WO2016125897A1 - 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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- WO2016125897A1 WO2016125897A1 PCT/JP2016/053522 JP2016053522W WO2016125897A1 WO 2016125897 A1 WO2016125897 A1 WO 2016125897A1 JP 2016053522 W JP2016053522 W JP 2016053522W WO 2016125897 A1 WO2016125897 A1 WO 2016125897A1
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- layer
- laminated glass
- intermediate film
- interlayer film
- heat shrinkage
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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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- 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
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- 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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- 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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- 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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- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- 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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- B32B2307/10—Properties of the layers or laminate having particular acoustical properties
- B32B2307/102—Insulating
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- B32B2307/308—Heat stability
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- 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
Definitions
- the present invention relates to an interlayer film for laminated glass used for obtaining laminated glass. Moreover, this invention relates to the laminated glass using the said intermediate film for laminated glasses.
- 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 2 discloses an intermediate film which is a polymer layer having a glass transition temperature of 33 ° C. or higher.
- Patent Document 3 discloses a polyvinyl acetal resin film having a thickness distribution in the width direction of 10% or less and a volatile content of 1.0% by mass or less.
- the heat shrinkage rate in the flow direction parallel to the film and perpendicular to the width direction is The larger value is the heat shrinkage rate MD1, the other value is the heat shrinkage rate MD2, and the flow direction is parallel to the film and perpendicular to the width direction when the central portion in the width direction of the film is heated at 150 ° C. for 30 minutes.
- the heat shrinkage rate is the heat shrinkage rate MD3, all of the heat shrinkage rate MD1, the heat shrinkage rate MD2, and the heat shrinkage rate MD3 are 3 to 20%.
- An object of the present invention is to provide an interlayer film for laminated glass that can increase the production efficiency of laminated glass. Another object of the present invention is to provide a laminated glass using the interlayer film for laminated glass.
- an interlayer film for laminated glass having a one-layer structure or a two-layer structure, comprising a first layer containing a thermoplastic resin, and the softening point of the first layer
- the intermediate film has an MD direction and a TD direction, and the following first inner portion, the following second inner portion, and the following central portion were heated at 140 ° C. for 20 minutes, respectively.
- an interlayer film for laminated glass in which the following heat shrinkage rate MD1MAX, the following heat shrinkage rate MD2MAX, and the following heat shrinkage rate MD3MAX are all 45% or less is provided.
- Center portion When the distance between one end and the other end of the intermediate film in the TD direction is X, it is a distance portion of 0.5X inward from each of the one end and the other end of the intermediate film in the TD direction. Represents a 5 cm square part.
- Thermal contraction rate MD1MAX and thermal contraction rate MD1MIN When the thermal contraction rate of the two sides parallel to the MD direction of the first inner portion is different, the thermal contraction rate of the side having a high thermal contraction rate is MD1MAX, and the thermal contraction rate is When the thermal contraction rate of the lower side is MD1MIN and the thermal contraction rate of the two sides parallel to the MD direction of the first inner portion is the same, one thermal contraction rate is MD1MAX and the other thermal contraction rate is MD1MIN. To do.
- Thermal contraction rate MD2MAX and thermal contraction rate MD2MIN When the thermal contraction rate of two sides that are parallel to the MD direction of the second inner part is different, the thermal contraction rate of the side having a high thermal contraction rate is MD2MAX, and the thermal contraction rate is When the thermal contraction rate of the low side is MD2MIN and the thermal contraction rate of the two sides parallel to the MD direction of the second inner portion is the same, one thermal contraction rate is MD2MAX and the other thermal contraction rate is MD2MIN. To do.
- Thermal contraction rate MD3MAX and thermal contraction rate MD3MIN When the thermal contraction rate of the two sides parallel to the MD direction of the central portion is different, the thermal contraction rate of the side with the high thermal contraction rate is MD3MAX, When the heat shrinkage rate is MD3MIN and the heat shrinkage rates of two sides parallel to the MD direction of the central portion are the same, one heat shrinkage rate is MD3MAX, and the other heat shrinkage rate is MD3MIN.
- the glass transition temperature of the first layer is 35 ° C. or higher.
- the hydroxyl group content of the polyvinyl acetal resin in the first layer is the hydroxyl group content of the polyvinyl acetal resin in the second layer. More than 9.5 mol%.
- the heat shrinkage rate MD1MAX, the heat shrinkage rate MD2MAX, and the heat shrinkage rate MD3MAX are all 40% or less.
- the interlayer film for laminated glass according to the present invention is an interlayer film for laminated glass having a one-layer structure or a structure of two or more layers, and includes a first layer containing a thermoplastic resin.
- the intermediate film has an MD direction and a TD direction, and the first inner portion, the second inner portion, and the central portion are each heated at 140 ° C. for 20 minutes.
- the heat shrinkage rate since the heat shrinkage rate MD1MAX, the heat shrinkage rate MD2MAX, and the heat shrinkage rate MD3MAX are all 45% or less, the production efficiency of the laminated glass can be 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.
