WO2017057499A1 - 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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- WO2017057499A1 WO2017057499A1 PCT/JP2016/078693 JP2016078693W WO2017057499A1 WO 2017057499 A1 WO2017057499 A1 WO 2017057499A1 JP 2016078693 W JP2016078693 W JP 2016078693W WO 2017057499 A1 WO2017057499 A1 WO 2017057499A1
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- laminated glass
- interlayer film
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- intermediate film
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- 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
- B32B17/1055—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
- B32B17/10761—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 containing vinyl acetal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- 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
- B32B17/1055—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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- 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
- B32B17/10009—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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- 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
- B32B17/1055—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
- B32B17/10614—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 comprising particles for purposes other than dyeing
- B32B17/10633—Infrared radiation absorbing or reflecting agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- 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
- B32B17/1055—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
- B32B17/10678—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 comprising UV absorbers or stabilizers, e.g. antioxidants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- 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
- B32B17/1055—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
- B32B17/10688—Adjustment of the adherence to the glass layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/748—Releasability
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2311/00—Metals, their alloys or their compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2315/00—Other materials containing non-metallic inorganic compounds not provided for in groups B32B2311/00 - B32B2313/04
- B32B2315/08—Glass
Definitions
- the present invention relates to an interlayer film for laminated glass used for laminated glass. Moreover, this invention relates to the laminated glass using the said intermediate film for laminated glasses.
- Laminated glass is superior in safety even if it is damaged by an external impact and the amount of glass fragments scattered is small. 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.
- Patent Document 1 discloses an interlayer film formed of a resin composition containing a near infrared absorber, an antioxidant, and a resin.
- the near-infrared absorber is particles of a specific copper phosphonate salt.
- the said antioxidant is at least 1 sort (s) of antioxidant selected from hindered phenolic antioxidant and specific phosphorus antioxidant.
- Patent Document 2 100 parts by weight of a polyvinyl acetal resin having a degree of acetalization of 60 to 85 mol%, and at least one metal salt of an alkali metal salt and an alkaline earth metal salt is 0.001 to 1
- a sound insulation layer comprising 0.0 parts by weight and more than 30 parts by weight of a plasticizer is disclosed. This sound insulation layer may be a single layer and used as an intermediate film.
- Patent Document 2 also describes a multilayer intermediate film in which the sound insulation layer and other layers are laminated.
- the other layer laminated on the sound insulation layer is composed of 100 parts by weight of a polyvinyl acetal resin having an acetalization degree of 60 to 85 mol%, and at least one metal salt of at least one of an alkali metal salt and an alkaline earth metal salt. 1.0 part by weight and a plasticizer that is 30 parts by weight or less are included.
- the laminated glass member is appropriately peeled from the intermediate film.
- the intermediate film can be prevented from breaking.
- the peelability of the laminated glass member from the interlayer film may be too low.
- an intermediate film contains a tin dope indium oxide particle, a tungsten oxide particle, etc., it is difficult to raise moderately the peelability from the intermediate film of a laminated glass member.
- an interlayer film for laminated glass that is a single-layer interlayer film including only the first layer or a multilayer interlayer film including the first layer and another layer.
- the first layer contains no magnesium or contains magnesium at 50 ppm or less, and the first layer contains a phosphorus compound having a polyoxyalkylene group or a silane compound having a polyoxyalkylene group.
- an interlayer film for laminated glass hereinafter sometimes abbreviated as an interlayer film
- at least one layer of the multilayer interlayer film includes heat shielding particles.
- the first layer includes heat shielding particles.
- the first layer does not contain an alkali metal or contains an alkali metal at 1000 ppm or less.
- the first layer includes a thermoplastic resin.
- thermoplastic resin contained in the first layer is a polyvinyl acetal resin.
- the first layer includes a plasticizer.
- the phosphorus compound having a polyoxyalkylene group or the silane compound having a polyoxyalkylene group has a polyoxyalkylene group and an alkyl group bonded to the polyoxyalkylene group. It is a phosphorus compound or a silane compound having a polyoxyalkylene group and an alkyl group bonded to the polyoxyalkylene group.
- the phosphorus compound having a polyoxyalkylene group is a phosphate ester having a polyoxyalkylene group.
- the silane compound having a polyoxyalkylene group is silsesquioxane having a polyoxyalkylene group.
- the first layer includes a phosphorus compound having the polyoxyalkylene group.
- the intermediate film includes the first layer as a surface layer in the intermediate film.
- the interlayer film is an interlayer film for laminated glass having a structure of two or more layers, and further includes a second layer containing a thermoplastic resin.
- the first layer is disposed on the first surface side of the layer.
- the interlayer film is an interlayer film for laminated glass having a structure of three or more layers, further including a third layer containing a thermoplastic resin, The third layer is disposed on the second surface side of the layer opposite to the first surface side.
- the first laminated glass member, the second laminated glass member, and the interlayer film for laminated glass described above are provided, and the first laminated glass member and the second laminated glass are provided.
- the interlayer film for laminated glass according to the present invention is a single-layer interlayer film including only the first layer, or a multilayer interlayer film including the first layer and another layer.
- the first layer contains a phosphorus compound having a polyoxyalkylene group or a silane compound having a polyoxyalkylene group, and the first layer contains no magnesium or 50 ppm or less of magnesium.
- the first layer includes a thermal barrier particle
- a multilayer intermediate film including the first layer and another layer a multilayer Since at least one layer in the intermediate film contains heat shielding particles, in the laminated glass using the intermediate film, the haze value can be lowered, and the peelability of the laminated glass member from the intermediate film can be appropriately increased.
- 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 abbreviated as an interlayer film) has a structure of one layer or a structure of two or more layers.
- the intermediate film according to the present invention may have a single-layer structure or a two-layer structure.
- the intermediate film according to the present invention includes a first layer.
- the interlayer film for laminated glass according to the present invention is a single-layer interlayer film including only the first layer, or a multilayer interlayer film including the first layer and another layer.
- the first layer in the present invention does not contain magnesium or contains magnesium at 50 ppm or less.
- the first layer in the present invention includes a phosphorus compound having a polyoxyalkylene group or a silane compound having a polyoxyalkylene group.
- the intermediate film according to the present invention is a single-layer intermediate film including only the first layer
- the first layer includes heat shielding particles.
- the intermediate film according to the present invention is a multilayer intermediate film including the first layer and the other layers, at least one layer in the multilayer intermediate film includes heat shielding particles. Therefore, the interlayer film according to the present invention includes heat shielding particles.
- the intermediate film according to the present invention has the above-described configuration, the haze value of the laminated glass can be lowered, and the peelability of the laminated glass member from the intermediate film can be appropriately increased.
- the laminated glass member is appropriately peeled from the intermediate film.
- the present invention provides good peelability.
- an intermediate film contains a heat shielding particle, it is difficult to moderately improve the peelability of the laminated glass member from the intermediate film.
- the peelability of the laminated glass member from the intermediate film can be appropriately increased even if the intermediate film contains heat shielding particles.
- the intermediate film according to the present invention may be a single-layer intermediate film including only the first layer, or may be a multilayer intermediate film including the first layer and another layer.
- the intermediate film according to the present invention may have a two-layer structure, may have a structure of two or more layers, or may have a structure of three or more layers.
- the intermediate film may have a structure of two or more layers, and may include a second layer in addition to the first layer.
- the intermediate film may include a second layer as the other layer.
- the intermediate film preferably further includes a second layer containing a thermoplastic resin. When the intermediate film includes the second layer, the first layer is disposed on the first surface side of the second layer.
