such as a crosslinking aid and a plasticizer can be contained as necessary.

  Any organic peroxide may be used in combination as long as it decomposes at a temperature of 100 ° C. or higher and generates radicals. The organic peroxide is generally selected in consideration of the film formation temperature, the adjustment conditions of the composition, the curing (bonding) temperature, the heat resistance of the adherend, and the storage stability. In particular, those having a decomposition temperature of 70 hours or more with a half-life of 10 hours are preferred.

  Examples of the organic peroxide include t-butylperoxy-2-ethylhexyl monocarbonate, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di ( t-butylperoxy) hexane-3-di-t-butyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, dicumyl peroxide, α, α′-bis (t-butylperoxyisopropyl) benzene, n-butyl-4,4-bis (t-butylperoxy) valerate, 1,1-bis (t-butylperoxy) cyclohexane, 1, 1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, t-butylperoxybenzoate, benzoyl peroxide , T-butyl peroxyacetate, methyl ethyl ketone peroxide, 2,5-dimethylhexyl-2,5-bisperoxybenzoate, butyl hydroperoxide, p-menthane hydroperoxide, p-chlorobenzoyl peroxide, hydroxyheptyl peroxide Oxide, chlorohexanone peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, cumyl peroxy octoate, succinic peroxide, acetyl peroxide, m-toluoyl peroxide, t-butyl peroxide isobutyl Mention may be made of leo and 2,4-dichlorobenzoyl peroxide.

  The content of the organic peroxide in the EVA resin composition is preferably 1 to 10 parts by mass, particularly 1 to 5 parts by mass with respect to 100 parts by mass of EVA.

  Examples of the crosslinking aid include esters obtained by esterifying a plurality of acrylic acid or methacrylic acid with glycerin, trimethylolpropane, pentaerythritol, and the like, and polyfunctional compounds of triallyl cyanurate and triallyl isocyanurate.

  Although it does not specifically limit as a plasticizer, Generally the ester of a polybasic acid and the ester of a polyhydric alcohol are used. Examples thereof include dioctyl phthalate, dihexyl adipate, triethylene glycol-di-2-ethylbutyrate, butyl sebacate, tetraethylene glycol diheptanoate, and triethylene glycol dipelargonate. One type of plasticizer may be used, or two or more types may be used in combination. The content of the plasticizer is preferably in the range of 5 parts by mass or less with respect to 100 parts by mass of EVA.

  EVA resin composition is used to improve or adjust various physical properties of the film (optical properties such as mechanical strength, adhesiveness and transparency, heat resistance, light resistance, crosslinking speed, etc.), especially to improve mechanical strength. , An acryloxy group-containing compound, a methacryloxy group-containing compound and / or an epoxy group-containing compound are preferably included.

  The acryloxy group-containing compound and methacryloxy group-containing compound to be used are generally acrylic acid or methacrylic acid derivatives, and examples thereof include acrylic acid or methacrylic acid esters and amides. Examples of ester residues include linear alkyl groups such as methyl, ethyl, dodecyl, stearyl, lauryl, cyclohexyl group, tetrahydrofurfuryl group, aminoethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group. Group, 3-chloro-2-hydroxypropyl group. In addition, polyhydric alcohols such as ethylene glycol, triethylene glycol, polypropylene glycol, polyethylene glycol, trimethylolpropane, and pentaerythritol, and esters of acrylic acid or methacrylic acid can also be used. Examples of amides include diacetone acrylamide.

Examples of epoxy-containing compounds include triglycidyl tris (2-hydroxyethyl) isocyanurate, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and phenol. (Ethyleneoxy) ₅ glycidyl ether, pt-butylphenyl glycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, glycidyl methacrylate, butyl glycidyl ether can be mentioned.

  A silane coupling agent can be added to the EVA resin composition as an adhesion improver in order to further enhance the adhesive force between the adhesive resin layer and each layer such as a glass plate and a transparent plastic film.

  Examples of this silane coupling agent include γ-chloropropylmethoxysilane, vinylethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltri Methoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrichlorosilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- Mention may be made of β- (aminoethyl) -γ-aminopropyltrimethoxysilane. These silane coupling agents may be used alone or in combination of two or more. Moreover, it is preferable that content of the said compound is 5 mass parts or less with respect to 100 mass parts of EVA.

