WO2012043819A1 - 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
- Publication number
- WO2012043819A1 WO2012043819A1 PCT/JP2011/072616 JP2011072616W WO2012043819A1 WO 2012043819 A1 WO2012043819 A1 WO 2012043819A1 JP 2011072616 W JP2011072616 W JP 2011072616W WO 2012043819 A1 WO2012043819 A1 WO 2012043819A1
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- WIPO (PCT)
- Prior art keywords
- layer
- plasticizer
- polyvinyl acetal
- laminated glass
- acetal resin
- Prior art date
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- 0 CCC(C)(*OC(C)(CC)[N+](*)[O-])O[N+](*)[O-] Chemical compound CCC(C)(*OC(C)(CC)[N+](*)[O-])O[N+](*)[O-] 0.000 description 3
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Classifications
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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
- B32B17/10009—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
- B32B17/10761—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
- B60—VEHICLES IN GENERAL
- B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
- B60J3/00—Antiglare equipment associated with windows or windscreens; Sun visors for vehicles
- B60J3/007—Sunglare reduction by coatings, interposed foils in laminar windows, or permanent screens
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/10—Properties of the layers or laminate having particular acoustical properties
- B32B2307/102—Insulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31627—Next to aldehyde or ketone condensation product
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31627—Next to aldehyde or ketone condensation product
- Y10T428/3163—Next to acetal of polymerized unsaturated alcohol [e.g., formal butyral, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31645—Next to addition polymer from unsaturated monomers
- Y10T428/31649—Ester, halide or nitrile of addition polymer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31859—Next to an aldehyde or ketone condensation product
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31928—Ester, halide or nitrile of addition polymer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31942—Of aldehyde or ketone condensation product
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31942—Of aldehyde or ketone condensation product
- Y10T428/31946—Next to second aldehyde or ketone condensation product
Definitions
- the present invention relates to an interlayer film for laminated glass used for laminated glass such as automobiles and buildings, and more specifically, an interlayer film for laminated glass containing a polyvinyl acetal resin and a plasticizer, and the interlayer film for laminated glass. It relates to the laminated glass used.
- 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 intermediate film between a pair of glass plates.
- Patent Document 1 discloses that 100 parts by weight of a polyvinyl acetal resin having an acetalization degree of 60 to 85 mol% and at least one of alkali metal salts and alkaline earth metal salts.
- a sound insulation layer containing 0.001 to 1.0 part by weight of a metal salt and 30 parts by weight or more of a plasticizer is disclosed. This sound insulation layer can be used as a single layer as an intermediate film or laminated with other layers as a multilayer intermediate film.
- a laminated glass used for a fuel vehicle using an internal combustion engine is particularly required to have sound insulation in a relatively low frequency range.
- the laminated glass used in a fuel vehicle using an internal combustion engine has high sound insulation in a high frequency range.
- the high sound-insulation property in a high frequency region is calculated
- the sound insulation in the high frequency region of the laminated glass is not sufficient, and therefore the sound insulation due to the coincidence effect may be inevitably lowered.
- the sound insulation properties at around 20 ° C. of this laminated glass may not be sufficient.
- the coincidence effect means that when a sound wave is incident on the glass plate, the transverse wave propagates on the glass surface due to the rigidity and inertia of the glass plate, and the transverse wave and the incident sound resonate. This is a phenomenon that occurs.
- the sound insulating property in the vicinity of 20 ° C. of the laminated glass can be increased to some extent. it can.
- the multilayer interlayer film has the sound insulating layer, foaming may occur in the laminated glass using the multilayer interlayer film.
- An object of the present invention is to provide an interlayer film for laminated glass that can enhance sound insulation in a high-frequency region in the obtained laminated glass, and the interlayer film for laminated glass when used for constituting laminated glass. It is to provide the used laminated glass.
- a limited object of the present invention is to provide an interlayer film for laminated glass capable of obtaining a laminated glass that not only has high sound insulation in a high frequency range, but can also suppress the occurrence of foaming and the growth of foam, and the intermediate for laminated glass It is to provide a laminated glass using a film.
- an interlayer film for laminated glass having a one-layer structure or a laminated structure of two or more layers, comprising a first layer containing a polyvinyl acetal resin and a plasticizer, the first layer
- the plasticizer contained in the layer contains the first plasticizer
- the polyvinyl acetal resin and the first plasticizer contained in the first layer are the first plasticizer.
- An interlayer film for laminated glass which is a polyvinyl acetal resin having a cloud point of 5 ° C. or less and a first plasticizer, measured using a solution obtained by dissolving 8 parts by weight of the polyvinyl acetal resin in 100 parts by weight, is provided.
- the interlayer film for laminated glass according to the present invention may be a single-layer interlayer film for laminated glass composed of only the first layer, or may be a multilayer interlayer film for laminated glass including the first layer. Good.
- the polyvinyl acetal resin and the first plasticizer contained in the first layer are added to 100 parts by weight of the first plasticizer.
- the plasticizer contained in the first layer further contains a second plasticizer different from the first plasticizer.
- the polyvinyl acetal resin and the second plasticizer contained in the first layer are 100 parts by weight of the second plasticizer.
- the plasticizer contained in the first layer does not contain a second plasticizer different from the first plasticizer.
- the content of the first plasticizer is 1% by weight or more, and the second plasticizer The content is 99% by weight or less.
- the plasticizer contained in the first layer includes a second plasticizer different from the first plasticizer,
- the content of the first plasticizer in the total of 100% by weight of all the plasticizers contained in the first layer is 1% by weight to 99% by weight, and the second plasticizer
- the content of the agent is 1% by weight or more and 99% by weight or less.
- the peak temperature of tan ⁇ appearing on the lowest temperature side measured at a frequency of 1 Hz is 0 ° C. or lower.
- the maximum value of tan ⁇ at the peak temperature of tan ⁇ appearing on the lowest temperature side measured at a frequency of 1 Hz is 1.15 or more.
- the maximum value of tan ⁇ at the peak temperature of tan ⁇ appearing on the highest temperature side measured at a frequency of 1 Hz is 0.55 or more.
- the degree of acetylation of the polyvinyl acetal resin contained in the first layer exceeds 30 mol%.