- the intermediate film may have a structure of three or more layers, and may include a third layer in addition to the first layer and the second layer.
- the intermediate film may include a second layer and a third layer as the other layers.
- the intermediate film preferably further includes a third layer containing a thermoplastic resin. When the intermediate film includes the second layer and the third layer, the third layer is disposed on the second surface side of the second layer opposite to the first surface side. Is done.
- the intermediate film preferably includes the first layer as a surface layer in the intermediate film.
- the intermediate film may include the second layer as a surface layer in the intermediate film.
- the intermediate film preferably includes the third layer as a surface layer in the intermediate film.
- the intermediate film preferably includes the first layer and the third layer as surface layers in the intermediate film, respectively.
- the surface of the first layer opposite to the second layer side is preferably the surface on which the laminated glass member is laminated.
- the surface (second surface) opposite to the first layer side of the second layer may be the surface on which the laminated glass member is laminated.
- the surface of the third layer opposite to the second layer side is preferably the surface on which the laminated glass member is laminated.
- 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 two 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 a first layer 1, a second layer 2, and a third layer 3.
- On the first surface 2a of the second layer 2, the first layer 1 is disposed and laminated.
- the third layer 3 is disposed on the second surface 2b opposite to the first surface 2a of the second layer 2 and laminated.
- the second layer 2 is an intermediate layer.
- Each of the first layer 1 and the third layer 3 is a protective layer, and is a surface layer in this embodiment.
- the second layer 2 is disposed between the first layer 1 and the third layer 3 and is sandwiched between them. Therefore, the intermediate film 11 has a multilayer structure (first layer 1 / second layer 2 / third layer in which the first layer 1, the second layer 2, and the third layer 3 are laminated in this order. Having layer 3).
- first layer 1 and the second layer 2 and between the second layer 2 and the third layer 3 are preferably laminated directly.
- layers containing polyethylene terephthalate and the like are examples of other layers.
- the first layer 1 includes a polyvinyl acetal resin and a plasticizer.
- the first layer 1 does not contain magnesium or contains magnesium at 50 ppm or less, and the first layer 1 contains a phosphorus compound having a polyoxyalkylene group or a silane compound having a polyoxyalkylene group.
- At least one of the first layer 1, the second layer 2, and the third layer includes heat shielding particles.
- the second layer 2 preferably includes a thermoplastic resin, preferably includes a polyvinyl acetal resin as the thermoplastic resin, and preferably includes a plasticizer.
- the third layer 3 preferably includes a thermoplastic resin, preferably includes a polyvinyl acetal resin as the thermoplastic resin, and preferably includes a plasticizer.
- the third layer 3 does not contain magnesium or contains magnesium at 50 ppm or less, and the third layer 3 contains poly (polyethylene). It is preferable to include a phosphorus compound having an oxyalkylene group or a silane compound having a polyoxyalkylene group. Since the effect of the present invention is more effectively exhibited, it is preferable that the first layer 1 includes heat shielding particles. In the case where the first layer 1 includes the heat shielding particles, the other layers (the second layer 2 and the third layer 3) may or may not include the heat shielding particles. Since the effect of the present invention is more effectively exhibited, it is preferable that the third layer 3 includes heat shielding particles. From the viewpoint of further improving the heat shielding properties, it is preferable that the second layer 2 contains heat shielding particles.
- 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 single-layer intermediate film having a single-layer structure.
- the intermediate film 11A is a first layer.
- 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 11A (first layer) includes a polyvinyl acetal resin and a plasticizer.
- the intermediate film 11A (first layer) does not contain magnesium or contains magnesium at 50 ppm or less, and the intermediate film 11A (first layer) is a phosphorus compound or polyoxyalkylene group having a polyoxyalkylene group.
- a silane compound having The intermediate film 11A (first layer) includes heat shielding particles.
- the first layer (including a single-layer intermediate film) constituting the intermediate film according to the present invention, the details of the second layer and the third layer, the first layer, the second layer, and the like. Details of each component contained in the layer and the third layer will be described.
- the first layer (including a single-layer intermediate film) preferably contains a thermoplastic resin (hereinafter sometimes referred to as a thermoplastic resin (1)), and polyvinyl acetal is used as the thermoplastic resin (1). It is preferable that resin (it may be described as polyvinyl acetal resin (1) hereafter) is included.
- the second layer preferably contains a thermoplastic resin (hereinafter sometimes referred to as a thermoplastic resin (2)), and a polyvinyl acetal resin (hereinafter referred to as a polyvinyl acetal resin (2) as the thermoplastic resin (2). )) May be included.
- the third layer preferably contains a thermoplastic resin (hereinafter sometimes referred to as a thermoplastic resin (3)), and as the thermoplastic resin (3), a polyvinyl acetal resin (hereinafter referred to as a polyvinyl acetal resin ( 3)) may be included.
- the polyvinyl acetal resin (1), the polyvinyl acetal resin (2), and the polyvinyl acetal resin (3) may be the same or different.
- the said polyvinyl acetal resin (1), the said polyvinyl acetal resin (2), and the said polyvinyl acetal resin (3) only 1 type may respectively be used and 2 or more types may be used together.
- the thermoplastic resin (1), the thermoplastic resin (2), and the thermoplastic resin (3) may be the same or different.
- the said thermoplastic resin (1), the said thermoplastic resin (2), and the said thermoplastic resin (3) 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, and polyvinyl alcohol resin. Thermoplastic resins other than these may be used.
- 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 produced, 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 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 5000 or less, More preferably, it is 4000 or less, More preferably, it is 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 intermediate film 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 intermediate film 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 (2) is preferably 17 mol% or more, more preferably 20 mol% or more, still more preferably 22 mol% or more, preferably 30 mol% or less, more preferably. Is less than 27 mol%, more preferably 25 mol% or less.
- the hydroxyl group content is at least the above lower limit, the adhesive strength of the interlayer film is further increased.
- the hydroxyl group content of the polyvinyl acetal resin (2) is 20 mol% or more, the reaction efficiency is high and the productivity is excellent, and when it is less than 27 mol%, the sound insulation of the laminated glass is further enhanced.
- the hydroxyl group content is not more than the above upper limit, the flexibility of the interlayer film is increased, and the handling of the interlayer film is facilitated.
- the content of each hydroxyl group in the polyvinyl acetal resin (1) and the polyvinyl acetal resin (3) is preferably 25 mol% or more, more preferably 28 mol% or more, still more preferably 30 mol% or more, and particularly preferably 31. It is at least mol%, preferably at most 40 mol%, more preferably at most 34.5 mol%, still more preferably at most 32 mol%.
- the hydroxyl group content is at least the above lower limit, the adhesive strength of the interlayer film is further increased. Further, when the hydroxyl group content is not more than the above upper limit, the flexibility of the interlayer film is increased, and the handling of the interlayer film is facilitated.
- 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 (2) is preferably 0.01 mol% or more, more preferably 0.1 mol% or more, still more preferably 7 mol% or more, and still more preferably 9 It is at least mol%, preferably at most 30 mol%, more preferably at most 25 mol%, still more preferably at most 15 mol%.
- 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 interlayer film and the laminated glass is increased.
- the degree of acetylation of the polyvinyl acetal resin (2) is 0.1 mol% or more and 25 mol% or less, the penetration resistance is excellent.
