WO2019189738A1 - 合わせガラス用中間膜及び合わせガラス - Google Patents
合わせガラス用中間膜及び合わせガラス Download PDFInfo
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- WO2019189738A1 WO2019189738A1 PCT/JP2019/013948 JP2019013948W WO2019189738A1 WO 2019189738 A1 WO2019189738 A1 WO 2019189738A1 JP 2019013948 W JP2019013948 W JP 2019013948W WO 2019189738 A1 WO2019189738 A1 WO 2019189738A1
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- laminated glass
- resin layer
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- SSKNCQWPZQCABD-UHFFFAOYSA-N 2-[2-[2-(2-heptanoyloxyethoxy)ethoxy]ethoxy]ethyl heptanoate Chemical compound CCCCCCC(=O)OCCOCCOCCOCCOC(=O)CCCCCC SSKNCQWPZQCABD-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
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- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
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- ALKCLFLTXBBMMP-UHFFFAOYSA-N 3,7-dimethylocta-1,6-dien-3-yl hexanoate Chemical compound CCCCCC(=O)OC(C)(C=C)CCC=C(C)C ALKCLFLTXBBMMP-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
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- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
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- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10165—Functional features of the laminated safety glass or glazing
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Definitions
- the present invention relates to an interlayer film for laminated glass having an infrared reflecting layer. Moreover, this invention relates to the laminated glass using the said intermediate film for laminated glasses.
- Laminated glass is generally 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.
- an intermediate film having an infrared reflection layer may be used.
- An intermediate film including an infrared reflective layer is disclosed in Patent Document 1 below.
- examples of the infrared reflective layer include metal films such as Au, Ag, Cu, Al, Pd, Pt, Sn, In, Zn, Ti, Cd, Fe, Co, Cr, and Ni; An alloy film of two or more metals; a multilayer film in which dielectric layers formed of TiO 2 , Nb 2 O 5 , Ta 2 O 5 , SiO 2 , Al 2 O 3 , ZrO 2 , MgF 2, etc. are stacked. Are listed.
- laminated glass using an intermediate film is attached to the opening of the vehicle.
- Sunlight is incident on the laminated glass attached to the opening of the vehicle, and the laminated glass is exposed to high temperatures.
- the laminated glass of a vehicle is also exposed to high humidity.
- Patent Document 1 discloses an infrared reflective layer having a metal film formed of metal. In the laminated glass using this infrared reflective layer, aggregation of the metal in the metal film may proceed due to heat and humidity. As a result, high heat shielding properties cannot be maintained, or variations in heat shielding properties occur.
- an infrared reflective layer and a first resin layer containing a thermoplastic resin are provided, and the first resin layer is disposed on the first surface side of the infrared reflective layer.
- the infrared reflection layer includes a silver layer, and in the In-Plane XRD measurement of the silver layer, the half width of the peak at the (111) diffraction plane is 1.3 or less, or the (200) diffraction plane
- An interlayer film for laminated glass hereinafter sometimes referred to as an interlayer film having a half width of a peak at 2.0 is 2.0 or less.
- the half width of the peak at the (111) diffraction plane is 1.3 or less, and the (200) diffraction plane is The half width of the peak is 2.0 or less.
- the infrared reflective layer includes a resin film and the silver layer, and the silver layer is disposed on at least one surface of the resin film.
- the first resin layer includes an ultraviolet shielding agent.
- the first resin layer includes a heat shielding material.
- thermoplastic resin in the first resin layer is a polyvinyl acetal resin.
- the first resin layer contains a plasticizer.
- the intermediate film includes a second resin layer, and the second surface is opposite to the first surface of the infrared reflective layer.
- a resin layer is disposed.
- the second resin layer includes an ultraviolet shielding agent.
- thermoplastic resin in the second resin layer is a polyvinyl acetal resin.
- the second resin layer contains a plasticizer.
- the first laminated glass member, the second laminated glass member, and the interlayer film for laminated glass described above, wherein the interlayer film has a second resin layer Alternatively, when the intermediate film has the second resin layer, the second resin layer is disposed on the second surface side opposite to the first surface of the infrared reflective layer. And when the intermediate film has the second resin layer, the first laminated glass member is disposed outside the first resin layer, and the first laminated glass member is disposed outside the second resin layer. 2 laminated glass members are disposed, and when the intermediate film does not have the second resin layer, the first laminated glass member is disposed outside the first resin layer, The second laminated glass member is disposed outside the infrared reflective layer, Then glass is provided.
- the said laminated glass is a building or a vehicle.
- said 2nd It is a laminated glass attached so that a laminated glass member may be located in the said external space side, and so that the said 1st laminated glass member may be located in the said internal space side.
- the interlayer film for laminated glass according to the present invention has an infrared reflecting layer and a first resin layer containing a thermoplastic resin.
- the first resin layer is disposed on the first surface side of the infrared reflective layer.
- the infrared reflective layer includes a silver layer.
- the half width of the peak at the (111) diffraction plane is 1.3 or less, or the peak at the (200) diffraction plane The half-value width is 2.0 or less. Since the interlayer film for laminated glass according to the present invention has the above-described configuration, the heat shielding property can be enhanced, the aggregation of silver can be suppressed, and the high heat shielding property can be maintained.
- FIG. 1 is a cross-sectional view schematically showing an interlayer film for laminated glass according to the first embodiment of the present invention.
- FIG. 2 is a cross-sectional view schematically showing an interlayer film for laminated glass according to the second embodiment of the present invention.
- FIG. 3 is a cross-sectional view schematically showing an example of a laminated glass using the laminated glass interlayer film shown in FIG.
- FIG. 4 is a cross-sectional view schematically showing an example of a laminated glass using the laminated glass interlayer film shown in FIG.
- the interlayer film for laminated glass according to the present invention (hereinafter sometimes referred to as an interlayer film) has an infrared reflecting layer and a first resin layer containing a thermoplastic resin.
- the first resin layer is disposed on the first surface side of the infrared reflective layer.
- the infrared reflective layer includes a silver layer.
- the half width of the peak on the (111) diffraction plane is 1.3 or less, or the half width of the peak on the (200) diffraction plane Is 2.0 or less.
- the intermediate film according to the present invention is provided with the above-described configuration, it is possible to enhance the heat shielding property, suppress the aggregation of silver, and maintain a high heat shielding property.
- the first resin layer is formed in an opening between an external space and an internal space where heat rays are incident from the external space. It can attach so that it may be located in the said internal space side.
- heat rays such as sunlight are effectively reflected by the infrared reflecting layer.
- silver aggregation is unlikely to occur in the silver layer in the infrared reflective layer.
- silver aggregation hardly occurs in the silver layer in the infrared reflective layer. For this reason, high heat insulation can be maintained, and it can be made difficult to produce dispersion
- the half width of the peak on the (111) diffraction plane when the half width of the peak on the (111) diffraction plane is 1.3 or less, the half width of the peak on the (200) diffraction plane may not be 2.0 or less. In the intermediate film according to the present invention, when the half width of the peak on the (200) diffraction plane is 2.0 or less, the half width of the peak on the (111) diffraction plane may not be 1.3 or less.
- the half width of the peak at the (111) diffraction plane is 1.3 or less, and ( 200) It is preferable that the half width of the peak on the diffraction surface is 2.0 or less.
- the half width of the peak on the (111) diffraction plane As a method of setting the half width of the peak on the (111) diffraction plane to 1.3 or less, or the half width of the peak on the (200) diffraction plane to 2.0 or less, sputtering power, argon gas flow rate, pressure at sputtering The method of adjusting is mentioned.
