WO2016052670A1 - 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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- WO2016052670A1 WO2016052670A1 PCT/JP2015/077862 JP2015077862W WO2016052670A1 WO 2016052670 A1 WO2016052670 A1 WO 2016052670A1 JP 2015077862 W JP2015077862 W JP 2015077862W WO 2016052670 A1 WO2016052670 A1 WO 2016052670A1
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- laminated glass
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- polyvinyl 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
- 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
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
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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
- B32B17/10605—Type of plasticiser
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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
- B32B17/1077—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 polyurethane
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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
- B32B17/10798—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 silicone
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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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
- B60J1/00—Windows; Windscreens; Accessories therefor
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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
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/418—Refractive
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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
- B32B2419/00—Buildings or parts thereof
-
- 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
- B32B2605/00—Vehicles
- B32B2605/006—Transparent parts other than made from inorganic glass, e.g. polycarbonate glazings
Definitions
- 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 two glass plates.
- the interlayer film for laminated glass includes a single-layer interlayer film having a single-layer structure and a multilayer interlayer film having a structure of two or more layers.
- Patent Document 1 As an example of the interlayer film for laminated glass, Patent Document 1 listed below discloses that 100 parts by weight of a polyvinyl acetal resin having a degree of acetalization of 60 to 85 mol% and at least one of alkali metal salts and alkaline earth metal salts. A sound insulating layer containing 0.001 to 1.0 parts by weight of a metal salt of the above and a plasticizer exceeding 30 parts by weight is disclosed. This sound insulation layer may be a single layer and used as an intermediate film.
- Patent Document 1 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 is often exposed to a high temperature of about 40 ° C. due to the influence of direct sunlight. Therefore, it is desirable that the laminated glass is excellent not only in the rigidity near 25 ° C. but also in the rigidity near 40 ° C.
- the total amount of the polyvinyl acetal resin in the first layer and the second resin component in the first layer is 100% by weight.
- the content of the polyvinyl acetal resin in one layer is 5% by weight or more and 60% by weight or less, and the content of the second resin component in the first layer is 40% by weight or more and 95% by weight or less. is there.
- the polyvinyl acetal resin and the second resin component form a sea-island structure or a co-continuous structure in the first layer.
- the average diameter of the island portions in the sea-island structure of the first layer is 500 nm or less.
- the second resin component in the first layer is an acrylic polymer, a urethane polymer, a silicone polymer, a rubber, or a vinyl acetate polymer. It is.
- the second resin component in the first layer is an acrylic polymer.
- the said intermediate film for laminated glasses is the 3rd arrange
- the third layer includes a polyvinyl acetal resin.
- the second layer includes a plasticizer
- the third layer includes a plasticizer
- the interlayer film for laminated glass according to the present invention includes a first layer and a second layer disposed on the first surface side of the first layer, and the first layer is a polyvinyl acetal resin. And the second resin component, the second layer contains a polyvinyl acetal resin, and the polyvinyl acetal resin and the second resin component form a phase separation structure in the first layer.
- the glass transition temperature derived from the second resin component in the first layer is 30 ° C. or more lower than the glass transition temperature derived from the polyvinyl acetal resin in the first layer.
- the rigidity of the laminated glass using the interlayer film can be increased, and the sound insulation of the laminated glass can be enhanced.
- interlayer film for laminated glass The interlayer film for laminated glass according to the present invention (in this specification, sometimes abbreviated as “intermediate film”) has a structure of two or more layers.
- the interlayer film according to the present invention has the above-described configuration, the rigidity of the laminated glass using the interlayer film can be increased, and the penetration resistance of the laminated glass can be increased. Moreover, in order to obtain a laminated glass, an intermediate film is arrange
- the rigidity can be sufficiently increased not only near 25 ° C. but also over a wide temperature range, and the penetration resistance of the laminated glass can be sufficiently enhanced over a wide temperature range. it can.
- the rigidity at 25 to 40 ° C. can be sufficiently increased.
- the laminated glass can be reduced in weight.
- the laminated glass is lightweight, the amount of material used for the laminated glass can be reduced, and the environmental load can be reduced.
- fuel efficiency can be improved, and as a result, environmental load can be reduced.
- the laminated glass can be reduced in weight.
- the sound insulation can be improved, and the peak frequency of the loss coefficient can be easily controlled within a suitable range.
- the peak frequency of the loss coefficient can be controlled in the range of 3000 to 8000 Hz, and can be controlled to 4000 Hz or higher.
- the intermediate film may have a two-layer structure or may have a structure of three or more layers, and includes a third layer in addition to the first layer and the second layer. It may be.
- the intermediate film preferably includes a third layer disposed on the second surface side opposite to the first surface of the first layer.