- Each degree of acetylation of the polyvinyl acetal resin (1) and the polyvinyl acetal resin (3) is preferably 0.01 mol% or more, more preferably 0.5 mol% or more, preferably 10 mol% or less, more preferably. Is 2 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 interlayer film and 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 (2) is preferably 47 mol% or more, more preferably 60 mol% or more, preferably 80 mol% or less, more preferably It is 70 mol% or less.
- 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 (degree of butyralization in the case of polyvinyl butyral resin) of the polyvinyl acetal resin (1) and the polyvinyl acetal resin (3) is preferably 55 mol% or more, more preferably 67 mol% or more, preferably Is 75 mol% or less, more preferably 71 mol% or less.
- 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 the 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 of the main chain. It is a value indicating the mole fraction obtained by dividing by the percentage.
- 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 is preferable to calculate from the results measured by.
- the polyvinyl acetal resin (2) has an acetylation degree (a) of 8 mol% or less and an acetalization degree (a) of 70 mol%.
- the polyvinyl acetal resin (A) as described above is preferable, or the polyvinyl acetal resin (B) having a degree of acetylation (b) exceeding 8 mol% is preferable.
- the polyvinyl acetal resin (1) may be the polyvinyl acetal resin (A) or the polyvinyl acetal resin (B).
- the polyvinyl acetal resin (3) may be the polyvinyl acetal resin (A) or the polyvinyl acetal resin (B).
- the degree of acetylation (a) of the polyvinyl acetal resin (A) is 8 mol% or less, preferably 7.5 mol% or less, more preferably 7 mol% or less, still more preferably 6.5 mol% or less, particularly preferably. It is 5 mol% or less, preferably 0.1 mol% or more, more preferably 0.5 mol% or more, still more preferably 0.8 mol% or more, and particularly preferably 1 mol% or more.
- the degree of acetylation (a) is not more than the above upper limit and not less than the above lower limit, the migration of the plasticizer can be easily controlled, and the sound insulation of the laminated glass is further enhanced.
- the degree of acetalization (a) of the polyvinyl acetal resin (A) is 70 mol% or more, preferably 70.5 mol% or more, more preferably 71 mol% or more, still more preferably 71.5 mol% or more, particularly preferably. It is 72 mol% or more, preferably 85 mol% or less, more preferably 83 mol% or less, still more preferably 81 mol% or less, and particularly preferably 79 mol% or less.
- the acetalization degree (a) is not less than the above lower limit, the sound insulating properties of the laminated glass are further enhanced.
- the reaction time required in order to manufacture polyvinyl acetal resin (A) as the said acetalization degree (a) is below the said upper limit can be shortened.
- the hydroxyl group content (a) of the polyvinyl acetal resin (A) is preferably 18 mol% or more, more preferably 19 mol% or more, still more preferably 20 mol% or more, particularly preferably 21 mol% or more, preferably 31.
- the hydroxyl group content (a) is equal to or higher than the lower limit, the adhesive strength of the second layer is further increased.
- the hydroxyl group content (a) is not more than the above upper limit, the sound insulation of the laminated glass is further enhanced.
- the degree of acetylation (b) of the polyvinyl acetal resin (B) exceeds 8 mol%, preferably 9 mol% or more, more preferably 9.5 mol% or more, still more preferably 10 mol% or more, particularly preferably. 10.5 mol% or more, preferably 30 mol% or less, more preferably 28 mol% or less, still more preferably 26 mol% or less, and particularly preferably 24 mol% or less.
- the acetylation degree (b) is not less than the above lower limit, the sound insulation of the laminated glass is further enhanced.
- the reaction time required in order to manufacture polyvinyl acetal resin (B) as the said acetylation degree (b) is below the said upper limit can be shortened.
- the degree of acetalization (b) of the polyvinyl acetal resin (B) is preferably 50 mol% or more, more preferably 53 mol% or more, still more preferably 55 mol% or more, particularly preferably 60 mol% or more, preferably 80 mol%. % Or less, more preferably 78 mol% or less, still more preferably 76 mol% or less, and particularly preferably 74 mol% or less.
- the acetalization degree (b) is not less than the above lower limit, the sound insulating properties of the laminated glass are further enhanced.
- the reaction time required in order to manufacture polyvinyl acetal resin (B) as the said acetalization degree (b) is below the said upper limit can be shortened.
- the content (b) of the hydroxyl group in the polyvinyl acetal resin (B) is preferably 18 mol% or more, more preferably 19 mol% or more, still more preferably 20 mol% or more, particularly preferably 21 mol% or more, preferably 31.
- the hydroxyl group content (b) is not less than the above lower limit, the adhesive strength of the second layer is further increased.
- the hydroxyl group content (b) is not more than the above upper limit, the sound insulating properties of the laminated glass are further enhanced.
- the polyvinyl acetal resin (A) and the polyvinyl acetal resin (B) are each preferably a polyvinyl butyral resin.
- the first layer (including a single-layer interlayer) preferably includes a plasticizer (hereinafter sometimes referred to as a plasticizer (1)).
- the second layer preferably contains a plasticizer (hereinafter sometimes referred to as a plasticizer (2)).
- the third layer preferably contains a plasticizer (hereinafter may be referred to as a plasticizer (3)).
- 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 represent an organic group having 2 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 5 to 10 carbon atoms, and more preferably an organic group having 6 to 10 carbon atoms.
- the plasticizer preferably contains triethylene glycol di-2-ethylhexanoate (3GO), triethylene glycol di-2-ethylbutyrate (3GH) or triethylene glycol di-2-ethylpropanoate. More preferably, it contains triethylene glycol di-2-ethylhexanoate or triethylene glycol di-2-ethylbutyrate, and more preferably contains triethylene glycol di-2-ethylhexanoate.
- 3GO triethylene glycol di-2-ethylhexanoate
- GGH triethylene glycol di-2-ethylbutyrate
- triethylene glycol di-2-ethylpropanoate More preferably, it contains triethylene glycol di-2-ethylhexanoate or triethylene glycol di-2-ethylbutyrate, and more preferably contains triethylene glycol di-2-ethylhexanoate.
- the amount (hereinafter sometimes referred to as content (2)) is preferably 40 parts by weight or more, more preferably 55 parts by weight or more, preferably 90 parts by weight or less, more preferably 85 parts by weight or less.
- content (2) is not less than the above lower limit, the flexibility of the interlayer film is increased, and the handling of the interlayer film is facilitated.
- content (2) is not more than the above upper limit, the transparency of the interlayer film is further increased.
- content (1) 100 parts by weight of the thermoplastic resin (3)
- the content of the plasticizer (3) relative to the resin (3) (100 parts by weight) is preferably 30 parts by weight or more, more preferably 35 parts by weight or more. , Preferably 44 parts by weight or less, more preferably 42 parts by weight or less.
- the content (1) and the content (3) are each equal to or higher than the lower limit, the flexibility of the interlayer film is increased, and the handling of the interlayer film is facilitated.
- the content (1) and the content (3) are each not more than the above upper limit, the penetration resistance of the laminated glass is further enhanced.
- the content (2) is preferably greater than the content (1), and the content (2). Is preferably greater than the above content (3).
- the absolute value of the difference between the content (2) and the content (1) and the content (2 ) And the above content (3) are each preferably 10 parts by weight or more, more preferably 20 parts by weight or more.
- the absolute value of the difference between the content (2) and the content (1) and the absolute value of the difference between the content (2) and the content (3) are each preferably 50 parts by weight or less. is there.
- the intermediate film preferably contains a heat shielding compound.
- the first layer preferably contains a heat shielding compound.
- the second layer preferably contains a heat shielding compound.
- the third layer preferably includes a heat shielding compound.