  The EVA resin composition preferably further contains an ultraviolet absorber for suppressing yellowing of the resin and preventing deterioration of the heat ray shielding layer. As the ultraviolet absorber, benzophenone compounds, triazine compounds, benzoate compounds, hindered amine compounds, and the like can be used. Benzophenone compounds are particularly preferred.

  Preferred examples of the benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-n-octylbenzophenone, 2,2 ′. 4,4′-tetrahydroxybenzophenone and 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, particularly 2-hydroxy-4-n-octylbenzophenone and 2,2′-dihydroxy-4 4,4'-dimethoxybenzophenone is preferred.

  The content of the ultraviolet absorber in the EVA resin composition is preferably 0.05 to 1.0 part by mass, particularly preferably 0.1 to 0.5 part by mass with respect to 100 parts by mass of EVA.

  As described above, a colorant may be included in the adhesive resin layer as shown in FIG. In this case, the content of the colorant is generally 0.00005 to 0.02 parts by mass, preferably 0.0002 to 0.01 parts by mass with respect to 100 parts by mass of EVA.

  In order to produce an adhesive resin layer by using an EVA resin composition, a method of forming the above-described EVA resin composition by mixing and then forming it by ordinary extrusion molding, calendar molding (calendering), or the like is used. The EVA resin composition is preferably mixed by heating and kneading at a temperature of 40 to 100 ° C, particularly 60 to 90 ° C. Moreover, it is preferable that the heating temperature at the time of film formation is a temperature at which the organic peroxide does not react or hardly reacts. For example, it is preferable to set it as 40-100 degreeC, especially 60-90 degreeC.

  Alternatively, a layered product can be obtained by dissolving the EVA resin composition in an organic solvent, and coating the solution on a suitable support with a suitable coating machine (coater) and drying to form a coating film. . The thickness of the adhesive resin layer is preferably 50 μm to 2 mm, particularly 400 μm to 1 mm.

[Heat ray shielding layer]
In the present invention, the heat ray shielding layer contains tungsten oxide and / or composite tungsten oxide as a heat ray shielding agent. In general, fine particles of tungsten oxide and / or composite tungsten oxide are used dispersed in a binder resin composition. The fine particles of tungsten oxide and / or composite tungsten oxide do not substantially block visible light, and are excellent in the blocking function of near infrared rays (particularly, near infrared rays in the vicinity of 850 to 1150 nm where the amount of radiation from sunlight is large). Excellent heat shielding properties. The content of fine particles of tungsten oxide and / or composite tungsten oxide in the heat ray shielding layer is not particularly limited, but generally 0.1 to 50 g and 0.1 to 20 g are preferable per 1 m ² , and further 0.1 to 20 g. 10 g is preferred. By including the fine particles of the composite tungsten oxide in such a range, it becomes possible to achieve both the heat ray shielding property and the visible light permeability of the obtained heat ray shielding glass.

  The tungsten oxide is an oxide represented by the general formula WyOz (W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999), and the composite tungsten oxide is the tungsten oxide. The element M (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, 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, 1 or more elements selected from Ta, Re, Be, Hf, Os, Bi, and I). As a result, free electrons are generated in WyOz, including the case of z / y = 3.0, the free electron-derived absorption characteristics are expressed in the near infrared region, and a near infrared absorbing material (heat ray shielding material near 1000 nm). (Also called). In the present invention, composite tungsten oxide is preferable.

In the tungsten oxide fine particles represented by the general formula WyOz (W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999), the preferable composition range of tungsten and oxygen is When the composition ratio of oxygen is less than 3, and the heat ray shielding material is described as WyOz, 2.2 ≦ z / y ≦ 2.999. If the value of z / y is 2.2 or more, it is possible to avoid the appearance of a WO ₂ crystal phase other than the objective in the heat ray shielding material and to obtain chemical stability as a material. Therefore, it can be applied as an effective infrared shielding material. On the other hand, if the value of z / y is 2.999 or less, a required amount of free electrons is generated and an efficient heat ray shielding material can be obtained.

  From the viewpoint of stability, the composite tungsten oxide fine particles are generally MxWyOz (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, 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, One or more elements selected from Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and I, W is tungsten, O is oxygen, (0.001 ≦ x / Y ≦ 1, 2.2 ≦ z / y ≦ 3) The alkali metal is a group 1 element of the periodic table excluding hydrogen, and the alkaline earth metal is the second element of the periodic table. Group elements and rare earth elements are Sc, Y and lanthanoid elements.

