JP2009051713A - Heat ray-shielding laminated glass - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide laminated glass comprising a heat ray-shielding film having improved durability by suppressing the formation of rust. <P>SOLUTION: The heat ray-shielding laminated glass has two transparent substrates 110 integrally bonded through the heat ray-shielding intermediate film 120. The intermediate film 120 has a structure formed by laminating an intermediate film for bonding 121, a transparent film 122, an alternately laminated product of a metal oxide-containing layer with a silver-containing layer 123, and the intermediate film 121 in this order. The intermediate film 121 is prepared by crosslinking and curing an uncured resin film mainly composed of an ethylene-vinyl acetate copolymer. The metal oxide-containing layer contains at least one oxide of a metal selected from the group consisting of Ti, Si, Al, In and Sn. The silver-containing layer additionally contains at least one selected from the group consisting of Au, Cu and In together with Ag. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a laminated glass excellent in heat ray (infrared ray) shielding properties used for windshields and side glasses of aircraft, automobiles, window glass of buildings, and the like.

  Conventionally, a laminated glass having a structure in which a transparent adhesive resin layer is sandwiched as an intermediate film between glass plates is known. Laminated glass has improved penetration resistance and the like due to the presence of the intermediate film. For this reason, for example, even if a laminated glass of an automobile is broken for the purpose of theft or intrusion, the window cannot be opened freely, so that it is useful as a security glass. In addition, broken glass fragments remain attached to the intermediate film in response to an impact from the outside, thus preventing scattering.

  Such a laminated glass is used as a windshield or side glass of an aircraft or automobile, or a window glass of a building. Therefore, the laminated glass is required to have high transparency while ensuring safety such as penetration resistance and prevention of scattering of broken glass. In addition to these characteristics, laminated glass to which higher functions are added is employed.

  As high-function laminated glass, for example, heat ray-shielded laminated glass for the purpose of suppressing an increase in the temperature of the inside of a vehicle or the interior of a room by sunlight incident through a window glass is also known. As heat ray shielding laminated glass, a glass substrate in which a heat ray shielding film is sandwiched in addition to an intermediate film made of a transparent adhesive resin layer inside a transparent substrate made of glass or the like is generally known. As described above, by providing a heat ray shielding film capable of shielding infrared rays having a wavelength of 780 nm or more that raises the temperature of sunlight, heat resistance can be imparted to the laminated glass.

  As a conventionally known heat ray shielding film, a film in which metal oxide fine particles such as tin-doped indium oxide are dispersed in a binder resin (Patent Document 1), a silver thin film formed by sputtering or the like (Patent Document 2), etc. It has been known.

  On the other hand, since the silver thin film can strongly “reflect” heat rays, it can exhibit high heat insulation. However, when laminated glass is used over a long period of time in an environment such as outdoors exposed to high temperature and high humidity or wind and rain, moisture or water may penetrate inside. Thus, the silver thin film rusts due to moisture that has entered the laminated glass so that the transparency and design of the laminated glass may be reduced.

  Therefore, conventionally, a laminated body in which a metal oxide layer containing titanium oxide and a silver-containing layer are laminated is also known as a heat ray shielding film (Patent Documents 3 and 4). For example, in Patent Document 3, a laminate of a metal oxide layer / silver-containing layer / metal oxide layer / silver-containing layer / metal oxide layer formed on a PET film is interposed through a polyvinyl butyral (PVB) resin layer. A laminated glass bonded and integrated with a transparent substrate is disclosed.

JP 2001-206743 A JP 2001-247342 A JP 2006-505811 A JP 2000-246831 A

  In the above-described dispersion film of metal oxide fine particles, the metal oxide fine particles “absorb” heat rays to exhibit heat insulation. However, in such a dispersion film of metal oxide fine particles, the laminated glass itself is heated by absorption of heat rays, and heat is transmitted by radiant heat, and as a result, high heat insulating properties may not be exhibited.

  On the other hand, a laminated body obtained by laminating a conventional metal oxide layer and a silver-containing layer can exhibit high heat insulating properties, but there are cases where the generation of rust in the silver-containing layer cannot be sufficiently suppressed as before. Therefore, there is a need for a laminated glass having a heat ray shielding film that can suppress the generation of rust over a longer period even in an extremely severe outdoor environment.

  Then, the objective of this invention is providing the laminated glass which has a heat ray shielding film which is more excellent in durability by generation | occurrence | production of rust being suppressed.