- the said heat-shielding compound only 1 type may be used and 2 or more types may be used together.
- the thermal barrier compound preferably contains at least one component X among phthalocyanine compounds, naphthalocyanine compounds and anthracocyanine compounds, or preferably contains thermal barrier particles. In this case, both the component X and the heat shielding particles may be included.
- the intermediate film preferably includes at least one component X among a phthalocyanine compound, a naphthalocyanine compound, and an anthracocyanine compound.
- the first layer preferably contains the component X.
- the second layer preferably contains the component X.
- the third layer preferably contains the component X.
- the component X is a heat shielding compound. 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 at least one selected from the group consisting of phthalocyanine, phthalocyanine derivatives, naphthalocyanine, and naphthalocyanine derivatives. More preferably, it is at least one of phthalocyanine and phthalocyanine derivatives.
- 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 or more, more preferably 0.01% by weight or more, particularly preferably 0.02% by weight or more, preferably 0.2% by weight or less, more preferably 0.1% by weight or less, still 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.
- Thermal barrier particles The intermediate film includes heat shielding particles in any layer.
- the first layer preferably contains the heat shielding particles.
- the second layer preferably includes the heat shielding particles.
- the third layer preferably contains the heat shielding particles.
- the heat shielding particles are heat shielding compounds. 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.
- Other examples of the heat shielding particles include carbon black particles.
- the heat shielding particles are preferably carbon black particles.
- 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 preferable because of their high heat ray shielding function, ATO particles, GZO particles, IZO particles, ITO particles or tungsten oxide particles are more preferable, and ITO particles or tungsten oxide particles are particularly preferable.
- tin-doped indium oxide particles ITO particles
- 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%. 0.1% by weight or more, more preferably 1% by weight or more, particularly preferably 1.5% by weight or more, preferably 6% by weight or less, more preferably 5.5% by weight or less, still more preferably 4% by weight or less, Preferably it is 3.5 weight% or less, Most preferably, it is 3.0 weight% or less.
- the content of the heat shielding particles 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 content of the heat shielding particles can be measured by an ICP emission spectrometer (“ICPE-9000” manufactured by Shimadzu Corporation) or TG-DTA (“TGA 8000” manufactured by PerkinElmer).
- the first layer does not contain magnesium or contains magnesium at 50 ppm or less.
- the third layer preferably does not contain magnesium or contains magnesium at 50 ppm or less.
- the first layer preferably does not contain an alkali metal or contains an alkali metal at 1000 ppm or less.
- the third layer preferably does not contain an alkali metal or contains an alkali metal at 1000 ppm or less.
- the interlayer film may be described as at least one metal salt (hereinafter referred to as metal salt M) among alkali metal salts, alkaline earth metal salts, and magnesium salts. ) Is preferably included.
- the second layer preferably contains the metal salt M
- the third layer preferably contains the metal salt M.
- the first layer may contain the metal salt M.
- Use of the metal salt M makes it easy to control the adhesion between the interlayer film and the glass plate or the adhesion between the layers in the interlayer film.
- 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 at least one metal selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr and Ba.
- the metal salt contained in the interlayer film preferably contains at least one metal of K and 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.
- magnesium salt of carboxylic acid having 2 to 16 carbon atoms and the potassium salt of carboxylic acid having 2 to 16 carbon atoms include, but are not limited to, for example, magnesium acetate, potassium acetate, magnesium propionate, potassium propionate, 2-ethylbutyric acid
- magnesium, potassium 2-ethylbutanoate, magnesium 2-ethylhexanoate and potassium 2-ethylhexanoate examples include magnesium, potassium 2-ethylbutanoate, magnesium 2-ethylhexanoate and potassium 2-ethylhexanoate.
- the total content of Mg (magnesium atoms) and K (potassium atoms) in the layer containing the metal salt M (first layer, second layer or third layer) is preferably 5 ppm or more, more preferably 10 ppm or more, more preferably 20 ppm or more, preferably 300 ppm or less, more preferably 250 ppm or less, still more preferably 200 ppm or less.
- the total content of Mg (magnesium atoms) and K (potassium atoms) in the layer containing the metal salt M (first layer, second layer or third layer) is preferably 5 ppm or more, more preferably 10 ppm or more, more preferably 20 ppm or more, preferably 300 ppm or less, more preferably 250 ppm or less, still more preferably 200 ppm or less.
- Mg in the first layer is 50 ppm or less.
- the first layer does not contain magnesium or contains magnesium in an amount of 50 ppm or less, and has a polyoxyalkylene group.
- a silane compound having an alkylene group is included.
- the first layer may contain only the phosphorus compound, may contain only the silane compound, or may contain both the phosphorus compound and the silane compound.
- the third layer contains no phosphorus or magnesium at 50 ppm or less and a phosphorus compound or polyoxy having a polyoxyalkylene group. It is preferable to include a silane compound having an alkylene group.
- the second layer may not contain magnesium or may contain magnesium at 50 ppm or less, and may contain a phosphorus compound having a polyoxyalkylene group or a silane compound having a polyoxyalkylene group.
- the phosphorus compound includes a phosphorus atom.
- the said phosphorus compound only 1 type may be used and 2 or more types may be used together.
- the said silane compound only 1 type may be used and 2 or more types may be used together.
- the carbon number of the alkylene group in the polyoxyalkylene group is preferably 4 or less, more preferably 3 or less, and particularly preferably 2 or less.
- the polyoxyalkylene group is particularly preferably a polyoxyethylene group.
- the phosphorus compound having a polyoxyalkylene group or the silane compound having a polyoxyalkylene group is bonded to the polyoxyalkylene group and the polyoxyalkylene group. It is preferable that it is a phosphorus compound having an alkyl group, or a silane compound having a polyoxyalkylene group and an alkyl group bonded to the polyoxyalkylene group.
- the phosphorus compound is preferably a phosphate ester.
- the silane compound is preferably silsesquioxane.
- the first layer preferably contains a phosphorus compound having a polyoxyalkylene group.
- the phosphorus compound having a polyoxyalkylene group is preferably a polyoxyethylene alkyl ether phosphate.
- polyoxyethylene alkyl ether phosphate ester polyoxyethylene lauryl ether phosphate ester or polyoxyethylene tridecyl ether phosphate ester is preferable.
- silane compounds examples include “PG1190” manufactured by Hybrid Plastics.
- the layers containing the above-mentioned phosphorus compound having a polyoxyalkylene group or a silane compound having a polyoxyalkylene group (first layer, second layer)
- the content of the phosphorus compound having a polyoxyalkylene group or the silane compound having a polyoxyalkylene group (total content) in 100% by weight is preferably 0.05% by weight or more.
- a layer containing the above-described phosphorus compound having a polyoxyalkylene group or a silane compound having a polyoxyalkylene group (first layer, second layer or third layer) ),
- the content of P (phosphorus atom) or the content of Si (silicon atom) is preferably 15 ppm or more, more preferably 50 ppm or more, still more preferably 100 ppm or more, particularly preferably 150 ppm or more, preferably 6000 ppm or less, More preferably, it is 2500 ppm or less, More preferably, it is 1000 ppm or less, Most preferably, it is 500 ppm or less.
- the contents of P (phosphorus atom) and Si (silicon atom) can be measured with an ICP emission analyzer (“ICPE-9000” manufactured by Shimadzu Corporation).
- the intermediate film preferably contains an ultraviolet shielding agent.
- the first layer preferably contains an ultraviolet shielding agent.
- the second layer preferably contains an ultraviolet shielding agent.