  In particular, from the viewpoint of improving optical characteristics and weather resistance as a heat ray shielding material, the M element is one or more of Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn. Some are preferred. The composite tungsten oxide is preferably treated with a silane coupling agent. Excellent dispersibility is obtained, and an excellent infrared cut function and transparency are obtained.

  If the value of x / y indicating the addition amount of the element M is larger than 0.001, a sufficient amount of free electrons is generated, and a sufficient shielding effect can be obtained. As the amount of the element M added increases, the supply amount of free electrons increases and the heat ray shielding effect increases, but the value of x / y is saturated at about 1. Moreover, if the value of x / y is smaller than 1, it is preferable because an impurity phase can be prevented from being generated in the fine particle-containing layer.

  As for the value of z / y indicating the control of the oxygen amount, in the composite tungsten oxide represented by MxWyOz, in addition to the same mechanism as that of the heat ray shielding material represented by WyOz described above, z / y = Even in 3.0, since there is a supply of free electrons due to the addition amount of the element M described above, 2.2 ≦ z / y ≦ 3.0 is preferable, and 2.45 ≦ z / y ≦ 3.0 is more preferable. It is.

  Further, when the composite tungsten oxide fine particles have a hexagonal crystal structure, the transmission of the fine particles in the visible light region is improved and the absorption in the near infrared region is improved.

When the cation of the element M is added to the hexagonal void, the transmission in the visible light region is improved and the absorption in the near infrared region is improved. Here, generally, when the element M having a large ionic radius is added, the hexagonal crystal is formed. Specifically, Cs, K, Rb, Tl, In, Ba, Sn, Li, Ca, Sr, When Fe is added, hexagonal crystals are easily formed. Of course, other elements may be added as long as the additive element M exists in the hexagonal void formed by the WO ₆ unit, and is not limited to the above elements.

  When the composite tungsten oxide fine particles having a hexagonal crystal structure have a uniform crystal structure, the addition amount of the additive element M is preferably 0.2 or more and 0.5 or less in terms of x / y, more preferably 0. .33. When the value of x / y is 0.33, it is considered that the additive element M is arranged in all of the hexagonal voids.

  Besides hexagonal crystals, tetragonal and cubic tungsten bronzes also have a heat ray shielding effect. These crystal structures tend to change the absorption position in the near infrared region, and the absorption position tends to move to the longer wavelength side in the order of cubic <tetragonal <hexagonal. Further, the accompanying absorption in the visible light region is small in the order of hexagonal crystal <tetragonal crystal <cubic crystal. For this reason, it is preferable to use hexagonal tungsten bronze for applications that transmit light in the visible light region and shield light in the infrared region. Moreover, it is preferable from the viewpoint of improving weather resistance that the surface of the composite tungsten oxide fine particles of the present invention is coated with an oxide containing one or more of Si, Ti, Zr, and Al.

  From the viewpoint of maintaining transparency, the average particle size of the composite tungsten oxide fine particles used in the present invention is preferably 10 to 800 nm, particularly preferably 10 to 400 nm. This is because particles smaller than 800 nm do not completely block light due to scattering, can maintain visibility in the visible light region, and at the same time can efficiently maintain transparency. In particular, when importance is attached to transparency in the visible light region, it is preferable to further consider scattering by particles. When importance is attached to the reduction of scattering by the particles, the average particle size is preferably 20 to 200 nm, and more preferably 20 to 100 nm.

  The average particle diameter of the fine particles is a number average value obtained by observing the cross section of the heat ray shielding layer with a transmission electron microscope at a magnification of about 1,000,000 and calculating the projected area circle equivalent diameter of at least 100 fine particles.

  The composite tungsten oxide fine particles are produced, for example, as follows.

  The tungsten oxide fine particles represented by the general formula WyOz and / or the composite tungsten oxide fine particles represented by MxWyOz are obtained by heat-treating a tungsten compound starting material in an inert gas atmosphere or a reducing gas atmosphere. Can do.