  As a result of various studies in view of the above problems, the inventor of the present invention further contains at least one of Au, Cu and In in a silver thin film that highly reflects heat rays, and a metal oxide layer is laminated on the silver thin film. Further, it was found that by using a crosslinked cured film of ethylene vinyl acetate copolymer as an adhesive intermediate film for bonding the laminate and the transparent substrate, the occurrence of rust in the silver thin film can be suppressed to a high level. .

That is, the present invention is a heat ray shielding laminated glass in which two transparent substrates are joined and integrated via a heat ray shielding intermediate film,
The heat ray shielding intermediate film has a configuration in which an adhesive intermediate film, a transparent film, an alternating laminate of a metal oxide-containing layer and a silver-containing layer, and an adhesive intermediate film are laminated in this order,
The adhesive intermediate film is a film obtained by crosslinking and curing an uncured resin film mainly composed of an ethylene vinyl acetate copolymer,
The metal oxide-containing layer contains an oxide of at least one metal selected from the group consisting of Ti, Si, Al, In and Sn;
In addition to Ag, the silver-containing layer further contains at least one selected from the group consisting of Au, Cu and In to solve the above-mentioned problems with a heat ray-shielding laminated glass.

  Preferred embodiments of the heat ray shielding laminated glass of the present invention are listed below.

  (1) The silver-containing layer contains 1 to 40 atomic% of at least one selected from the group consisting of Au, Cu, and In.

  (2) The silver-containing layer has a thickness of 10 to 50 nm.

  (3) The titanium oxide-containing layer has a thickness of 10 to 50 nm.

(4) The metal oxide-containing layer contains TiO ₂ as a main component, and 80 atomic% or more of all metal elements in the metal oxide-containing layer is Ti.

  (5) The metal oxide-containing layer has a thickness of 10 to 80 nm.

(6) The dynamic storage elastic modulus G ′ at a frequency of 15 Hz at 90 ° C. of the uncured resin film is 1.0 × 10 ^{4 to} 1.0 × 10 ⁶ Pa.

(7) The dynamic storage elastic modulus G ′ at a frequency of 15 Hz at 90 ° C. of the adhesive interlayer is 1.0 × 10 ^{5 to} 1.0 × 10 ⁷ Pa.

  (8) The uncured resin film contains an organic peroxide.

  (9) The thickness of the adhesive intermediate film is 0.3 to 1.2 mm, and the total thickness of the adhesive intermediate film included in the heat ray shielding intermediate film is 0.6 to 2.4 mm.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to implement | achieve the heat ray shielding laminated glass excellent in durability in which rust resistance was remarkably improved, without reducing transparency and heat ray shielding property.

  First, in FIG. 1, the schematic cross section of the heat ray shielding laminated glass of this invention is shown.

  The heat ray shielding laminated glass 100 of the present invention is obtained by joining and integrating two transparent substrates 110 via a heat ray shielding intermediate film 120. The heat ray shielding intermediate film 120 is formed by laminating an adhesive intermediate film 121, a transparent film 122, an alternating laminate 123 of a metal oxide-containing layer and a silver-containing layer, and an adhesive intermediate film 121 in this order. It has the structure made.

  In the heat ray shielding laminated glass of the present invention, the silver-containing layer contained in the heat ray shielding intermediate film further contains at least one of Au, Cu and In in addition to Ag. Thereby, generation | occurrence | production of rust can be suppressed significantly, without reducing the high heat ray reflectivity of a silver content layer. In the heat ray shielding laminated glass of the present invention, a layer containing a predetermined metal oxide such as titanium oxide is laminated with the silver-containing layer. The metal oxide-containing layer has high adhesiveness with the silver-containing layer and is excellent in binding force with oxygen. Therefore, by using such a metal oxide-containing layer, it becomes possible to further increase the suppression of rusting of the silver-containing layer. Furthermore, in the heat ray shielding laminated glass of the present invention of the present invention, by using a crosslinked cured film of an ethylene vinyl acetate copolymer as an intermediate film for adhesion, each layer included in the heat ray shielding intermediate film and the transparent substrate are high. Adhesiveness can be ensured. Thereby, it is possible to prevent moisture from entering into the heat ray-shielding laminated glass, and to prevent the generation of rust in the silver-containing layer higher.

  In the heat ray shielding laminated glass of the present invention having the above-described configuration, the occurrence of rust in the silver-containing layer contained in the heat ray shielding intermediate film is highly suppressed, so that even under extremely severe natural environments outdoors. High heat ray shielding, transparency, and design can be maintained over a longer period of time and have excellent durability.