- the third layer preferably contains an ultraviolet shielding agent.
- 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, more preferably a benzotriazole structure.
- an ultraviolet shielding agent having a benzotriazole structure 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 is preferably 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 diamides having an aryl group substituted on the nitrogen atom such as N ′-(2-ethoxy-phenyl) oxalic acid diamide, 2-ethyl-2′-ethoxy-oxyanilide (“SlandorVSU” manufactured by Clariant)kind.
- 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 ultraviolet shielding is performed in 100% by weight of the layer containing the ultraviolet shielding agent (first layer, second layer, or third layer).
- the content of the agent and the content of the benttriazole compound are preferably 0.1% by weight or more, more preferably 0.2% by weight or more, still more preferably 0.3% by weight or more, and particularly preferably 0.5% by weight.
- the content is preferably 2.5% by weight or less, more preferably 2% by weight or less, still more preferably 1% by weight or less, and particularly preferably 0.8% by weight or less.
- the content of the ultraviolet shielding agent is 0.2% by weight or more, thereby reducing the visible light transmittance after the passage of the intermediate film and the laminated glass. Remarkably suppressed.
- the intermediate film preferably contains an antioxidant.
- the first layer preferably contains an antioxidant.
- the second layer preferably contains an antioxidant.
- the third 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, and “ IRGANOX 1010 ".
- a layer in 100% by weight of the interlayer film or containing an antioxidant.
- the content of the antioxidant is preferably 0.035% by weight or more, and more preferably 0.05% by weight or more.
- the content of the antioxidant is preferably 2% by weight or less in 100% by weight of the intermediate film or 100% by weight of the layer containing the antioxidant. .
- the intermediate film preferably contains a light stabilizer.
- the first layer preferably contains a light stabilizer.
- the second layer preferably contains a light stabilizer.
- the third layer preferably contains a light stabilizer. As for the said light stabilizer, only 1 type may be used and 2 or more types may be used together.
- the light stabilizer is preferably a hindered amine light stabilizer.
- the hindered amine light stabilizer include a hindered amine light stabilizer in which an alkyl group, an alkoxy group, or a hydrogen atom is bonded to a nitrogen atom of a piperidine structure. From the viewpoint of further suppressing the increase in the YI value in the laminated glass, a hindered amine light stabilizer in which an alkyl group or an alkoxy group is bonded to the nitrogen atom of the piperidine structure is preferable.
- the hindered amine light stabilizer is preferably a hindered amine light stabilizer in which an alkyl group is bonded to the nitrogen atom of the piperidine structure, and is a hindered amine light stabilizer in which an alkoxy group is bonded to the nitrogen atom of the piperidine structure. It is also preferable that there is.
- Examples of compounds in which a carbon atom (preferably an alkyl group) is bonded to the nitrogen atom of the piperidine structure include Tinuvin 765, Tinuvin 144, Tinuvin 723, Tinuvin 622SF, and Adeka Stub LA-52.
- Examples of the compound in which an oxygen atom (preferably an alkoxy group) is bonded to the nitrogen atom of the piperidine structure include Tinuvin NOR371, Tinuvin XT850FF, Tinuvin XT855FF, and ADK STAB LA-81.
- Examples of the compound in which a hydrogen atom is bonded to a nitrogen atom of the piperidine structure include Tinuvin 770DF and Hostavin N24.
- Each content of the light stabilizer is preferably 0.0035% in 100% by weight of the intermediate film or 100% by weight of the layer containing the light stabilizer (first layer, second layer, or third layer). % Or more, more preferably 0.025% by weight or more, preferably 0.5% by weight or less, more preferably 0.3% by weight or less.
- the content of the light stabilizer is not less than the above lower limit and not more than the above upper limit, an increase in the YI value in the laminated glass can be further suppressed.
- the first layer, the second layer, and the third layer are each added with a flame retardant, an antistatic agent, a pigment, a dye, a moisture-proofing agent, a fluorescent brightening agent, an infrared absorber, and the like as necessary.
- An agent 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 intermediate film is not less than the above lower limit, the penetration resistance of the laminated glass is 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.
- T is the thickness of the intermediate film.
- the thickness of the second layer is preferably 0.0625T or more, more preferably 0.1T or more, preferably 0.375T or less, more preferably 0.25T or less.
- the thickness of the second layer is not less than the above lower limit and not more than the above upper limit, the penetration resistance of the laminated glass is further enhanced, and bleed out of the plasticizer can be suppressed.
- each of the first layer and the third layer is preferably 0.3125T or more, more preferably 0.375T or more, preferably 0.9375T or less, more preferably 0.9T or less.
- Each thickness of the first layer and the third layer may be 0.46875T or less, or 0.45T or less.
- 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 disposed and laminated on the first surface 11 a of the intermediate film 11.
- the second laminated glass member 22 is disposed and laminated on the second surface 11b opposite to the first surface 11a of the intermediate film 11.
- a first laminated glass member 21 is disposed and laminated on the outer surface 1 a of the first layer 1.
- a second laminated glass member 22 is disposed and laminated on the outer surface 3 a of the third layer 3.
- 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 disposed and laminated on the first surface 11a of the intermediate film 11A.
- the second laminated glass member 22 is disposed and laminated on the second surface 11b opposite to the first surface 11a of the intermediate film 11A.
- 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.
- 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.
- 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, wire-containing plate glass, and green glass.
- the organic glass is a synthetic resin glass substituted for inorganic glass.
- the organic glass examples include polycarbonate plates and poly (meth) acrylic resin plates.
- the poly (meth) acrylic resin plate examples include a polymethyl (meth) acrylate plate.
- the thickness of the laminated glass member is preferably 1 mm or more, preferably 5 mm or less, more preferably 3 mm or less.
- the thickness of the glass plate is preferably 1 mm or more, preferably 5 mm or less, more preferably 3 mm or less.
- the thickness of the PET film is preferably 0.03 mm or more, and preferably 0.5 mm or less.
- the method for producing the laminated glass is not particularly limited.
- the intermediate film is sandwiched between the first laminated glass member and the second laminated glass member, passed through a pressing roll, or put in a rubber bag and sucked under reduced pressure, and the first The air remaining between the laminated glass member, the second laminated glass member and the intermediate film is degassed. Thereafter, it is pre-bonded at about 70 to 110 ° C. to obtain a laminate.
- the 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.
- 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 a vehicle or architectural interlayer film and a laminated glass, and more preferably a vehicle interlayer film and a laminated glass.
- 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.
- PVB1 polyvinyl acetal resin, n-butyraldehyde having 4 carbon atoms is used for acetalization, polyvinyl alcohol average polymerization degree 1700, hydroxyl group content 30.7 mol%, acetalization degree 68.5 mol%, acetylation degree 0.8 mol%)
- PVB2 polyvinyl acetal resin, n-butyraldehyde having 4 carbon atoms is used for acetalization, average polymerization degree of polyvinyl alcohol 2300, hydroxyl group content 23.3 mol%, acetalization degree 64.2 mol%, acetylation degree 12.5 mol%)
- the degree of acetalization degree of butyralization
- the degree of acetylation degree of acetylation
- the hydroxyl group content was measured by a method in accordance with 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 tin-doped indium oxide particles
- ATO antimony-doped tin oxide particles
- BHT (2,6-di-t-butyl-p-cresol)
- Example 1 (1) Production of a composition for forming the first layer 100 parts by weight of PVB1, 40 parts by weight of 3GO, and an amount of 0.7% by weight in the first layer from which Plysurf A208B can be obtained And an amount of 0.15% by weight in the interlayer film from which ITO can be obtained and 0.2 part by weight of antioxidant (BHT) were mixed to obtain a composition for forming the first layer. .