- 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 1a of the first layer 1, the second layer 2 is disposed and laminated.
- the third layer 3 is disposed on the second surface 1b opposite to the first surface 1a of the first layer 1 and laminated.
- the first layer 1 is an intermediate layer.
- Each of the second layer 2 and the third layer 3 is a protective layer, and is a surface layer in the present embodiment.
- the first layer 1 is arranged between the second layer 2 and the third layer 3 and is sandwiched between them. Therefore, the intermediate film 11 has a multilayer structure (second layer 2 / first layer 1 / third layer) in which the second layer 2, the first layer 1, and the third layer 3 are laminated in this order. Having layer
- layers may be disposed between the second layer 2 and the first layer 1 and between the first layer 1 and the third layer 3, respectively.
- the second layer 2 and the first layer 1 and the first layer 1 and the third layer 3 are preferably laminated directly.
- examples of other layers include layers containing polyethylene terephthalate and the like.
- the first layer 1 includes a polyvinyl acetal resin and a second resin component.
- the second layer 2 includes a polyvinyl acetal resin.
- the third layer 3 preferably contains a polyvinyl acetal resin.
- the first layer includes a polyvinyl acetal resin (hereinafter sometimes referred to as a polyvinyl acetal resin (1)).
- the second layer contains a polyvinyl acetal resin (hereinafter may be referred to as a polyvinyl acetal resin (2)).
- the third layer preferably contains a polyvinyl acetal resin (hereinafter sometimes referred to as a polyvinyl acetal resin (3)).
- the polyvinyl acetal resin (1), the polyvinyl acetal resin (2), and the polyvinyl acetal resin (3) may be the same or different.
- the polyvinyl acetal resin (1) As for 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 polyvinyl acetal resin includes an acetoacetalized resin.
- the polyvinyl acetal resin can be produced, for example, by acetalizing polyvinyl alcohol with an aldehyde.
- the polyvinyl acetal resin is preferably an acetalized product of polyvinyl alcohol.
- the polyvinyl alcohol can be obtained, for example, by saponifying polyvinyl acetate.
- the saponification degree of the polyvinyl alcohol is generally 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 in the polyvinyl acetal resin is preferably 2 to 5, and preferably 2, 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 carbon number of the acetal group in the polyvinyl acetal resin is preferably 2 or 4, and in this case, the production of the polyvinyl acetal resin is efficient.
- an aldehyde having 1 to 10 carbon atoms is preferably used as the aldehyde.
- the aldehyde having 1 to 10 carbon atoms include formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, n-octylaldehyde, Examples include n-nonyl aldehyde, n-decyl aldehyde, and benzaldehyde.
- acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-hexylaldehyde or n-valeraldehyde is preferable
- acetaldehyde, propionaldehyde, n-butyraldehyde or isobutyraldehyde is more preferable
- acetaldehyde, propionaldehyde or n More preferred is butyraldehyde.
- the said aldehyde only 1 type may be used and 2 or more types may be used together.
- the content of each hydroxyl group in the polyvinyl acetal resin (2) and the polyvinyl acetal resin (3) is preferably 25 mol% or more, preferably 38 mol% or less, more preferably 35 mol% or less, still more preferably 32 mol%. % Or less, particularly preferably 30 mol% or less, and most preferably 27.5 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 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. Moreover, rigidity becomes high effectively that the content rate of the said hydroxyl group is below the said upper limit.
- the degree of acetylation (acetyl group amount) of the polyvinyl acetal resin (1) is preferably 0.01 mol% or more, more preferably 0.1 mol% or more, still more preferably 7 mol% or more, 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 degree of acetylation is not less than the above lower limit, sound insulation is increased and 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 (1) is 0.1 mol% or more and 25 mol% or less, the penetration resistance is excellent.
- 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 (degree of butyralization in the case of polyvinyl butyral resin) of the polyvinyl acetal resin (2) 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 hydroxyl group content (hydroxyl content), acetalization degree (butyralization degree), and acetylation degree are preferably calculated from results measured by a method in accordance with JIS K6728 “Testing methods for polyvinyl butyral”. However, measurement by ASTM D1396-92 may be used.
- the polyvinyl acetal resin is a polyvinyl butyral resin
- the hydroxyl group content (hydroxyl amount), the acetalization degree (butyralization degree), and the acetylation degree are determined in accordance with JIS K6728 “Testing methods for polyvinyl butyral”. It can be calculated from the results measured by
- the 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 content (a) of the hydroxyl group in 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 40 Mol% or less, more preferably 37 mol% or less, even more preferably 34 mol% or less, still more preferably 31 mol% or less, still more preferably 30 mol% or less, particularly preferably 29 mol% or less, and most preferably 28 mol% or less. It is less than mol%.