  Hereinafter, the heat ray shielding laminated glass of the present invention will be described in order.

[Alternate laminate of metal oxide-containing layer and silver-containing layer]
The heat ray shielding intermediate film contained in the heat ray shielding laminated glass of the present invention has an alternating laminate of metal oxide-containing layers and silver-containing layers formed on a transparent film.

(Silver-containing layer)
The silver-containing layer contains at least one of Au, Cu and In in addition to Ag. In the silver-containing layer, Ag and at least one metal of Au, Cu, and In may exist as a mixture, but to improve rust resistance without reducing high heat ray reflectivity. Is preferably present as an alloy of Ag containing Ag as a main component and at least one metal selected from Au, Cu and In.

  The silver-containing layer is preferably a layer containing silver as a main component in order to obtain high rust resistance. Specifically, the silver content in the silver-containing layer is preferably 60 to 99 atomic%, particularly 60 to 85 atomic%.

  The content of at least one metal among Au, Cu and In in the silver-containing layer is preferably 1 to 40 atomic%, particularly preferably 15 to 40 atomic%. Thereby, generation | occurrence | production of rust can be suppressed significantly, without reducing the high heat ray reflectivity of a silver content layer.

  In the silver-containing layer, Au, Cu and In metals may be used alone or in combination of two or more. The composition of the silver-containing layer is (1) a silver-containing layer containing 0.5 to 10 atomic percent of Au and 0.5 to 30 atomic percent of Cu, and (2) a silver containing layer containing 1 to 40 atomic percent of In. A layer etc. are mentioned preferably.

  The thickness of the silver-containing layer is preferably 10 to 50 nm, particularly 20 to 40 nm. Thereby, the silver content layer in which high heat ray shielding and transparency were compatible can be obtained.

(Metal oxide containing layer)
The metal oxide-containing layer is a layer containing an oxide of at least one metal selected from the group consisting of Ti, Si, Al, In, and Sn. Preferred examples of the metal oxide include TiO _x (X = 0.5 to 2.0), SiO, SiO ₂ , Al ₂ O ₃ , In ₂ O ₃ , and SnO ₂ . The metal oxide-containing layer, more preferably at least TiO _{X (X} = 0.5~2.0), contain the TiO ₂ formed of TiO _2, especially rutile phase is particularly preferred.

The metal oxide-containing layer is mainly composed of TiO ₂ , particularly TiO ₂ composed of a rutile phase, and 80 atomic% or more, particularly 90 atomic% or more of all metal elements in the metal oxide-containing layer is Ti. Is preferred. Thereby, generation | occurrence | production of the rust in a silver content layer can be suppressed highly.

  The thickness of the metal oxide-containing layer is preferably 10 to 80 nm, more preferably 10 to 50 nm, and particularly preferably 20 to 40 nm. Thereby, generation | occurrence | production of the rust in a silver content layer can be suppressed highly, without reducing transparency.

  In the alternating laminate, the metal oxide-containing layer and the silver-containing layer may be stacked in any order as long as the metal oxide-containing layer and the silver-containing layer are alternately stacked. For example, the metal oxide-containing layer and the silver-containing layer may be laminated only one layer at a time, or a plurality of layers may be laminated. When a plurality of layers are laminated, even if the silver-containing layer, the metal oxide-containing layer, and the silver-containing layer are laminated in this order, the occurrence of rusting of the silver-containing layer is highly suppressed. it can.

  However, in order to obtain a higher suppression effect of rusting of the silver-containing layer, a plurality of the metal oxide-containing layers and the silver-containing layers are laminated in this order, and the metal oxide-containing layer is disposed in the outermost layer. It is preferable. For example, an alternate laminate in which the metal oxide-containing layer, the silver-containing layer, and the metal oxide-containing layer are laminated in this order is preferable.

  Moreover, since the high suppression effect of the rusting of a silver containing layer is acquired, as shown in FIG. 2, the metal oxide containing layer 223b, the silver containing layer 223a, the metal oxide containing layer 223b, the silver containing layer 223a, and Particularly preferred is an alternate laminate in which the metal oxide-containing layers 223b are laminated in this order.

In the alternate laminate in which a plurality of the metal oxide-containing layers and the silver-containing layers are laminated in this order, the thickness and composition of the metal oxide-containing layer and the silver-containing layer may be different from each other. It may be. Since the generation of rust in the silver-containing layer can be suppressed to a high level, the metal oxide-containing layer disposed at least in the outermost layer in the alternating laminate is a layer mainly composed of TiO ₂ , particularly TiO ₂ composed of a rutile phase. Is preferred. In such a metal oxide-containing layer disposed in the outermost layer, it is preferable that 80 atomic% or more, particularly 90 atomic% of all metal elements is Ti.