- BHT antioxidant
- Examples 2 to 8 Reference Examples 9 to 15, Examples 16 to 20, Reference Example 21, Examples 22, 23 and Comparative Examples 1 to 5
- An interlayer film and a laminated glass were obtained in the same manner as in Example 1 except that the types and blending amounts of the blending components in the first layer were changed as shown in Tables 1 to 3 below.
- the blending amount of magnesium acetate was set so that the magnesium concentration in the obtained first layer was the amount shown in Tables 1 to 3.
- the heat shielding particles were blended so that the content of the heat shielding particles in the obtained first layer was the amount shown in Tables 1 to 3.
- the phosphorus compound and the silane compound were blended so that the contents of the phosphorus compound and the silane compound were as shown in Tables 1 to 3 in the obtained first layer.
- Example 1 In all of Examples 2 to 8, Reference Examples 9 to 15, Examples 16 to 20, Reference Example 21, Examples 22 and 23, and Comparative Examples 1 to 5, the first layer is the same as Example 1. Was added in the same amount as in Example 1 (amount relative to the polyvinyl acetal resin). In Tables 1 to 3, the description of the antioxidant content is omitted.
- Example 24 (1) Preparation of composition for forming first and third layers 100 parts by weight of PVB1, 40 parts by weight of 3GO, 0.1% in the first and third layers to obtain plysurf A208B. The amount of 7% by weight, the amount of 0.16% by weight in the interlayer film from which ITO is obtained, and 0.2 part by weight of antioxidant (BHT) are mixed, and the first and third layers are mixed. A composition for forming was obtained.
- composition for forming second layer 100 parts by weight of PVB2 and 60 parts by weight of 3GO were mixed to obtain a composition for forming the second layer.
- the first layer (average thickness) in the thickness direction was coextruded with the composition for forming the first and third layers and the composition for forming the second layer. 350 ⁇ m), a second layer (average thickness 100 ⁇ m), and a first layer and a third layer (average thickness 350 ⁇ m) were laminated in this order to produce an interlayer film for laminated glass.
- Examples 25 to 29 and Comparative Example 6 An interlayer film and a laminated glass were obtained in the same manner as in Example 24 except that the types and blending amounts of the blending components in the first, third and second layers were changed as shown in Table 4 below. .
- the compounding quantity of magnesium acetate was set so that the density
- the heat shielding particles were blended so that the content of the heat shielding particles would be the amount shown in Table 4 in the obtained first, third and second layers.
- the phosphorus compound and the silane compound were blended so that the contents of the phosphorus compound and the silane compound were as shown in Table 4 in the obtained first, third and second layers.
- Example 25 to 29 and Comparative Example 6 the same antioxidant as in Example 24 was blended in the first layer in the same amount as in Example 24 (amount relative to the polyvinyl acetal resin).
- amount relative to the polyvinyl acetal resin amount relative to the polyvinyl acetal resin.
- Haze value is 1.0% or less ⁇ : Haze value exceeds 1.0%, 1.5% or less ⁇ : Haze value exceeds 1.5%, 2.0% or less ⁇ : Haze value is Over 2.0%
- the laminated glass was adjusted by allowing it to stand at a temperature of 24 ° C. ⁇ 1 ° C. for 16 hours, and this was crushed with a hammer having a head of 0.45 kg until the particle size of the glass became 6 mm or less.
- the peelability of the glass was visually determined based on the following criteria.
- the peeled portion is 50% or more of the whole ⁇ : The peeled portion is 5% or more and less than 50% of the whole ⁇ : The peeled portion is less than 5% of the whole
- the intermediate film of the reference example had lower heat-shielding property than the intermediate film of the example.
- the specific Example of the single layer intermediate film of only the 1st layer was shown. Even in the case of the two-layer and three-layer intermediate films, it was confirmed that the effects of the present invention were obtained from the first layer by providing the configuration of the present invention.
- the content of P (phosphorus atom) or the content of Si (silicon atom) in the intermediate film is the same, by using a phosphorus compound having a polyoxyalkylene group or a silane compound having a polyoxyalkylene group Compared with the case where other phosphorus compounds or silane compounds are used, the peelability of the laminated glass member such as a glass plate from the intermediate film can be improved.
Abstract
Description