- the hydroxyl group content (a) is not less than the above lower limit, the adhesive strength of the first 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 hydroxyl group content (b) of 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 38. It is not more than mol%, more preferably not more than 35 mol%, still more preferably not more than 31 mol%, still more preferably not more than 30 mol%, still more preferably not more than 29 mol%, particularly preferably not more than 28 mol%.
- 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, a polyvinyl acetoacetal resin, or a polyvinyl butyral-polyvinyl acetoacetal resin (co-acetal resin). It is more preferable that
- the second resin component in the first layer is The resin is preferably different from the polyvinyl acetal resin.
- the second resin component is an acrylic polymer, urethane polymer, silicone polymer, rubber.
- a vinyl acetate polymer more preferably an acrylic polymer or a vinyl acetate polymer, and still more preferably an acrylic polymer.
- the polymer includes a copolymer.
- the acrylic polymer should be a polymer of a polymerization component containing a (meth) acrylic acid ester. Is preferred. By selecting the kind and blending amount of (meth) acrylic acid ester, the glass transition temperature derived from the second resin component can be easily controlled.
- the weight average molecular weight of the second resin component is preferably 8000 or more, more preferably 10,000 or more. More preferably, it is 30000 or more, preferably 1000000 or less, more preferably 800000 or less, and further preferably 500000 or less.
- the said weight average molecular weight shows the molecular weight in polystyrene conversion calculated
- the second resin component may be interspersed in the polyvinyl acetal resin, and the polyvinyl acetal resin may be interspersed in the second resin component. .
- the polyvinyl acetal resin and the second resin component may form a sea-island structure.
- the polyvinyl acetal resin may be a sea part, and the second resin component may be an island part, the second resin component may be a sea part, and the polyvinyl acetal resin may be an island part.
- the polyvinyl acetal resin may be continuous (may have a continuous structure), and the second resin component may be continuous (have a continuous structure).
- the polyvinyl acetal resin and the second resin component may form a co-continuous structure.
- the polyvinyl acetal resin may be present in a network form
- the second resin component may be present in a network form. Since the effect of the present invention is excellent, it is preferable that the polyvinyl acetal resin and the second resin component have a sea-island structure or a bicontinuous structure.
- the polyvinyl acetal resin and the second resin component preferably form a sea-island structure or a co-continuous structure, and the polyvinyl acetal resin and the second resin component It is more preferable to form a sea-island structure, and it is preferable that the first layer has a sea-island structure with the polyvinyl acetal resin and the second resin component.
- a sea-island structure in which the polyvinyl acetal resin constitutes the sea is preferable.
- the average diameter of the island part is preferably 15 nm or more, more preferably 20 nm or more, still more preferably 30 nm or more, preferably 13 ⁇ m or less, more preferably 10 ⁇ m or less, still more preferably 2 ⁇ m or less, particularly preferably 500 m or less.
- the diameter of one island part indicates the maximum diameter, and the average of the island parts is obtained by averaging the diameters (maximum diameters) of a plurality of islands.
- the content of the polyvinyl acetal resin in the first layer is 5% by weight or more (preferably 10% by weight or more, more preferably 15% by weight or more), 60% by weight or less (preferably 55% by weight or less, more preferably 50% by weight or less), and the content of the skeleton derived from the second resin component in the copolymer in the first layer is 40% by weight or more (preferably 45% by weight or more, more preferably 50% by weight). Above), 95% by weight or less (preferably 90% by weight or less, more preferably 85% by weight or less).
- the first layer does not contain or contains a plasticizer (hereinafter sometimes referred to as plasticizer (1)).
- the first layer preferably contains 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 (1), the plasticizer (2), and the plasticizer (3) may be the same or different. As for the said plasticizer, only 1 type may be used and 2 or more types may be used together.
- plasticizer examples include organic ester plasticizers such as monobasic organic acid esters and polybasic organic acid esters, and organic phosphate plasticizers such as organic phosphoric acid plasticizers and organic phosphorous acid plasticizers. . Of these, 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
- the plasticizer is preferably a diester plasticizer represented by the following formula (1).
- 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.
- Content of the plasticizer (2) with respect to 100 parts by weight of the polyvinyl acetal resin (2) (hereinafter sometimes referred to as content (2)), and plastic with respect to 100 parts by weight of the polyvinyl acetal resin (3)
- the content of the agent (3) (hereinafter sometimes referred to as “content (3)”) is preferably 1 part by weight or more, more preferably 3 parts by weight or more, still more preferably 20 parts by weight or more, particularly preferably. Is 25 parts by weight or more, preferably 40 parts by weight or less, more preferably 35 parts by weight or less, still more preferably 32 parts by weight or less, and particularly preferably 30 parts by weight or less.