- the half width of the peak at the (111) diffraction plane is 1.3 or less, or half of the peak at the (200) diffraction plane.
- the price range can be adjusted to 2.0 or less.
- the half width of the peak on the (111) diffraction plane is preferably 1.2 or less, more preferably 1.1 or less.
- the half width of the peak on the (200) diffraction plane is preferably 1.9 or less, more preferably 1.8 or less.
- the half width of the peak on the (111) diffraction plane of the silver layer and the half width of the peak on the (200) diffraction plane are measured as follows.
- ATX-G type for surface structure evaluation manufactured by Rigaku Denki Co., Ltd.
- a diffraction spectrum is measured with a scanning axis 2 ⁇ / ⁇ (In-Plane diffraction method) using a multifunctional X-ray diffractometer.
- Profile fitting of 2 ⁇ : about 38 ° ⁇ (111) diffraction plane and 2 ⁇ : about 44 ° ⁇ (200) plane is performed, and the half width of the peak is calculated.
- the visible light transmittance of the interlayer film is preferably 20% or more, more preferably 50% or more, and further preferably 70% or more. From the viewpoint of further improving the visibility through the laminated glass, the visible light transmittance of the laminated glass is preferably 20% or more, more preferably 50% or more, and further preferably 70% or more.
- the visible light transmittance is measured at a wavelength of 380 nm to 780 nm in accordance with JIS R3211: 1998 using a spectrophotometer (“U-4100” manufactured by Hitachi High-Tech).
- the visible light transmittance of the intermediate film may be measured by disposing the intermediate film between clear glass and green glass.
- the solar radiation acquisition rate of the interlayer film is preferably 60% or less, more preferably 59% or less, and still more preferably 58% or less.
- the solar radiation acquisition rate of the laminated glass is preferably 60% or less, more preferably 59% or less, and still more preferably 58% or less.
- the solar radiation acquisition rate is measured and calculated as follows.
- the transmittance / reflectance of the obtained laminated glass at a wavelength of 300 nm to 2500 nm was measured in accordance with ISO 13837, and the above-mentioned solar radiation acquisition rate was determined. It can be calculated.
- the solar radiation acquisition rate of the intermediate film may be measured by arranging the intermediate film between clear glass and green glass.
- the intermediate film has or does not have the second resin layer.
- the intermediate film may have a second resin layer.
- the second resin layer is disposed on the second surface side opposite to the first surface of the infrared reflective layer.
- the intermediate film may be rolled into a roll body of the intermediate film.
- the roll body may include a winding core and an intermediate film.
- the intermediate film may be wound around the outer periphery of the winding core.
- FIG. 1 is a cross-sectional view schematically showing an interlayer film for laminated glass according to the first embodiment of the present invention.
- the intermediate film 11 shown in FIG. 1 is a multilayer intermediate film having a structure of three or more layers.
- the intermediate film 11 is used to obtain a laminated glass.
- the intermediate film 11 is an intermediate film for laminated glass.
- the intermediate film 11 includes an infrared reflection layer 1, a first resin layer 2, and a second resin layer 3.
- the infrared reflecting layer 1 is an intermediate layer.
- Each of the first resin layer 2 and the second resin layer 3 is a protective layer, and is a surface layer in the present embodiment.
- the infrared reflection layer 1 is disposed between the first resin layer 2 and the second resin layer 3 and is sandwiched. Therefore, the intermediate film 11 has a multilayer structure (first resin layer 2 / infrared reflective layer 1 / second) in which the first resin layer 2, the infrared reflective layer 1, and the second resin layer 3 are laminated in this order. The resin layer 3).
- FIG. 2 is a cross-sectional view schematically showing an interlayer film for laminated glass according to the second embodiment of the present invention.
- the intermediate film 11A shown in FIG. 2 is a multilayer intermediate film having a two-layer structure.
- the intermediate film 11A is used to obtain a laminated glass.
- the intermediate film 11A is an intermediate film for laminated glass.
- the intermediate film 11 ⁇ / b> A includes an infrared reflective layer 1 and a first resin layer 2. On the first surface 1a side of the infrared reflecting layer 1, the first resin layer 2 is disposed and laminated.
- the intermediate film 11A has a multilayer structure (first resin layer 2 / infrared reflective layer 1) in which the first resin layer 2 and the infrared reflective layer 1 are laminated in this order.
- the other layer include a layer containing an adhesive layer, polyethylene terephthalate and the like.
- the infrared reflection layer reflects infrared rays.
- the infrared reflection layer is not particularly limited as long as it has the ability to reflect infrared rays.
- the infrared reflection layer includes a silver layer.
- the silver layer may be a single layer or two or more layers.
- the silver layer is preferably a silver sputtering layer.
- the silver sputtering layer can be formed by silver sputtering.
- the infrared reflective layer preferably includes a resin film and the silver layer.
- the silver layer is preferably disposed on at least one surface of the resin film.
- the silver layer may be disposed only on the first surface of the resin film, on the first surface of the resin film and on the second surface opposite to the first surface. It may be arranged.
- the infrared reflecting layer preferably has a property that the infrared transmittance is 40% or less at at least one wavelength in the range of 800 nm to 2000 nm because of excellent performance of reflecting infrared rays.
- the infrared transmittance of the infrared reflective layer used in the examples described later satisfies the above preferable conditions. At least one wavelength within the range of 800 nm to 2000 nm, the infrared transmittance is more preferably 30% or less, and still more preferably 20% or less.
- the transmittance of each wavelength in the wavelength range of 800 nm to 2000 nm of the infrared reflective layer is specifically measured as follows.
- a single infrared reflecting layer is prepared.
- the spectral transmittance of each wavelength in the wavelength range of 800 nm to 2000 nm of the infrared reflective layer is obtained in accordance with JIS R3106: 1998 or JIS R3107: 2013. In accordance with JIS R3107: 2013, it is preferable to obtain the spectral transmittance of each wavelength in the wavelength range of 800 nm to 2000 nm of the infrared reflective layer.
- Thermoplastic resin contains a thermoplastic resin (hereinafter may be referred to as a thermoplastic resin (1)). It is preferable that a 1st resin layer contains polyvinyl acetal resin (Hereinafter, it may be described as polyvinyl acetal resin (1).) As a thermoplastic resin (1).
- the second resin layer contains a thermoplastic resin (hereinafter sometimes referred to as a thermoplastic resin (2)). It is preferable that a 2nd resin layer contains polyvinyl acetal resin (Hereinafter, it may be described as polyvinyl acetal resin (2).) As a thermoplastic resin (2).
- thermoplastic resin (1) and the thermoplastic resin (2) may be the same or different. As for the said thermoplastic resin (1) and the said thermoplastic resin (2), only 1 type may respectively be used and 2 or more types may be used together. As for the said polyvinyl acetal resin (1) and the said polyvinyl acetal resin (2), only 1 type may respectively be used and 2 or more types may be used together.
- thermoplastic resin examples include polyvinyl acetal resin, ethylene-vinyl acetate copolymer resin, ethylene-acrylic acid copolymer resin, polyurethane resin, polyvinyl alcohol resin, polyolefin resin, polyvinyl acetate resin, polystyrene resin, and ionomer resin. Is mentioned. Thermoplastic resins other than these may be used.
- the thermoplastic resin is preferably a polyvinyl acetal resin.
- the adhesive force of the resin layer to other layers such as the laminated glass member and the infrared reflection layer is further increased.
