JP2012131659A - Laminated glass, and method for fixing glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated glass which can maintain a high visible light transmittance over a long period because of high heat shieldability and excellent weatherability.SOLUTION: The laminated glass 1 has an interlayer 2, a first laminated glass-constituting member 21 arranged on a first surface 2a side of the interlayer 2, and a second laminated glass-constituting member 22 arranged on a second surface 2b side of the interlayer 2 opposite to the first surface 2a side. The interlayer 2 includes a thermoplastic resin and a tungsten oxide particle. The first laminated glass-constituting member 21 is a heat-absorbing glass plate.

Description

  The present invention relates to laminated glass used in automobiles, buildings, and the like, and more particularly, to a laminated glass having an intermediate film containing heat shielding particles and having excellent heat shielding properties, and a method for attaching the laminated glass. .

  Laminated glass is excellent in safety because it has less scattering of glass fragments even if it is damaged by external impact. For this reason, the said laminated glass is widely used for a motor vehicle, a rail vehicle, an aircraft, a ship, a building, etc. The laminated glass is manufactured by sandwiching an interlayer film for laminated glass between a pair of glass plates. High heat-insulating properties are required for laminated glass used in such vehicle and building openings.

  Infrared rays having a wavelength longer than 780 nm longer than visible light have a smaller amount of energy than ultraviolet rays. However, infrared rays have a large thermal effect, and when infrared rays are absorbed by a substance, they are released as heat. For this reason, infrared rays are generally called heat rays. Therefore, in order to improve the heat shielding property of the laminated glass, it is necessary to sufficiently block infrared rays.

  In order to effectively block the infrared rays (heat rays), the following Patent Document 1 discloses an intermediate film containing tin-doped indium oxide particles (ITO particles) or antimony-doped tin oxide particles (ATO particles). . Patent Document 2 below discloses an intermediate film containing tungsten oxide particles.

WO2001 / 025162A1 WO2005 / 087680A1

  A laminated glass using an intermediate film containing heat shielding particles such as ITO particles, ATO particles, or tungsten oxide particles is required to have both high heat shielding properties and high visible light transmittance (Visible Transmittance). That is, in the laminated glass, it is necessary to increase the heat shielding property while keeping the visible light transmittance high. Furthermore, high visible light transmittance is required to be maintained over a long period of time.

  However, the conventional laminated glass as described in Patent Documents 1 and 2 may not be able to achieve both high heat shielding properties and high visible light transmittance. Furthermore, the visible light transmittance may be reduced while using the laminated glass. In particular, when a laminated glass using an intermediate film containing tungsten oxide particles is used for a long period of time, there is a problem that the visible light transmittance is likely to be greatly reduced.

  An object of the present invention is to provide a laminated glass capable of maintaining a high visible light transmittance over a long period of time because of its high heat shielding properties and excellent weather resistance, and a method for attaching the laminated glass.

  According to a wide aspect of the present invention, the intermediate film, the first laminated glass constituent member disposed on the first surface side of the intermediate film, and the second opposite to the first surface side of the intermediate film A second laminated glass constituent member disposed on the surface side of the first laminated glass, wherein the intermediate film includes a thermoplastic resin and tungsten oxide particles, and the first laminated glass constituent member is a heat-absorbing plate glass. Laminated glass is provided.

  On the specific situation with the laminated glass which concerns on this invention, the said 2nd laminated glass structural member is heat ray absorbing plate glass.

  In another specific aspect of the laminated glass according to the present invention, the tungsten oxide particles are cesium-doped tungsten oxide particles.

  In still another specific aspect of the laminated glass according to the present invention, the thermoplastic resin is a polyvinyl acetal resin.

  In another specific aspect of the laminated glass according to the present invention, the interlayer film further includes a plasticizer.

  On the other specific situation of the laminated glass which concerns on this invention, the said 1st laminated glass structural member is laminated | stacked on the said 1st surface of the said intermediate film.

  In still another specific aspect of the laminated glass according to the present invention, the second laminated glass constituent member is laminated on the second surface of the intermediate film.

  Moreover, according to the wide aspect of this invention, it is the method of attaching the laminated glass comprised according to this invention in the opening part between exterior space and interior space in which a heat ray injects from this exterior space in a building or a vehicle. And opening the laminated glass so that the first laminated glass component is located on the outer space side and the second laminated glass component is located on the inner space side. A method of attaching a laminated glass is provided.

  In the laminated glass according to the present invention, an intermediate film containing a thermoplastic resin and tungsten oxide particles is disposed between the first and second laminated glass constituent members, and the first laminated glass constituent member absorbs heat rays. Since it is plate glass, heat-insulating property can be improved. Moreover, the weather resistance of the laminated glass is increased by the specific first laminated glass constituent member, and a high visible light transmittance can be maintained over a long period of time.

FIG. 1 is a partially cutaway sectional view showing a laminated glass according to an embodiment of the present invention. FIG. 2 is a partially cutaway sectional view showing a laminated glass according to another embodiment of the present invention.

  Hereinafter, the present invention will be clarified by describing specific embodiments and examples of the present invention with reference to the drawings.

  In FIG. 1, the laminated glass which concerns on one Embodiment of this invention is shown with a partial notch sectional drawing.

  A laminated glass 1 shown in FIG. 1 includes an intermediate film 2, a first laminated glass component 21 disposed on the first surface 2 a side of the intermediate film 2, and the first surface 2 a side of the intermediate film 2. And a second laminated glass constituent member 22 disposed on the opposite second surface 2b side. The first laminated glass constituting member 21 is laminated on the first surface 2 a of the intermediate film 2. The second laminated glass constituent member 22 is laminated on the second surface 2 b of the intermediate film 2. The intermediate film 2 is disposed between the first laminated glass constituent member 21 and the second laminated glass constituent member 22. The intermediate film 2 is sandwiched between the first and second laminated glass constituent members 21 and 22. Accordingly, the laminated glass 1 has a multilayer structure in which the first laminated glass constituting member 21, the intermediate film 2, and the second laminated glass constituting member 22 are laminated in this order.