- the degree of acetylation of the polyvinyl acetal resin contained in the first layer is 10 to 45 mol%, and the content of hydroxyl groups Is 35 mol% or less.
- the SP value of the first plasticizer contained in the first layer is 13.5 to 14.5.
- the plasticizer contained in the first layer is a diester plasticizer represented by the following formula (1).
- R1 and R2 each represent an organic group having 1 to 10 carbon atoms
- R3 represents an ethylene group, an isopropylene group or an n-propylene group
- p represents an integer of 2 to 10 .
- the first plasticizer contained in the first layer is a diester plasticizer represented by the following formula (1A). .
- R1 and R2 each represent an organic group having 2 to 5 carbon atoms
- R3 represents an ethylene group, an isopropylene group or an n-propylene group
- p represents an integer of 2 to 10 .
- the plasticizer contained in the first layer includes a second plasticizer different from the first plasticizer,
- the second plasticizer contained in the first layer is a diester plasticizer represented by the following formula (1B).
- R1 and R2 each represents an organic group having 6 to 10 carbon atoms
- R3 represents an ethylene group, an isopropylene group or an n-propylene group
- p represents an integer of 2 to 10 .
- the interlayer film for laminated glass has a laminated structure of two or more layers, and is laminated on the first surface of the first layer, And a second layer containing a polyvinyl acetal resin and a plasticizer is further provided, and the total content of all the plasticizers relative to 100 parts by weight of the polyvinyl acetal resin in the first layer is 50 parts by weight or more.
- the hydroxyl content of the polyvinyl acetal resin in the first layer is lower than the hydroxyl content of the polyvinyl acetal resin in the second layer, and the polyvinyl acetal in the first layer.
- the difference between the hydroxyl group content of the resin and the hydroxyl group content of the polyvinyl acetal resin in the second layer is 9.2 mol% or less, and the polyvinyl acetate in the first layer is When the difference between the hydroxyl group content of the tar resin and the hydroxyl group content of the polyvinyl acetal resin in the second layer is more than 8.5 mol% and 9.2 mol% or less, The degree of acetylation of the polyvinyl acetal resin in the first layer is 8 mol% or less.
- the polyvinyl acetal resin in the first layer contains a high molecular weight component having an absolute molecular weight of 1,000,000 or more, and in the first layer.
- the proportion of the high molecular weight component in the polyvinyl acetal resin is 7.4% or more, or the polyvinyl acetal resin in the first layer includes a high molecular weight component having a polystyrene equivalent molecular weight of 1 million or more, And the ratio of the said high molecular weight component to the said polyvinyl acetal resin in the said 1st layer is 9% or more.
- the glass transition temperature of the resin film is Tg. (Tg + 80) Ratio of elastic modulus G ′ (Tg + 80) at (Tg + 80) ° C. to elastic modulus G ′ (Tg + 30) at (Tg + 30) ° C. (G ′ (Tg + 80) / G ′ (Tg + 30)) Is 0.65 or more.
- the polyvinyl acetal resin in the first layer is obtained by acetalizing polyvinyl alcohol having an average degree of polymerization exceeding 3000.
- the degree of acetylation of the polyvinyl acetal resin in the first layer is 8 mol% or more, or the polyvinyl in the first layer. It is preferable that the degree of acetylation of the acetal resin is less than 8 mol% and the degree of acetalization is 68 mol% or more.
- the degree of acetylation of the polyvinyl acetal resin in the first layer is preferably 8 mol% or more. Furthermore, it is also preferable that the degree of acetylation of the polyvinyl acetal resin in the first layer is less than 8 mol% and the degree of acetalization is 68 mol% or more.
- the number of carbon atoms of the acetal group of the polyvinyl acetal resin contained in the second and third layers is 3 or 4, respectively.
- the degrees are 60 to 75 mol%, respectively, and the degree of acetylation is 10 mol% or less.
- the content of the plasticizer in the second and third layers with respect to 100 parts by weight of the polyvinyl acetal resin is 5 to 50 parts by weight, respectively.
- the laminated glass according to the present invention includes a first laminated glass constituent member, a second laminated glass constituent member, and an intermediate film sandwiched between the first and second laminated glass constituent members.
- the interlayer film is an interlayer film for laminated glass constructed according to the present invention.
- the interlayer film for laminated glass according to the present invention includes a first layer containing a polyvinyl acetal resin and a plasticizer, and the plasticizer contained in the first layer contains the first plasticizer.
- the polyvinyl acetal resin and the first plasticizer contained in the first layer are prepared by using 8 parts by weight of the polyvinyl acetal resin dissolved in 100 parts by weight of the first plasticizer. Since the measured cloud point is a polyvinyl acetal resin having a temperature of 5 ° C. or less and the first plasticizer, it is possible to improve the sound insulation in the high frequency range of the laminated glass using the interlayer film for laminated glass according to the present invention. .
- FIG. 1 is a partially cutaway cross-sectional view schematically showing an interlayer film for laminated glass according to an embodiment of the present invention.
- FIG. 2 is a partially cutaway cross-sectional view schematically showing an example of laminated glass using the interlayer film for laminated glass shown in FIG.
- FIG. 3 shows a loss tangent tan ⁇ when the viscoelasticity of the resin film is measured by using a resin film containing polyvinyl acetal resin contained in the first layer and triethylene glycol di-2-ethylhexanoate. It is a figure for demonstrating the relationship between temperature, and the relationship between elastic modulus G 'and temperature.
- FIG. 1 schematically shows a laminated glass using an interlayer film for laminated glass according to an embodiment of the present invention in a partially cutaway sectional view.
- the intermediate film 1 shown in FIG. 1 is a multilayer intermediate film.
- the intermediate film 1 is used to obtain a laminated glass.
- the intermediate film 1 is an intermediate film for laminated glass.
- the intermediate film 1 includes a first layer 2, a second layer 3 stacked on the first surface 2 a of the first layer 2, and a first layer 2 opposite to the first surface 2 a of the first layer 2. 2 and the third layer 4 laminated on the surface 2b of the second.
- the first layer 2 is an intermediate layer and mainly functions as a sound insulation layer.
- the second and third layers 3 and 4 are protective layers, and are surface layers in this embodiment.