- the flexibility of the intermediate film is increased and the handling of the intermediate film is facilitated.
- the rigidity is effectively increased.
- the content (2) and the content (3) are not more than the above upper limit, the mechanical strength of the interlayer film is further increased, and the penetration resistance of the laminated glass is further increased. In particular, when the content (2) and the content (3) are 35 parts by weight or less, the penetration resistance of the laminated glass is effectively increased.
- 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 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 preferably contains heat shielding particles.
- 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.
- 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 generally represented by the following formula (X1) or the following formula (X2).
- tungsten oxide particles represented by the following formula (X1) or the following formula (X2) are preferably used.
- W represents tungsten
- O represents oxygen
- y and z satisfy 2.0 ⁇ z / y ⁇ 3.0.
- 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 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 layer (the first layer, the second layer, or the third layer) containing the heat shielding particles may contain the heat shielding particles at a ratio of 0.1 g / m 2 or more and 12 g / m 2 or less. preferable. When the ratio of the heat shielding particles is within the above range, the heat shielding property is sufficiently high and the visible light transmittance is sufficiently high.
- the intermediate film preferably contains at least one metal salt (hereinafter sometimes referred to as a metal salt M) of an alkali metal salt and an alkaline earth metal salt.
- the first layer preferably includes the metal salt M.
- the second layer preferably contains the metal salt M.
- the third layer preferably contains the metal salt M.
- Use of the metal salt M makes it easy to control the adhesion between the interlayer film and the laminated glass member 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 more preferably an alkali metal salt of an organic acid having 2 to 16 carbon atoms or an alkaline earth metal salt of an organic acid having 2 to 16 carbon atoms, and a carboxylic acid having 2 to 16 carbon atoms. More preferably, it is a magnesium salt or a potassium salt of a carboxylic acid 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 and K in the layer containing the metal salt M is preferably 5 ppm or more, more preferably 10 ppm or more, and even 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 adhesion between the interlayer film and the laminated glass member or the adhesion between the layers in the interlayer film can be controlled even better.
- 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 a metal-based ultraviolet shielding agent (a metal-containing ultraviolet shielding agent), a metal oxide-based ultraviolet shielding agent (an ultraviolet shielding agent containing a metal oxide), and a benzotriazole-based ultraviolet shielding agent ( UV shielding agent having a benzotriazole structure), benzophenone UV shielding agent (UV shielding agent having a benzophenone structure), triazine UV shielding agent (UV shielding agent having a triazine structure), malonic ester UV shielding agent (malonic acid) And an oxalic acid anilide type ultraviolet shielding agent (ultraviolet shielding agent having an oxalic acid anilide structure) and a benzoate type ultraviolet shielding agent (ultraviolet shielding agent having a benzoate structure).
- a metal-based ultraviolet shielding agent a metal-containing ultraviolet shielding agent
- a metal oxide-based ultraviolet shielding agent an ultraviolet shielding agent containing a metal oxide
- the metallic ultraviolet shielding agent examples include platinum particles, particles in which the surface of the platinum particles is coated with silica, palladium particles, particles in which the surface of the palladium particles is coated with silica, and the like.
- the ultraviolet shielding agent is preferably not a heat shielding particle.
- the ultraviolet shielding agent is preferably a benzotriazole ultraviolet shielding agent, a benzophenone ultraviolet shielding agent, a triazine ultraviolet shielding agent or a benzoate ultraviolet shielding agent, more preferably a benzotriazole ultraviolet shielding agent or a benzophenone ultraviolet shielding agent. More preferably, it is a benzotriazole ultraviolet shielding agent.
- metal oxide ultraviolet shielding agent examples include zinc oxide, titanium oxide, and cerium oxide. Furthermore, the surface of the metal oxide ultraviolet shielding agent may be coated. Examples of the coating material on the surface of the metal oxide ultraviolet shielding agent include insulating metal oxides, hydrolyzable organosilicon compounds, and silicone compounds.
- 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.
- benzotriazole ultraviolet shielding agent examples include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole (“TinvinP” manufactured by BASF), 2- (2′-hydroxy-3 ′, 5 ′). -Di-t-butylphenyl) benzotriazole (“Tinvin 320” manufactured by BASF), 2- (2'-hydroxy-3'-t-butyl-5-methylphenyl) -5-chlorobenzotriazole (manufactured by BASF " And benzotriazole-based UV screening agents such as 2- (2′-hydroxy-3 ′, 5′-di-amylphenyl) benzotriazole (“Tinvin 328” manufactured by BASF)).
- benzophenone-based ultraviolet shielding agent examples include octabenzone (“Chimasorb 81” manufactured by BASF).