  Other layers may be disposed between the intermediate film 2 and the first laminated glass constituent member 21 and between the intermediate film 2 and the second laminated glass constituent member 22, respectively. The first laminated glass component 21 and the intermediate film 2 are preferably laminated directly, and the intermediate film 2 and the second laminated glass component 22 are preferably laminated directly. The other layer may be an intermediate film. Examples of the other layers include a layer containing a thermoplastic resin such as a polyvinyl acetal resin, a layer containing polyethylene terephthalate, and the like.

  The intermediate film 2 includes a thermoplastic resin and tungsten oxide particles. The interlayer film 2 is an interlayer film for laminated glass.

  In the present embodiment, a heat ray absorbing plate glass is used as the first laminated glass constituent member 21. The second laminated glass constituent member 22 is also preferably a heat ray absorbing plate glass.

  Conventionally, laminated glass using an interlayer film may have low heat shielding properties and high solar transmittance. Furthermore, the conventional laminated glass has a problem that it is difficult to achieve both low solar transmittance and high visible light transmittance (Visible Transmittance).

  In order to sufficiently enhance the heat shielding property and visible light transmittance of the laminated glass, one of the main features of the present embodiment is that the intermediate film 2 contains a thermoplastic resin and tungsten oxide particles. In particular, the tungsten oxide particles effectively enhance the heat shielding properties of the laminated glass. Furthermore, by using the intermediate film 2 containing a thermoplastic resin and tungsten oxide particles, a laminated glass having a low solar transmittance, which is an index of heat shielding properties, can be obtained, and further, a laminated glass having a high visible light transmittance can be obtained. Can do. For example, the solar radiation transmittance (Ts2500) at a wavelength of 300 to 2500 nm of the laminated glass can be 65% or less, and the visible light transmittance can be 65% or more. Furthermore, the solar radiation transmittance (Ts2500) can be 50% or less, and the visible light transmittance can be 70% or more.

  Furthermore, as a result of investigations by the present inventors, only by producing a laminated glass using a thermoplastic resin and tungsten oxide particles, the visible light transmittance decreases when the laminated glass is used for a long period of time. I understood. Thus, as a result of further studies by the present inventors, a configuration of a laminated glass capable of maintaining a high visible light transmittance for a long period of time has also been found.

  Another main feature of the present embodiment is that a heat ray absorbing plate glass is used as the first laminated glass constituting member 21 disposed on the first surface 2a side of the intermediate film 2 containing a thermoplastic resin and tungsten oxide particles. Is to use. Accordingly, heat rays are effectively blocked out of the light rays incident on the intermediate film 2 from the first laminated glass constituent member 21 side. That is, heat rays are absorbed by the first laminated glass constituent member 21. For this reason, the amount of heat rays reaching the intermediate film 2 can be effectively reduced. Therefore, it is thought that the heat-shielding fall accompanying the chemical change etc. of the tungsten oxide particle contained in the intermediate film 2 can be suppressed. As a result, the weather resistance of the laminated glass 1 is increased, and excellent visible light transmittance can be maintained for a long period of time.

  When the laminated glass 1 is attached to the opening of an automobile or a building, the laminated glass 1 may be attached so that the first laminated glass constituting member 21 is on the side where the heat rays are incident on the laminated glass 1. Thereby, the first laminated glass constituent member 21 absorbs heat rays, and the amount of heat rays reaching the intermediate film 2 can be effectively reduced. In this case, since it is possible to prevent light from entering the intermediate film 2 from the second laminated glass constituent member 22 side, a heat ray absorbing plate glass is not necessarily used as the second laminated glass constituent member 22. It does not have to be done.

  In FIG. 2, the laminated glass which concerns on other embodiment of this invention is shown with a partial notch front sectional drawing.

  A laminated glass 11 shown in FIG. 2 includes a multilayer intermediate film 12 and first and second laminated glass constituting members 21 and 22. The multilayer intermediate film 12 has a structure in which three intermediate films of an intermediate film 13, an intermediate film 14, and an intermediate film 15 are laminated in this order. The intermediate film 14 is a heat shielding layer and includes a thermoplastic resin and tungsten oxide particles. The intermediate films 13 and 15 are protective layers and are the other layers (other intermediate films) described above. As the intermediate films 13 and 15, an intermediate film containing a thermoplastic resin and tungsten oxide particles may be used. The intermediate film 13 may be an intermediate film containing a thermoplastic resin and tungsten oxide particles, and the intermediate films 14 and 15 may be other layers described above. The intermediate film 15 may be an intermediate film containing a thermoplastic resin and tungsten oxide particles, and the intermediate films 13 and 14 may be the other layers described above. The interlayer films 13 to 15 are interlayer films for laminated glass.

  The multilayer intermediate film 12 is sandwiched between the first and second laminated glass constituent members 21 and 22. A first laminated glass constituting member 21 is laminated on the outer surface 13 a of the intermediate film 13. A second laminated glass constituting member 22 is laminated on the outer surface 15 a of the intermediate film 15.

  Also in the laminated glass 11 shown in FIG. 2, since the intermediate film 13 contains a thermoplastic resin and tungsten oxide particles, the heat shielding property is sufficiently high. Furthermore, since the 1st laminated glass structural member 21 which is a heat ray absorption plate glass is used, the weather resistance of the laminated glass 11 becomes high and can maintain a high visible light transmittance over a long period of time.