上記第1の層(単層の中間膜を含む)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)を含むことが好ましく、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。上記第2の層は、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)を含むことが好ましく、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。上記第3の層は、熱可塑性樹脂(以下、熱可塑性樹脂(3)と記載することがある)を含むことが好ましく、熱可塑性樹脂(3)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(3)と記載することがある)を含むことが好ましい。上記ポリビニルアセタール樹脂(1)と上記ポリビニルアセタール樹脂(2)と上記ポリビニルアセタール樹脂(3)とは、同一であってもよく、異なっていてもよい。上記ポリビニルアセタール樹脂(1)、上記ポリビニルアセタール樹脂(2)及び上記ポリビニルアセタール樹脂(3)はそれぞれ、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。上記熱可塑性樹脂(1)と上記熱可塑性樹脂(2)と上記熱可塑性樹脂(3)とは、同一であってもよく、異なっていてもよい。上記熱可塑性樹脂(1)、上記熱可塑性樹脂(2)及び上記熱可塑性樹脂(3)はそれぞれ、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の層(単層の中間膜を含む)は、可塑剤(以下、可塑剤(1)と記載することがある)を含むことが好ましい。上記第2の層は、可塑剤(以下、可塑剤(2)と記載することがある)を含むことが好ましい。上記第3の層は、可塑剤(以下、可塑剤(3)と記載することがある)を含むことが好ましい。ポリビニルアセタール樹脂と可塑剤との併用により、ポリビニルアセタール樹脂と可塑剤とを含む層の合わせガラス部材又は他の層に対する接着力が適度に高くなる。上記可塑剤は特に限定されない。上記可塑剤(1)と上記可塑剤(2)と上記可塑剤(3)とは同一であってもよく、異なっていてもよい。上記可塑剤は、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。
上記中間膜は、遮熱性化合物を含むことが好ましい。上記第1の層は、遮熱性化合物を含むことが好ましい。上記第2の層は、遮熱性化合物を含むことが好ましい。上記第3の層は、遮熱性化合物を含むことが好ましい。上記遮熱性化合物は、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。
上記中間膜は、フタロシアニン化合物、ナフタロシアニン化合物及びアントラシアニン化合物の内の少なくとも1種の成分Xを含むことが好ましい。上記第1の層は、上記成分Xを含むことが好ましい。上記第2の層は、上記成分Xを含むことが好ましい。上記第3の層は、上記成分Xを含むことが好ましい。上記成分Xは遮熱性化合物である。上記成分X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。
上記中間膜は、いずれかの層に遮熱粒子を含む。上記第1の層は、上記遮熱粒子を含むことが好ましい。上記第2の層は、上記遮熱粒子を含むことが好ましい。上記第3の層は、上記遮熱粒子を含むことが好ましい。上記遮熱粒子は遮熱性化合物である。遮熱粒子の使用により、赤外線(熱線)を効果的に遮断できる。上記遮熱粒子は、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。
合わせガラス部材の中間膜からの剥離性を適度に高める観点から、上記第1の層は、マグネシウムを含まないか又はマグネシウムを50ppm以下で含み、かつ、ポリオキシアルキレン基を有するリン化合物又はポリオキシアルキレン基を有するシラン化合物を含む。上記第1の層は、上記リン化合物のみを含んでいてもよく、上記シラン化合物のみを含んでいてもよく、上記リン化合物と上記シラン化合物との双方を含んでいてもよい。合わせガラス部材の中間膜からの剥離性を適度に高める観点から、上記第3の層は、マグネシウムを含まないか又はマグネシウムを50ppm以下で含み、かつ、ポリオキシアルキレン基を有するリン化合物又はポリオキシアルキレン基を有するシラン化合物を含むことが好ましい。上記第2の層は、マグネシウムを含まないか又はマグネシウムを50ppm以下で含み、かつ、ポリオキシアルキレン基を有するリン化合物又はポリオキシアルキレン基を有するシラン化合物を含んでいてもよい。上記リン化合物は、リン原子を含む。上記リン化合物は、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。上記シラン化合物は、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。
上記中間膜は、紫外線遮蔽剤を含むことが好ましい。上記第1の層は、紫外線遮蔽剤を含むことが好ましい。上記第2の層は、紫外線遮蔽剤を含むことが好ましい。上記第3の層は、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、中間膜及び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。
上記中間膜は、酸化防止剤を含むことが好ましい。上記第1の層は、酸化防止剤を含むことが好ましい。上記第2の層は、酸化防止剤を含むことが好ましい。上記第3の層は、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。
合わせガラスにおけるYI値の上昇を抑える観点から、上記中間膜は、光安定剤を含むことが好ましい。上記第1の層は、光安定剤を含むことが好ましい。上記第2の層は光安定剤を含むことが好ましい。上記第3の層は、光安定剤を含むことが好ましい。上記光安定剤は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の層、上記第2の層及び上記第3の層はそれぞれ、必要に応じて、難燃剤、帯電防止剤、顔料、染料、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が高くなる。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。
PVB1(ポリビニルアセタール樹脂、アセタール化に炭素数4のn-ブチルアルデヒドを使用、ポリビニルアルコールの平均重合度1700、水酸基の含有率30.7モル%、アセタール化度68.5モル%、アセチル化度0.8モル%)
3GO(トリエチレングリコールジ-2-エチルヘキサノエート)
ITO(錫ドープ酸化インジウム粒子)
ATO(アンチモンドープ酸化錫粒子)
カーボンブラック
酢酸Mg(酢酸マグネシウム)
ポリオキシエチレンラウリルエーテルリン酸エステル プライサーフA208B(第一工業製薬社製)(表中、A208Bと記載する)
ポリオキシエチレンラウリルエーテルリン酸エステル プライサーフA219B(第一工業製薬社製)(表中、A219Bと記載する)
ポリオキシエチレントリデシルエーテルリン酸エステル プライサーフA212C(第一工業製薬社製)(表中、A212Cと記載する)
ポリオキシエチレンアルキルエーテルリン酸エステル プライサーフA208F(第一工業製薬社製)(表中、A208Fと記載する)
リン酸ジブチル
リン酸トリブチル
リン酸トリス(2-エチルヘキシル)
PEG(重合度400、関東化学社製「ポリエチレングリコール400」)
PG1190(Hybrid Plastics社製「POSS PG1190」)
BHT(2,6-ジ-t-ブチル-p-クレゾール)
(1)第1の層を形成するための組成物の作製
PVB1を100重量部と、3GOを40重量部と、プライサーフA208Bを得られる第1の層中で0.7重量%となる量と、ITOを得られる中間膜中で0.15重量%となる量と、酸化防止剤(BHT)0.2重量部とを混合し、第1の層を形成するための組成物を得た。
第1の層を形成するための組成物を、押出機を用いて押出しすることにより、第1の層(厚み760μm)のみの単層の中間膜(厚み760μm)を作製した。
洗浄及び乾燥した2つのガラス板(クリアフロートガラス、縦25cm×横10cm×厚み2.5mm)を用意した。この2つのガラス板の間に、得られた中間膜を挟み込み、積層体を得た。得られた積層体をゴムバック内に入れ、2660Pa(20torr)の真空度で20分間脱気した。その後、脱気したままで積層体をオートクレーブ中で更に90℃で30分間保持しつつ、真空プレスした。このようにして予備圧着された積層体を、オートクレーブ中で135℃、圧力1.2MPa(12kg/cm2)の条件で20分間圧着を行い、合わせガラスを得た。
第1の層における配合成分の種類及び配合量を以下の表1~3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、中間膜及び合わせガラスを得た。
(1)第1,第3の層を形成するための組成物の作製
PVB1を100重量部と、3GOを40重量部と、プライサーフA208Bを得られる第1,第3の層中で0.7重量%となる量と、ITOを得られる中間膜中で0.16重量%となる量と、酸化防止剤(BHT)0.2重量部とを混合し、第1,第3の層を形成するための組成物を得た。
PVB2を100重量部と、3GOを60重量部とを混合し、第2の層を形成するための組成物を得た。
第1,第3の層を形成するための組成物及び第2の層を形成するための組成物を共押出することにより、厚み方向に第1の層(平均厚み350μm)、第2の層(平均厚み100μm)、第1,第3の層(平均厚み350μm)の順に積層された三層構造の合わせガラス用中間膜を作製した。
洗浄及び乾燥した2つのガラス板(クリアフロートガラス、縦25cm×横10cm×厚み2.5mm)を用意した。この2つのガラス板の間に、得られた中間膜を挟み込み、積層体を得た。得られた積層体をゴムバック内に入れ、2660Pa(20torr)の真空度で20分間脱気した。その後、脱気したままで積層体をオートクレーブ中で更に90℃で30分間保持しつつ、真空プレスした。このようにして予備圧着された積層体を、オートクレーブ中で135℃、圧力1.2MPa(12kg/cm2)の条件で20分間圧着を行い、合わせガラスを得た。
第1,第3の層及び第2の層における配合成分の種類及び配合量を以下の表4に示すように変更したこと以外は実施例24と同様にして、中間膜及び合わせガラスを得た。
(1)ヘーズ値
ヘーズメーター(東京電色社製「TC-HIIIDPK」)を用いて、JIS K6714に準拠して、得られた合わせガラスのヘーズ値を測定した。ヘーズ値を以下の基準で判定した。
○○:ヘーズ値が1.0%以下
○:ヘーズ値が1.0%を超え、1.5%以下
△:ヘーズ値が1.5%を超え、2.0%以下
×:ヘーズ値が2.0%を超える
合わせガラスをハンマーで叩き割ることにより、ガラスの剥離性を評価した。詳細は次の通りである。
○○:剥離している箇所が全体の50%以上である
○:剥離している箇所が全体の5%以上50%未満である
×:剥離している箇所が全体の5%未満である
1a…外側の表面
2…第2の層
2a…第1の表面
2b…第2の表面
3…第3の層
3a…外側の表面
11…中間膜
11A…中間膜(第1の層)
11a…第1の表面
11b…第2の表面
21…第1のガラス板
22…第2のガラス板
31…合わせガラス
31A…合わせガラス
Claims (14)