- triazine-based ultraviolet shielding agent examples include “LA-F70” manufactured by ADEKA and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy].
- -Phenol Teuvin 1577FF manufactured by BASF
- malonic ester-based ultraviolet shielding agent examples include 2- (p-methoxybenzylidene) malonic acid dimethyl, tetraethyl-2,2- (1,4-phenylenedimethylidene) bismalonate, 2- (p-methoxybenzylidene) -bis. (1,2,2,6,6-pentamethyl 4-piperidinyl) malonate and the like.
- Hostavin B-CAP As commercial products of the above-mentioned malonic ester-based ultraviolet screening agents, there are Hostavin B-CAP, Hostavin PR-25, and Hostavin PR-31 (all manufactured by Clariant).
- benzoate ultraviolet shielding agent 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 is preferably 0.1% by weight or more, more preferably 0.2% by weight or more, further preferably 0.3% by weight or more, particularly preferably 0.5% by weight or more, preferably 2.5%.
- % By weight or less, more preferably 2% by weight or less, further 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 lapse of the period of the interlayer 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), butylated hydroxyanisole (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-tert-butylphenyl) Butane, tetrakis [methylene-3- (3 ′, 5′-butyl-4-hydroxyphenyl) propionate] methane, 1,3,3-tris- (2-methyl-4- Droxy-5-tert-butylphenol) butane, 1,3,5-trimethyl-2,
- 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 ".
- the intermediate film, the first layer, the second layer, and the third layer may each include a flame retardant, an antistatic agent, a pigment, a dye, an adhesive force adjusting agent, a moisture resistant agent, a fluorescent enhancement agent, as necessary.
- Additives such as whitening agents and infrared absorbers may be included. As for these additives, only 1 type may be used and 2 or more types may be used together.
- the glass transition temperatures derived from the second layer and the third layer are each preferably 31 ° C. or higher, more preferably 33 ° C. or higher, and even more preferably 35. It is above °C.
- the upper limit of the glass transition temperature derived from the second layer and the third layer is not particularly limited. From the viewpoint of further improving the sound insulation of the interlayer film, the glass transition temperature derived from the second layer and the third layer may be 60 ° C. or lower.
- the thickness of the intermediate film is not particularly limited. From the viewpoint of practical use and the viewpoint of sufficiently increasing the penetration resistance and 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. Is 1.5 mm or less. When the thickness of the interlayer film is not less than the above lower limit, the penetration resistance and rigidity of the laminated glass are 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 first 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 thicknesses of the second layer and the third layer are preferably 0.3125T or more, more preferably 0.375T or more, preferably 0.9375T or less, and more preferably 0.9T or less.
- Each thickness of the second layer and the third layer may be 0.46875T or less, or 0.45T or less.
- the rigidity of a laminated glass becomes still higher that each thickness of the said 2nd layer and said 3rd layer is more than the said minimum and below the said upper limit, and it can suppress the bleed-out of a plasticizer.
- Laminated glass production Two glass plates washed and dried (first laminated glass member and second laminated glass member, clear float glass, length 25 cm ⁇ width 10 cm ⁇ thickness 2.5 mm) were prepared. The obtained interlayer film was sandwiched between the two glass plates to obtain a laminate. The obtained laminate was put in a rubber bag and deaerated at a vacuum degree of 2660 Pa (20 torr) for 20 minutes. Thereafter, the laminate was vacuum-pressed while being deaerated while being further kept at 90 ° C. for 30 minutes in an autoclave. The laminated body preliminarily pressure-bonded in this manner was pressure-bonded for 20 minutes in an autoclave under conditions of 135 ° C. and a pressure of 1.2 MPa (12 kg / cm 2 ) to obtain a laminated glass.