  Further, in the alternating laminate shown in FIG. 2, the thickness of the metal oxide-containing layer 223b disposed in the outermost layer is 20 to 30 nm, and the metal oxide layer 223b disposed between the two types of silver-containing layers. The thickness is preferably 60 to 80 nm.

(Middle layer)
In the alternate laminate of the metal oxide-containing layer and the silver-containing layer described above, an intermediate layer made of only gold or an alloy of gold and silver is formed at least at one location between the metal oxide-containing layer and the silver-containing layer. You may have. Such an intermediate layer can prevent movement of the metal component from the silver-containing layer to the metal oxide-containing layer. The thickness of the intermediate layer is preferably 0.5 to 10 nm, particularly 1 to 5 nm.

  In addition, the composition of the metal contained in each layer of the silver-containing layer, the metal oxide-containing layer, and the intermediate layer in the alternating laminate, and the thickness of each layer can be measured with a transmission electron microscope (TEM).

(Transparent film)
The alternating laminate described above is formed on a transparent film. As the transparent film, polyethylene terephthalate, polyester film, polycarbonate film, polymethyl methacrylate film, polypropylene film, polyimide film and the like can be used. Polyethylene terephthalate is particularly preferable because it is excellent in cost and durability and can suppress moisture permeation.

  The thickness of the transparent film is preferably 1 μm to 5 mm, particularly preferably 1 to 100 μm from the viewpoint of being able to suppress moisture permeation highly and ensuring handleability and durability.

  The silver-containing layer, the metal oxide-containing layer, and the intermediate layer can be easily formed on the transparent film by using a sputtering method, a vacuum evaporation method, an ion plating method, a CVD method, or the like.

(Adhesive interlayer)
In the heat ray-shielding intermediate film used for the heat ray-shielding laminated glass of the present invention, the alternate laminate of the metal oxide-containing layer and the silver-containing layer formed on the transparent film described above further comprises two adhesive intermediate films. It has the structure pinched | interposed between. A transparent film, an alternating laminate of a metal oxide-containing layer and a silver-containing layer, and a transparent substrate can be joined and integrated by the adhesive intermediate film.

  In the heat ray-shielding laminated glass of the present invention, an uncured resin film mainly composed of an ethylene-vinyl acetate copolymer is used as such an adhesive intermediate film, and this uncured resin film is cross-linked and cured to be integrated. To do. In the joint integration, the resin film containing EVA used for the adhesive intermediate film is crosslinked and cured by irradiation with active rays such as ultraviolet rays, electron beams, and radiation (α rays, β rays, γ rays) or heating. Can be performed.

  According to the uncured resin film, by including an ethylene vinyl acetate copolymer (EVA), it has excellent adhesiveness, and an alternating laminate or a transparent substrate can be strongly joined and integrated. The uncured resin film containing ethylene vinyl acetate copolymer as a main component is 40 parts by mass or less with respect to 100 parts by mass of ethylene vinyl acetate copolymer, and other components such as a crosslinking agent and a crosslinking aid are used. May be included.

  As the ethylene vinyl acetate copolymer, it is preferable to use a vinyl acetate unit content of 20 to 26 parts by mass, particularly 24 to 26 parts by mass with respect to 100 parts by mass of the ethylene vinyl acetate copolymer. By setting the content of vinyl acetate units to 26 parts by mass or less, generation of free acetic acid caused by hydrolysis of the ethylene vinyl acetate copolymer can be prevented, and rusting of the silver-containing layer can be suppressed. Moreover, the intermediate film for adhesion which has high transparency is obtained by content of a vinyl acetate unit being 20 mass parts or more.

The uncured resin film mainly composed of EVA preferably has a dynamic storage elastic modulus G ′ at a frequency of 15 Hz at 90 ° C. of 1.0 × 10 ^{4 to} 1.0 × 10 ⁶ Pa. As a result, it is possible to obtain an adhesive intermediate film having high adhesiveness by suppressing the flow of the uncured resin film during crosslinking and curing.