- FIG. 5 is a diagram for explaining a measurement object (intermediate film) for measuring the heat shrinkage rate.
- the interlayer film for laminated glass When the interlayer film for laminated glass is exposed to a high temperature environment when producing laminated glass, the interlayer film for hard laminated glass is laminated more than the relatively soft interlayer film for laminated glass.
- the glass interlayer film tends to shrink in the MD direction.
- the trim has become thick due to the shrinkage of the interlayer film for laminated glass.
- an interlayer film for laminated glass provided with a thermoplastic resin layer having a softening point of 60 ° C. or higher is an intermediate film for laminated glass in an environment of high temperature (eg, autoclave (140 ° C., 20 minutes)).
- high temperature eg, autoclave (140 ° C., 20 minutes
- the intermediate film according to the present invention has an MD direction and a TD direction.
- the intermediate film is obtained by, for example, melt extrusion molding.
- the MD direction is the flow direction of the intermediate film during the production of the intermediate film.
- the TD direction is a direction orthogonal to the flow direction of the intermediate film at the time of manufacturing the intermediate film, and is a direction orthogonal to the thickness direction of the intermediate film.
- the following heat shrinkage ratio MD2MAX and the following heat shrinkage ratio MD3MAX are all 45% or less.
- First inner portion When the distance between one end and the other end of the intermediate film in the TD direction is X, a distance portion (0.05X from the one end of the intermediate film in the TD direction toward the inner side) This represents a 5 cm square part which is a distant part).
- Thermal contraction rate MD1MAX and thermal contraction rate MD1MIN When the thermal contraction rate of the two sides parallel to the MD direction of the first inner portion is different, the thermal contraction rate of the side having a high thermal contraction rate is MD1MAX, and the thermal contraction rate is When the thermal contraction rate of the lower side is MD1MIN and the thermal contraction rate of the two sides parallel to the MD direction of the first inner portion is the same, one thermal contraction rate is MD1MAX and the other thermal contraction rate is MD1MIN. To do.
- Thermal contraction rate MD3MAX and thermal contraction rate MD3MIN When the thermal contraction rate of the two sides parallel to the MD direction of the central portion is different, the thermal contraction rate of the side with the high thermal contraction rate is MD3MAX, When the heat shrinkage rate is MD3MIN and the heat shrinkage rates of two sides parallel to the MD direction of the central portion are the same, one heat shrinkage rate is MD3MAX, and the other heat shrinkage rate is MD3MIN.
- a method for relaxing the stress of the interlayer film, etc. can be mentioned. Specifically, there are methods such as annealing the intermediate film, or weakening the pulling force of the intermediate film in the extrusion process. Moreover, the heat shrinkage of the obtained intermediate film can be controlled by adjusting the aging temperature during the synthesis of the polyvinyl acetal resin. In the extrusion process, when the intermediate film is pulled in a state where the temperature of the intermediate film is high (for example, when it exceeds 90 ° C.), and in the state where the temperature of the intermediate film is low (for example, when it is 90 ° C.
- the thermal contraction rate of the intermediate film in the above case 2 tends to be higher than the thermal contraction rate of the intermediate film in the above case 1. Furthermore, in the extrusion process, even when the temperature of the intermediate film is the same, when the force for pulling the intermediate film is strong 3 (for example, when the linear velocity is relatively high) and when the force for pulling the intermediate film is weak 4 (for example, when the linear velocity is relatively low), the thermal contraction rate of the intermediate film in the above case 3 tends to be higher than the thermal contraction rate of the intermediate film in the above case 4.
- Measurement object for measuring the MD thermal contraction rate of the first inner portion, the MD thermal contraction rate of the second inner portion, and the MD thermal contraction rate of the central portion A1, intermediate film A2 and intermediate film A3) can be obtained as follows.
- An intermediate film A2 (test piece) of a 5 cm square portion which is a 0.05X distance portion from the other end to the inside, and 0.5X from the one end and the other end of the intermediate film in the TD direction toward the inside.
- An intermediate film A3 (test piece) having a 5 cm square portion, which is a distance portion, is obtained.
- the intermediate film A1 having a square size of 5 cm square is obtained so that the position of 0.05X inward from one end in the TD direction overlaps the center line of the intermediate film A1.
- the intermediate film A2 having a square size of 5 cm square is obtained so that the position of 0.05X inward from the other end in the TD direction overlaps the center line of the intermediate film A2.
- the intermediate film A3 having a square size of 5 cm square is obtained so that the position 0.5X inward from each of the one end and the other end in the TD direction overlaps the center line of the intermediate film A3.
- the thermal contraction rate at one end side in the TD direction of the intermediate film A1 is compared with the thermal contraction rate at the other end side in the TD direction, and the thermal contraction rate with the higher thermal contraction rate is MD1MAX, and the thermal contraction rate is low.
- the thermal contraction rate of the one is MD1MIN.
- MD1MAX and MD1MIN have the same numerical value.
- MD2MAX, MD2MIN, MD3MAX, and MD3MIN of each of the intermediate film A2 and the intermediate film A3 are obtained.