- the first layer 2 is sandwiched between the second and third layers 3 and 4. Therefore, the intermediate film 1 has a multilayer structure in which the second layer 3, the first layer 2, and the third layer 4 are laminated in this order.
- the composition of the second layer 3 and the third layer 4 may be the same or different.
- the adhesive force between the second and third layers 3 and 4 and the laminated glass constituent member is sufficiently increased.
- the main feature of the present embodiment is that the first layer 2 includes the first layer 2 containing a polyvinyl acetal resin and a plasticizer, the first layer 2 contains the first plasticizer, and The polyvinyl acetal resin and the first plasticizer contained in the first layer 2 are measured using a solution obtained by dissolving 8 parts by weight of the polyvinyl acetal resin in 100 parts by weight of the first plasticizer.
- the polyvinyl acetal resin having a cloud point of 5 ° C. or lower and the first plasticizer.
- the polyvinyl acetal resin and the first plasticizer contained in the first layer 2 are contained in 100 parts by weight of the first plasticizer. It is preferable that it is a polyvinyl acetal resin and a 1st plasticizer whose cloud point measured using the liquid which melt
- ⁇ 5 ° C. or less further preferably ⁇ 5 ° C. or less, particularly preferably ⁇ 7 ° C. or less, most preferably ⁇ 10 ° C. or less, more preferably ⁇ 150 ° C. or more, and more preferably ⁇ 100 ° C. or more.
- -80 ° C or higher is more preferable, and -60 ° C or higher is particularly preferable.
- the plasticizer contained in the first layer 2 includes a second plasticizer different from the first plasticizer.
- measurement was performed using a solution in which 8 parts by weight of the polyvinyl acetal resin was dissolved in 100 parts by weight of the second plasticizer.
- the cloud point is preferably 30 ° C. or less, more preferably 25 ° C. or less, particularly preferably 20 ° C. or less, preferably ⁇ 10 ° C. or more, more preferably ⁇ 8 ° C. or more, still more preferably ⁇ 6 ° C. or more, ⁇ 4 ° C. or higher is particularly preferable.
- the polyvinyl acetal resin and the second plasticizer contained in the first layer 2 are measured using a solution obtained by dissolving 8 parts by weight of the polyvinyl acetal resin in 100 parts by weight of the second plasticizer. It may be a polyvinyl acetal resin and a second plasticizer having a cloud point of more than 0 ° C. Further, the polyvinyl acetal resin and the second plasticizer contained in the first layer 2 are prepared by using a solution obtained by dissolving 8 parts by weight of the polyvinyl acetal resin in 100 parts by weight of the second plasticizer. A polyvinyl acetal resin and a second plasticizer having a cloud point of more than 5 ° C. may be used. Even when such a second plasticizer is used, by using the first plasticizer together with the second plasticizer, it is possible to sufficiently enhance the sound insulation in the high frequency range of the laminated glass.
- the polyvinyl acetal resin and the first plasticizer contained in the first layer 2 are prepared by using a solution obtained by dissolving 8 parts by weight of the polyvinyl acetal resin in 100 parts by weight of the first plasticizer.
- the polyvinyl acetal resin and the first plasticizer, which are a polyvinyl acetal resin and a first plasticizer, whose cloud point to be measured is 5 ° C. or less, and the second plasticizer contained in the first layer 2 are the second It is preferable that the cloud point measured using a solution obtained by dissolving 8 parts by weight of the polyvinyl acetal resin in 100 parts by weight of the plasticizer is a polyvinyl acetal resin and a second plasticizer that exceed 5 ° C.
- the polyvinyl acetal resin and the first plasticizer contained in the first layer 2 are prepared using a solution obtained by dissolving 8 parts by weight of the polyvinyl acetal resin in 100 parts by weight of the first plasticizer.
- the polyvinyl acetal resin and the first plasticizer that have a cloud point of 0 ° C. or less and the polyvinyl acetal resin and the second plasticizer contained in the first layer 2 are the second It is also preferable that the cloud point measured using a solution obtained by dissolving 8 parts by weight of the polyvinyl acetal resin in 100 parts by weight of the plasticizer is a polyvinyl acetal resin and a second plasticizer that exceed 0 ° C.
- the above cloud point is a cloud point measured according to JIS K2266 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”. Specifically, the cloud point measured using the polyvinyl acetal resin and the first plasticizer is 3.5 g (100 parts by weight) of the first plasticizer and 0.28 g (8 wt.) Of the polyvinyl acetal resin.
- test tube Part) and in a test tube (diameter 2 cm), 3.5 g (100 parts by weight) of the first plasticizer and 0.28 g (8 parts by weight) of the polyvinyl acetal resin are mixed, After heating the solution in which the polyvinyl acetal resin is dissolved in the first plasticizer to 150 ° C., the test tube is left in an atmosphere of ⁇ 20 ° C. to lower the temperature of the solution to ⁇ 15 ° C. When the tube is left in an atmosphere of ⁇ 196 ° C. and the temperature of the solution is lowered to the pour point temperature of the first plasticizer, it means a temperature at which part of the solution starts to become cloudy (first Cloud point judgment method).
- the test tube is not ⁇ 196 ° C. but ⁇ 20 ° C. Leave in an atmosphere of °C.
- the cloud point measured using the polyvinyl acetal resin and the second plasticizer is 3.5 g (100 parts by weight) of the second plasticizer and 0.28 g (8 parts by weight) of the polyvinyl acetal resin.
- the second plasticizer 3.5 g (100 parts by weight) and the polyvinyl acetal resin 0.28 g (8 parts by weight) are mixed, and the second plasticizer is mixed. After heating the solution in which the polyvinyl acetal resin is dissolved in a plasticizer to 150 ° C., the test tube is left in an atmosphere of ⁇ 20 ° C.
- the test tube is When the temperature of the solution is lowered to the pour point temperature of the second plasticizer by being left in an atmosphere of 196 ° C., it means a temperature at which part of the solution starts to cloud (first cloud point) Judgment method). In the case where the test tube is left in an atmosphere of ⁇ 20 ° C. and the temperature of the solution is lowered to ⁇ 15 ° C. and clouding starts to occur in a part of the solution, the test tube is not ⁇ 196 ° C. but ⁇ 20 ° C. Leave in an atmosphere of °C.