  Hereinafter, first, details of materials constituting the interlayer film in the laminated glass according to the present invention will be described. In the following description, an intermediate film containing a thermoplastic resin and tungsten oxide particles may be abbreviated as an intermediate film A.

(Thermoplastic resin)
The thermoplastic resin contained in the interlayer film A is not particularly limited. A conventionally well-known thermoplastic resin can be used as a thermoplastic resin. As for a thermoplastic resin, only 1 type may be used and 2 or more types may be used together.

  Examples of the thermoplastic resin include polyvinyl acetal resin, ethylene-vinyl acetate copolymer resin, ethylene-acrylic copolymer resin, polyurethane resin, and polyvinyl alcohol resin. Thermoplastic resins other than these may be used.

  The thermoplastic resin is preferably a polyvinyl acetal resin. By the combined use of the polyvinyl acetal resin and the plasticizer, the adhesive force of the intermediate film A to the laminated glass constituent member or other layer (other intermediate film) can be further increased.

  The polyvinyl acetal resin can be produced, for example, by acetalizing polyvinyl alcohol with an aldehyde. The polyvinyl alcohol can be produced, for example, by saponifying polyvinyl acetate. The degree of saponification of the polyvinyl alcohol is generally in the range of 70 to 99.9 mol%.

  The average degree of polymerization of the polyvinyl alcohol is preferably 200 or more, more preferably 500 or more, preferably 3000 or less, more preferably 2500 or less. When the average degree of polymerization is not less than the above lower limit, the penetration resistance of the laminated glass is further enhanced. When the average degree of polymerization is not more than the above upper limit, the intermediate film A can be easily molded.

  The number of carbon atoms of the acetal group contained in the polyvinyl acetal resin is not particularly limited. The aldehyde used when manufacturing the said polyvinyl acetal resin is not specifically limited. The carbon number of the acetal group in the polyvinyl acetal resin is preferably 3 or 4. When the carbon number of the acetal group in the polyvinyl acetal resin is 3 or more, the glass transition temperature of the intermediate film A is sufficiently low.

  The aldehyde is not particularly limited. In general, an aldehyde having 1 to 10 carbon atoms is preferably used as the aldehyde. Examples of the aldehyde having 1 to 10 carbon atoms include propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, n-octylaldehyde, and n-nonylaldehyde. , N-decylaldehyde, formaldehyde, acetaldehyde, benzaldehyde and the like. Among these, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-hexylaldehyde or n-valeraldehyde is preferable, propionaldehyde, n-butyraldehyde or isobutyraldehyde is more preferable, and n-butyraldehyde is still more preferable. As for the said aldehyde, only 1 type may be used and 2 or more types may be used together.

  The hydroxyl group content (hydroxyl group amount) of the polyvinyl acetal resin is preferably 15 mol% or more, more preferably 18 mol% or more, preferably 40 mol% or less, more preferably 35 mol% or less. When the hydroxyl group content is equal to or higher than the lower limit, the adhesive strength of the intermediate film A is further increased. Further, when the hydroxyl group content is not more than the above upper limit, the flexibility of the intermediate film A is increased, and the handling of the intermediate film A becomes easy.

  The hydroxyl group content of the polyvinyl acetal resin is a value indicating the mole fraction obtained by dividing the amount of ethylene groups to which the hydroxyl group is bonded by the total amount of ethylene groups in the main chain, as a percentage. The amount of ethylene group to which the hydroxyl group is bonded can be determined, for example, by measuring the amount of ethylene group to which the hydroxyl group of polyvinyl alcohol as a raw material is bonded in accordance with JIS K6726 “Testing method for polyvinyl alcohol”. it can.

  The degree of acetylation (acetyl group amount) of the polyvinyl acetal resin is preferably 0.1 mol% or more, more preferably 0.3 mol% or more, still more preferably 0.5 mol% or more, preferably 30 mol% or less. More preferably, it is 25 mol% or less, More preferably, it is 20 mol% or less. When the acetylation degree is not less than the above lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer is increased. When the acetylation degree is not more than the above upper limit, the moisture resistance of the interlayer film A and the laminated glass is increased.

  The degree of acetylation is obtained by subtracting the amount of ethylene groups to which acetal groups are bonded and the amount of ethylene groups to which hydroxyl groups are bonded from the total amount of ethylene groups of the main chain, It is a value indicating the mole fraction obtained by dividing by the percentage. The amount of ethylene group to which the acetal group is bonded can be measured, for example, according to JIS K6728 “Testing method for polyvinyl butyral”.

  The degree of acetalization of the polyvinyl acetal resin (in the case of polyvinyl butyral resin, the degree of butyralization) is preferably 60 mol% or more, more preferably 63 mol% or more, preferably 85 mol% or less, more preferably 75 mol%. Hereinafter, it is 70 mol% or less more preferably. When the degree of acetalization is not less than the above lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer increases. When the degree of acetalization is less than or equal to the above upper limit, the reaction time required for producing a polyvinyl acetal resin is shortened.

  The degree of acetalization is a value indicating the mole fraction obtained by dividing the amount of ethylene groups to which acetal groups are bonded by the total amount of ethylene groups in the main chain, as a percentage.

  The degree of acetalization is determined by measuring the degree of acetylation and the hydroxyl group content by a method in accordance with JIS K6728 “Testing methods for polyvinyl butyral”, and calculating the mole fraction from the obtained measurement results. % Can be calculated by subtracting the acetylation degree and the hydroxyl group content.

  When the polyvinyl acetal resin is a polyvinyl butyral resin, the hydroxyl group content (hydroxyl amount), the acetalization degree (butyralization degree), and the acetyl group amount are based on JIS K6728 “Testing methods for polyvinyl butyral”. It can be calculated from the result measured by the method.