- the heat shrinkage rate is obtained by the following formula (X).
- Heat shrinkage percentage (size in MD direction before heat treatment-size in MD direction after heat treatment) / dimension in MD direction before heat treatment x 100 (formula (X)
- the intermediate film A1 and the intermediate film A2 are respectively 5 cm in the TD direction and 5 cm in the MD direction from one end and the other end of the intermediate film. Cut out the square interlayer film. Further, when the dimension in the TD direction of the intermediate film is less than 15 cm, the intermediate film A1, the intermediate film A2, and the intermediate film A3 are square with reference to the dimension in the TD direction when the distance in the TD direction is equally divided into three. Cut out the intermediate film.
- the preferred lower limit of the dimension in the TD direction of the interlayer film is 50 cm, the more preferred lower limit is 70 cm, the still more preferred lower limit is 80 cm, the preferred upper limit is 500 cm, the more preferred upper limit is 400 cm, and the still more preferred upper limit is 300 cm.
- the intermediate film may have a single layer structure, a two layer structure, a two or more layer structure, or a three layer structure. It may have a structure of three or more layers.
- the first layer is an intermediate film.
- the intermediate film includes the first layer and other layers (second layer, third layer, etc.).
- FIG. 1 schematically shows a cross-sectional view of an interlayer film for laminated glass according to a 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 and laminated on the second surface 2b opposite to the first surface 2a of the second layer 2.
- 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 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 may include a second layer as a layer that is not an intermediate layer in the intermediate film or a surface layer in the intermediate film.
- the intermediate film preferably includes a first layer as a surface layer in the intermediate film.
- the intermediate film preferably includes a third layer as a surface layer in the intermediate film.
- the details of the first layer, the second layer, and the third layer constituting the intermediate film according to the present invention, and the first layer, the second layer, and the third layer are as follows. The detail of each component contained is demonstrated.
- 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 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 with an aldehyde.
- 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 (PVA) is preferably 200 or more, more preferably 500 or more, still more preferably 1500 or more, still more preferably 1600 or more, particularly preferably 2600 or more, most preferably 2700 or more, preferably It is 5000 or less, more preferably 4000 or less, and still more preferably 3500 or less.
- the average degree of polymerization is not less than the above lower limit, the penetration resistance of the laminated glass is further enhanced.
- the average degree of polymerization is not more than the above upper limit, the intermediate film can be easily molded.
- 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, isobutyraldehyde or n-valeraldehyde is more preferable
- n More preferred is butyraldehyde or n-valeraldehyde.
- 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, and particularly preferably less than 25 mol%.
- 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.
- each content of hydroxyl groups in the polyvinyl acetal resin (1) and the polyvinyl acetal resin (3) is 33 mol% or more. It is particularly preferred.
- the absolute value of the difference between the hydroxyl group content of the polyvinyl acetal resin (1) and the hydroxyl group content of the polyvinyl acetal resin (2), and the polyvinyl acetal resin is preferably 1 mol% or more, more preferably 5 mol% or more, still more preferably 9 mol. % Or more, still more preferably 9.5 mol% or more, particularly preferably 10 mol% or more, and most preferably 12 mol% or more.
- Each absolute value of the difference from the hydroxyl group content of the polyvinyl acetal resin (2) is preferably 20 mol% or less.
- 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 determined by measuring, 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%, further preferably at most 24 mol%, particularly preferably at most 20 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 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 60 mol% or more, preferably Is 75 mol% or less, more preferably 71 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 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 polyvinyl acetal resin (2) has an acetylation degree (a) of less than 8 mol% and an acetalization degree (a) of 65 mol%. It is preferably the polyvinyl acetal resin (A) as described above, or the polyvinyl acetal resin (B) having a degree of acetylation (b) of 8 mol% or more.
- the polyvinyl acetal resin (1) and 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 less than 8 mol%, preferably 7.9 mol% or less, more preferably 7.8 mol% or less, still more preferably 6.5 mol% or less, particularly Preferably it is 6 mol% or less, Preferably it is 0.1 mol% or more, More preferably, it is 0.5 mol% or more, More preferably, it is 5 mol% or more, Most preferably, it is 5.5 mol% or more.
- the degree of acetylation (a) is 0.1 mol% or more and less than 8 mol%, 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 65 mol% or more, preferably 66 mol% or more, more preferably 67 mol% or more, further preferably 67.5 mol% or more, and particularly preferably 75 mol%. % Or more, preferably 85 mol% or less, more preferably 84 mol% or less, still more preferably 83 mol% or less, and particularly preferably 82 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 degree of acetylation (b) of the polyvinyl acetal resin (B) is 8 mol% or more, preferably 9 mol% or more, more preferably 9.5 mol% or more, still more preferably 10 mol% or more, particularly preferably 10 0.5 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 78 mol. % Or less, more preferably 75 mol% or less, still more preferably 72 mol% or less, and particularly preferably 70 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 polyvinyl acetal resin (A) and the polyvinyl acetal resin (B) are each preferably a polyvinyl butyral resin.