- the cloud point is determined to be a temperature considerably lower than 0 ° C. Furthermore, in this case, the compatibility between the polyvinyl acetal resin and the first plasticizer or the second plasticizer is considerably high.
- Examples of methods for measuring the temperature at which part of the solution starts to cloud include, for example, a method of visually observing the appearance of the solution, a method of measuring the haze of the solution with a haze meter, and a plurality of methods related to clouding in advance. For example, a limit sample of the stage is prepared, and the cloudiness is judged against this limit sample. Especially, the method of observing the external appearance of a solution visually is preferable. When the haze of the solution is measured with a haze meter, the temperature at which the haze is 10% or more is defined as the cloud point.
- the cloud point measured using the polyvinyl acetal resin and the first plasticizer or the second plasticizer is 3.5 g (100 parts by weight) of the first plasticizer or the second plasticizer.
- the haze of the solution in the test tube is measured with a haze meter while maintaining the temperature of the temperature-controlled room Can be determined (second cloud point determination method). For example, after leaving a test tube in a constant temperature room at 5 ° C., 0 ° C. and ⁇ 5 ° C. for 1 hour, the haze of the solution in the test tube is measured with a haze meter while maintaining the temperature of the constant temperature room. You may measure the temperature which showed 10% or more. When the test tube was left in a temperature-controlled room at 5 ° C., 0 ° C. or ⁇ 5 ° C. for 1 hour, the haze was 10% when the haze of the solution in the test tube was measured with a haze meter while maintaining the temperature of the temperature-controlled room It is preferable that it is less than.
- the cloud point may be determined by the first cloud point determination method, or may be determined by the second cloud point determination method. Although it is preferable to determine by the first cloud point determination method, the second cloud point determination method may be employed for the purpose of specifying the cloud point with higher accuracy.
- the interlayer film for laminated glass according to the present invention has a single-layer structure or a laminated structure of two or more layers.
- the interlayer film for laminated glass according to the present invention may be a single-layer interlayer film including only the first layer. That is, the first layer may be a single layer and may be used as an interlayer film for laminated glass.
- the second layer may be laminated on at least one surface of the first layer. It is preferable that the second layer is laminated on the first surface of the first layer.
- the second layer may be stacked only on the first surface of the first layer, and the third layer may not be stacked on the second surface of the first layer.
- the second layer is stacked on the first surface of the first layer, and the third layer is stacked on the second surface of the first layer.
- the interlayer film for laminated glass having a multilayer structure with improved sound insulation has a problem that foaming is likely to occur in the laminated glass.
- the present inventors have found that in the interlayer film for laminated glass having a multilayer structure, the plasticizer migrates between the respective layers, and as a result, a layer having a high plasticizer content is formed.
- the plasticizer migrates from the second and third layers to the first layer, and as a result, the plasticizer content in the first layer increases.
- foaming is likely to occur in the laminated glass using the interlayer film for laminated glass. It has also been found that once foaming occurs, foaming grows with the resulting foam as a nucleus.
- the total content of all the plasticizers relative to 100 parts by weight of the polyvinyl acetal resin in the first layer 2 is 50 parts by weight or more
- the hydroxyl group content of the polyvinyl acetal resin in the first layer 2 is lower than the hydroxyl group content of the polyvinyl acetal resin in the second layer 3, and the polyvinyl acetal resin in the first layer 2
- the difference between the hydroxyl group content and the hydroxyl content of the polyvinyl acetal resin in the second layer 3 (hereinafter may be referred to as a content rate difference (1-2)) is 9.2 mol% or less.
- the difference between the hydroxyl group content of the polyvinyl acetal resin in the first layer 2 and the hydroxyl group content of the polyvinyl acetal resin in the second layer 3 (content difference (1-2)). Greater than 8.5 mol%, if not more than 9.2 mol% is preferably acetylation degree of the polyvinyl acetal resin in the first layer 2 is not more than 8 mol%.
- the content difference (1-2) may be more than 8.5 mol% and 9.2 mol% or less, and may be 8.5 mol% or less.
- the hydroxyl group content of the polyvinyl acetal resin in the first layer 2 is lower than the hydroxyl group content of the polyvinyl acetal resin in the third layer 4, and the polyvinyl acetal in the first layer 2.
- the difference between the hydroxyl group content of the resin and the hydroxyl group content of the polyvinyl acetal resin in the third layer 4 was 9.2 mol.
- the acetylation degree of the polyvinyl acetal resin in the first layer 2 is preferably 8 mol% or less.
- the content difference (1-3) is 8.5 mol% or less
- the content difference (1-2) exceeds 8.5 mol% and is 9.2 mol% or less.
- the degree of acetylation of the polyvinyl acetal resin in the first layer 2 is preferably 8 mol% or less.
- the content difference (1-3) exceeds 8.5 mol%, may be 9.2 mol% or less, and may be 8.5 mol% or less.
- the present inventors have controlled the content of each hydroxyl group of the polyvinyl acetal resin in the first to third layers as described above.
- the occurrence of foaming and the growth of foaming in the laminated glass can be sufficiently suppressed. Since the migration of the plasticizer can be suppressed and the occurrence of foaming and the growth of foaming in the laminated glass can be sufficiently suppressed, the content of the plasticizer in each layer, particularly the content of the plasticizer in the first layer 2 is increased. be able to. For this reason, the sound insulation of a laminated glass can be improved further.
- the total content of all the plasticizers with respect to 100 parts by weight of the polyvinyl acetal resin in the first layer 2 is the above with respect to 100 parts by weight of the polyvinyl acetal resin in the second and third layers 3 and 4.
- the content is greater than the plasticizer content, foaming tends to occur more easily. Furthermore, once foaming occurs, the generated foam becomes a nucleus and the foam tends to grow.
- the content of each hydroxyl group of the polyvinyl acetal resin in the first to third layers as described above, the occurrence of foaming and the growth of foam in the laminated glass can be sufficiently suppressed.
- the preferred lower limit of the difference from the content of each hydroxyl group in the acetal resin is 0.1 mol%, more preferred lower limit is 1 mol%, still more preferred.