- the polyvinyl acetal resin can be produced, for example, by acetalizing polyvinyl alcohol (PVA) with an aldehyde.
- PVA polyvinyl alcohol
- the polyvinyl acetal resin is preferably an acetalized product of polyvinyl alcohol.
- the polyvinyl alcohol can be obtained, for example, by saponifying polyvinyl acetate.
- the saponification degree of the polyvinyl alcohol is generally in the range of 70 to 99.9 mol%.
- the average degree of polymerization of the polyvinyl alcohol (PVA) is preferably 200 or more, more preferably 500 or more, still more preferably 1500 or more, still more preferably 1600 or more, particularly preferably 2600 or more, most preferably 2700 or more, preferably It is 5000 or less, more preferably 4000 or less, and still more preferably 3500 or less.
- the average degree of polymerization is not less than the above lower limit, the penetration resistance of the laminated glass is further enhanced.
- the average degree of polymerization is not more than the above upper limit, the resin layer can be easily molded.
- the average degree of polymerization of the polyvinyl alcohol is determined by a method based on JIS K6726 “Testing method for polyvinyl alcohol”.
- the carbon number 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 acetal group in the polyvinyl acetal resin preferably has 3 to 5 carbon atoms, more 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 resin layer is sufficiently low.
- the aldehyde is not particularly limited. In general, aldehydes having 1 to 10 carbon atoms are preferably used. 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.
- Propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-hexylaldehyde or n-valeraldehyde is preferred, propionaldehyde, n-butyraldehyde or isobutyraldehyde is more preferred, and n-butyraldehyde is still more preferred.
- 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, still more preferably 20 mol% or more, particularly preferably 28 mol% or more, preferably 40 mol. % Or less, more preferably 35 mol% or less, still more preferably 32 mol% or less.
- the hydroxyl group content is at least the above lower limit, the adhesive strength of the resin layer is further increased.
- the flexibility of a resin layer becomes it high that the content rate of the said hydroxyl group is below the said upper limit, and the handling of a resin layer 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 the ethylene group to which the hydroxyl group is bonded can be measured, for example, according to JIS K6728 “Testing method for polyvinyl butyral”.
- 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 20 mol% or less, particularly preferably 15 mol% or less, and most preferably 3 mol% or less.
- the acetylation degree is not less than the above lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer is increased.
- the acetylation degree is not more than the above upper limit, the moisture resistance of the laminated glass is increased.
- the degree of acetylation is a value obtained by dividing the amount of ethylene groups to which the acetyl 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 acetyl 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 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.
- the degree of acetalization is not less than the above lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer increases.
- 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 obtained as follows. First, a value obtained by subtracting the amount of ethylene groups bonded with hydroxyl groups and the amount of ethylene groups bonded with acetyl groups from the total amount of ethylene groups in the main chain is obtained. The obtained value is divided by the total amount of ethylene groups in the main chain to obtain the mole fraction. A value indicating the mole fraction as a percentage is the degree of acetalization.
- the hydroxyl group content (hydroxyl content), acetalization degree (butyralization degree), and acetylation degree are preferably calculated from results measured by a method in accordance with JIS K6728 “Testing methods for polyvinyl butyral”. However, measurement by ASTM D1396-92 may be used.
- the polyvinyl acetal resin is a polyvinyl butyral resin
- the hydroxyl group content (hydroxyl amount), the acetalization degree (butyralization degree), and the acetylation degree are determined in accordance with JIS K6728 “Testing methods for polyvinyl butyral”. It can be calculated from the results measured by
- the first resin layer preferably contains a plasticizer.
- the second resin layer preferably contains a plasticizer.
- the thermoplastic resin contained in the resin layer is a polyvinyl acetal resin
- the resin layer particularly preferably contains a plasticizer.
- the layer containing the polyvinyl acetal resin 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.
- plasticizer examples include organic ester plasticizers such as monobasic organic acid esters and polybasic organic acid esters, and organic phosphate plasticizers such as organic phosphoric acid plasticizers and organic phosphorous acid plasticizers. .
- organic ester plasticizers are preferred.
- the plasticizer is preferably a liquid plasticizer.
- Examples of the monobasic organic acid ester include glycol esters obtained by a reaction between glycol and a monobasic organic acid.
- 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.
- polybasic organic acid ester examples include ester compounds of a polybasic organic acid and an alcohol having a linear or branched structure having 4 to 8 carbon atoms.
- polybasic organic acid examples include adipic acid, sebacic acid, and azelaic acid.
- organic ester plasticizer examples include triethylene glycol di-2-ethylpropanoate, 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-ethylbutyrate, 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-eth
- organic phosphate plasticizer examples include tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphate, and the like.
- the plasticizer is preferably a diester plasticizer represented by the following formula (1).
- R1 and R2 each represents an organic group having 5 to 10 carbon atoms
- R3 represents an ethylene group, an isopropylene group or an n-propylene group
- p represents an integer of 3 to 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 triethylene glycol di-2-ethylhexanoate (3GO) or triethylene glycol di-2-ethylbutyrate (3GH). Triethylene glycol di-2-ethylhexanoate It is more preferable to contain.
- the content of the plasticizer is not particularly limited.
- the content of the plasticizer is preferably 25 parts by weight or more with respect to 100 parts by weight of the thermoplastic resin. Is 30 parts by weight or more, more preferably 35 parts by weight or more.
- the content of the plasticizer is preferably 75 parts by weight or less, more preferably 100 parts by weight or more. Is 60 parts by weight or less, more preferably 50 parts by weight or less, and particularly preferably 40 parts by weight or less.
- the first resin layer preferably contains a heat shielding material.
- the content of the heat shielding material in the second resin layer may be less than the content of the heat shielding material in the first resin layer.
- the second resin layer preferably contains a heat shielding material.
- the second resin layer may not contain a heat shielding material. As for the said heat-shielding substance, only 1 type may be used and 2 or more types may be used together.
- the heat-insulating substance preferably contains at least one component X of phthalocyanine compounds, naphthalocyanine compounds and anthracocyanine compounds, or contains heat-shielding particles. In this case, both the component X and the heat shielding particles may be included.
- the first resin layer preferably contains at least one component X of phthalocyanine compounds, naphthalocyanine compounds and anthracocyanine compounds.
- the content of the component X in the second resin layer may be less than the content of the component X in the first resin layer.
- the second resin layer preferably contains the component X.
- the second resin layer may not contain the component X. As for the said component X, only 1 type may be used and 2 or more types may be used together.
- the component X corresponds to a heat shielding material.
- the first resin layer preferably contains the component X from the viewpoint of effectively increasing the heat shielding property.
- the content of the component X in the second resin layer may be less than the content of the component X in the first resin layer.
- the second resin layer preferably contains the component X.
- the second resin layer may not contain the component X.
- As for the said component X only 1 type may be used and 2 or more types may be used together.
- the component X is not particularly limited.
- component X conventionally known phthalocyanine compounds, naphthalocyanine compounds and anthracocyanine compounds can be used.
- Examples of the component X include phthalocyanine, a derivative of phthalocyanine, naphthalocyanine, a derivative of naphthalocyanine, an anthocyanin, and an anthocyanin derivative.
- the phthalocyanine compound and the phthalocyanine derivative preferably each have a phthalocyanine skeleton.
- the naphthalocyanine compound and the naphthalocyanine derivative preferably each have a naphthalocyanine skeleton. It is preferable that each of the anthocyanin compound and the derivative of the anthracyanine has an anthracyanine skeleton.