(Plasticizer)
From the viewpoint of further increasing the adhesive strength of the interlayer film A, the interlayer film A preferably contains a plasticizer. When the thermoplastic resin contained in the intermediate film A is a polyvinyl acetal resin, the intermediate film A particularly preferably contains a plasticizer.

  The plasticizer is not particularly limited. A conventionally known plasticizer can be used as the plasticizer. As for the said plasticizer, only 1 type may be used and 2 or more types may be used together.

  Examples of the plasticizer include organic ester plasticizers such as monobasic organic acid esters and polybasic organic acid esters, and phosphate plasticizers such as organic phosphate plasticizers and organic phosphorous acid plasticizers. It is done. Of these, organic ester plasticizers are preferred. The plasticizer is preferably a liquid plasticizer.

  The monobasic organic acid ester is not particularly limited. For example, a glycol ester obtained by reaction of glycol with a monobasic organic acid, and triethylene glycol or tripropylene glycol with a monobasic organic acid. Examples include esters. Examples of the glycol include triethylene glycol, tetraethylene glycol, and tripropylene glycol. Examples of the monobasic organic acid include butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptylic acid, n-octylic acid, 2-ethylhexylic acid, n-nonylic acid, and decylic acid.

  The polybasic organic acid ester is not particularly limited, and examples thereof include an ester compound of a polybasic organic acid and an alcohol having a linear or branched structure having 4 to 8 carbon atoms. Examples of the polybasic organic acid include adipic acid, sebacic acid, and azelaic acid.

  The organic ester plasticizer is not particularly limited, and triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol dicaprylate, triethylene glycol di-n- Octanoate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate, ethylene glycol di-2-ethyl butyrate, 1,3-propylene glycol di 2-ethyl butyrate, 1,4-butylene glycol di-2-ethyl butyrate, diethylene glycol di-2-ethyl butyrate, diethylene glycol di-2-ethyl hexanoate, dipropylene glycol Di-2-ethylbutyrate, triethylene glycol di-2-ethylpentanoate, tetraethylene glycol di-2-ethylbutyrate, diethylene glycol dicapryate, dihexyl adipate, dioctyl adipate, hexylcyclohexyl adipate, adipine Examples include a mixture of heptyl acid and nonyl adipate, diisononyl adipate, diisodecyl adipate, heptylnonyl adipate, dibutyl sebacate, alkyd oil-modified sebacic acid, and a mixture of phosphate ester and adipate. Organic ester plasticizers other than these may be used.

  The organophosphate plasticizer is not particularly limited, and examples thereof include tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphate, and the like.

  The plasticizer is preferably a diester plasticizer represented by the following formula (1).

  In said formula (1), R1 and R2 respectively represent a C5-C10 organic group, R3 represents an ethylene group, an isopropylene group, or n-propylene group, p represents the integer of 3-10. . R1 and R2 in the above formula (1) are each preferably an organic group having 6 to 10 carbon atoms.

  The plasticizer preferably contains at least one of triethylene glycol di-2-ethylhexanoate (3GO) and triethylene glycol di-2-ethylbutyrate (3GH), and triethylene glycol di-2 -More preferably, it contains ethyl hexanoate.

  The content of the plasticizer is not particularly limited. The content of the plasticizer is preferably 25 parts by weight or more, more preferably 30 parts by weight or more, preferably 60 parts by weight or less, more preferably 50 parts by weight or less with respect to 100 parts by weight of the thermoplastic resin. . When the content of the plasticizer is not less than the above lower limit, the penetration resistance of the laminated glass is further enhanced. When the content of the plasticizer is not more than the above upper limit, the transparency of the interlayer film A is further increased.

(Tungsten oxide particles)
The tungsten oxide particles contained in the intermediate film A are heat shielding particles.

  The tungsten oxide particles are generally represented by the following formula (X1) or the following formula (X2). In the intermediate film A, tungsten oxide particles represented by the following formula (X1) or the following formula (X2) are preferably used.

WyOz Formula (X1)
In the above formula (X1), W represents tungsten, O represents oxygen, and y and z satisfy 2.0 <z / y <3.0.

MxWyOz Formula (X2)
In the above formula (X2), 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 And at least one element selected from the group consisting of Re, W represents tungsten, O represents oxygen, and x, y, and z represent 0.001 ≦ x / y ≦ 1, and 2.0 <z / y ≦ 3.0 is satisfied.

  From the viewpoint of further increasing the heat shielding properties of the interlayer film A and the laminated glass, the tungsten oxide particles are preferably metal-doped tungsten oxide particles. The “tungsten oxide particles” include metal-doped tungsten oxide particles. Specific examples of the metal-doped tungsten oxide particles include sodium-doped tungsten oxide particles, cesium-doped tungsten oxide particles, thallium-doped tungsten oxide particles, and rubidium-doped tungsten oxide particles.

From the viewpoint of further increasing the heat shielding properties of the interlayer film A and the laminated glass, cesium-doped tungsten oxide particles are particularly preferable. From the viewpoint of further increasing the heat shielding properties of the interlayer film A and the laminated glass, the cesium-doped tungsten oxide particles are preferably tungsten oxide particles represented by the formula: Cs _0.33 WO ₃ .

  The average particle diameter of the tungsten oxide particles is preferably 0.01 μm or more, more preferably 0.02 μm or more, preferably 0.1 μm or less, more preferably 0.05 μm or less. When the average particle size is not less than the above lower limit, the heat ray shielding property is sufficiently increased. When the average particle size is not more than the above upper limit, the transparency of the interlayer film A is increased.

  The “average particle diameter” indicates a volume average particle diameter. The average particle diameter can be measured using a particle size distribution measuring apparatus (“UPA-EX150” manufactured by Nikkiso Co., Ltd.) or the like.