- the lower limit is 2 mol%, the preferred upper limit is 8.5 mol%, the more preferred upper limit is 7.8 mol%, the still more preferred upper limit is 7 mol%, and the particularly preferred upper limit is 5.6 mol%.
- the hydroxyl group content of the polyvinyl acetal resin in the first layer 2 and the above in the second and third layers 3 and 4 The difference from the content of each hydroxyl group in the polyvinyl acetal resin (content difference (1-2) and content difference (1-3)) is preferably 5 mol% or less, more preferably 4.5 mol% or less, more More preferably, it is 4 mol% or less, More preferably, it is 3.5 mol% or less.
- the polyvinyl acetal resin in the first layer 2 contains a high molecular weight component having an absolute molecular weight of 1,000,000 or more (hereinafter sometimes referred to as a high molecular weight component X), or in the first layer 2
- the polyvinyl acetal resin preferably contains a high molecular weight component (hereinafter sometimes referred to as a high molecular weight component Y) having a molecular weight of polystyrene equivalent (hereinafter sometimes referred to as a molecular weight y) of 1,000,000 or more.
- the high molecular weight components X and Y are polyvinyl acetal resins.
- the proportion of the high molecular weight component X in the polyvinyl acetal resin in the first layer 2 is 7.4% or more, or the high molecular weight component in the polyvinyl acetal resin in the first layer 2
- the proportion of Y is preferably 9% or more.
- the polyvinyl acetal resin in the first layer 2 contains the high molecular weight component X having an absolute molecular weight of 1 million or more in the specific ratio, it is possible to suppress foaming from occurring in the laminated glass. Even when the polyvinyl acetal resin in the first layer 2 contains the high molecular weight component Y having a molecular weight y of 1,000,000 or more in the above specific ratio, foaming of the laminated glass can be suppressed.
- the ratio of the high molecular weight component X in the polyvinyl acetal resin in the first layer 2 is the high molecular weight component X in the peak area of the polyvinyl acetal resin component obtained when measuring the absolute molecular weight. Is defined as a value expressed as a percentage (%).
- the proportion of the high molecular weight component Y in the polyvinyl acetal resin in the first layer 2 is the high molecular weight component in the peak area of the polyvinyl acetal resin component obtained when measuring the polystyrene equivalent molecular weight.
- the area ratio of the area corresponding to Y is defined as a value expressed as a percentage (%).
- compositions of the second and third layers 3 and 4 are preferably different from the composition of the first layer 2.
- the polyvinyl acetal resin in the second and third layers 3 and 4 contains the high molecular weight component X having an absolute molecular weight of 1 million or more, and occupies the polyvinyl acetal resin in the second and third layers 3 and 4.
- the ratio of the high molecular weight component X may be 7.4% or more, the high molecular weight component Y having a molecular weight y of 1,000,000 or more is included, and the polyvinyl in the second and third layers 3 and 4
- the proportion of the high molecular weight component Y in the acetal resin may be 9% or more.
- a high molecular weight component having an absolute molecular weight of 1 million or more in the polyvinyl acetal resin in the first layer 2 The preferable lower limit of the ratio of X is 8%, the more preferable lower limit is 8.5%, the still more preferable lower limit is 9%, the particularly preferable lower limit is 9.5%, and the most preferable lower limit is 10%.
- the ratio of the high molecular weight component X is preferably 11% or more, more preferably 12% or more, and still more preferably 14 because the sound insulation of the laminated glass can be further enhanced and the generation of foaming and the growth of foaming can be further suppressed. % Or more, particularly preferably 16% or more.
- the upper limit of the ratio of the high molecular weight component X is not particularly limited, the preferable upper limit is 40%, the more preferable upper limit is 30%, and the further preferable upper limit is 25%.
- the polyvinyl acetal resin in the first layer 2 contains a high molecular weight component Y having a molecular weight y of 1,000,000 or more, it accounts for the polyvinyl acetal resin in the first layer 2 containing the high molecular weight component Y.
- the preferable lower limit of the proportion of the high molecular weight component Y having a molecular weight y of 1,000,000 or more is 10%, the more preferable lower limit is 11%, the still more preferable lower limit is 11.5%, and the particularly preferable lower limit is 12%.
- the ratio of the high molecular weight component Y is preferably 12.5% or more, more preferably 13.5% or more, since the sound insulation of the laminated glass can be further enhanced and the occurrence of foaming and the growth of foaming can be further suppressed. More preferably, it is 14% or more, particularly preferably 15% or more, and most preferably 18% or more.
- the upper limit of the proportion of the high molecular weight component Y is not particularly limited, but the preferable upper limit is 40%, the more preferable upper limit is 30%, and the further preferable upper limit is 25%. When the proportion of the high molecular weight component Y is not less than the above lower limit, the sound insulating properties of the laminated glass can be further enhanced, and the generation of foam and the growth of foam can be further suppressed.
- the resin film A containing 100 parts by weight of the polyvinyl acetal resin contained in the first layer 2 and 60 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer, the resin film
- Tg glass transition temperature
- Tg + 30 glass transition temperature
- the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) to the elastic modulus G ′ (Tg + 30) at ° C. is preferably 0.65 or more.
- the glass transition temperature of the resin film B is Tg (° C.)
- the ratio of the elastic modulus G ′ (Tg + 80) at Tg + 80) ° C. to the elastic modulus G ′ (Tg + 30) at (Tg + 30) ° C. is 0.65 or more. Is also preferable.
- the first layer 2 is used as the resin film B, and the first layer 2 itself is the resin film B.
- the resin film B is the first layer 2, and the polyvinyl acetal resin and the plasticizer (the first plasticizer or the first plasticizer and the second plasticizer) are combined with the first layer 2. It is included in the weight ratio in the inside.
- the laminated glass interlayer film 1 is stored at a humidity of 30% ( ⁇ 3%) and a temperature of 23 ° C. for one month, and after transferring the plasticizer in the laminated glass interlayer film 1, the elasticity It is more preferable to measure the modulus G ′ (Tg + 80) and the elastic modulus G ′ (Tg + 30).
- the present inventors have found that the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) according to Test Method A or Test Method B is It was also found that the occurrence of foaming and the growth of foaming in the laminated glass can be sufficiently suppressed by being 0.65 or more. Even if the total content of all the plasticizers in the first layer 2 is large, the occurrence of foaming and the growth of foaming in the laminated glass can be sufficiently suppressed, so that the sound insulation of the laminated glass can be enhanced.