- the component X is preferably phthalocyanine, a phthalocyanine derivative, naphthalocyanine or a naphthalocyanine derivative, and more preferably a phthalocyanine or a phthalocyanine derivative.
- the component X preferably contains a vanadium atom or a copper atom.
- the component X preferably contains a vanadium atom, and preferably contains a copper atom.
- the component X is more preferably at least one of a phthalocyanine containing a vanadium atom or a copper atom and a phthalocyanine derivative containing a vanadium atom or a copper atom.
- the component X preferably has a structural unit in which an oxygen atom is bonded to a vanadium atom.
- the content of the component X is preferably 0.001% by weight or more, more preferably 0.005% by weight. Above, more preferably 0.01% by weight or more, particularly preferably 0.02% by weight or more. In 100% by weight of the layer containing the component X (first resin layer or second resin layer), the content of the component X is preferably 0.2% by weight or less, more preferably 0.1% by weight. Hereinafter, it is more preferably 0.05% by weight or less, particularly preferably 0.04% by weight or less.
- the content of the component X is not less than the above lower limit and not more than the above upper limit, the heat shielding property is sufficiently high and the visible light transmittance is sufficiently high.
- the visible light transmittance can be 70% or more.
- the first resin layer preferably contains heat shielding particles.
- the content of the heat shielding particles in the second resin layer may be less than the content of the heat shielding particles in the first resin layer.
- the second resin layer preferably contains the heat shielding particles.
- the second resin layer may not contain heat shielding particles.
- the heat shielding particles are heat shielding materials. By using heat shielding particles, infrared rays (heat rays) can be effectively blocked. As for the said heat-shielding particle, only 1 type may be used and 2 or more types may be used together.
- the heat shielding particles are more preferably metal oxide particles.
- the heat shielding particles are preferably particles (metal oxide particles) formed of a metal oxide.
- Infrared rays having a wavelength longer than 780 nm longer than visible light have a smaller amount of energy than ultraviolet rays.
- 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.
- heat shielding particles By using the heat shielding particles, infrared rays (heat rays) can be effectively blocked.
- the heat shielding particles mean particles that can absorb infrared rays.
- heat shielding particles include aluminum-doped tin oxide particles, indium-doped tin oxide particles, antimony-doped tin oxide particles (ATO particles), gallium-doped zinc oxide particles (GZO particles), and indium-doped zinc oxide particles (IZO particles).
- Aluminum doped zinc oxide particles (AZO particles), niobium doped titanium oxide particles, sodium doped tungsten oxide particles, cesium doped tungsten oxide particles, thallium doped tungsten oxide particles, rubidium doped tungsten oxide particles, tin doped indium oxide particles (ITO particles) And metal oxide particles such as tin-doped zinc oxide particles and silicon-doped zinc oxide particles, and lanthanum hexaboride (LaB 6 ) particles. Heat shielding particles other than these may be used.
- Metal oxide particles are preferred because of their high heat ray shielding function, ATO particles, GZO particles, IZO particles, ITO particles or tungsten oxide particles are more preferred, and ITO particles or tungsten oxide particles are particularly preferred.
- tin-doped indium oxide particles (ITO particles) are preferable, and tungsten oxide particles are also preferable because they have a high heat ray shielding function and are easily available.
- 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.
- cesium-doped tungsten oxide particles are particularly preferable.
- 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 heat shielding particles is preferably 0.01 ⁇ m or more, more preferably 0.02 ⁇ m or more, preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less.
- the average particle size is not less than the above lower limit, the heat ray shielding property is sufficiently increased.
- the average particle size is not more than the above upper limit, the dispersibility of the heat shielding particles is increased.
- the above “average particle diameter” indicates the volume average particle diameter.
- the average particle diameter can be measured using a particle size distribution measuring device (“UPA-EX150” manufactured by Nikkiso Co., Ltd.) or the like.
- the content of the heat shielding particles is preferably 0.01% by weight or more, more preferably 0.1%. % By weight or more, more preferably 1% by weight or more, particularly preferably 1.5% by weight or more.
- the content of the heat shielding particles is preferably 6% by weight or less, more preferably 5.5% by weight.
- it is further preferably 4% by weight or less, particularly preferably 3.5% by weight or less, and most preferably 3% by weight or less.
- the first resin layer preferably contains a metal salt (hereinafter sometimes referred to as metal salt M) which is an alkali metal salt, an alkaline earth metal salt or a magnesium salt.
- the second resin layer preferably contains the metal salt M.
- metal salt M By using the metal salt M, it becomes easy to control the adhesion between the resin layer, the infrared reflective layer, and the laminated glass member.
- the said metal salt M only 1 type may be used and 2 or more types may be used together.
- the metal salt M preferably contains a metal that is Li, Na, K, Rb, Cs, Mg, Ca, Sr or Ba.
- the metal salt contained in the resin layer preferably contains K or Mg.
- the metal salt M is an alkali metal salt of an organic acid having 2 to 16 carbon atoms, an alkaline earth metal salt of an organic acid having 2 to 16 carbon atoms, or a magnesium salt of an organic acid having 2 to 16 carbon atoms. Is more preferable, and it is more preferably a carboxylic acid magnesium salt having 2 to 16 carbon atoms or a carboxylic acid potassium salt having 2 to 16 carbon atoms.
- Examples of the C 2-16 carboxylic acid magnesium salt and the C 2-16 carboxylic acid potassium salt include magnesium acetate, potassium acetate, magnesium propionate, potassium propionate, magnesium 2-ethylbutyrate, 2-ethylbutanoic acid. Examples include potassium, magnesium 2-ethylhexanoate, and potassium 2-ethylhexanoate.
- the total content of Mg and K in the layer containing the metal salt M is preferably 5 ppm or more, more preferably 10 ppm or more, still more preferably 20 ppm or more, preferably Is 300 ppm or less, more preferably 250 ppm or less, still more preferably 200 ppm or less.
- the adhesion between the resin layer, the infrared reflecting layer, and the laminated glass member can be controlled even better.
- the first resin layer preferably contains an ultraviolet shielding agent.
- the second resin layer preferably contains an ultraviolet shielding agent.
- the 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.
- the said 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.
- the ultraviolet shielding agent examples include an ultraviolet shielding agent containing a metal atom, an ultraviolet shielding agent containing a metal oxide, an ultraviolet shielding agent having a benzotriazole structure (benzotriazole compound), and an ultraviolet shielding agent having a benzophenone structure (benzophenone compound). ), UV screening agent having triazine structure (triazine compound), UV screening agent having malonate ester structure (malonic acid ester compound), UV screening agent having oxalic acid anilide structure (oxalic acid anilide compound) and benzoate structure Examples thereof include an ultraviolet shielding agent (benzoate compound).
- Examples of the ultraviolet shielding agent containing a metal atom include platinum particles, particles having platinum particles coated with silica, palladium particles, and particles having palladium particles coated with silica.
- the ultraviolet shielding agent is preferably not a heat shielding particle.
- the ultraviolet shielding agent is preferably an ultraviolet shielding agent having a benzotriazole structure, an ultraviolet shielding agent having a benzophenone structure, an ultraviolet shielding agent having a triazine structure, or an ultraviolet shielding agent having a benzoate structure.
- the ultraviolet shielding agent is more preferably an ultraviolet shielding agent having a benzotriazole structure or an ultraviolet shielding agent having a benzophenone structure, and more preferably an ultraviolet shielding agent having a benzotriazole structure.