The adhesive intermediate film obtained by crosslinking and curing the above-described uncured resin film has a dynamic storage elastic modulus G ′ at a frequency of 15 Hz at 90 ° C. of 1.0 × 10 ^{5 to} 1.0 × 10 ⁷ Pa. Is preferred. When the dynamic storage elastic modulus G ′ of the adhesive interlayer is too small, there is a possibility that excellent adhesiveness cannot be maintained in a high temperature and high humidity environment. On the other hand, if the dynamic storage elastic modulus G ′ of the adhesive intermediate film is too high, the uncured resin film may be thermally expanded and peeled when it is crosslinked and cured.

  The dynamic storage elastic modulus G ′ was determined by punching an uncured resin film or an adhesive intermediate film into a cylindrical shape having a diameter of 8 mm, and using a viscoelasticity measuring device (RDA-II type, manufactured by Rheometrics), the temperature 90 It is a value measured under the conditions of ° C., temperature rising rate 5 ° C./min, frequency 15 Hz, and strain 1%.

  The uncured resin film containing EVA as a main component used for the adhesive intermediate film is preferably a heat curable type. Thereby, a transparent substrate and a heat ray shielding intermediate film can be strongly bonded by a simple heating means. Therefore, the uncured resin film containing EVA as a main component preferably contains an organic peroxide as a crosslinking agent in addition to EVA.

  As the organic oxide, an organic peroxide that decomposes at a temperature of 100 ° C. or higher to generate radicals can be used. The organic peroxide is generally selected in consideration of the film formation temperature, the adjustment conditions of the composition, the curing temperature, the flame heat resistance of the adherend, and the storage stability. In particular, the one having a decomposition temperature of 70 ° C. or more with a half-life of 10 hours is preferable.

  Examples of the organic peroxide include, from the viewpoint of resin processing temperature and storage stability, for example, benzoyl peroxide curing agent, tert-hexyl peroxypivalate, tert-butyl peroxypivalate, 3, 5, 5- Trimethylhexanoyl peroxide, di-n-octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, succinic acid peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, tert-hexylperoxy-2-ethylhexa Noate, 4-methylbenzoyl peroxide tert-butylperoxy-2-ethylhexanoate, m-toluoyl + benzoyl peroxide, benzoyl peroxide, 1,1-bis (tert-butylperoxy) -2-methylcyclohexanate, 1,1-bis (Tert-hexylperoxy) -3,3,5-trimethylcyclohexanate, 1,1-bis (tert-hexylperoxy) cyclohexanate, 1,1-bis (tert-butylperoxy) cyclohexanate 2,2-bis (4,4-di-tert-butylperoxycyclohexyl) propane, 1,1-bis (tert-butylperoxy) cyclododecane, 1,1-bis (tert-hexylperoxy)- 3,3,5-trimethylcyclohexane tert-hexylperoxyisopropyl Rumonocarbonate, tert-butylperoxymaleic acid, tert-butylperoxy-3,3,5-trimethylhexanoate, tert-butylperoxylaurate, 2,5-dimethyl-2,5-di (methyl) Benzoylperoxy) hexane, tert-butylperoxyisopropyl monocarbonate, tert-butylperoxy-2-ethylhexyl monocarbonate, tert-hexylperoxybenzoate, 2,5-di-methyl-2,5-di (benzoylper) Oxy) hexane and the like.

  Examples of the benzoyl peroxide curing agent include benzoyl peroxide, 2,5-dimethylhexyl-2,5-bisperoxybenzoate, p-chlorobenzoyl peroxide, m-toluoyl peroxide, 2, Examples include 4-dichlorobenzoyl peroxide and t-butyl peroxybenzoate. Moreover, you may use a crosslinking agent 1 type or in combination of 2 or more types.

  Particularly preferred examples of the organic peroxide include tert-butylperoxy-2-ethylhexyl monocarbonate and 1,1-bis (tert-hexylperoxy) -3,3,5-trimethylcyclohexane. With this organic peroxide, the crosslinking density of the ethylene vinyl acetate copolymer can be improved.

  The content of the organic peroxide in the uncured resin film is preferably 0.05 to 5.0 parts by mass, more preferably 0.1 to 3.0 parts by mass with respect to 100 parts by mass of EVA. Thus, an adhesive interlayer having a desired dynamic storage elastic modulus G ′ can be obtained.

  Furthermore, the uncured resin film containing EVA as a main component may contain a crosslinking aid as necessary. The cross-linking aid can improve the gel fraction of EVA and improve the mechanical strength of the adhesive interlayer. As a crosslinking aid (compound having a radical polymerizable group as a functional group) used for this purpose, as well-known trifunctional crosslinking aids such as triallyl cyanurate and triallyl isocyanurate, ) Monofunctional or bifunctional crosslinking aids of acrylic esters (eg, NK esters, etc.) can also be mentioned. Of these, triallyl cyanurate and triallyl isocyanurate are preferable, and triallyl isocyanurate is particularly preferable. These crosslinking aids are generally used in an amount of 10 parts by mass or less, preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of EVA.