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Abstract
Description
本発明に係る合わせガラス用中間膜(本明細書において、「中間膜」と略記することがある)は、2層以上の構造を有する。
上記第1の層は、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。上記第2の層は、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。上記第3の層は、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。なお、本明細書において、ポリビニルアセタール樹脂には、アセトアセタール化された樹脂が含まれる。
上記第1の層中で、上記ポリビニルアセタール樹脂と上記第2の樹脂成分とが相分離構造を形成している。上記第1の層は、上記第1の層中で上記ポリビニルアセタール樹脂と相溶していない第2の樹脂成分を含む。上記第2の層は、第2の樹脂成分を含んでいてもよい。上記第3の層は、第2の樹脂成分を含んでいてもよい。上記第2の樹脂成分は、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の層は、可塑剤(以下、可塑剤(1)と記載することがある)を含まないか又は含む。上記第1の層は、可塑剤(1)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、遮熱粒子を含むことが好ましい。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。
上記式(X2)において、Mは、H、He、アルカリ金属、アルカリ土類金属、希土類元素、Mg、Zr、Cr、Mn、Fe、Ru、Co、Rh、Ir、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Al、Ga、In、Tl、Si、Ge、Sn、Pb、Sb、B、F、P、S、Se、Br、Te、Ti、Nb、V、Mo、Ta及びReからなる群から選択される少なくとも1種の元素、Wはタングステン、Oは酸素を表し、x、y及びzは、0.001≦x/y≦1、及び2.0<z/y≦3.0を満たす。
上記中間膜は、アルカリ金属塩及びアルカリ土類金属塩の内の少なくとも1種の金属塩(以下、金属塩Mと記載することがある)を含むことが好ましい。上記第1の層は、上記金属塩Mを含むことが好ましい。上記第2の層は、上記金属塩Mを含むことが好ましい。上記第3の層は、上記金属塩Mを含むことが好ましい。上記金属塩Mの使用により、中間膜と合わせガラス部材との接着性又は中間膜における各層間の接着性を制御することが容易になる。上記金属塩Mは、1種のみが用いられてもよく、2種以上が併用されてもよい。
上記中間膜は、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。
上記中間膜、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、接着力調整剤、耐湿剤、蛍光増白剤及び赤外線吸収剤等の添加剤を含んでいてもよい。これらの添加剤は、1種のみが用いられてもよく、2種以上が併用されてもよい。
合わせガラスの剛性をより一層高める観点からは、上記第2の層及び上記第3の層に由来するガラス転移温度はそれぞれ、好ましくは31℃以上、より好ましくは33℃以上、より一層好ましくは35℃以上である。上記第2の層及び上記第3の層に由来するガラス転移温度の上限は特に限定されない。中間膜の遮音性をより一層高める観点から、上記第2の層及び上記第3の層に由来するガラス転移温度は60℃以下であってもよい。
図2は、図1に示す合わせガラス用中間膜を用いた合わせガラスの一例を模式的に示す断面図である。
ポリビニルアセタール樹脂(A):n-ブチルアルデヒドを使用、ポリビニルアルコール(PVA)の平均重合度1700、水酸基の含有率30.6モル%、アセチル化度0.9モル%、アセタール化度(ブチラール化度)68.5モル%
ポリビニルアセタール樹脂(B):n-ブチルアルデヒドを使用、ポリビニルアルコール(PVA)の平均重合度800、水酸基の含有率34モル%、アセチル化度0.9モル%、アセタール化度(ブチラール化度)65.1モル%
ポリビニルアセタール樹脂(C):n-ブチルアルデヒドを使用、ポリビニルアルコール(PVA)の平均重合度1700、水酸基の含有率34モル%、アセチル化度5モル%、アセタール化度(ブチラール化度)61モル%
ポリビニルアセタール樹脂(D):n-ブチルアルデヒドを使用、ポリビニルアルコール(PVA)の平均重合度1700、水酸基の含有率24モル%、アセチル化度10モル%、アセタール化度(ブチラール化度)66モル%
アクリル重合体(A):アクリル酸エチル20重量%と、アクリル酸ブチル30重量%と、アクリル酸ベンジル20重量%と、アクリル酸2-ヒドロキシエチル30重量%とを含む重合成分を重合させたアクリル重合体
アクリル重合体(B):アクリル酸エチル28重量%と、アクリル酸ブチル22重量%と、アクリル酸ベンジル30重量%と、アクリル酸2-ヒドロキシエチル20重量%とを含む重合成分を重合させたアクリル重合体
アクリル重合体(C):アクリル酸エチル75重量%と、アクリル酸ベンジル25重量%とを含む重合成分を重合させたアクリル重合体
アクリル重合体(D):アクリル酸エチル30重量%と、アクリル酸ブチル29重量%と、アクリル酸ベンジル21重量%と、アクリル酸2-ヒドロキシエチル20重量%とを含む重合成分を重合させたアクリル重合体