  The content of the tungsten oxide particles is not particularly limited. The content of tungsten oxide particles in 100% by weight of the intermediate film A is preferably 0.001% by weight or more, more preferably 0.01% by weight or more, still more preferably 0.05% by weight or more, preferably 3% by weight or less. More preferably, it is 1% by weight or less, and further preferably 0.5% by weight or less. When the content of the tungsten oxide particles is not less than the above lower limit and not more than the above upper limit, the heat shielding property can be sufficiently increased and the visible light transmittance can be sufficiently increased. For example, the visible light transmittance of the laminated glass can be 70% or more.

(Antioxidant)
The interlayer film A preferably contains an antioxidant. As for this antioxidant, only 1 type may be used and 2 or more types may be used together.

  Examples of the antioxidant include fail-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants. The phenolic antioxidant is an antioxidant having a phenol skeleton. The sulfur-based antioxidant is an antioxidant containing a sulfur atom. The phosphorus antioxidant is an antioxidant containing a phosphorus atom.

  The antioxidant is preferably a phenolic antioxidant. Examples of the phenolic antioxidant include 2,6-di-t-butyl-p-cresol (BHT), butylated hydroxyanisole (BHA), 2,6-di-t-butyl-4-ethylphenol, stearyl -Β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis- (4-methyl-6-butylphenol), 2,2'-methylenebis- (4-ethyl- 6-t-butylphenol), 4,4′-butylidene-bis- (3-methyl-6-tert-butylphenol), 1,1,3-tris- (2-methyl-hydroxy-5-tert-butylphenyl) Butane, tetrakis [methylene-3- (3 ′, 5′-butyl-4-hydroxyphenyl) propionate] methane, 1,3,3-tris- (2-methyl-4-hydride) Xyl-5-tert-butylphenol) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, and bis (3,3 ' -T-butylphenol) butyric acid glycol ester and pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]. One or more of these antioxidants are preferably used.

  From the viewpoint of more effectively maintaining the high visible light transmittance of the laminated glass over a long period of time, the antioxidant is 2,6-di-t-butyl-p-cresol (BHT), tetrakis [methylene. -3- (3 ′, 5′-butyl-4-hydroxyphenyl) propionate] methane or pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] BHT or 2,6-di-t-butyl-p-cresol (BHT) or tetrakis [methylene-3- (3 ′, 5′-butyl-4-hydroxyphenyl) propionate] methane is more preferable. .

  As a commercial item of the said antioxidant, the brand name "Sumilyzer BHT" by Sumitomo Chemical Co., Ltd., the brand name "Irganox 1010" by Ciba Geigy, etc. are mentioned, for example.

  In order to maintain the high visible light transmittance of the laminated glass more effectively over a long period of time, the content of the antioxidant is preferably 0.01% by weight or more in 100% by weight of the interlayer film A. Further, since the effect of adding the antioxidant is saturated, the content of the antioxidant is preferably 2% by weight or less in 100% by weight of the intermediate film A. In addition, in order to maintain the visible light transmittance of the laminated glass after the lapse of time, the higher the content of the antioxidant, the better.

  From the viewpoint of further increasing the heat shielding property and visible light transmittance of the laminated glass, and the visible light transmittance after aging of the laminated glass, the content of the antioxidant in 100% by weight of the interlayer film A is more preferably 0.00. 02% by weight or more, more preferably 0.05% by weight or more. In order to suppress coloring of the intermediate film A due to the influence of the antioxidant, the content of the antioxidant is more preferably 1.8% by weight or less, and still more preferably 1.5% in 100% by weight of the intermediate film A. % By weight or less.

  The intermediate film A preferably contains the tungsten oxide particles and the antioxidant in a weight ratio (tungsten oxide particles: antioxidant) at 10: 1 to 1: 100, and 5: 1 to 1:50. More preferably. When the weight ratio of the tungsten oxide particles to the antioxidant is within the above range, the heat shielding property and visible light transmittance of the laminated glass, and the visible light transmittance after aging of the laminated glass can be further increased. The weight ratio is a ratio of the content (wt%) of the tungsten oxide particles in 100 wt% of the intermediate film A to the content (wt%) of the antioxidant in 100 wt% of the intermediate film A. Show.

(UV shielding agent)
The intermediate film A preferably contains an ultraviolet shielding agent. By using the ultraviolet shielding agent, even when the laminated glass is used for a long period of time, the visible light transmittance is further hardly lowered. As for this ultraviolet shielding agent, only 1 type may be used and 2 or more types may be used together.

  The ultraviolet shielding agent includes an ultraviolet absorber. The ultraviolet shielding agent is preferably an ultraviolet absorber.

  Conventionally known general ultraviolet shielding agents include, for example, metal ultraviolet shielding agents, metal oxide ultraviolet shielding agents, benzotriazole ultraviolet shielding agents, benzophenone ultraviolet shielding agents, triazine ultraviolet shielding agents, and the like. Examples include benzoate-based ultraviolet shielding agents.

  Examples of the metallic ultraviolet shielding agent include platinum particles, particles in which the surface of the platinum particles is coated with silica, palladium particles, particles in which the surface of the palladium particles is coated with silica, and the like. The ultraviolet shielding agent is preferably not a heat shielding particle. The ultraviolet shielding agent is preferably a benzotriazole ultraviolet shielding agent, a benzophenone ultraviolet shielding agent, a triazine ultraviolet shielding agent or a benzoate ultraviolet shielding agent, more preferably a benzotriazole ultraviolet shielding agent or a benzophenone ultraviolet shielding agent. And more preferably a benzotriazole-based ultraviolet screening agent.