  Furthermore, the uncured resin film containing EVA as a main component improves or adjusts various physical properties of the film (optical properties such as mechanical strength, adhesion, transparency, flame heat resistance, light resistance, crosslinking speed, etc.). In order to improve the mechanical strength, various additives such as a plasticizer and an adhesion improver may be further included as necessary.

  The plasticizer is not particularly limited, but polybasic acid esters and polyhydric alcohol esters are generally 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 the ethylene vinyl acetate copolymer.

  As the adhesion improver, a silane coupling agent can be used. Examples of the 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 adhesive improvement agent is 5 mass parts or less with respect to 100 mass parts of EVA.

  Furthermore, the uncured resin film containing EVA as a main component may contain an ultraviolet absorber, a light stabilizer and an anti-aging agent.

  The ultraviolet absorber is not particularly limited, but 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4- Preferred examples include benzophenone ultraviolet absorbers such as methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, and 2-hydroxy-4-n-octoxybenzophenone. In addition, it is preferable that the compounding quantity of the said benzophenone series ultraviolet absorber is 0.01-5 mass parts with respect to 100 mass parts of EVA.

  As the light stabilizer, a light stabilizer called a hindered amine type is preferably used. For example, LA-52, LA-57, LA-62, LA-63LA-63p, LA-67, LA-68 (all of which are stocks) ADEKA), Tinuvin 744, Tinuvin 770, Tinuvin 765, Tinuvin 144, Tinuvin 622LD, CHIMASSORB 944LD (all manufactured by Ciba Specialty Chemicals Co., Ltd.), UV-3034 (manufactured by BF Goodrich) Can do. In addition, the said light stabilizer may be used individually or may be used in combination of 2 or more types, and it is preferable that the compounding quantity is 0.01-5 mass parts with respect to 100 mass parts of EVA.

  Examples of the antioxidant include hindered phenol antioxidants such as N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide]. , Phosphorus heat stabilizers, lactone heat stabilizers, vitamin E heat stabilizers, sulfur heat stabilizers, and the like.

  The thickness of the adhesive intermediate film is preferably 0.3 to 1.2 mm, particularly preferably 0.5 to 1.0 mm. Therefore, the total thickness of the two adhesive interlayers included in the heat ray-shielding interlayer is preferably 0.6 to 2.4 mm, particularly 1.0 to 2.0 mm. Thereby, sufficient adhesiveness can be exhibited.

  In order to produce an uncured resin film containing EVA as a main component, in addition to EVA, a composition containing each of the above main components as necessary is kneaded with a roll mill while heating, and a mixture obtained thereby Is formed into a sheet by a film forming method such as extrusion molding, calendar molding, or T-die molding. Alternatively, the mixture is dissolved in a suitable solvent to form a solution, and this solution is coated on a suitable support using a coater such as a roll coater, knife coater or doctor blade, and dried to form a sheet. Thus, a method of obtaining an uncured resin film can also be used. The uncured resin film thus obtained is used as an adhesive intermediate film, and, as will be described later, by laminating with a transparent substrate and an alternating laminate, etc., and then heating to form a crosslinked cured film, thereby forming a transparent substrate and the like. It can be joined and integrated.

(Transparent substrate)
In the laminated glass of the present invention, the respective transparent substrates disposed on both sides of the heat ray shielding intermediate film described above may be the same transparent substrate or a combination of different transparent substrates. The combination of the transparent substrates is preferably determined in consideration of the strength of the transparent substrate and the use of the laminated glass.

  In the present invention, the “glass” in the laminated glass means the whole transparent substrate, and therefore the “laminated glass” means one obtained by sandwiching at least an intermediate film on the transparent substrate.

  Although it does not specifically limit as said transparent substrate, For example, you may use a plastic film other than glass plates, such as a silicate glass, an inorganic glass plate, a non-colored transparent glass plate. Examples of the plastic film include a polyethylene terephthalate (PET) film, a polyethylene aphthalate (PEN) film, and a polyethylene butyrate film, and a PET film is preferred. The thickness of the transparent substrate is generally about 1 to 20 mm.