- the second and third layers 3 and 4 are laminated on both surfaces of the first layer 2 configured so that the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) is 0.65 or more.
- the use of the interlayer film 1 for laminated glass can further suppress the generation of foam and the growth of foam in the laminated glass.
- the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) is 0.65 or more, preferably 1.0 or less.
- the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) is 0.65 or more, even if the laminated glass is stored under considerably severe conditions or for a long period of time, the occurrence of foaming and foaming in the laminated glass Can be sufficiently suppressed.
- the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) is not less than the above lower limit and not more than the above upper limit, even if the laminated glass is stored under considerably severe conditions or for a long time, Generation of foaming and growth of foaming can be more effectively suppressed.
- the total content of all the plasticizers with respect to 100 parts by weight of the polyvinyl acetal resin in the first layer 2 is preferably 40 parts by weight or more. .
- the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) is 0.65 or more even if the plasticizer content of the first layer is large. The occurrence of foaming and the growth of foaming in laminated glass can be suppressed.
- the glass transition temperature Tg (° C.) indicates the peak temperature of the loss tangent tan ⁇ obtained from the measurement result obtained by measuring the viscoelasticity.
- the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) is more preferably 0.7 or more, and more preferably 0.95. It is below, More preferably, it is 0.75 or more, More preferably, it is 0.9 or less.
- the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) is controlled by the average degree of polymerization of polyvinyl alcohol, the occurrence of foaming and the growth of foam in the laminated glass are sufficiently suppressed, and the sound insulation of the laminated glass is achieved.
- the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) is preferably 0.65 or more, more preferably 0.66 or more, and still more preferably 0.67 or more. Particularly preferably, it is 0.7 or more, preferably 0.82 or less, more preferably 0.8 or less. Further, when the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) is 0.82 or less, or 0.8 or less, the intermediate film can be easily formed.
- the intermediate film 1 can be easily formed with an extruder, when synthesizing the polyvinyl acetal resin in the first layer 2, a method of using polyvinyl alcohol having a relatively high average degree of polymerization, A method of physically cross-linking the molecules of the polyvinyl acetal resin in the first layer 2 is preferable.
- the loss tangent tan ⁇ and the temperature have a relationship as shown in FIG.
- the temperature at the peak P of the loss tangent tan ⁇ is the glass transition temperature Tg.
- the glass transition temperature Tg at the elastic modulus G ′ of the broken line A2 shown in FIG. 3 and the glass transition temperature Tg at the elastic modulus G ′ of the solid line A1 are the same temperature.
- the change amount D1 in the elastic modulus G ′ of the solid line A1 is smaller than the change amount D2 in the elastic modulus G ′ of the broken line A2. Therefore, in FIG.
- the G ′ (Tg + 30) is preferably 200,000 Pa or more.
- G ′ (Tg + 30) is more preferably 220,000 Pa or more, further preferably 230,000 Pa or more, particularly preferably 240,000 Pa or more, preferably 10 million Pa or less, more preferably 5 million Pa or less, particularly preferably It is 1,000,000 Pa or less, most preferably 500,000 Pa or less, and most preferably 300,000 Pa or less.
- production of foaming and growth of foaming in a laminated glass can be suppressed more effectively as said G '(Tg + 30) is more than the said minimum.
- the relationship between the elastic modulus G ′ and temperature is greatly influenced by the type of polyvinyl acetal resin, particularly greatly influenced by the average degree of polymerization of the polyvinyl alcohol used to obtain the polyvinyl acetal resin, and the type of plasticizer.
- the plasticizer content is not greatly affected by the content of the general plasticizer.
- the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) is more preferably 0.65 or more.
- the said polyvinyl acetal resin in the 1st layer 2 is obtained by acetalizing polyvinyl alcohol with an average degree of polymerization exceeding 3000. Is also preferable.
- the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) may not be 0.65 or more, but is preferably 0.65 or more.
- the polyvinyl acetal obtained by acetalizing polyvinyl alcohol having an average degree of polymerization exceeding 3000 in the first layer 2 The total content of all the plasticizers with respect to 100 parts by weight of the resin is preferably 40 parts by weight or more. Furthermore, from the viewpoint of further suppressing the generation of foaming and the growth of foaming in the laminated glass, the polyvinyl acetal obtained by acetalizing polyvinyl alcohol having an average degree of polymerization exceeding 3000 in the first layer 2
- the hydroxyl group content of the resin is preferably 30 mol% or less.
- the total content of all the plasticizers with respect to 100 parts by weight of the polyvinyl acetal resin in the first layer 2 is preferably 40 parts by weight or more. Is 50 parts by weight or more, more preferably 55 parts by weight or more, and particularly preferably 60 parts by weight or more.
- the content of each hydroxyl group of the polyvinyl acetal resin in the first to third layers is controlled as described above, or the absolute molecular weight is The ratio of the high molecular weight component X of 1 million or more or the ratio of the high molecular weight component Y having the molecular weight y of 1 million or more is controlled, or the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) is controlled.
- production of foaming and the growth of foaming in a laminated glass can be suppressed much more effectively.
- the first layer includes a polyvinyl acetal resin (hereinafter sometimes referred to as a polyvinyl acetal resin (1)).
- the second layer preferably contains a polyvinyl acetal resin (hereinafter sometimes 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)).
- Each of the polyvinyl acetal resins (1) to (3) may be used alone or in combination of two or more.
- the “polyvinyl acetal resin 8 parts by weight” when measuring the cloud point is the two or more kinds of polyvinyl acetal resins. It is obtained by blending so that the total weight ratio in the layer is 8 parts by weight.
- the polyvinyl acetal resin (1) contained in the first layer is not particularly limited as long as the resin satisfies the cloud point.
- the polyvinyl acetal resins (2) and (3) contained in the second and third layers are not particularly limited.
- the polyvinyl acetal resins (1) to (3) 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 in the range of 70 to 99.9 mol%, preferably in the range of 75 to 99.8 mol%, and preferably in the range of 80 to 99.8 mol%. It is more preferable.