- Examples of the ultraviolet shielding agent containing the metal oxide include zinc oxide, titanium oxide, and cerium oxide. Furthermore, the surface may be coat
- the insulating metal oxide examples 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 ultraviolet screening agent having the benzotriazole structure 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 (BASF) And “Tinuvin 326” manufactured by BASF, etc.) and the like.
- the ultraviolet shielding agent is preferably an ultraviolet shielding agent having a benzotriazole structure containing a halogen atom, and may be an ultraviolet shielding agent having a benzotriazole structure containing a chlorine atom. More preferred.
- Examples of the ultraviolet shielding agent having the benzophenone structure include octabenzone (“Chimasorb 81” manufactured by BASF).
- UV shielding agent having the triazine structure examples include “LA-F70” manufactured by ADEKA and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl). Oxy] -phenol (“Tinuvin 1577FF” manufactured by BASF) and the like.
- UV screening agent having a malonic ester structure examples include dimethyl 2- (p-methoxybenzylidene) malonate, tetraethyl-2,2- (1,4-phenylenedimethylidene) bismalonate, and 2- (p-methoxybenzylidene).
- 2- (p-methoxybenzylidene) malonate examples include dimethyl 2- (p-methoxybenzylidene) malonate, tetraethyl-2,2- (1,4-phenylenedimethylidene) bismalonate, and 2- (p-methoxybenzylidene).
- Examples of commercially available ultraviolet screening agents having a malonic ester structure include Hostavin B-CAP, Hostavin PR-25, and Hostavin PR-31 (all manufactured by Clariant).
- Examples of the ultraviolet shielding agent having the oxalic anilide structure include N- (2-ethylphenyl) -N ′-(2-ethoxy-5-tert-butylphenyl) oxalic acid diamide, N- (2-ethylphenyl)- Oxalic acid having an aryl group substituted on the nitrogen atom, such as N ′-(2-ethoxy-phenyl) oxalic acid diamide, 2-ethyl-2′-ethoxy-oxalanilide (“Sanduvor VSU” manufactured by Clariant) And diamides.
- ultraviolet shielding agent having the benzoate structure examples include 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate (“Tinuvin 120” manufactured by BASF). .
- the content of the ultraviolet shielding agent is preferably 0.1% by weight or more, more preferably 0.2%. % By weight or more, more preferably 0.3% by weight or more, particularly preferably 0.5% by weight or more. In 100% by weight of the layer containing the ultraviolet shielding agent (first resin layer or second resin layer), the content of the ultraviolet shielding agent is preferably 2.5% by weight or less, more preferably 2% by weight. Hereinafter, it is more preferably 1% by weight or less, particularly preferably 0.8% by weight or less.
- the content of the ultraviolet shielding agent is not less than the above lower limit and not more than the above upper limit, a decrease in visible light transmittance after a lapse of time is further suppressed.
- the content of the ultraviolet shielding agent is 0.2% by weight or more, so that a decrease in visible light transmittance after a lapse of the laminated glass period is remarkably suppressed. it can.
- the first resin layer preferably contains an antioxidant.
- the second resin layer preferably contains an antioxidant. As for the said antioxidant, only 1 type may be used and 2 or more types may be used together.
- antioxidants examples include phenol-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 or a phosphorus antioxidant.
- phenolic antioxidant examples include 2,6-di-t-butyl-p-cresol (BHT), butylhydroxyanisole (BHA), 2,6-di-t-butyl-4-ethylphenol, stearyl- ⁇ - (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-t-butylphenol), 1,1,3-tris- (2-methyl-hydroxy-5-t-butylphenyl) butane Tetrakis [methylene-3- (3 ′, 5′-butyl-4-hydroxyphenyl) propionate] methane, 1,3,3-tris- (2-methyl-4-hydro) Loxy-5-t-butylphenol) butane, 1,3,5-trimethyl-2,4,6
- Examples of the phosphorus antioxidant include tridecyl phosphite, tris (tridecyl) phosphite, triphenyl phosphite, trinonylphenyl phosphite, bis (tridecyl) pentaerythritol diphosphite, bis (decyl) pentaerythritol diphos.
- antioxidants examples include “IRGANOX 245” manufactured by BASF, “IRGAFOS 168” manufactured by BASF, “IRGAFOS 38” manufactured by BASF, “Smilizer BHT” manufactured by Sumitomo Chemical Co., Ltd., and Sakai Chemical Industry Examples thereof include “H-BHT” and “IRGANOX 1010” manufactured by BASF.
- the antioxidant is contained in 100% by weight of the layer containing the antioxidant (first resin layer or second resin layer).
- the amount is preferably 0.1% by weight or more.
- content of the said antioxidant is 2 weight% or less in 100 weight% of layers containing the said antioxidant.
- the first resin layer and the second resin layer are respectively adjusted for adhesive strength other than coupling agents, dispersants, surfactants, flame retardants, antistatic agents, pigments, dyes, and metal salts as necessary.
- Additives such as an agent, a moisture-proofing agent, a fluorescent brightening agent and an infrared absorber may be included. As for these additives, only 1 type may be used and 2 or more types may be used together.
- the thickness of the intermediate film is not particularly limited. From the viewpoint of practical use and from the viewpoint of sufficiently enhancing the penetration resistance and bending rigidity of the laminated glass, the thickness of the interlayer film is preferably 0.1 mm or more, more preferably 0.25 mm or more, preferably 3 mm or less, more Preferably it is 1.5 mm or less. When the thickness of the interlayer film is not less than the above lower limit, the penetration resistance and bending rigidity of the laminated glass are further increased. When the thickness of the interlayer film is not more than the above upper limit, the transparency of the interlayer film is further improved.
- the intermediate film may be an intermediate film having a uniform thickness or an intermediate film having a changed thickness.
- the cross-sectional shape of the intermediate film may be rectangular or wedge-shaped.
- the intermediate film preferably has an uneven shape on the outer surface.
- the intermediate film only needs to have an uneven shape on at least one of the outer surfaces on both sides.
- the intermediate film preferably has an uneven shape on at least one of the outer surfaces on both sides. More preferably, the intermediate film has an uneven shape on both outer surfaces.
- the outer surface of the intermediate film is preferably embossed. In this case, at least one of the outer surfaces on both sides may be embossed. It is preferable that at least one of the outer surfaces on both sides of the intermediate film is embossed. More preferably, the outer surfaces on both sides of the intermediate film are embossed.
- the lip embossing method the embossing roll method, the calender roll method, a profile extrusion method, etc. are mentioned.
- the embossing roll method is preferable because it can form a large number of concavo-convex embossments that are quantitatively constant.
- FIG. 3 is a cross-sectional view schematically showing an example of a laminated glass using the laminated glass interlayer film shown in FIG.
- the intermediate film 11 is disposed between the first laminated glass member 21 and the second laminated glass member 22 and is sandwiched.
- the first laminated glass member 21 is laminated on the first surface 11 a of the intermediate film 11.
- a second laminated glass member 22 is laminated on the second surface 11 b opposite to the first surface 11 a of the intermediate film 11.
- a first laminated glass member 21 is disposed on the outer surface 2a of the first resin layer 2 and laminated.
- a second laminated glass member 22 is disposed on the outer surface 3a of the second resin layer 3 and laminated.
- FIG. 4 is a cross-sectional view schematically showing an example of laminated glass using the interlayer film for laminated glass shown in FIG.
- a laminated glass 31A shown in FIG. 4 includes a first laminated glass member 21, a second laminated glass member 22, and an intermediate film 11A.
- 11 A of intermediate films are arrange
- the first laminated glass member 21 is laminated on the first surface 11a of the intermediate film 11A.