  The tungsten compound starting material is obtained by dissolving tungsten trioxide powder, tungsten oxide hydrate, tungsten hexachloride powder, ammonium tungstate powder, or tungsten hexachloride in alcohol and then drying. Tungsten oxide hydrate powder, or tungsten oxide hydrate powder obtained by dissolving tungsten hexachloride in alcohol and then adding water to precipitate and drying it, or ammonium tungstate It is preferable that it is at least one selected from a tungsten compound powder obtained by drying an aqueous solution and a metal tungsten powder.

  Here, when producing tungsten oxide fine particles, it is preferable to use tungsten oxide hydrate powder or tungsten compound powder obtained by drying an ammonium tungstate aqueous solution from the viewpoint of the ease of the production process. More preferably, when producing the composite tungsten oxide fine particles, an ammonium tungstate aqueous solution or a tungsten hexachloride solution is further used from the viewpoint that each element can be easily and uniformly mixed when the starting material is a solution. preferable. These raw materials are used and heat-treated in an inert gas atmosphere or a reducing gas atmosphere to obtain tungsten oxide fine particles and / or composite tungsten oxide fine particles having the above-mentioned particle diameter.

  The composite tungsten oxide fine particles represented by the general formula MxWyOz containing the element M are the same as the tungsten compound starting material of the tungsten oxide fine particles represented by the general formula WyOz described above. A tungsten compound contained in the form of a simple substance or a compound is used as a starting material. Here, in order to produce a starting material in which each component is uniformly mixed at the molecular level, it is preferable to mix each material with a solution, and the tungsten compound starting material containing the element M is dissolved in a solvent such as water or an organic solvent. Preferably it is possible. Examples thereof include tungstate, chloride, nitrate, sulfate, oxalate, oxide, and the like containing element M, but are not limited to these and are preferably in the form of a solution.

Here, the heat treatment condition in the inert atmosphere is preferably 650 ° C. or higher. The starting material heat-treated at 650 ° C. or higher has sufficient coloring power and is efficient as heat ray shielding fine particles. As the inert gas, an inert gas such as Ar or N ₂ is preferably used. As the heat treatment conditions in the reducing atmosphere, first, the starting material is heat-treated at 100 to 650 ° C. in a reducing gas atmosphere, and then heat-treated at a temperature of 650 to 1200 ° C. in an inert gas atmosphere. . The reducing gas at this time is not particularly limited, but H ₂ is preferable. When H ₂ is used as the reducing gas, the volume ratio of H ₂ is preferably 0.1% or more, more preferably 2% or more, as the composition of the reducing atmosphere. If it is 0.1% or more, the reduction can proceed efficiently.

The raw material powder reduced with hydrogen contains a magnetic phase and exhibits good heat ray shielding characteristics, and can be used as heat ray shielding fine particles in this state. However, since hydrogen contained in tungsten oxide is unstable, application may be limited in terms of weather resistance. Therefore, a more stable heat ray shielding fine particle can be obtained by heat-treating this tungsten oxide compound containing hydrogen at 650 ° C. or higher in an inert atmosphere. The atmosphere during the heat treatment at 650 ° C. or higher is not particularly limited, but N ₂ and Ar are preferable from an industrial viewpoint. By the heat treatment at 650 ° C. or higher, a magnetic phase is obtained in the heat ray shielding fine particles, and the weather resistance is improved.

  The composite tungsten oxide fine particles of the present invention are preferably surface-treated with a coupling agent such as a silane coupling agent, a titanate coupling agent, or an aluminum coupling agent. Silane coupling agents are preferred. Thereby, the affinity with the binder resin is improved, and various physical properties are improved in addition to transparency and heat ray shielding properties.

  Examples of silane coupling agents include γ-chloropropylmethoxysilane, vinylethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxy. Silane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrichlorosilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β -(Aminoethyl) -γ-aminopropyltrimethoxysilane and trimethoxyacrylsilane can be mentioned. Vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, and trimethoxyacrylsilane are preferred. These silane coupling agents may be used alone or in combination of two or more. Moreover, it is preferable to use 5-20 mass parts of content of the said compound with respect to 100 mass parts of microparticles | fine-particles.