- the first layer 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)).
- 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. . 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
- 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 content (1) is preferably 25 parts by weight or more and 35 parts by weight or less. From the viewpoint of effectively increasing the production efficiency of the laminated glass, the content (3) is preferably 25 parts by weight or more and 35 parts by weight or less.
- Content of the plasticizer (2) with respect to 100 parts by weight of the thermoplastic resin (2) (when the thermoplastic resin (2) is a polyvinyl acetal resin (2), 100 parts by weight of the polyvinyl acetal resin (2)) (Hereinafter sometimes referred to as the content (2)) is preferably 50 parts by weight or more, more preferably 55 parts by weight or more, still more preferably 60 parts by weight or more, preferably 100 parts by weight or less, more preferably It is 90 parts by weight or less, more preferably 85 parts by weight or less, and particularly preferably 80 parts by weight or less.
- the 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.
- the content (2) is 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 content (3).
- the absolute value of the difference between the content (1) and the content (2), and the difference between the content (3) and the content (2) is preferably 10 parts by weight or more, more preferably 15 parts by weight or more, still more preferably 20 parts by weight or more, and particularly preferably more than 25 parts by weight.
- the absolute value of the difference between the content (1) and the content (2) and the absolute value of the difference between the content (3) and the content (2) are each preferably 80 parts by weight or less. More preferably, it is 75 weight part or less, More preferably, it is 70 weight part or less.
- the second layer preferably contains a filler.
- the first layer may contain a filler.
- the third layer may contain a filler.
- 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 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.
- 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.
- 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).
- 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 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 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 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 an ultraviolet shielding agent containing a metal atom, an ultraviolet shielding agent containing a metal oxide, an ultraviolet shielding agent having a benzotriazole structure, an ultraviolet shielding agent having a benzophenone structure, and an ultraviolet shielding agent having a triazine structure. And an ultraviolet shielding agent having a malonic ester structure, an ultraviolet shielding agent having an oxalic acid anilide structure, and an ultraviolet shielding agent having a benzoate structure.
- 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 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 UV shielding agents having a benzotriazole structure such as 2- (2′-hydroxy-3 ′, 5′-di-amylphenyl) benzotriazole (“Tinvin 328” manufactured by BASF)).
- the ultraviolet shielding agent is preferably an ultraviolet shielding agent having a benzotriazole structure containing a halogen atom, and may be an ultraviolet shielding agent having a benzotriazole structure containing a chlorine atom. More preferred.
- Examples of the ultraviolet shielding agent having the benzophenone structure include octabenzone (“Chimasorb 81” manufactured by BASF).
- UV shielding agent having the triazine structure examples include “LA-F70” manufactured by ADEKA and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl). Oxy] -phenol (“Tinuvin 1577FF” manufactured by BASF) and the like.
- UV screening agent having a malonic ester structure examples include dimethyl 2- (p-methoxybenzylidene) malonate, tetraethyl-2,2- (1,4-phenylenedimethylidene) bismalonate, and 2- (p-methoxybenzylidene).
- 2- (p-methoxybenzylidene) malonate examples include dimethyl 2- (p-methoxybenzylidene) malonate, tetraethyl-2,2- (1,4-phenylenedimethylidene) bismalonate, and 2- (p-methoxybenzylidene).
- Examples of commercially available ultraviolet screening agents having a malonic ester structure include Hostavin B-CAP, Hostavin PR-25, and Hostavin PR-31 (all manufactured by Clariant).
- Examples of the ultraviolet shielding agent having the oxalic anilide structure include N- (2-ethylphenyl) -N ′-(2-ethoxy-5-tert-butylphenyl) oxalic acid diamide, N- (2-ethylphenyl)- Oxalic acid 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 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.
- 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 ".
- a layer in 100% by weight of the interlayer film or containing an antioxidant.
- the content of the antioxidant is preferably 0.1% 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 first layer, the second layer, and the third layer are respectively a coupling agent containing silicon, aluminum, or titanium, a dispersant, a surfactant, a flame retardant, an antistatic agent, if necessary.
- Additives such as pigments, dyes, adhesive strength modifiers, moisture-proofing agents, fluorescent brighteners 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 softening point of the first layer is 60 ° C. or higher.
- the softening point of the first layer is preferably 61.5 ° C. or higher, more preferably 62. 0.5 ° C. or higher, more preferably 64 ° C. or higher, still more preferably 65 ° C. or higher, still more preferably 66 ° C. or higher, and particularly preferably 70 ° C. or higher.
- the softening point of the third layer is preferably 58 ° C. or higher, more preferably 60 ° C. or higher. More preferably, it is 61.5 ° C. or more, more preferably 62.5 ° C. or more, further preferably 64 ° C. or more, further preferably 65 ° C. or more, still more preferably 66 ° C. or more, and most preferably 70 ° C. or more. .
- the upper limit of each softening point of the first layer and the third layer is not particularly limited.