- a second laminated glass member 22 is laminated on the second surface 11b opposite to the first surface 11a of the intermediate film 11A.
- a first laminated glass member 21 is disposed on the outer surface 2a of the first resin layer 2 and laminated.
- a second laminated glass member 22 is disposed on the second surface 1b (outer surface) of the infrared reflective layer 1 and laminated.
- the laminated glass which concerns on this invention is equipped with the 1st laminated glass member, the 2nd laminated glass member, and the intermediate film, and this intermediate film is the intermediate film for laminated glasses which concerns on this invention. It is.
- the interlayer film is disposed between the first laminated glass member and the second laminated glass member.
- the intermediate film has the second resin layer
- the first laminated glass member is disposed outside the first resin layer
- the second resin layer is disposed outside the second resin layer.
- a laminated glass member is disposed.
- the intermediate film does not have the second resin layer
- the first laminated glass member is disposed outside the first resin layer
- the second laminated glass is disposed outside the infrared reflecting layer.
- a glass member is disposed.
- the laminated glass has an opening between an external space and an internal space where heat rays are incident from the external space, and the first laminated glass member is positioned on the external space side, and It is preferable that the second laminated glass member is attached so as to be positioned on the inner space side.
- the first laminated glass member is preferably a first glass plate.
- the second laminated glass member is preferably a second glass plate.
- the laminated glass member examples include a glass plate and a PET (polyethylene terephthalate) film.
- Laminated glass includes not only laminated glass in which an intermediate film is sandwiched between two glass plates, but also laminated glass in which an intermediate film is sandwiched between a glass plate and a PET film or the like.
- the laminated glass is a laminate including a glass plate, and preferably at least one glass plate is used.
- Each of the first laminated glass member and the second laminated glass member is a glass plate or a PET film, and the laminated glass is one of the first laminated glass member and the second laminated glass member. It is preferable to provide a glass plate as at least one.
- the glass plate examples include inorganic glass and organic glass.
- the inorganic glass examples include float plate glass, heat ray absorbing plate glass, heat ray reflecting plate glass, polished plate glass, mold plate glass, and wire-containing plate glass.
- the organic glass is a synthetic resin glass that replaces the 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 thickness of the laminated glass member is preferably 1 mm or more, more preferably 1.8 mm or more, further preferably 2 mm or more, particularly preferably 2.1 mm or more, preferably 5 mm or less, more preferably 3 mm or less. Further, when the laminated glass member is a glass plate, the thickness of the glass plate is preferably 1 mm or more, more preferably 1.8 mm or more, further preferably 2 mm or more, particularly preferably 2.1 mm or more, preferably It is 5 mm or less, More preferably, it is 3 mm or less, More preferably, it is 2.6 mm or less. When the laminated glass member 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 first laminated glass member and the second laminated glass member are each preferably clear glass or heat ray absorbing plate glass. Since the infrared transmittance is high and the heat shielding property of the laminated glass is further enhanced, the second laminated glass member is preferably clear glass. Since the infrared transmittance is low and the heat shielding property of the laminated glass is further increased, the first laminated glass member is preferably a heat-absorbing plate glass. The heat ray absorbing plate glass is preferably green glass. The second laminated glass member is preferably clear glass, and the first laminated glass member is preferably a heat ray absorbing plate glass. The heat ray absorbing plate glass is a heat ray absorbing plate glass based on JIS R3208.
- the method for producing the laminated glass is not particularly limited. First, an interlayer film is sandwiched between the first laminated glass member and the second laminated glass member to obtain a laminate. Next, for example, by passing the obtained laminate through a pressing roll or putting it in a rubber bag and sucking under reduced pressure, the first laminated glass member, the second laminated glass member, and the intermediate film The remaining air is deaerated. Thereafter, pre-bonding is performed at about 70 to 110 ° C. to obtain a pre-bonded laminate. Next, the pre-pressed laminate 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. You may laminate
- the interlayer film and the laminated glass can be used for automobiles, railway vehicles, aircraft, ships, buildings, and the like.
- the said intermediate film and the said laminated glass can be used besides these uses.
- the interlayer film and the laminated glass are preferably an interlayer film and laminated glass for vehicles or buildings, and more preferably an interlayer film and laminated glass for vehicles.
- the intermediate film and the laminated glass can be used for an automobile windshield, side glass, rear glass, roof glass, or the like.
- the interlayer film and the laminated glass are suitably used for automobiles.
- the interlayer film is used for obtaining laminated glass for automobiles.
- the laminated glass is suitably used for a car windshield.
- the laminated glass is preferably a laminated glass that can be used for a windshield of a car.
- Polyvinyl acetal resin (PVB, average polymerization degree 1700, hydroxyl group content 30.5 mol%, acetylation degree 1 mol%, acetalization degree 68.5 mol%)
- n-butyraldehyde having 4 carbon atoms is used for acetalization.
- the degree of acetalization degree of butyralization
- the degree of acetylation degree of acetylation
- the hydroxyl group content were measured by a method based on JIS K6728 “Testing methods for polyvinyl butyral”.
- ASTM D1396-92 the same numerical value as the method based on JIS K6728 “Testing method for polyvinyl butyral” was shown.
- ITO ITO particles, tin-doped indium oxide particles
- CWO CWO particles, cesium-doped tungsten oxide (Cs 0.33 WO 3 ) particles
- Tinuvin 326 (2- (2′-hydroxy-3′-t-butyl-5-methylphenyl) -5-chlorobenzotriazole, “Tinvin 326” manufactured by BASF) 0.2 parts by weight
- Infrared reflective layer Infrared reflective films 1-9 and AC (films with a silver sputtering layer formed on the film, manufactured in-house)
- the (111) diffraction surface of the silver layer is obtained by setting the sputtering power, the argon gas flow rate, and the sputtering pressure as shown in Tables 1 and 2 below during silver sputtering.
- the half width of the peak at and the half width of the peak at the (200) diffraction plane were adjusted to the values shown in Tables 1 and 2 below.
- Example 1 Production of first resin layer: The following components were blended and sufficiently kneaded with a mixing roll to obtain a composition for forming the first resin layer.
- Polyvinyl acetal resin (PVB, average polymerization degree 1700, hydroxyl group content 30.5 mol%, acetylation degree 1 mol%, acetalization degree 68.5 mol%) 100 parts by weight Triethylene glycol di-2-ethylhexano Eate (3GO) 40 parts by weight
- Tinuvin 326 (2- (2′-hydroxy-3′-t-butyl-5-methylphenyl) -5-chlorobenzotriazole, an amount of 0.2% by weight in the obtained resin layer, “Tinvin 326” manufactured by BASF Corporation )
- the composition for forming the obtained first resin layer was extruded with an extruder to obtain a first resin layer.
- the first resin layer was rectangular, and the thickness of the first resin layer was 380 ⁇ m.
- Second resin layer production The following components were blended and sufficiently kneaded with a mixing roll to obtain a composition for forming the second resin layer.
- Polyvinyl acetal resin (PVB, average polymerization degree 1700, hydroxyl group content 30.5 mol%, acetylation degree 1 mol%, acetalization degree 68.5 mol%) 100 parts by weight Triethylene glycol di-2-ethylhexano Eate (3GO) 40 parts by weight
- Tinuvin 326 (2- (2′-hydroxy-3′-t-butyl-5-methylphenyl) -5-chlorobenzotriazole, an amount of 0.2% by weight in the obtained resin layer, “Tinvin 326” manufactured by BASF Corporation )
- the composition for forming the obtained second resin layer was extruded with an extruder to obtain a second resin layer.