  As the binder resin contained in the binder resin composition, known thermoplastic resins, ultraviolet curable resins, and thermosetting resins can be used. For example, silicone resin, fluorine resin, olefin resin, acrylic resin, polyester resin, epoxy resin, urethane resin, phenol resin, resorcinol resin, urea resin, melamine resin, furan resin, EVA, PVB, and the like can be given. Silicone resin, fluororesin, olefin resin, and acrylic resin are preferable in terms of weather resistance. These resins may be used alone or in combination of two or more. A thermoplastic resin and an ultraviolet curable resin are preferable, and an ultraviolet curable resin is particularly preferable. The ultraviolet curable resin is preferable because it can be cured in a short time and has excellent productivity. The binder resin composition contains a thermal polymerization initiator and a photopolymerization initiator depending on the curing method. Examples of these binder resins and polymerization initiators are the same as those in the above-described colorant layer.

  Moreover, when using a heat ray shielding layer as an adhesive resin layer, adhesive resin compositions, such as the EVA resin composition similar to the above-mentioned adhesive resin layer, can be used as a binder resin composition.

  The heat ray shielding layer may also have a color tone adjusting function by containing a neon-emitting selective absorption dye. As selective absorption dyes for neon emission, porphyrin dyes, azaporphyrin dyes, cyanine dyes, squarylium dyes, anthraquinone dyes, phthalocyanine dyes, polymethine dyes, polyazo dyes, azurenium dyes, diphenylmethane dyes, A triphenylmethane type pigment | dye can be mentioned. Such a selective absorption dye is required to have a selective absorption of neon emission near 585 nm and a small absorption at other visible light wavelengths. Therefore, the absorption maximum wavelength is 560 to 610 nm, and the absorption spectrum half width is What is 40 nm or less is preferable.

  In addition, an ultraviolet absorber, a colorant, an antioxidant and the like may be further added to the heat ray reflective layer as long as the optical characteristics are not greatly affected.

  When forming the heat ray shielding layer, the binder resin composition containing the above (composite) tungsten oxide, a binder resin, a polymerization initiator if necessary, and an organic solvent if necessary is applied to a suitable coating material such as a bar coater. A method in which the film is coated on a transparent plastic film using a machine and dried, and then cured by heating or irradiation with light such as ultraviolet rays, X-rays, γ-rays, and electron beams is preferably used. Drying is preferably performed by heating the binder resin composition coated on the plastic film at 60 to 150 ° C, particularly 70 to 110 ° C. The drying time may be about 1 to 10 minutes. The light irradiation can be performed by irradiating ultraviolet rays emitted from light rays such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp.

  Examples of the organic solvent include aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and butyl acetate, and alcohols such as isopropyl alcohol.

  The heat ray shielding layer preferably contains 10 to 500 parts by mass, more preferably 20 to 500 parts by mass, and particularly preferably 30 to 300 parts by mass of the (composite) tungsten oxide with respect to 100 parts by mass of the binder resin. The thickness of the heat ray shielding layer is generally 0.1 to 50 μm, preferably 0.1 to 10 μm, particularly preferably 0.1 to 5 μm.

[Transparent plastic film]
The transparent plastic film is not particularly limited as long as it is a transparent plastic film (meaning “transparent to visible light”). Examples of the plastic film include a polyethylene terephthalate (PET) film, a polyethylene naphthalate (PEN) film, and a polyethylene butyrate film, and a PET film is preferred. The thickness of the plastic film is preferably 10 to 400 μm, particularly 20 to 200 μm. Further, in order to improve the adhesiveness, the plastic film surface may be subjected in advance to an adhesion treatment such as a corona treatment, a plasma treatment, a flame treatment, and a primer layer coating treatment.

[Heat ray shielding laminated glass]
The heat ray shielding laminated glass of the present invention has a structure in which the intermediate film for heat ray shielding laminated glass of the present invention is sandwiched between two glass plates and these are bonded and integrated. In the present invention, “glass” in the heat ray-shielding laminated glass means all transparent substrates, and therefore “heat ray-shielding laminated glass” sandwiches an intermediate film for heat ray-shielding laminated glass on a transparent substrate. Means something.

  FIG. 3 shows a typical example of the heat ray shielding laminated glass of the present invention. As illustrated, in the heat ray shielding laminated glass of the present invention, the intermediate film 40 for heat ray shielding laminated glass of the present invention is sandwiched between two glass plates 41A and 41B, and these are bonded and integrated. The intermediate film 40 for heat ray shielding laminated glass has a transparent plastic film 33 provided with a heat ray shielding layer 34 and a colorant layer 35 sandwiched between an adhesive resin layer 32A and an adhesive resin layer 32B, and these are bonded and integrated. Is. In addition, the heat ray shielding laminated glass of this invention should just be a laminated structure as shown in FIG. 3, and when each layer of the intermediate film for heat ray shielding laminated glass of this invention manufactures heat ray shielding laminated glass, it separates. It may be laminated and bonded and integrated.