- the softening point of each of the first layer and the third layer is preferably 80 ° C. or less, more preferably 78 ° C. or less, still more preferably 76 ° C. or less, and particularly preferably 75 ° C. or less.
- the softening point and the glass transition temperature are measured as follows.
- the intermediate film After the obtained intermediate film is stored at a temperature of 23 ° C. and a humidity of 30% for 1 month or more or for 1 month, if the intermediate film is a multilayer, it is isolated by peeling off the first layer and the third layer, and press A measurement object press-molded with a molding machine is measured using “ARES-G2” manufactured by TAINSTRUMENTS.
- the intermediate film When the intermediate film is a single layer, it is cut into a diameter of 8 mm and measured. A parallel plate having a diameter of 8 mm is used as a jig, and the measurement is performed under the condition that the temperature is decreased from 100 ° C. to ⁇ 10 ° C.
- the peak temperature of the loss tangent is defined as the glass transition temperature Tg (° C.).
- the temperature at which the value of the loss tangent is minimum in the temperature region between 100 ° C. and Tg (° C.) is defined as the softening point.
- the period for storing the obtained interlayer film at a temperature of 23 ° C. and a humidity of 30% is not particularly limited as long as it is one month or longer, but it is preferably one month.
- the thickness of the measurement object is not particularly limited, but for example, the thickness is preferably in the range of 300 to 800 ⁇ m.
- the thickness of the intermediate film is not particularly limited. From the viewpoint of practical use and from the viewpoint of sufficiently improving the penetration resistance 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 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.
- the intermediate film is preferably obtained by melt extrusion molding.
- the method for producing the intermediate film is not particularly limited.
- Examples of the method for producing the intermediate film include a method of extruding the resin composition using an extruder in the case of a single-layer intermediate film.
- the method for producing the interlayer film in the case of a multilayer interlayer film, for example, a method of laminating each layer obtained after forming each layer using each resin composition for forming each layer, and each layer The method of laminating
- the same polyvinyl acetal resin is contained in the first layer and the third layer, and the first layer, the third layer, It is more preferable that the same polyvinyl acetal resin and the same plasticizer are contained, and it is more preferable that the first layer and the third layer are formed of the same resin composition.
- the cross-sectional shape of the intermediate film may be rectangular or wedge-shaped.
- the rigidity of can be increased.
- an intermediate film with a high softening point may be difficult to match the curved shape of the curved glass, but by embossing the intermediate film, the interlayer film can be matched to the curved shape of the curved glass. It becomes easy.
- 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.
- Type (1) (described as (1) in the following table): Nipgel AZ201 (silica particles, manufactured by Tosoh Silica Co., Ltd., specific surface area of 300 m 2 / g by BET method)
- Type (2) (described as (2) in the following table): AEROSIL 380 (silica particles, manufactured by Nippon Aerosil Co., Ltd., specific surface area 380 ⁇ 30 m 2 / g by BET method)
- Type (3) (described as (3) in the following table): Nipgel AZ204 (silica particles, manufactured by Tosoh Silica Co., Ltd., specific surface area of 300 m 2 / g by BET method)
- Type (4) (described as (4) in the table below): SYLYSIA 310P (silica particles, manufactured by Fuji Silysia Chemical Ltd., specific surface area of 300 m 2 / g by BET method)
- compositions for forming the first layer and the third layer 100 parts by weight of a polyvinyl acetal resin of the type shown in Table 1 below, 31 parts by weight of a plasticizer (3GO), 0.2 parts by weight of an ultraviolet shielding agent (Tinvin 326), and 0.2 parts by weight of an antioxidant (BHT) To obtain a composition for forming the first layer and the third layer.
- a polyvinyl acetal resin of the type shown in Table 1 below 31 parts by weight of a plasticizer (3GO), 0.2 parts by weight of an ultraviolet shielding agent (Tinvin 326), and 0.2 parts by weight of an antioxidant (BHT)
- composition for forming the second layer 100 parts by weight of a polyvinyl acetal resin of the type shown in Table 1 below, 60 parts by weight of plasticizer (3GO), 20 parts by weight of filler (Nipgel AZ201), 0.2 part by weight of UV screening agent (Tinvin 326), and oxidation
- a composition for forming the second layer was obtained by mixing 0.2 part by weight of a inhibitor (BHT).
- Example 2 The composition for forming the first layer and the third layer, the kind and amount of the composition component of the composition for forming the second layer, and the first layer, the second layer, and the second layer Example 3 except that the thickness of layer 3 was set as shown in Table 1 below, and the thicknesses of the first layer, the second layer, and the third layer were set as shown in Table 1 below. In the same manner as in Example 1, an intermediate film was produced.
- Example 16 to 20 The composition for forming the first layer and the third layer, the type and amount of the composition of the composition for forming the second layer were set as shown in Tables 3 to 4 below. A composition for producing an interlayer film was produced.
- the specimen was pulled up and down at a moving speed of 200 mm / min, and a tear test of the test piece was performed.
- the maximum value of the load until the test piece was cut was read, and the trim cut performance was evaluated by the average value (the maximum tear load value) of the results obtained from the three test pieces.