- the second resin layer was rectangular, and the thickness of the second resin layer was 380 ⁇ m.
- Infrared reflective film 1 was prepared as an infrared reflective layer.
- Clear glass (thickness 2.5 mm) was prepared as a second laminated glass member.
- Laminated glass production The 1st laminated glass member, the 1st resin layer, the infrared reflective layer, the 2nd resin layer, and the 2nd laminated glass member were laminated in this order, and laminated glass was obtained. A first resin layer was laminated on the silver layer in the infrared reflective layer.
- Examples 2 to 9 and Comparative Examples 1 to 3 A laminated glass was obtained in the same manner as in Example 1 except that the structure of the interlayer film was changed as shown in Tables 1 and 2 below.
- Example 2 to 9 and Comparative Examples 1 to 3 the same ultraviolet shielding agent and antioxidant as in Example 1 were used in the first and second resin layers in the same manner as in Example 1 in the resin layer. It mix
- the heat shielding material was blended in the blending amounts shown in Tables 1 and 2 below at 100% by weight of the resulting resin layer.
- Incident optical system Parabolic mirror with artificial multilayer film.
- Incident optical system (I) Parabolic mirror with artificial multilayer film.
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Abstract
Description
本発明に係る合わせガラス用中間膜(以下、中間膜と記載することがある)は、赤外線反射層と、熱可塑性樹脂を含む第1の樹脂層とを有する。本発明に係る中間膜では、上記赤外線反射層の第1の表面側に上記第1の樹脂層が配置されている。本発明に係る中間膜では、上記赤外線反射層が、銀層を含む。本発明に係る中間膜では、上記銀層のIn-Plane XRD測定において、(111)回折面におけるピークの半値幅が1.3以下であるか、又は、(200)回折面におけるピークの半値幅が2.0以下である。
上記赤外線反射層は赤外線を反射する。上記赤外線反射層は、赤外線を反射する性能を有していれば特に限定されない。
熱可塑性樹脂:
第1の樹脂層は、熱可塑性樹脂(以下、熱可塑性樹脂(1)と記載することがある)を含む。第1の樹脂層は、熱可塑性樹脂(1)として、ポリビニルアセタール樹脂(以下、ポリビニルアセタール樹脂(1)と記載することがある)を含むことが好ましい。第2の樹脂層は、熱可塑性樹脂(以下、熱可塑性樹脂(2)と記載することがある)を含む。第2の樹脂層は、熱可塑性樹脂(2)として、ポリビニルアセタール樹脂(以下、ポリビニルアセタール樹脂(2)と記載することがある)を含むことが好ましい。
樹脂層の接着力をより一層高める観点からは、上記第1の樹脂層は、可塑剤を含むことが好ましい。樹脂層の接着力をより一層高める観点からは、上記第2の樹脂層は、可塑剤を含むことが好ましい。樹脂層に含まれている熱可塑性樹脂が、ポリビニルアセタール樹脂である場合に、樹脂層は、可塑剤を含むことが特に好ましい。ポリビニルアセタール樹脂を含む層は、可塑剤を含むことが好ましい。
上記第1の樹脂層は、遮熱性物質を含むことが好ましい。上記第2の樹脂層における遮熱性物質の含有量は、上記第1の樹脂層における遮熱性物質の含有量よりも少なくてもよい。上記第2の樹脂層は、遮熱性物質を含むことが好ましい。上記第2の樹脂層は、遮熱性物質を含んでいなくてもよい。上記遮熱性物質は、1種のみが用いられてもよく、2種以上が併用されてもよい。
上記第1の樹脂層は、アルカリ金属塩、アルカリ土類金属塩又はマグネシウム塩である金属塩(以下、金属塩Mと記載することがある)を含むことが好ましい。上記第2の樹脂層は、上記金属塩Mを含むことが好ましい。上記金属塩Mの使用により、樹脂層と赤外線反射層及び合わせガラス部材との接着性を制御することが容易になる。上記金属塩Mは、1種のみが用いられてもよく、2種以上が併用されてもよい。
上記第1の樹脂層は、紫外線遮蔽剤を含むことが好ましい。上記第2の樹脂層は、紫外線遮蔽剤を含むことが好ましい。紫外線遮蔽剤の使用により、合わせガラスが長期間使用されても、可視光線透過率がより一層低下し難くなる。上記紫外線遮蔽剤は、1種のみが用いられてもよく、2種以上が併用されてもよい。
上記第1の樹脂層は、酸化防止剤を含むことが好ましい。上記第2の樹脂層は、酸化防止剤を含むことが好ましい。上記酸化防止剤は、1種のみが用いられてもよく、2種以上が併用されてもよい。
上記第1の樹脂層及び上記第2の樹脂層はそれぞれ、必要に応じて、カップリング剤、分散剤、界面活性剤、難燃剤、帯電防止剤、顔料、染料、金属塩以外の接着力調整剤、耐湿剤、蛍光増白剤及び赤外線吸収剤等の添加剤を含んでいてもよい。これらの添加剤は、1種のみが用いられてもよく、2種以上が併用されてもよい。
上記中間膜の厚みは特に限定されない。実用面の観点、並びに合わせガラスの耐貫通性及び曲げ剛性を充分に高める観点からは、中間膜の厚みは、好ましくは0.1mm以上、より好ましくは0.25mm以上、好ましくは3mm以下、より好ましくは1.5mm以下である。中間膜の厚みが上記下限以上であると、合わせガラスの耐貫通性及び曲げ剛性がより一層高くなる。中間膜の厚みが上記上限以下であると、中間膜の透明性がより一層良好になる。
図3は、図1に示す合わせガラス用中間膜を用いた合わせガラスの一例を模式的に示す断面図である。
ポリビニルアセタール樹脂(PVB、平均重合度1700、水酸基の含有率30.5モル%、アセチル化度1モル%、アセタール化度68.5モル%)
トリエチレングリコールジ-2-エチルヘキサノエート(3GO)
ITO(ITO粒子、錫ドープ酸化インジウム粒子)
CWO(CWO粒子、セシウムドープ酸化タングステン(Cs0.33WO3)粒子)
Tinuvin326(2-(2’-ヒドロキシ-3’-t-ブチル-5-メチルフェニル)-5-クロロベンゾトリアゾール、BASF社製「Tinuvin326」)0.2重量部
BHT(2,6-ジ-t-ブチル-p-クレゾール)
赤外線反射フィルム1~9及びA~C(フィルム上に銀スパッタリング層が形成されたフィルム、自社製造品)
クリアガラス(厚さ2.5mm)
第1の樹脂層の作製:
以下の成分を配合し、ミキシングロールで充分に混練し、第1の樹脂層を形成するための組成物を得た。
トリエチレングリコールジ-2-エチルヘキサノエート(3GO)40重量部
以下の成分を配合し、ミキシングロールで充分に混練し、第2の樹脂層を形成するための組成物を得た。
トリエチレングリコールジ-2-エチルヘキサノエート(3GO)40重量部
赤外線反射層として、赤外線反射フィルム1を用意した。
第1の合わせガラス部材と、第1の樹脂層と、赤外線反射層と、第2の樹脂層と、第2の合わせガラス部材とをこの順で積層して、合わせガラスを得た。赤外線反射層における銀層上に、第1の樹脂層を積層した。
中間膜の構成を下記の表1,2に示すように変更したこと以外は、実施例1と同様にして、合わせガラスを得た。
(1)銀層の(111)回折面におけるピークの半値幅、及び、(200)回折面におけるピークの半値幅の測定