アクリル重合体(E):アクリル酸エチル18重量%と、アクリル酸ブチル32重量%と、アクリル酸ベンジル20重量%と、アクリル酸2-ヒドロキシエチル30重量%とを含む重合成分を重合させたアクリル重合体
アクリル重合体(F):アクリル酸エチル15重量%と、アクリル酸ブチル35重量%と、アクリル酸ベンジル20重量%と、アクリル酸2-ヒドロキシエチル30重量%とを含む重合成分を重合させたアクリル重合体
アクリル重合体(G):アクリル酸2-エチルヘキシル60重量%と、アクリル酸ベンジル20重量%と、アクリル酸2-ヒドロキシエチル20重量%とを含む重合成分を重合させたアクリル重合体
アクリル重合体(H):アクリル酸エチル30重量%と、アクリル酸ブチル30重量%と、アクリル酸ベンジル20重量%と、アクリル酸2-ヒドロキシエチル20重量%とを含む重合成分を重合させたアクリル重合体
酢酸ビニル重合体(I):酢酸ビニル100重量%を重合させた酢酸ビニル重合体
トリエチレングリコールジ-2-エチルヘキサノエート(3GO)
Tinuvin326(2-(2’-ヒドロキシ-3’-t-ブチル-5-メチルフェニル)-5-クロロベンゾトリアゾール、BASF社製「Tinuvin326」)
BHT(2,6-ジ-t-ブチル-p-クレゾール)
第1の層を形成するための組成物の作製:
ポリビニルアセタール樹脂(A)100重量部と、アクリル重合体(A)300重量部と、紫外線遮蔽剤(Tinuvin326)0.2重量部と、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。
ポリビニルアセタール樹脂(A)100重量部と、可塑剤(3GO)20重量部と、紫外線遮蔽剤(Tinuvin326)0.2重量部と、酸化防止剤(BHT)0.2重量部とを混合し、第2の層及び第3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と、第2の層及び第3の層を形成するための組成物とを、共押出機を用いて共押出しすることにより、第2の層(厚み330μm)/第1の層(厚み100μm)/第3の層(厚み330μm)の積層構造を有する中間膜(厚み760μm)を作製した。
洗浄及び乾燥した2つのガラス板(第1の合わせガラス部材及び第2の合わせガラス部材、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の層を形成するための組成物に用いる配合成分の種類及び配合量、第2の層及び第3の層を形成するための組成物に用いる配合成分の種類及び配合量、第1の層の厚み、第2の層の厚み、第3の層の厚み、第1の合わせガラス部材及び第2の合わせガラス部材の厚みを、下記の表1~4に示すように設定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。なお、全ての実施例及び比較例では、実施例1と同じ種類の紫外線遮蔽剤及び酸化防止剤を、実施例1と同様の配合量(0.2重量部)で配合した。なお、共押出により中間膜を製造できない場合は、第1の層、第2の層及び第3の層を、溶液キャスト法又は熱プレス法でそれぞれ成形した後に積層することにより、容易に中間膜が得られた。
(0)第1の層における構造の確認
得られた中間膜をマイクロトームで処理することにより、厚さ100nm程度の切片を作製した。得られた切片を四酸化オスミウムにて染色し、透過型電子顕微鏡で観察した。1)第1の層において、ポリビニルアセタール樹脂と第2の樹脂成分とが相分離構造(共連続構造又は海島構造など)を有するか否か、2)海島構造である場合に、島部の径(最大径)を確認した。3000倍又は5000倍で観察し、島部1000個の径の平均を計算した。
実施例及び比較例における第1の層の各組成を有する混練物を用意した。得られた混練物をプレス成型機でプレス成型して、厚みが0.35mmである樹脂膜Aを得た。得られた樹脂膜Aを25℃及び相対湿度30%の条件で2時間放置した。2時間放置した後に、TAINSTRUMENTS社製「ARES-G2」を用いて、粘弾性を測定した。治具として、直径8mmのパラレルプレートを用いた。3℃/分の降温速度で100℃から-50℃まで温度を低下させる条件、及び周波数1Hz及び歪1%の条件で測定を行った。得られた測定結果において、損失正接のピーク温度をガラス転移温度Tg(℃)とした。なお、高温側のピークが、ポリビニルアセタール樹脂に由来し、低温側のピークが、第2の樹脂成分に由来していた。
得られた合わせガラスを用意した。図3に模式的に示す試験方法で、曲げ剛性を評価した。測定装置としては、静的3点曲げ試験治具2810を備えたインストロンジャパンカンパニイリミテッド社製の万能材料試験機5966を使用した。測定条件としては、測定温度は20±3℃及び40±3℃、距離D1は18cm、距離D2は25cmとし、変位速度1mm/分でFの方向に合わせガラスに変形を加え、1.5mmの変位を加えたときの応力を測定し、曲げ剛性を算出した。曲げ剛性を下記の基準で判定した。
○:応力が5MPa以上
△:応力が2MPa以上、5MPa未満
×:応力が2MPa未満
厚みが400μm程度の第1の層を形成するための組成物を用意し、オートグラフ(島津製作所社製「AG-IS」)を用いて引張速度200mm/分で引張試験を行い25℃及び40℃でのヤング率をそれぞれ評価した。引張特性を下記の基準で判定した。
○○:ヤング率が2MPa以上
○:ヤング率が1MPa以上、2MPa未満
△:ヤング率が0.5MPa以上、1MPa未満
×:ヤング率が0.5MPa未満