- the average degree of polymerization of the polyvinyl alcohol for obtaining the polyvinyl acetal resins (1) to (3) is preferably 200 or more, more preferably 500 or more, still more preferably 1600 or more, particularly preferably 2600 or more, and most preferably. It is 2700 or more, preferably 5000 or less, more preferably 4000 or less, and further 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.
- the average degree of polymerization of the polyvinyl alcohol is particularly preferably 2700 or more and 5000 or less.
- the preferred lower limit of the average degree of polymerization of the polyvinyl alcohol used to obtain the polyvinyl acetal resin (1) in the first layer is 3010.
- the preferred lower limit is 3050, the preferred lower limit is 3500, the preferred lower limit is 3600, the preferred lower limit is 4000, the preferred lower limit is 4050, the preferred upper limit is 7000, the preferred upper limit is 6000, the preferred upper limit is 5000, the preferred upper limit is 4900, and the preferred upper limit is 4500. It is.
- the polyvinyl acetal resin (1
- the average degree of polymerization of the polyvinyl alcohol used to obtain the above is preferably 3010 or more, more preferably 3020 or more, preferably 4000 or less, more preferably less than 4000, 3800 More preferably, it is more preferably 3600 or less, and most preferably 3500 or less.
- the polyvinyl acetal resins (2) and (3) in the second and third layers can be produced by acetalizing polyvinyl alcohol.
- the preferable lower limit of the average degree of polymerization of polyvinyl alcohol for obtaining the polyvinyl acetal resins (2) and (3) in the second and third layers is 200, the more preferable lower limit is 500, the still more preferable lower limit is 1000, and the particularly preferable lower limit. Is 1500, the preferred upper limit is 4000, the more preferred upper limit is 3500, the still more preferred upper limit is 3000, and the particularly preferred upper limit is 2500.
- the average degree of polymerization satisfies the preferable lower limit, the penetration resistance of the laminated glass can be further enhanced.
- the average degree of polymerization satisfies the preferable upper limit the intermediate film can be easily formed.
- the average degree of polymerization of the polyvinyl alcohol used to obtain the polyvinyl acetal resin (1) in the first layer is used to obtain the polyvinyl acetal resins (2) and (3) in the second and third layers. It is preferably higher than the average degree of polymerization of polyvinyl alcohol, preferably 500 or higher, preferably 800 or higher, more preferably 1000 or higher, still more preferably 1300 or higher, particularly preferably 1800 or higher. .
- the average degree of polymerization of the polyvinyl alcohol is determined by a method based on JIS K6726 “Testing method for polyvinyl alcohol”.
- the carbon number of the acetal group contained in the polyvinyl acetal resin is not particularly limited.
- the aldehyde used when manufacturing the said polyvinyl acetal resin is not specifically limited.
- the acetal group in the polyvinyl acetal resin preferably has 3 to 5 carbon atoms, more preferably 3 or 4. When the carbon number of the acetal group in the polyvinyl acetal resin is 3 or more, the glass transition temperature of the intermediate film is sufficiently low, and the sound insulation of solid sound at a low temperature is further enhanced.
- the aldehyde is not particularly limited. In general, an aldehyde having 1 to 10 carbon atoms is preferably used as the aldehyde.
- Examples of the aldehyde having 1 to 10 carbon atoms include propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, n-octylaldehyde, and n-nonylaldehyde.
- propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-hexylaldehyde or n-valeraldehyde is preferable, propionaldehyde, n-butyraldehyde or isobutyraldehyde is more preferable, and n-butyraldehyde is further preferable.
- the said aldehyde only 1 type may be used and 2 or more types may be used together.
- the polyvinyl acetal resin is preferably a polyvinyl butyral resin.
- the interlayer film for laminated glass according to the present invention preferably contains a polyvinyl butyral resin as the polyvinyl acetal resin contained in the first to third layers. Synthesis of polyvinyl butyral resin is easy. Furthermore, the use of the polyvinyl butyral resin allows the intermediate film to have a more appropriate adhesive force with respect to the laminated glass component. Furthermore, light resistance, weather resistance, etc. can be further improved.
- the hydroxyl group content (hydroxyl content) of the polyvinyl acetal resin (1) is 0 mol% or more, preferably 40 mol% or less.
- the hydroxyl group content (hydroxyl group amount) of the polyvinyl acetal resin (1) is more preferably 35 mol% or less, still more preferably 30 mol% or less. It is. From the viewpoint of further improving the sound insulation in the high frequency region of the laminated glass, the lower the hydroxyl group content of the polyvinyl acetal resin (1), the better.
- the hydroxyl group content of the polyvinyl acetal resin (1) may be 0 mol%. 10 mol% or more may be sufficient as the content rate of the hydroxyl group of the said polyvinyl acetal resin (1).
- the hydroxyl group content (hydroxyl content) of the polyvinyl acetal resins (2) and (3) is preferably 20 mol% or more, and preferably 50 mol% or less.
- the penetration resistance of a laminated glass becomes still higher that the content rate of the said hydroxyl group is more than the said minimum. Further, when the content of the hydroxyl group is not more than the upper limit, bleeding out of the plasticizer is difficult to occur. Furthermore, the flexibility of the interlayer film is increased, and the handling of the interlayer film is facilitated.
- the content of hydroxyl groups (hydroxyl content) in the polyvinyl acetal resins (2) and (3) is more preferably 25 mol% or more, and more preferably. Is 45 mol% or less.
- the hydroxyl group contents of the polyvinyl acetal resins (2) and (3) are more preferably 30 mol% or more, and still more preferably 40 mol% or less.
- the hydroxyl group content of the polyvinyl acetal resin (1) contained in the first layer is the polyvinyl contained in the second and third layers. It is preferable that the content of each hydroxyl group of the acetal resins (2) and (3) is lower. From the viewpoint of further enhancing the sound insulation of the laminated glass, the hydroxyl group content of the polyvinyl acetal resin (1) contained in the first layer is the polyvinyl content contained in the second and third layers. It is preferably 1 mol% or less, more preferably 3 mol% or less, still more preferably 5 mol% or less, more preferably 7 mol% or more than the respective hydroxyl group contents of the acetal resins (2) and (3). A low value is particularly preferred.