  Examples of the metal oxide ultraviolet shielding agent include zinc oxide, titanium oxide, and cerium oxide. Furthermore, the surface may be coat | covered as said metal oxide type ultraviolet-ray shielding agent. Examples of the coating material on the surface of the metal oxide ultraviolet shielding agent include insulating metal oxides, hydrolyzable organosilicon compounds, and silicone compounds.

  Examples of the insulating metal oxide include silica, alumina and zirconia. The insulating metal oxide has a band gap energy of 5.0 eV or more, for example.

  Examples of the benzotriazole-based ultraviolet shielding agent include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole (“TinvinP” manufactured by BASF), 2- (2′-hydroxy-3 ′, 5 ′). -Di-t-butylphenyl) benzotriazole ("Tinvin 320" manufactured by BASF), 2- (2'-hydroxy-3'-t-butyl-5-methylphenyl) -5-chlorobenzotriazole (manufactured by BASF " Tinuvin 326 "), and 2- (2'-hydroxy-3 ', 5'-di-amylphenyl) benzotriazole (" Tinvin 328 "manufactured by BASF) and the like. The ultraviolet shielding agent is preferably a benzotriazole-based ultraviolet absorber containing a halogen atom, and more preferably a benzotriazole-based ultraviolet absorber containing a chlorine atom, because of its excellent ability to absorb ultraviolet rays.

  Examples of the benzophenone-based ultraviolet shielding agent include octabenzone (“Chimasorb 81” manufactured by BASF).

  Examples of the triazine-based ultraviolet shielding agent include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol (manufactured by BASF Corporation, “Tinuvin 1577FF”). ]) And the like.

  Examples of the benzoate-based ultraviolet shielding agent include 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate (manufactured by BASF, “tinuvin 120”).

  From the viewpoint of further suppressing the decrease in the visible light transmittance of the laminated glass over time, the ultraviolet shielding agent is 2- (2′-hydroxy-3′-t-butyl-5-methylphenyl) -5-chloro. It is preferably benzotriazole (“Tinvin 326” manufactured by BASF) or 2- (2′-hydroxy-3 ′, 5′-di-amylphenyl) benzotriazole (“Tinvin 328” manufactured by BASF), and 2- ( 2′-hydroxy-3′-t-butyl-5-methylphenyl) -5-chlorobenzotriazole is more preferable.

  The content of the ultraviolet shielding agent in the intermediate film A is not particularly limited. From the viewpoint of further suppressing the decrease in visible light transmittance of the laminated glass after the lapse of time, the content of the ultraviolet shielding agent in 100% by weight of the intermediate film A is preferably 0.1% by weight or more, more preferably 0.8%. 2% by weight or more, more preferably 0.3% by weight or more, particularly preferably 0.5% by weight or more, preferably 2.5% by weight or less, more preferably 2% by weight or less, still more preferably 1% by weight or less, Particularly preferred is 0.8% by weight or less. In particular, when the content of the ultraviolet shielding agent is 0.2% by weight or more in 100% by weight of the intermediate film A, it is possible to remarkably suppress a decrease in visible light transmittance after aging of the laminated glass.

(Other ingredients)
The intermediate film A may contain additives such as a light stabilizer, a flame retardant, an antistatic agent, a pigment, a dye, an adhesive force adjusting agent, a moisture-resistant agent, a fluorescent brightening agent, and an infrared absorber as necessary. Good. As for these additives, only 1 type may be used and 2 or more types may be used together.

(Details of interlayer film A)
The thickness of the intermediate film A is not particularly limited. From the viewpoint of practical use and the viewpoint of sufficiently increasing the heat shielding property, the thickness of the intermediate film A is preferably 0.1 mm or more, more preferably 0.25 mm or more, preferably 3 mm or less, more preferably 1.5 mm or less. It is. When the thickness of the intermediate film A is not less than the above lower limit, the penetration resistance of the laminated glass is increased.

  The manufacturing method of the intermediate film A is not particularly limited. As a method for producing the interlayer film A, a conventionally known method can be used. For example, the manufacturing method etc. which knead | mix the thermoplastic resin, the tungsten oxide particle, and the other component mix | blended as needed, and shape | mold the intermediate film A etc. are mentioned. Since it is suitable for continuous production, an extrusion method is preferred.

  The kneading method is not particularly limited. Examples of this method include a method using an extruder, a plastograph, a kneader, a Banbury mixer, a calendar roll, or the like. Especially, since it is suitable for continuous production, a method using an extruder is preferable, and a method using a twin screw extruder is more preferable.

  The intermediate film A containing a thermoplastic resin and tungsten oxide particles can be used as a single layer. Furthermore, a plurality of intermediate films A may be laminated and used as a multilayer intermediate film. Furthermore, another intermediate film may be laminated on at least one surface of the intermediate film A to be used as a multilayer intermediate film. In this case, any of a multilayer intermediate film in which another intermediate film is laminated on one side of the intermediate film A and a multilayer intermediate film in which other intermediate films are laminated on both sides of the intermediate film A can be used. . The other interlayer film can be used as a protective layer in laminated glass, for example.

  The thickness of the other intermediate film is preferably 0.1 mm or more, more preferably 0.2 mm or more, preferably 1 mm or less, more preferably 0.5 mm or less. When the thickness of the other interlayer film is not less than the above lower limit and not more than the above upper limit, the thickness of the multilayer interlayer film does not become too thick, and the heat shielding properties of the multilayer interlayer film and the laminated glass are further enhanced.

(Details of laminated glass)
The laminated glass according to the present invention includes a first laminated glass constituent member, a second laminated glass constituent member, and a single-layer or multilayer intermediate film sandwiched between the first and second laminated glass constituent members. The single-layer or multilayer intermediate film includes the intermediate film A.