- the test piece was pulled up and down, it tested so that an up-down direction and MD direction might correspond. When pulling up and down, the same result was obtained even when the test was performed so that the vertical direction and the TD direction coincided.
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Abstract
Description
上記第1の層は、熱可塑性樹脂(以下、熱可塑性樹脂(1)と記載することがある)を含み、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)を含み、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)を含み、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が、遮音性がより一層高くなることから、上記ポリビニルアセタール樹脂(2)は、上記ポリビニルアセタール樹脂(1)及び上記ポリビニルアセタール樹脂(3)と異なっていることが好ましい。上記熱可塑性樹脂(1)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)、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。可塑剤の使用により、また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(1)、上記可塑剤(2)及び上記可塑剤(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2の層はフィラーを含むことが好ましい。上記第1の層はフィラーを含んでいてもよい。上記第3の層はフィラーを含んでいてもよい。
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、ケイ素、アルミニウム又はチタンを含むカップリング剤、分散剤、界面活性剤、難燃剤、帯電防止剤、顔料、染料、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高くし、合わせガラスの製造効率を効果的に高める観点から、上記第1の層の軟化点は60℃以上である。中間膜の剛性をより一層高くし、空隙が抑制された合わせガラスの製造効率を効果的に高める観点からは、上記第1の層の軟化点は好ましくは61.5℃以上、より好ましくは62.5℃以上、より一層好ましくは64℃以上、更に好ましくは65℃以上、更に一層好ましくは66℃以上、特に好ましくは70℃以上である。中間膜の剛性をより一層高くし、空隙が抑制された合わせガラスの製造効率を効果的に高める観点からは、上記第3の層の軟化点は好ましくは58℃以上、より好ましくは60℃以上、より一層好ましくは61.5℃以上、更に好ましくは62.5℃以上、更に好ましくは64℃以上、更に好ましくは65℃以上、更に一層好ましくは66℃以上、最も好ましくは70℃以上である。上記第1の層及び上記第3の層のそれぞれの軟化点の上限は特に限定されない。上記第1の層及び上記第3の層のそれぞれの軟化点は好ましくは80℃以下、より好ましくは78℃以下、更に好ましくは76℃以下、特に好ましくは75℃以下である。
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。
下記の表1~4に示すポリビニルアセタール樹脂を適宜用いた。用いたポリビニルアセタール樹脂では全て、アセタール化に、炭素数4のn-ブチルアルデヒドが用いられている。
トリエチレングリコールジ-2-エチルヘキサノエート(3GO)
種類(1)(下記表において(1)と記載する):Nipgel AZ201(シリカ粒子、東ソー・シリカ社製、BET法による比表面積300m2/g)
種類(2)(下記表において(2)と記載する):AEROSIL380(シリカ粒子、日本アエロジル社製、BET法による比表面積380±30m2/g)
種類(3)(下記表において(3)と記載する):Nipgel AZ204(シリカ粒子、東ソー・シリカ社製、BET法による比表面積300m2/g)
種類(4)(下記表において(4)と記載する):SYLYSIA 310P(シリカ粒子、富士シリシア化学社製、BET法による比表面積300m2/g)
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の層及び第3の層を形成するための組成物の作製:
下記の表1に示す種類のポリビニルアセタール樹脂100重量部と、可塑剤(3GO)31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の層及び第3の層を形成するための組成物を得た。
下記の表1に示す種類のポリビニルアセタール樹脂100重量部と、可塑剤(3GO)60重量部と、フィラー(Nipgel AZ201)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の層を形成するための組成物を得た。
第1の層及び第3の層を形成するための組成物と、第2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1の層(厚み340μm)/第2の層(厚み100μm)/第3の層(厚み340μm)の積層構造を有する中間膜(厚み780μm)を作製した。
第1の層及び第3の層を形成するための組成物、第2の層を形成するための組成物の配合成分の種類及び配合量、並びに、第1の層、第2の層及び第3の層の厚みを下記の表1に示すように設定し、更に第1の層、第2の層及び第3の層の厚みを下記の表1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、中間膜を作製した。
第3ロールを中間膜が通過した際に、中間膜の温度が100℃となるように調整し、第3ロールに対する第4ロールの速度比を1.48倍とした以外は実施例1と同様の条件で中間膜を得た。
第1の層及び第3の層を形成するための組成物、第2の層を形成するための組成物の配合成分の種類及び配合量、並びに、第1の層、第2の層及び第3の層の厚みを下記の表2~4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、中間膜を作製した。なお、共押出の条件は、実施例1と同じである。
第1の層及び第3の層を形成するための組成物、第2の層を形成するための組成物の配合成分の種類及び配合量を下記の表3~4に示すように設定し、中間膜を作製するための組成物を作製した。