Since the heat-shielding laminated glass of the present invention includes the intermediate film for heat-shielding laminated glass of the present invention in the laminated structure, the color tone is adjusted according to the design and other requirements without using colored glass, and compared. It is a heat ray shielding laminated glass having high visible light transmittance and high heat ray shielding properties.
In order to produce the heat ray shielding laminated glass of the present invention, the intermediate film for heat ray shielding laminated glass of the present invention is sandwiched between two transparent substrates, and the obtained laminate is degassed and then heated. A method of pressing down is used. These processes are performed using, for example, a vacuum bag method, a nip roll method, or the like. Thereby, the adhesive resin layer is cured, and the heat ray shielding laminate and the transparent substrate can be bonded and integrated. For example, when EVA resin is used for the adhesive resin layer, the laminate is pre-pressed at a temperature of 80 to 120 ° C., and is heat treated at 100 to 150 ° C. (especially around 130 ° C.) for 10 minutes to 1 hour. Is crosslinked. Further, the heat treatment may be performed under pressure. At this time, it is preferable that the laminate is pressed while being pressurized at a pressure of 1.0 × 10 ³ Pa to 5.0 × 10 ⁷ Pa. Cooling after crosslinking is generally performed at room temperature, and in particular, the faster the cooling, the better.

  The glass plate in the present invention may be a transparent substrate, for example, a glass plate such as green glass, silicate glass, inorganic glass plate, non-colored transparent glass plate, polyethylene terephthalate (PET), polyethylene naphthalate (PEN). Alternatively, a plastic substrate or film such as polyethylene butyrate or polymethyl methacrylate (PMMA) may be used. A glass plate is preferable in terms of weather resistance, impact resistance and the like. As for the thickness of a glass plate, about 1-20 mm is common. The same glass plate may be used on each side of the heat ray shielding laminated glass, or different base materials may be used in combination. The combination is determined in consideration of the strength of the base material and the use of the laminated glass.

  The heat ray-shielding laminated glass of the present invention is a window glass for buildings and vehicles (automobiles, railway vehicles, ships), electronic devices such as plasma displays, doors and walls of various devices such as refrigerators and heat insulation devices, etc. Can be used in various applications.

Hereinafter, the present invention will be described in more detail with reference to examples.
1. Production of interlayer film for heat ray-shielding laminated glass (1) Production of transparent adhesive resin layer (transparent EVA) A transparent EVA sheet having a thickness of 0.4 mm was produced as a transparent adhesive resin layer by a calendar molding method using the following composition as a raw material. Obtained. The kneading of the blend was carried out at 80 ° C. for 15 minutes, the calender roll temperature was 80 ° C., and the processing speed was 5 m / min.
(Combination)
EVA (vinyl acetate content 25% by mass,
Product name: Ultrasen 635, manufactured by Tosoh Corporation): 100 parts by mass crosslinking agent (Perbutyl E; manufactured by NOF Corporation (t-butylperoxy-2-ethylhexyl monocarbonate)): 2.2 mass Part silane coupling agent (KBM503; manufactured by Shin-Etsu Chemical Co., Ltd.): 1.0 part by mass UV absorber (Ubinal 3049; manufactured by BASF Japan Ltd.): 0.5 part by mass

(2) Production of Colorant-Containing Adhesive Resin Layer (1) Using the compound of the adhesive resin layer of (1), which is compounded with carbon black or aniline black so as to have the content shown in Table 2, Similarly, a black EVA sheet having a thickness of 0.4 mm was obtained as a colorant-containing adhesive resin layer.