  In the laminated glass according to the present invention, not only the laminated glass sandwiched between the first and second laminated glass constituent members, but also a multilayer intermediate in which two or more intermediate films A are laminated. A laminated glass in which a film is sandwiched between first and second laminated glass constituent members is also included. Furthermore, in the laminated glass according to the present invention, the multilayer interlayer film having the interlayer film A and another interlayer film laminated on at least one surface of the interlayer film A includes the first and second laminated glass constituent members. Laminated glass sandwiched between the two is also included. In this case, any of a multilayer intermediate film in which another intermediate film is laminated on one side of the intermediate film A and a multilayer intermediate film in which other intermediate films are laminated on both sides of the intermediate film A can be used. .

  From the viewpoint of further increasing the visible light transmittance after aging of the laminated glass, the other intermediate film (second intermediate film) laminated on at least one surface of the intermediate film A contains the above-described ultraviolet shielding agent. It is preferable. The other interlayer film preferably contains a thermoplastic resin and a plasticizer. The other interlayer film may contain an antioxidant. The preferred types and preferred contents of the thermoplastic resin, plasticizer, antioxidant and ultraviolet shielding agent in the other interlayer film are the preferred types of the thermoplastic resin, plasticizer, antioxidant and ultraviolet shielding agent in the interlayer film A. And it is the same as that of preferable content.

  The first laminated glass constituent member is a heat ray absorbing plate glass. Examples of the second laminated glass constituting member include a glass plate and a PET (polyethylene terephthalate) film. The second laminated glass constituent member is preferably a heat ray absorbing plate glass. In this case, it is possible to effectively block the heat rays in the light rays incident from both surfaces of the laminated glass.

  The heat ray absorbing plate glass is a heat ray absorbing plate glass based on JIS R3208.

  When a glass plate other than the heat ray absorbing plate glass is used as the second laminated glass constituent member, examples of the glass plate include inorganic glass and organic glass. Examples of the inorganic glass include float plate glass, polished plate glass, mold plate glass, mesh-containing plate glass, wire-containing plate glass, and clear glass. The organic glass is a synthetic resin glass substituted for inorganic glass. Examples of the organic glass include polycarbonate plates and poly (meth) acrylic resin plates. Examples of the poly (meth) acrylic resin plate include a polymethyl (meth) acrylate plate.

  The laminated glass includes not only the laminated glass in which the intermediate film A is disposed between the two glass plates, but also the laminated glass in which the intermediate film A is disposed between the glass plate and the PET film or the like. The laminated glass is a glass plate-containing laminate, and preferably at least one glass plate is used.

  Although the thickness of the said laminated glass structural member is not specifically limited, Preferably it is 1 mm or more, Preferably it is 5 mm or less, More preferably, it is 3 mm or less. Moreover, when a laminated glass structural member is a glass plate, the thickness of this glass plate becomes like this. Preferably it is 1 mm or more, Preferably it is 5 mm or less, More preferably, it is 3 mm or less. When the laminated glass component is a PET film, the thickness of the PET film is preferably 0.03 mm or more, and preferably 0.5 mm or less.

  The manufacturing method of the said laminated glass is not specifically limited. For example, the intermediate film A or a multilayer intermediate film including the intermediate film A is sandwiched between the first and second laminated glass constituent members, passed through a pressing roll, or put in a rubber bag and sucked under reduced pressure. The air remaining between the first and second laminated glass constituent members and the intermediate film A or the multilayer intermediate film is degassed. Then, it pre-adheres at about 70-110 degreeC, and a laminated body is obtained. Next, the laminated body is put in an autoclave or pressed, and pressed at about 120 to 150 ° C. and a pressure of 1 to 1.5 MPa. In this way, a laminated glass can be obtained. Laminated glass can be used for automobiles, railway vehicles, aircraft, ships, buildings, and the like. Laminated glass can be used for other purposes. Laminated glass can be used for a windshield, side glass, rear glass, roof glass, or the like of an automobile.

  From the viewpoint of obtaining a laminated glass that is more excellent in transparency, the visible light transmittance of the laminated glass is preferably 65% or more, more preferably 70% or more. The visible light transmittance of the laminated glass can be measured according to JIS R3211 (1998).

  The solar transmittance (Ts2500) of the laminated glass is preferably 65% or less, more preferably 50% or less. The solar transmittance of the laminated glass can be measured according to JIS R3106 (1998).

  The haze value of the laminated glass is preferably 2% or less, more preferably 1% or less, still more preferably 0.5% or less, and particularly preferably 0.4% or less. The haze value of the laminated glass can be measured according to JIS K6714.

(How to attach the laminated glass)
The attachment method of the laminated glass which concerns on this invention is a method of attaching the laminated glass mentioned above to the opening part between external space and internal space into which a heat ray injects from this external space in a building or a vehicle.

  Specifically, the laminated glass is attached to the opening so that the first laminated glass constituent member is located on the outer space side and the second laminated glass constituent member is located on the inner space side. That is, the laminated glass is arranged in the order of external space / first laminated glass component / (other layer /) intermediate film A / (other layer /) second laminated glass component / internal space. Install. In the above laminated structure, other layers may or may not exist. Sunlight including heat rays enters the laminated glass from the external space, and the sunlight including heat rays passing through the laminated glass is guided to the internal space. When the laminated glass is attached to the opening as described above, the outer surface of the first laminated glass constituting member becomes the incident surface for the heat rays. As a result, the amount of heat rays reaching the intermediate film A can be effectively reduced by the first laminated glass constituent member that is a heat ray absorbing plate glass.

  Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited only to the following examples.

  In the examples and comparative examples, the following materials were used to produce the intermediate film A.