  The heat ray shielding laminated glass of the present invention has a structure in which a heat ray shielding intermediate film is sandwiched between two transparent substrates and bonded and integrated. Such a laminated glass includes the transparent substrate described above, an uncured resin film (adhesive intermediate film) mainly composed of EVA, a transparent film, an alternating laminate of a metal oxide-containing layer and a silver-containing layer, and EVA as a main component. After laminating the uncured resin film (adhesive intermediate film) and the transparent substrate in this order, the laminate is degassed and pressed under heating to cross-link and cure EVA contained in the uncured resin film. Then, it is obtained by joining and integrating the layers.

The joint integration is performed by heat-treating the laminate generally at 100 to 150 ° C., particularly around 140 ° C., for 10 to 120 minutes, preferably 10 to 60 minutes. The cross-linking may be performed after pre-bonding at a temperature of, for example, 80 to 120 ° C. The heat treatment is particularly preferably, for example, at 140 ° C. for 10 to 30 minutes (atmospheric temperature). Moreover, it is preferable to perform the said heat processing, applying the press pressure of 2 * 10 < ⁴ > -2 * 10 < ⁵ > Pa to a laminated body. The layered product after crosslinking is generally performed at room temperature, and in particular, the faster the cooling, the better.

  The laminated glass according to the present invention is capable of maintaining characteristics such as excellent heat insulation, transparency, and designability over a long period of time by suppressing the occurrence of rust in the silver-containing layer to a high level. It can use suitably for such a use. In other words, glass fitted in automobiles, side glass and rear glass, railway vehicles such as ordinary vehicles, express vehicles, express vehicles and sleeper vehicles, door windows for passenger access doors, window glasses and indoor door glasses, windows in buildings, etc. Glass and indoor door glass, indoor display showcases and show windows, and water tanks. However, the application is not limited to these.

  Hereinafter, the present invention will be described with reference to examples. The present invention is not limited by the following examples.

(Example 1)
1. Production of Alternating Laminate A layer made of titanium dioxide (thickness 30 nm) and a silver-containing layer (thickness containing 10 atomic% gold and 10 atomic% copper) on a PET film (thickness 50 μm) by magnetron sputtering. 20 nm), a layer made of titanium dioxide (thickness 70 nm), a silver-containing layer (thickness 20 nm) containing 10 atomic% gold and 10 atomic% copper, and a layer made of titanium dioxide (thickness 30 nm) in this order. By laminating, an alternating laminate was obtained.

2. Production of Uncured Resin Film (Adhesive Intermediate Film) Each material was supplied to a roll mill with the following composition and kneaded at 80 ° C. The resulting composition was calendered at a roll temperature of 80 ° C and a processing speed of 5 m / min. By calendering and allowing to cool, an uncured resin film (thickness 0.4 mm) used for the adhesive interlayer film was produced. The dynamic storage elastic modulus G ′ at a frequency of 15 Hz at 90 ° C. of the uncured resin film was 1.5 × 10 ⁵ Pa.

Formulation;
EVA (content of vinyl acetate 25 parts by mass with respect to 100 parts by mass of EVA) 100 parts by mass,
2.0 parts by mass of a crosslinking agent (1,1-bis (tert-hexylperoxy) -3,3,5-trimethylcyclohexane),
2.0 parts by mass of a crosslinking aid (triallyl isocyanurate),
0.5 part by mass of a silane coupling agent (γ-methacryloxypropyltrimethoxysilane).

3. Production of heat ray shielding laminated glass The alternating laminate formed on the PET film is sandwiched between the two uncured resin films (adhesive intermediate films) produced above to obtain a heat ray shielding intermediate film. The shielding intermediate film was further sandwiched between two glass substrates (thickness 3 mm), and the resulting laminate was placed in a rubber bag, vacuum degassed, and pre-pressed at a temperature of 100 ° C. Further, this was put in an autoclave and subjected to pressure heat treatment for 30 minutes under the conditions of a pressure of 13 × 10 ⁵ Pa and a temperature of 140 ° C. to obtain a heat ray shielding laminated glass. The dynamic storage elastic modulus G ′ at a frequency of 15 Hz at 90 ° C. of the adhesive intermediate film obtained by crosslinking and curing the uncured resin film contained in the heat ray shielding laminated glass was 9.5 × 10 ⁵ Pa.

(Comparative Example 1)
A laminate (XIR 72-47 manufactured by South Wall Technologies, Inc.) in which a layer (thickness 335 nm) made of silver was formed on a PET film (thickness 50 μm) by a magnetron sputtering method was alternately formed on the PET film. A heat ray shielding laminated glass was produced in the same manner as in Example 1 except that it was used in place of the laminate.