(3) Preparation of PET film with heat ray shielding layer A PET film was prepared by applying a composition having the following composition on a PET film (thickness: 100 μm) using a bar coater and drying it in an oven at 80 ° C. for 2 minutes. A heat ray shielding layer (thickness: 5 μm) was produced thereon.
(Combination)
Dipentaerythritol hexaacrylate: 100 parts by mass Photopolymerization initiator (Irgacure (registered trademark) 184): 5 parts by mass Cs _0.33 WO ₃ (average particle size 80 nm): 20 parts by mass Methyl isobutyl ketone: 200 parts by mass

(4) Production of PET film with heat ray shielding layer and colorant layer On the surface of the PET film with heat ray shielding layer produced in (3) on which the heat ray shielding layer is not formed, the following coating for forming a colorant layer The working solution was applied by a bar coater and dried at 120 ° C. for 2 minutes to form a colorant layer having a thickness of 3 μm.
(Combination)
Dipentaerythritol hexaacrylate: 100 parts by weight Photopolymerization initiator (Irgacure (registered trademark) 184): 5 parts by weight Colorant (carbon black or aniline black): blending amount that results in the contents shown in Table 1 Methyl isobutyl ketone: 200 parts by mass

(5) Production of interlayer film [Examples 1 to 5]
Using the two transparent EVA sheets obtained in (1), the heat ray shielding layer obtained in (4) and the PET film with a colorant layer are sandwiched from both sides, for the heat ray shielding laminated glass of Examples 1 to 5. An interlayer film was obtained (see FIG. 1).
[Examples 6 to 12, Comparative Examples 1 to 3]
Using one transparent EVA sheet obtained in (1) and one black EVA sheet obtained in (2), the PET film with a heat ray shielding layer obtained in (3) was sandwiched from both sides, and the test was carried out. The interlayer film for heat ray shielding laminated glass of Examples 6-12 and Comparative Examples 1-3 was obtained (refer FIG. 2).
[Comparative Example 4]
Two black EVA sheets obtained in (2) were bonded together to obtain an intermediate film of Comparative Example 4.
[Comparative Example 5]
Using two transparent EVA sheets obtained in (1), the PET film with a heat ray shielding layer obtained in (3) was sandwiched from both sides to obtain an intermediate film of Comparative Example 5.

2. Preparation of laminated glass [Examples 1 to 12, Comparative Examples 1 to 5]
The interlayer films for laminated glass of Examples 1 to 12 and Comparative Examples 1 to 5 obtained above were laminated by sandwiching them with a glass plate (thickness 3 mm), and this was put in a rubber bag and vacuum degassed, 110 ° C. Pre-crimped at a temperature of Next, this pre-pressed glass was put in an oven and pressurized for 30 minutes under the condition of a temperature of 130 ° C. to produce a laminated glass.

3. Evaluation method (1) Total light transmittance The total light transmittance (based on JISK7105 (1981)) of each laminated glass was measured (using a fully automatic direct reading haze computer HGM-2DP (manufactured by Suga Test Instruments Co., Ltd.)). . In the present invention, the value of the total light transmittance is the total light transmittance of each intermediate film. A total light transmittance of 40% or more was evaluated as ○, and a value less than 40% was evaluated as ×.
(2) Solar radiation transmittance It measured based on JISR3106.
(3) Solar heat acquisition rate It measured based on JISR3106.
The solar heat acquisition rate is a kind of index indicating the heat shielding performance, and is a numerical value indicating the ratio of the amount of heat flowing into the room when the solar radiation incident on the glass is 1.0. That is, it means the sum of the component that directly permeates the glass (sunlight transmittance) and the component that reheats from the glass to the room (reheat radiation rate to the room). It can be said that the smaller the numerical value, the higher the heat shielding performance. As for the solar radiation acquisition rate, 0.53 or less was evaluated as ◯, 0.54 to 0.55 as Δ, and 0.56 or more as X.

4). Evaluation results The results are shown in Tables 1 and 2.

As shown in Tables 1 and 2, the intermediate films of Examples 1 to 12 having a heat ray shielding layer and containing a colorant so that the total light transmittance is 40% or more adjust the color tone, A low solar transmittance and a solar heat gain rate were shown. In Examples 6 and 10 with a small content of the colorant, the total light transmittance is high, but the solar heat acquisition rate is Δ, and the content of the colorant is large. The rate fell. Therefore, the preferred range of the colorant, for example, in the case of carbon black 0.0002~0.02g / m ^2, that the case of aniline black is 0.001~1.0g / m ² was shown. Moreover, when comparing the intermediate films having the same colorant content, since the solar heat acquisition rate is lower in Examples 1 to 5 than in Examples 6 to 12, the colorant layer containing the colorant is separated. It has been shown that the formation is more preferable than containing the colorant in the adhesive resin layer.