理学電気社製のATX-G型 表面構造評価用 多機能X線回折装置を下記の条件を適用して、走査軸2θχ/φ(In-Plane回折法)により回折スペクトルを測定した。2θ:約38°・(111)回折面及び2θ:約44°・(200)面のプロファイルフィッティングを行い、ピークの半値幅を算出した。
管電圧―管電流 :50kV-300mA
入射光学系(I) :人口多層膜放物面ミラー.(半価幅0.057°)
第1スリット(幅1.0mm、高さ10mm)
入射光学系(II) :ソーラースリット(鉛直発散抑制、0.48°)
第2スリット(幅0.2mm、高さ10mm)
受光光学系(検出部) :ソーラースリット(鉛直発散抑制、0.41°)
走査軸 :2θχ/φ(In-Plane回折法)
入射角度(ω) :0.252°(全反射)
測定間隔 :0.02°
測定速度 :0.2°/min
分光光度計(日立ハイテク社製「U-4100」)を用いて、JIS R3211:1998に準拠して、合わせガラスの波長380nm~780nmにおける上記可視光線透過率を測定した。
分光光度計(日立ハイテク社製「U-4100」)を用いて、ISO 13837に準拠して、得られた合わせガラスの波長300nm~2500nmにおける透過率/反射率を測定し、日射取得率を算出した。
得られた合わせガラスを温度80℃、相対湿度95ROH%の恒温槽中で放置し、3日後及び28日後に、HAZEメーター(村上色彩社製)でヘーズを測定した。銀の凝集抑制性(コロージョン耐性)を以下の基準で判定した。
○○:3日後及び28日後にヘーズ値が初期から0.2%以上上昇しない
○:3日後にヘーズ値が初期から0.2%以上上昇しないが、28日後にヘーズ値が初期から0.2%以上上昇
×:3日後にヘーズ値が初期から0.2%以上上昇
1a…第1の表面
1b…第2の表面
2…第1の樹脂層
2a…外側の表面
3…第2の樹脂層
3a…外側の表面
11,11A…中間膜
11a…第1の表面
11b…第2の表面
21…第1の合わせガラス部材
22…第2の合わせガラス部材
31,31A…合わせガラス
Claims (13)
- 赤外線反射層と、熱可塑性樹脂を含む第1の樹脂層とを有し、
前記赤外線反射層の第1の表面側に前記第1の樹脂層が配置されており、
前記赤外線反射層が、銀層を含み、
前記銀層のIn-Plane XRD測定において、(111)回折面におけるピークの半値幅が1.3以下であるか、又は、(200)回折面におけるピークの半値幅が2.0以下である、合わせガラス用中間膜。 - 前記銀層のIn-Plane XRD測定において、(111)回折面におけるピークの半値幅が1.3以下であり、かつ、(200)回折面におけるピークの半値幅が2.0以下である、請求項1に記載の合わせガラス用中間膜。
- 前記赤外線反射層が、樹脂フィルムと、前記銀層とを含み、
前記銀層が、前記樹脂フィルムの少なくとも一方の表面上に配置されている、請求項1又は2に記載の合わせガラス用中間膜。 - 前記第1の樹脂層が、紫外線遮蔽剤を含む、請求項1~3のいずれか1項に記載の合わせガラス用中間膜。
- 前記第1の樹脂層が、遮熱性物質を含む、請求項1~4のいずれか1項に記載の合わせガラス用中間膜。
- 前記第1の樹脂層中の前記熱可塑性樹脂が、ポリビニルアセタール樹脂である、請求項1~5のいずれか1項に記載の合わせガラス用中間膜。
- 前記第1の樹脂層が可塑剤を含む、請求項1~6のいずれか1項に記載の合わせガラス用中間膜。
- 第2の樹脂層を備え、
前記赤外線反射層の前記第1の表面とは反対の第2の表面側に前記第2の樹脂層が配置されている、請求項1~7のいずれか1項に記載の合わせガラス用中間膜。 - 前記第2の樹脂層が、紫外線遮蔽剤を含む、請求項8に記載の合わせガラス用中間膜。
- 前記第2の樹脂層中の前記熱可塑性樹脂が、ポリビニルアセタール樹脂である、請求項8又は9に記載の合わせガラス用中間膜。
- 前記第2の樹脂層が可塑剤を含む、請求項8~10のいずれか1項に記載の合わせガラス用中間膜。
- 第1の合わせガラス部材と、第2の合わせガラス部材と、請求項1~11のいずれか1項に記載の合わせガラス用中間膜とを備え、
前記中間膜が、第2の樹脂層を有するか、又は有さず、
前記中間膜が前記第2の樹脂層を有する場合に、前記赤外線反射層の前記第1の表面とは反対の第2の表面側に前記第2の樹脂層が配置されており、
前記中間膜が前記第2の樹脂層を有する場合に、前記第1の樹脂層の外側に前記第1の合わせガラス部材が配置されており、前記第2の樹脂層の外側に前記第2の合わせガラス部材が配置されており、
中間膜が前記第2の樹脂層を有しない場合に、前記第1の樹脂層の外側に前記第1の合わせガラス部材が配置されており、前記赤外線反射層の外側に前記第2の合わせガラス部材が配置されている、合わせガラス。 - 建築物又は車両において、外部空間と前記外部空間から熱線が入射される内部空間との間の開口部に、前記第2の合わせガラス部材が、前記外部空間側に位置するように、かつ前記第1の合わせガラス部材が前記内部空間側に位置するように取り付けられる合わせガラスである、請求項12に記載の合わせガラス。
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EP19777939.0A EP3778518A4 (en) | 2018-03-29 | 2019-03-29 | Intermediate film for laminated glass, and laminated glass |
JP2019519027A JP7271418B2 (ja) | 2018-03-29 | 2019-03-29 | 合わせガラス用中間膜及び合わせガラス |
US17/040,475 US20210023823A1 (en) | 2018-03-29 | 2019-03-29 | Intermediate film for laminated glass, and laminated glass |
CN201980022996.7A CN111918848B (zh) | 2018-03-29 | 2019-03-29 | 夹层玻璃用中间膜和夹层玻璃 |
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JP3068924B2 (ja) * | 1990-11-29 | 2000-07-24 | 旭硝子株式会社 | 熱線遮断膜 |
US6933051B2 (en) * | 2002-08-17 | 2005-08-23 | 3M Innovative Properties Company | Flexible electrically conductive film |
EP3912809A1 (en) * | 2014-01-31 | 2021-11-24 | Sekisui Chemical Co., Ltd. | Intermediate film for laminated glass, laminated glass and method for fitting laminated glas |
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- 2019-03-29 TW TW108111418A patent/TW202003237A/zh unknown
- 2019-03-29 WO PCT/JP2019/013948 patent/WO2019189738A1/ja active Application Filing
- 2019-03-29 US US17/040,475 patent/US20210023823A1/en not_active Abandoned
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- 2019-03-29 EP EP19777939.0A patent/EP3778518A4/en active Pending
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KR20200138189A (ko) | 2020-12-09 |
JPWO2019189738A1 (ja) | 2021-02-12 |
CN111918848A (zh) | 2020-11-10 |
US20210023823A1 (en) | 2021-01-28 |
CN111918848B (zh) | 2024-03-15 |
EP3778518A4 (en) | 2021-12-29 |
EP3778518A1 (en) | 2021-02-17 |
TW202003237A (zh) | 2020-01-16 |
JP7271418B2 (ja) | 2023-05-11 |
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