(Evaluation)
Each laminated glass produced in Example 1 and Comparative Example 1 was left in an environment of a temperature of 85 ° C. and a humidity of 85% RH, and the presence or absence of rust was evaluated visually.

  In the laminated glass of Comparative Example 1, generation of rust was confirmed after 1 week, but in the laminated glass of Example 1, generation of rust was not confirmed even after 2 weeks.

The schematic cross section of the heat ray shielding laminated glass of this invention is shown. The schematic cross section of the alternately laminated body of a metal oxide content layer and a silver content layer is shown.

Explanation of symbols

100 heat ray shielding laminated glass,
110 transparent substrate,
120 heat ray shielding interlayer,
121 interlayer film for bonding,
122 transparent film,
123 Alternating laminate of metal oxide-containing layers and silver-containing layers,
223a metal oxide-containing layer,
223b Silver-containing layer.

Claims (15)

Two transparent substrates are heat ray shielding laminated glass formed by joining and integrating via a heat ray shielding intermediate film,
The heat ray shielding intermediate film has a configuration in which an adhesive intermediate film, a transparent film, an alternating laminate of a metal oxide-containing layer and a silver-containing layer, and an adhesive intermediate film are laminated in this order,
The adhesive intermediate film is a film obtained by crosslinking and curing an uncured resin film mainly composed of an ethylene vinyl acetate copolymer,
The metal oxide-containing layer contains an oxide of at least one metal selected from the group consisting of Ti, Si, Al, In and Sn;
The heat-shielding laminated glass, wherein the silver-containing layer further contains at least one selected from the group consisting of Au, Cu and In in addition to Ag.   The heat-shielding laminated glass according to claim 1, wherein the silver-containing layer contains 1 to 40 atomic% of at least one selected from the group consisting of Au, Cu, and In.   The heat ray-shielding laminated glass according to claim 1 or 2, wherein the silver-containing layer has a thickness of 10 to 50 nm. The metal oxide-containing layer, a TiO ₂ as a main component, any one of claims 1-3 or 80 atomic% of all metal elements of the metal oxide-containing layer is characterized in that it is a Ti Heat-shielding laminated glass as described in 1.   The heat ray shielding laminated glass according to any one of claims 1 to 4, wherein the metal oxide-containing layer has a thickness of 10 to 80 nm.   The said alternating laminated body has the structure by which the said silver containing layer, the said metal oxide containing layer, and the said silver containing layer were laminated | stacked in this order, The any one of Claims 1-5 characterized by the above-mentioned. Heat-shielding laminated glass.   The alternating laminate has a configuration in which a plurality of the metal oxide-containing layers and the silver-containing layers are laminated in this order, and the metal oxide-containing layer is disposed as an outermost layer. Heat ray shielding laminated glass of any one of 1-5.   The alternating laminate has a configuration in which the metal oxide-containing layer, the silver-containing layer, the metal oxide-containing layer, the silver-containing layer, and the metal oxide-containing layer are laminated in this order. The heat ray-shielding laminated glass according to claim 7. The metal oxide-containing layer disposed in the outermost layer in the alternating laminate is mainly composed of TiO ₂ and 80 atomic% or more of all metal elements in the metal oxide-containing layer is Ti. The heat ray shielding laminated glass according to claim 7 or 8.   The heat ray-shielding laminated glass according to any one of claims 1 to 9, wherein the transparent film is made of polyethylene terephthalate.   The heat ray-shielding laminated glass according to any one of claims 1 to 10, wherein the transparent film has a thickness of 1 to 100 µm. The dynamic storage modulus G 'at a frequency 15Hz at 90 ° C. of the uncured resin film, according to any one of claims 1 to 11 is ^{1.0 × 10 4 ~1.0 × 10 6} Pa Heat-shielding laminated glass. 13. The dynamic storage elastic modulus G ′ at a frequency of 15 Hz at 90 ° C. of the adhesive interlayer film is 1.0 × 10 ^{5 to} 1.0 × 10 ⁷ Pa. 13. Heat-shielding laminated glass.   The heat ray shielding laminated glass according to any one of claims 1 to 13, wherein the uncured resin film contains an organic peroxide.   The thickness of the adhesive intermediate film is 0.3 to 1.2 mm, and the total thickness of the adhesive intermediate film included in the heat ray shielding intermediate film is 0.6 to 2.4 mm. 14. Heat ray shielding laminated glass of any one of 14.

Images