(1)軟化点及びガラス転移温度
得られた中間膜を温度23℃、湿度30%で1ヶ月間保管した後に、表面層(第1の層及び第3の層)を剥がすことによって単離し、プレス成型機でプレス成型した測定対象物について、TAINSTRUMENTS社製「ARES-G2」を用いて測定を行った。治具として、直径8mmのパラレルプレートを用い、3℃/分の降温速度で100℃から-10℃まで温度を低下させる条件、及び周波数1Hz及び歪1%の条件で測定した。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。また、100℃からTg(℃)の間の温度領域において損失正接の値が極小となる温度を軟化点とした。なお、単離された表面層をプレス成型機でプレス成型する際に測定対象物の厚みを800μmに制御しても同様の結果が得られた。
上述した方法により、TD方向の一端から内側に向かって0.05Xの距離部分である5cm角の部分の中間膜A1(試験片)、TD方向の他端から内側に向かって0.05Xの距離部分である5cm角の部分の中間膜A2(試験片)、及び、中間膜のTD方向の一端及び他端のそれぞれから内側に向かって0.5Xの距離部分である5cm角の部分の中間膜A3(試験片)を得て、上述した方法により熱収縮率を測定した。
得られた中間膜のTD方向の一端から他端にわたって、中間膜のMD方向の長さが20cmとなるように中間膜を切り出し、中間膜Bを得た。中間膜Bの寸法変化を抑制しないように、網棚の上に水平となるように設置し、23℃、30%RHにて2日間調湿を行った。その後、調湿された中間膜Bから、中間膜のTD方向の一端及び他端のそれぞれから内側に向かって0.5Xの距離部分である5cm角の部分の中間膜B1(試験片)を得た。TD方向の一端及び他端のそれぞれから内側に向かって0.5Xの位置が、中間膜B1の中心線と重なるように、15cm角の正方形の大きさの中間膜B1を得た。140℃の熱風乾燥機内で20分間予熱したフッ素樹脂シート(アズワン社製「品番7-363」、厚み5mm)の上に、中間膜B1を固定することなく水平に置き、中間膜B1を140℃で20分間加熱した。加熱された中間膜B1を、ダンベル社製のスーパーダンベルカッター:SDBK-1000-Tで打ち抜いて試験片3枚を得た。得られた試験片を23℃、30%RHで12時間保管した。その後、25℃の恒温室でエー・アンド・デイ社製のテンシロンを用い、200mm/minの移動速度で上下に引っ張り、試験片の引裂き試験を行った。試験片が切断に至るまでの荷重の最大値を読み取り、3枚の試験片から得られた結果の平均値(引裂最大荷重値)によりトリムカット性能を評価した。なお、試験片を上下に引っ張る際に、上下方向とMD方向とが一致するように試験した。なお、上下に引っ張る際に、上下方向とTD方向とが一致するように試験しても同様の結果が得られた。
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
11,11A…中間膜
11a…第1の表面
11b…第2の表面
21…第1の合わせガラス部材
22…第2の合わせガラス部材
31,31A…合わせガラス
Claims (13)
- 1層の構造又は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1の層を備え、
前記第1の層の軟化点が60℃以上であり、
中間膜は、MD方向とTD方向とを有し、
下記の第1の内側部分、下記の第2の内側部分及び下記の中央部分をそれぞれ140℃で20分間加熱したときの熱収縮率に関して、下記の熱収縮率MD1MAX、下記の熱収縮率MD2MAX、及び下記の熱収縮率MD3MAXの全てが、45%以下である、合わせガラス用中間膜。
第1の内側部分:中間膜のTD方向の一端と他端との間の距離をXとしたときに、中間膜のTD方向の一端から内側に向かって0.05Xの距離部分である5cm角の部分を表す
第2の内側部分:中間膜のTD方向の一端と他端との間の距離をXとしたときに、中間膜のTD方向の他端から内側に向かって0.05Xの距離部分である5cm角の部分を表す
中央部分:中間膜のTD方向の一端と他端との間の距離をXとしたときに、中間膜のTD方向の一端及び他端のそれぞれから内側に向かって0.5Xの距離部分である5cm角の部分を表す
熱収縮率MD1MAX及び熱収縮率MD1MIN:第1の内側部分のMD方向と平行である2辺の熱収縮率が異なる場合は、熱収縮率が高い辺の熱収縮率をMD1MAX、熱収縮率が低い辺の熱収縮率をMD1MINとし、第1の内側部分のMD方向と平行である2辺の熱収縮率が同じ場合は、一方の熱収縮率をMD1MAXとし、他方の熱収縮率をMD1MINとする
熱収縮率MD2MAX及び熱収縮率MD2MIN:第2の内側部分のMD方向と平行である2辺の熱収縮率が異なる場合は、熱収縮率が高い辺の熱収縮率をMD2MAX、熱収縮率が低い辺の熱収縮率をMD2MINとし、第2の内側部分のMD方向と平行である2辺の熱収縮率が同じ場合は、一方の熱収縮率をMD2MAXとし、他方の熱収縮率をMD2MINとする
熱収縮率MD3MAX及び熱収縮率MD3MIN:中央部分のMD方向と平行である2辺の熱収縮率が異なる場合は、熱収縮率が高い辺の熱収縮率をMD3MAX、熱収縮率が低い辺の熱収縮率をMD3MINとし、中央部分のMD方向と平行である2辺の熱収縮率が同じ場合は、一方の熱収縮率をMD3MAXとし、他方の熱収縮率をMD3MINとする - 前記第1の層の軟化点が61.5℃以上である、請求項1に記載の合わせガラス用中間膜。
- 前記第1の層のガラス転移温度が35℃以上である、請求項1又は2に記載の合わせガラス用中間膜。
- 熱可塑性樹脂を含む第2の層を備え、
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1~3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の層中の前記熱可塑性樹脂が、ポリビニルアセタール樹脂であり、
前記第2の層中の前記熱可塑性樹脂が、ポリビニルアセタール樹脂である、請求項4に記載の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の水酸基の含有率が、前記第2の層中の前記ポリビニルアセタール樹脂の水酸基の含有率よりも9.5モル%以上多い、請求項5に記載の合わせガラス用中間膜。
- 前記第2の層がフィラーを含む、請求項4~6のいずれか1項に記載の合わせガラス用中間膜。
- 熱可塑性樹脂を含む第3の層を備え、
前記第2の層の前記第1の表面とは反対側の第2の表面側に、前記第3の層が配置されている、請求項4~7のいずれか1項に記載の合わせガラス用中間膜。 - 前記第1の層中の前記熱可塑性樹脂が、ポリビニルアセタール樹脂であり、
前記第1の層中の前記ポリビニルアセタール樹脂の水酸基の含有率が33モル%以上である、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の層が可塑剤を含み、