Example 1
(1) Preparation of intermediate film 40 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) and an amount of 0.030% by weight in 100% by weight of the intermediate film from which cesium-doped tungsten oxide particles can be obtained Were mixed in a horizontal microbead mill to obtain a dispersion.

  Polyvinyl butyral resin (PVB, polyvinyl butyral resin acetalized with n-butyraldehyde, average polymerization degree 1700, hydroxyl group content 30.5 mol%, acetylation degree 1 mol%, butyralization degree 68.5 mol% ) 100 parts by weight of the total amount of the dispersion and the antioxidant (2,6-di-t-butyl-p-cresol (BHT), trade name “Sumilyzer BHT” manufactured by Sumitomo Chemical Co., Ltd.) An amount of 0.57% by weight in 100% by weight of the obtained intermediate film and an amount of 0.57% by weight in 100% by weight of the intermediate film from which Tinuvin 326 as an ultraviolet shielding agent is obtained are added, and a mixing roll Were sufficiently kneaded to obtain a composition.

  The obtained composition was sandwiched between two fluororesin sheets via a clearance plate (the same thickness as the obtained intermediate film), and press molded at 150 ° C. for 30 minutes to obtain an intermediate film having a thickness of 760 μm. .

(2) Production of laminated glass The obtained intermediate film was cut into a size of 30 cm in length and 30 cm in width. Next, two heat ray absorbing plate glasses (conforming to JIS R3208, length 30 cm × width 30 cm × thickness 2 mm) were prepared. The obtained interlayer film was sandwiched between the two heat ray absorbing plate glasses, held at 90 ° C. for 30 minutes with a vacuum laminator, and vacuum pressed to obtain a laminate. In the laminated body, the intermediate film portion protruding from the glass plate was cut off to obtain a laminated glass.

(Examples 2-3)
An interlayer film was produced in the same manner as in Example 1 except that the contents of tungsten oxide particles (heat shielding particles), antioxidants and ultraviolet shielding agents were set as shown in Table 1 below. Using the obtained interlayer film, an interlayer film and a laminated glass were produced in the same manner as in Example 1.

(Comparative Example 1)
In the production of laminated glass, two heat ray absorbing plate glasses (conforming to JIS R3208, length 30 cm × width 30 cm × thickness 2 mm) and two float glass (clear glass, conforming to JIS 3202, length 30 cm × width 30 cm × thickness) A laminated glass was obtained in the same manner as in Example 1 except that it was changed to 2 mm).

(Comparative Example 2)
An interlayer film and a laminated glass were produced in the same manner as in Example 1 except that tungsten oxide particles (heat shielding particles) were not used.

(Evaluation)
(1) Measurement of visible light transmittance (A light Y value, initial AY (380 to 780 nm)) Using a spectrophotometer ("U-4100" manufactured by Hitachi High-Tech), conforming to JIS R3211 (1998) And the said visible light transmittance in wavelength 380-780 nm of the obtained laminated glass was measured.

(2) Measurement of solar transmittance (initial Ts2500 (300-2500 nm)) Using a spectrophotometer ("U-4100" manufactured by Hitachi High-Tech), laminated glass obtained according to JIS R3106 (1998) The solar radiation transmittance Ts (Ts2500) at a wavelength of 300 to 2500 nm was determined.

(3) Long-term stability (light resistance)
Using an ultraviolet irradiation device (“HLG-2S” manufactured by Suga Test Instruments Co., Ltd.), the laminated glass was irradiated with ultraviolet rays (quartz glass mercury lamp (750 W)) for 500 hours and 1000 hours in accordance with JIS R3205. AY of the laminated glass after irradiation for 500 hours and after irradiation for 1000 hours was measured by the above method.

  From the obtained measured value, ΔA−Y ((AY after irradiation with ultraviolet rays) − (initial AY)) was determined.

  The results are shown in Table 1 below. In Table 1 below, the contents of cesium-doped tungsten oxide particles (heat-shielding particles), antioxidants and UV-screening agents indicate the content (% by weight) in 100% by weight of the intermediate film.

DESCRIPTION OF SYMBOLS 1 ... Laminated glass 2 ... Intermediate film 2a ... 1st surface 2b ... 2nd surface 11 ... Laminated glass 12 ... Multilayer intermediate film 13-15 ... Intermediate film 13a ... Outer surface 15a ... Outer surface 21 ... 1st Laminated glass constituent member 22 ... second laminated glass constituent member

Claims (8)

An interlayer film,
A first laminated glass component disposed on the first surface side of the intermediate film;
A second laminated glass component disposed on the second surface side opposite to the first surface side of the intermediate film,
The interlayer film includes a thermoplastic resin and tungsten oxide particles,
Laminated glass, wherein the first laminated glass constituent member is a heat ray absorbing plate glass.   The laminated glass according to claim 1, wherein the second laminated glass constituent member is a heat ray absorbing plate glass.   The laminated glass according to claim 1 or 2, wherein the tungsten oxide particles are cesium-doped tungsten oxide particles.   The laminated glass according to any one of claims 1 to 3, wherein the thermoplastic resin is a polyvinyl acetal resin.   The laminated glass of any one of Claims 1-4 in which the said intermediate film further contains a plasticizer.   The laminated glass according to any one of claims 1 to 5, wherein the first laminated glass constituent member is laminated on the first surface of the intermediate film.   The laminated glass according to any one of claims 1 to 6, wherein the second laminated glass constituent member is laminated on the second surface of the intermediate film. A method for attaching the laminated glass according to any one of claims 1 to 7 to an opening between an external space and an internal space into which heat rays are incident from the external space in a building or a vehicle,
The laminated glass is attached to the opening so that the first laminated glass constituent member is located on the outer space side and the second laminated glass constituent member is located on the inner space side. How to attach the laminated glass.

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