  On the other hand, in Comparative Example 4 in which the color tone was adjusted only by the colorant-containing adhesive resin layer, and in Comparative Example 5 having a heat ray shielding layer and no colorant, the solar heat gain rate was x.

  As described above, the heat ray-shielding laminated glass of the present invention has a color tone adjusted according to the design and other demands, and a heat ray-shielding laminated glass having relatively high visible light permeability and high heat ray shielding properties is obtained. It was shown that.

  In addition, this invention is not limited to said embodiment and Example, A various deformation | transformation is possible within the range of the summary of invention.

  It is possible to reduce the air-conditioning load on buildings such as office buildings and buses, passenger cars, trains, etc., railways, etc., and to provide a heat ray shielding glass capable of adjusting the color tone according to design and other demands at low cost.

12A, 12B Adhesive layer 22A, 22B Adhesive layer 32A, 32B Adhesive layer 13, 23, 33 Transparent plastic film 14, 24, 34 Heat ray shielding layer 15, 35 Colorant layer 20, 30, 40 For heat ray shielding laminated glass Intermediate film 41A, 41B Glass plate

Claims (12)

Transparent plastic film,
A heat ray shielding layer provided on one surface of the transparent plastic film and containing tungsten oxide and / or composite tungsten oxide;
An intermediate film for heat ray shielding laminated glass comprising a laminate comprising at least an adhesive resin layer provided on the heat ray shielding layer ,
On the surface of the transparent plastic film where the heat ray shielding layer is not provided, another layer is provided,
It said further layer contains a silicone resin, a fluorine resin, a binder resin selected from olefin resins and acrylic resins, et al Canal group, a colorant,
And the intermediate film for heat ray shielding laminated glass characterized by having a total light transmittance (JISK7105 (1981)) of 40% or more. The intermediate film for heat ray shielding laminated glass according to claim 1, wherein the adhesive resin layer is also provided on the surface of the other layer opposite to the transparent plastic film . The interlayer film for heat ray-shielding laminated glass according to claim 1 or 2 , wherein the colorant is an organic pigment and / or an inorganic pigment. The interlayer film for heat ray-shielding laminated glass according to claim 3 , wherein the inorganic pigment is a carbon pigment and / or a metal oxide pigment. The intermediate film for heat ray-shielding laminated glass according to any one of claims 1 to 4 , wherein the colorant is at least one selected from the group consisting of a black pigment, a brown pigment, and a red pigment. The intermediate film for heat ray-shielding laminated glass according to any one of claims 1 to 5 , wherein the colorant is at least one selected from the group consisting of carbon black, aniline black, and magnetite-type triiron tetroxide. . Content of the said coloring agent is 0.0002-1.0g / m < ² > on the basis of the area of a heat ray shielding laminated glass intermediate film, For heat ray shielding laminated glass of any one of Claims 1-6 . Interlayer film. The colorant is a carbon black, the content of the carbon black, based on the area of the heat ray shielding laminated glass intermediate film, it claims 1-7 is 0.0002~0.02g / ^{m 2} The intermediate film for heat ray-shielding laminated glass according to item 1. The coloring agent is aniline black, the content of the aniline black, based on the area of the heat ray shielding laminated glass intermediate film, it claims 1-7 is 0.001~1.0g / ^{m 2} The intermediate film for heat ray-shielding laminated glass according to item 1. The interlayer film for heat ray-shielding laminated glass according to any one of claims 1 to 9 , wherein the adhesive resin layer is a layer made of an ethylene vinyl acetate copolymer. Tungsten oxide is represented by the general formula WyOz (where W is tungsten, O represents oxygen and 2.2 ≦ z / y ≦ 2.999), and the composite tungsten oxide is represented by the general formula MxWyOz. (However, M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, 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 , Hf, Os, Bi, 1 or more elements inner shell selected in I, W is tungsten, O represents oxygen, and 0.001 ≦ x / y ≦ 1,2.2 ≦ z / y ≦ 3 claim 1-10 noise, characterized by being represented by a is) Heat ray shielding laminated glass intermediate film according to any one of claims. The heat ray-shielding laminated glass intermediate film according to any one of claims 1 to 11 is sandwiched between two transparent base materials, and these are bonded and integrated. .

Images