合わせガラスをダンピング試験用の振動発生機(振研社製「加振機G21-005D」)により加振し、そこから得られた振動特性を機械インピーダンス測定装置(リオン社製「XG-81」)にて増幅し、振動スペクトルをFFTスペクトラムアナライザー(横河ヒューレッドパッカード社製「FFTアナライザー HP3582A」)により解析した。損失係数のピーク周波数を求め、更に20℃における3000Hzでの合わせガラスの損失係数を算出した。損失係数から遮音性を下記の基準で判定した。なお、損失係数が0.1以上であれば遮音性に優れており、損失係数が0.2以上であれば遮音性により一層優れている。
○:損失係数が0.2以上
△:損失係数が0.1以上、0.2未満
×:損失係数が0.1未満
1a…第1の表面
1b…第2の表面
2…第2の層
2a…外側の表面
3…第3の層
3a…外側の表面
11…中間膜
11a…第1の表面
11b…第2の表面
21…第1の合わせガラス部材
22…第2の合わせガラス部材
31…合わせガラス
Claims (12)
- 第1の層と、前記第1の層の第1の表面側に配置された第2の層とを備え、
前記第1の層が、ポリビニルアセタール樹脂と、第2の樹脂成分とを含み、
前記第2の層が、ポリビニルアセタール樹脂を含み、
前記第1の層中で、前記ポリビニルアセタール樹脂と前記第2の樹脂成分とが相分離構造を形成しており、
前記第1の層中の前記第2の樹脂成分に由来するガラス転移温度は、前記第1の層中の前記ポリビニルアセタール樹脂に由来するガラス転移温度よりも30℃以上低い、合わせガラス用中間膜。 - 前記第1の層中の前記ポリビニルアセタール樹脂及び前記第1の層中の前記第2の樹脂成分の合計100重量%中、前記第1の層中の前記ポリビニルアセタール樹脂の含有量が5重量%以上、60重量%以下、前記第1の層中の前記第2の樹脂成分の含有量が40重量%以上、95重量%以下である、請求項1に記載の合わせガラス用中間膜。
- 前記第1の層中で、前記ポリビニルアセタール樹脂と前記第2の樹脂成分とが海島構造又は共連続構造を形成している、請求項1又は2に記載の合わせガラス用中間膜。
- 前記第1の層中で、前記ポリビニルアセタール樹脂と前記第2の樹脂成分とが海島構造を形成している、請求項3に記載の合わせガラス用中間膜。
- 前記第1の層の前記海島構造における島部の径の平均が2μm以下である、請求項4に記載の合わせガラス用中間膜。
- 前記第1の層の前記海島構造における島部の径の平均が500nm以下である、請求項5に記載の合わせガラス用中間膜。
- 前記第1の層中の前記第2の樹脂成分が、ポリビニルアセタール樹脂とは異なる樹脂である、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。
- 前記第1の層中の前記第2の樹脂成分が、アクリル重合体、ウレタン重合体、シリコーン重合体、ゴム、又は酢酸ビニル重合体である、請求項7に記載の合わせガラス用中間膜。
- 前記第1の層中の前記第2の樹脂成分が、アクリル重合体である、請求項8に記載の合わせガラス用中間膜。
- 前記第1の層の前記第1の表面とは反対の第2の表面側に配置された第3の層を備え、
前記第3の層が、ポリビニルアセタール樹脂を含む、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2の層が可塑剤を含み、
前記第3の層が可塑剤を含む、請求項10に記載の合わせガラス用中間膜。 - 第1の合わせガラス部材と、
第2の合わせガラス部材と、
請求項1~11のいずれか1項に記載の合わせガラス用中間膜とを備え、
前記第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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- 2015-09-30 JP JP2015549877A patent/JPWO2016052670A1/ja active Pending
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US20170266928A1 (en) | 2017-09-21 |
EP3202728A1 (en) | 2017-08-09 |
MX2017002652A (es) | 2017-05-30 |
EP3202728A4 (en) | 2018-06-27 |
KR20170063431A (ko) | 2017-06-08 |
EP3202736A1 (en) | 2017-08-09 |
CN106660867A (zh) | 2017-05-10 |
JPWO2016052670A1 (ja) | 2017-07-13 |
JPWO2016052671A1 (ja) | 2017-07-13 |
CN106470955A (zh) | 2017-03-01 |
EP3202736A4 (en) | 2018-06-27 |
KR20170063430A (ko) | 2017-06-08 |
MX2017002639A (es) | 2017-06-07 |
BR112017003531A2 (pt) | 2017-12-05 |
WO2016052671A1 (ja) | 2016-04-07 |
US20170266927A1 (en) | 2017-09-21 |
BR112017003540A2 (pt) | 2017-12-05 |
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