- 第1の層のみを備える単層の中間膜であるか、又は、第1の層と他の層とを備える多層の中間膜である合わせガラス用中間膜であって、
前記第1の層が、マグネシウムを含まないか又はマグネシウムを50ppm以下で含み、かつ、前記第1の層が、ポリオキシアルキレン基を有するリン化合物又はポリオキシアルキレン基を有するシラン化合物を含み、
前記第1の層のみを備える単層の中間膜の場合には、前記第1の層が、遮熱粒子を含み、
前記第1の層と他の層とを備える多層の中間膜の場合には、多層の中間膜における少なくとも1層が、遮熱粒子を含む、合わせガラス用中間膜。 - 前記第1の層が、遮熱粒子を含む、請求項1記載の合わせガラス用中間膜。
- 前記第1の層が、アルカリ金属を含まないか又はアルカリ金属を1000ppm以下で含む、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の層が、熱可塑性樹脂を含む、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の層に含まれる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1~4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の層が、可塑剤を含む、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。
- 前記ポリオキシアルキレン基を有するリン化合物又はポリオキシアルキレン基を有するシラン化合物が、ポリオキシアルキレン基とポリオキシアルキレン基に結合したアルキル基とを有するリン化合物、又は、ポリオキシアルキレン基とポリオキシアルキレン基に結合したアルキル基とを有するシラン化合物である、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。
- 前記ポリオキシアルキレン基を有するリン化合物が、ポリオキシアルキレン基を有するリン酸エステルである、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。
- 前記ポリオキシアルキレン基を有するシラン化合物が、ポリオキシアルキレン基を有するシルセスキオキサンである、請求項1~8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の層が、前記ポリオキシアルキレン基を有するリン化合物を含む、請求項1~9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の層を、中間膜における表面層として備える、請求項1~10のいずれか1項に記載の合わせガラス用中間膜。
- 2層以上の構造を有する合わせガラス用中間膜であって、
熱可塑性樹脂を含む第2の層をさらに備え、
前記第2の層の第1の表面側に、前記第1の層が配置されている、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。 - 3層以上の構造を有する合わせガラス用中間膜であって、
熱可塑性樹脂を含む第3の層をさらに備え、
前記第2の層の前記第1の表面側とは反対の第2の表面側に、前記第3の層が配置されている、請求項12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1~13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、
前記第1の合わせガラス部材と前記第2の合わせガラス部材との間に、前記合わせガラス用中間膜が配置されている、合わせガラス。
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009123186A1 (ja) * | 2008-03-31 | 2009-10-08 | 積水化学工業株式会社 | 合わせガラス用中間膜、合わせガラス、及び、酸化亜鉛微粒子分散液 |
JP2012254924A (ja) * | 2004-07-06 | 2012-12-27 | Sekisui Chem Co Ltd | 合わせガラス用中間膜及び合わせガラス |
JP2014166959A (ja) * | 2014-05-27 | 2014-09-11 | Sekisui Chem Co Ltd | 合わせガラス用中間膜及び合わせガラス |
JP2015040165A (ja) * | 2013-08-23 | 2015-03-02 | 積水化学工業株式会社 | 合わせガラス用中間膜及び合わせガラス |
JP2015134893A (ja) * | 2014-01-20 | 2015-07-27 | 株式会社クレハ | 近赤外線吸収剤分散液の製造方法、近赤外線吸収剤分散液およびその用途 |
JP2016060903A (ja) * | 2014-09-22 | 2016-04-25 | 株式会社クレハ | 近赤外線吸収剤微粒子分散液の製造方法、近赤外線吸収剤微粒子分散液およびその用途 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6372352B1 (en) * | 1998-03-04 | 2002-04-16 | E. I. Du Pont De Nemours And Co. | Delamination-resistant laminated glass structures |
JP4560251B2 (ja) * | 2001-09-10 | 2010-10-13 | パイオニア株式会社 | 情報記録装置および情報記録方法 |
US7067606B2 (en) * | 2002-07-30 | 2006-06-27 | University Of Connecticut | Nonionic telechelic polymers incorporating polyhedral oligosilsesquioxane (POSS) and uses thereof |
JP4759512B2 (ja) * | 2004-06-01 | 2011-08-31 | 積水化学工業株式会社 | 合わせガラス用中間膜及び合わせガラス |
JP4481728B2 (ja) * | 2004-06-01 | 2010-06-16 | 積水化学工業株式会社 | 遮熱粒子分散液、合わせガラス用中間膜及び合わせガラス |
JP2006021950A (ja) * | 2004-07-07 | 2006-01-26 | Sekisui Chem Co Ltd | 遮熱合わせガラス用中間膜及び合わせガラス |
AU2005268127A1 (en) * | 2004-08-05 | 2006-02-09 | Sekisui Chemical Co., Ltd. | Method of reforming intermembrane of heat shield glass laminate |
WO2009035081A1 (ja) * | 2007-09-12 | 2009-03-19 | Sekisui Chemical Co., Ltd. | 合わせガラス用中間膜 |
CN101903172A (zh) * | 2007-12-18 | 2010-12-01 | 可乐丽股份有限公司 | 层合玻璃用夹层膜、其制造方法和含有其的层合玻璃 |
WO2009123187A1 (ja) * | 2008-03-31 | 2009-10-08 | 積水化学工業株式会社 | 合わせガラス用中間膜、合わせガラス、及び、酸化亜鉛微粒子分散液 |
JP5401232B2 (ja) * | 2008-09-24 | 2014-01-29 | 積水化学工業株式会社 | 合わせガラス用中間膜及び合わせガラス |
WO2012077689A1 (ja) * | 2010-12-10 | 2012-06-14 | 株式会社クラレ | 合わせガラス用中間膜、その製造方法およびそれを用いた合わせガラス |
JP5903810B2 (ja) * | 2011-09-09 | 2016-04-13 | 住友金属鉱山株式会社 | 赤外線遮蔽材料微粒子分散液とその製造方法および熱線遮蔽膜と熱線遮蔽合わせ透明基材 |
-
2016
- 2016-09-28 US US15/762,555 patent/US20180257343A1/en not_active Abandoned
- 2016-09-28 KR KR1020187008281A patent/KR20180055830A/ko not_active Application Discontinuation
- 2016-09-28 CN CN201680056486.8A patent/CN108137402A/zh active Pending
- 2016-09-28 JP JP2016563153A patent/JP6908382B2/ja active Active
- 2016-09-28 EP EP16851670.6A patent/EP3357890A4/en not_active Withdrawn
- 2016-09-28 WO PCT/JP2016/078693 patent/WO2017057499A1/ja active Application Filing
-
2022
- 2022-03-11 US US17/654,491 patent/US20220194059A1/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012254924A (ja) * | 2004-07-06 | 2012-12-27 | Sekisui Chem Co Ltd | 合わせガラス用中間膜及び合わせガラス |
WO2009123186A1 (ja) * | 2008-03-31 | 2009-10-08 | 積水化学工業株式会社 | 合わせガラス用中間膜、合わせガラス、及び、酸化亜鉛微粒子分散液 |
JP2015040165A (ja) * | 2013-08-23 | 2015-03-02 | 積水化学工業株式会社 | 合わせガラス用中間膜及び合わせガラス |
JP2015134893A (ja) * | 2014-01-20 | 2015-07-27 | 株式会社クレハ | 近赤外線吸収剤分散液の製造方法、近赤外線吸収剤分散液およびその用途 |
JP2014166959A (ja) * | 2014-05-27 | 2014-09-11 | Sekisui Chem Co Ltd | 合わせガラス用中間膜及び合わせガラス |
JP2016060903A (ja) * | 2014-09-22 | 2016-04-25 | 株式会社クレハ | 近赤外線吸収剤微粒子分散液の製造方法、近赤外線吸収剤微粒子分散液およびその用途 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3357890A4 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110828596A (zh) * | 2019-11-18 | 2020-02-21 | 苏州浩纳新材料科技有限公司 | 一种透明聚酯太阳能背板及其制备方法 |
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