前記第1の層中の前記熱可塑性樹脂100重量部に対して、前記第1の層中の前記可塑剤の含有量が25重量部以上、35重量部以下である、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。 - 前記熱収縮率MD1MAX、前記熱収縮率MD2MAX、及び前記熱収縮率MD3MAXの全てが、40%以下である、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。
- 前記熱収縮率MD1MIN、前記熱収縮率MD2MIN、及び前記熱収縮率MD3MINの全てが、20%以上である、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。
- 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1~12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。
Priority Applications (12)
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| MX2017010138A MX2017010138A (es) | 2015-02-05 | 2016-02-05 | Pelicula intercapa para vidrio laminado, y vidrio laminado. |
| CA2975587A CA2975587A1 (en) | 2015-02-05 | 2016-02-05 | Interlayer film for laminated glass, and laminated glass |
| AU2016216329A AU2016216329A1 (en) | 2015-02-05 | 2016-02-05 | Interlayer film for laminated glass, and laminated glass |
| EP16746728.1A EP3255020A4 (en) | 2015-02-05 | 2016-02-05 | Interlayer film for laminated glass, and laminated glass |
| KR1020177021675A KR102591279B1 (ko) | 2015-02-05 | 2016-02-05 | 접합 유리용 중간막 및 접합 유리 |
| US15/549,113 US10576714B2 (en) | 2015-02-05 | 2016-02-05 | Interlayer film for laminated glass, and laminated glass |
| RU2017131062A RU2696736C2 (ru) | 2015-02-05 | 2016-02-05 | Промежуточная пленка для многослойного стекла и многослойное стекло |
| JP2016508877A JP6683599B2 (ja) | 2015-02-05 | 2016-02-05 | 合わせガラス用中間膜及び合わせガラス |
| CN201680009105.0A CN107207339B (zh) | 2015-02-05 | 2016-02-05 | 夹层玻璃用中间膜及夹层玻璃 |
| BR112017016616-0A BR112017016616B1 (pt) | 2015-02-05 | 2016-02-05 | Película de intercamada para vidro laminado, e vidro laminado |
| ZA2017/05568A ZA201705568B (en) | 2015-02-05 | 2017-08-16 | Interlayer film for laminated glass, and laminated glass |
| US16/669,072 US10913245B2 (en) | 2015-02-05 | 2019-10-30 | Interlayer film for laminated glass, and laminated glass |
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| JP2015-021628 | 2015-02-05 | ||
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| JP2015-021629 | 2015-02-05 | ||
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| US15/549,113 A-371-Of-International US10576714B2 (en) | 2015-02-05 | 2016-02-05 | Interlayer film for laminated glass, and laminated glass |
| US16/669,072 Continuation US10913245B2 (en) | 2015-02-05 | 2019-10-30 | Interlayer film for laminated glass, and laminated glass |
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| PCT/JP2016/053520 Ceased WO2016125895A1 (ja) | 2015-02-05 | 2016-02-05 | 合わせガラス用中間膜及び合わせガラス |
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| US (6) | US10611127B2 (ja) |
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| MX (5) | MX2017010136A (ja) |
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| WO2012043816A1 (ja) * | 2010-09-30 | 2012-04-05 | 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 |
| WO2012133668A1 (ja) * | 2011-03-29 | 2012-10-04 | 株式会社クラレ | ポリビニルアセタール系樹脂フィルムおよびそれを用いた多層構造体 |
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