- the content of hydroxyl groups in the polyvinyl acetal resins (1) to (3) is a percentage (mol%) obtained by dividing the amount of ethylene groups to which hydroxyl groups are bonded by the total amount of ethylene groups in the main chain. ).
- the amount of the ethylene group to which the hydroxyl group is bonded can be calculated from the result measured by a method based on JIS K6728 “Testing method for polyvinyl butyral” or ASTM D1396-92.
- the degree of acetylation (acetyl group amount) of the polyvinyl acetal resin (1) is 0 mol% or more, preferably 50 mol% or less. From the viewpoint of further improving the sound insulation in the high frequency range of the laminated glass, the degree of acetylation (acetyl group amount) of the polyvinyl acetal resin (1) is more preferably 10 mol% or more, and further preferably 15 mol% or more. Especially preferably, it is 20 mol% or more, More preferably, it is 45 mol% or less.
- the polyvinyl acetal resin (1) may have a degree of acetylation of 30 mol% or less.
- the degree of acetylation of the polyvinyl acetal resin (1) contained in the first layer is preferably more than 30 mol%.
- the below-mentioned plasticizer (1) contains a diester plasticizer represented by the formula (1) or triethylene glycol di-2-ethylhexanoate (3GO), it is contained in the first layer.
- the degree of acetylation of the polyvinyl acetal resin (1) is preferably more than 30 mol%.
- the degree of acetylation of the polyvinyl acetal resins (2) and (3) is 0 mol% or more, preferably 10 mol% or less.
- the degree of acetylation degree is less than or equal to the above upper limit, the strength of the intermediate film is increased and the mechanical properties are improved.
- the degree of acetylation of the polyvinyl acetal resins (2) and (3) is more preferably 8 mol% or less, more preferably less than 3 mol%, respectively. It is.
- the degree of acetylation of the polyvinyl acetal resins (2) and (3) is more preferably 0.1 mol% or more, and particularly preferably 2 mol% or less. Further, when the degree of acetylation of the polyvinyl acetal resins (2) and (3) is less than 3 mol%, the mechanical properties of the interlayer film are further improved. As a result, the penetration resistance of the laminated glass can be further improved.
- the degree of acetylation is obtained by subtracting the amount of ethylene groups to which acetal groups are bonded and the amount of ethylene groups to which hydroxyl groups are bonded from the total amount of ethylene groups of the main chain, This is a value expressed as a percentage (mol%) of the mole fraction obtained by dividing by.
- the amount of the ethylene group to which the acetal group is bonded can be calculated from, for example, a result measured by a method based on JIS K6728 “Testing method for polyvinyl butyral” or a method based on ASTM D1396-92.
- the method for measuring the degree of acetylation is preferably a method based on ASTM D1396-92.
- the degree of acetalization of the polyvinyl acetal resin (1) is preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 40 mol% or more, preferably 80 The mol% or less, more preferably 75 mol% or less, still more preferably 65 mol% or less.
- the degree of acetalization is not less than the above lower limit, the compatibility between the polyvinyl acetal resin (1) and the plasticizer increases, and bleeding out can be suppressed.
- the degree of acetalization is less than or equal to the above upper limit, the reaction time required for producing a polyvinyl acetal resin is shortened.
- the degree of acetalization of the polyvinyl acetal resins (2) and (3) is preferably 55 mol% or more, more preferably 60 mol% or more, still more preferably 63 mol% or more. , Preferably 85 mol% or less, more preferably 75 mol% or less, and still more preferably 70 mol% or less.
- the degree of acetalization is not less than the above lower limit, the compatibility between the polyvinyl acetal resins (2) and (3) and the plasticizer is increased.
- the degree of acetalization is not more than the above upper limit, the reaction time required for producing the polyvinyl acetal resins (2) and (3) is shortened.
- the degree of acetalization is a value obtained by dividing a mole fraction obtained by dividing the amount of ethylene groups to which acetal groups are bonded by the total amount of ethylene groups in the main chain, as a percentage (mol%).
- the degree of acetalization is determined by measuring the degree of acetylation and the hydroxyl group content (vinyl alcohol content) by a method based on JIS K6728 “Testing methods for polyvinyl butyral”, and calculating the mole fraction from the obtained measurement results. Then, it can be calculated by subtracting the degree of acetylation and the hydroxyl group content from 100 mol%.
- the hydroxyl group content, the acetalization degree (butyralization degree), and the acetylation degree are determined in accordance with JIS K6728 “Testing methods for polyvinyl butyral” or ASTM D1396-92. It can be calculated from the results measured by a compliant method. It is preferable to measure by a method based on ASTM D1396-92.
- the content difference (1-2) is more than 8.5 mol% and not more than 9.2 mol%.
- the degree of acetalization of the polyvinyl acetal resin (1) in the first layer is 68 mol% or more.
- the hydroxyl group content is less than 31.5 mol%. Since the migration of the plasticizer can be easily controlled and the sound insulating properties of the laminated glass can be further enhanced, the content difference (1-3) is more than 8.5 mol% and not more than 9.2 mol%.
- the degree of acetalization of the polyvinyl acetal resin (1) in the first layer is 68 mol% or more.
- the hydroxyl group content is less than 31.5 mol%.
- the polyvinyl acetal resin (1 ) Is a polyvinyl acetal resin (hereinafter also referred to as “polyvinyl acetal resin A”) having an acetylation degree of less than 8 mol%, or a polyvinyl acetal resin (hereinafter referred to as “polyvinyl acetal” having an acetylation degree of 8 mol% or more.
- Resin B is preferable.
- the degree of acetylation a of the polyvinyl acetal resin A is less than 8 mol%, preferably 7.5 mol% or less, preferably 7 mol% or less, and preferably 6 mol% or less, 5 mol% or less is preferable, 0.1 mol% or more is preferable, 0.5 mol% or more is preferable, 0.8 mol% or more is preferable, and 1 mol% or more is preferable. Preferably, it is 2 mol% or more, preferably 3 mol% or more, and preferably 4 mol% or more.
- the acetylation degree a is not more than the above upper limit and not less than the above lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer is further enhanced, and the sound insulation of the laminated glass can be further enhanced.
- a preferable lower limit of the degree of acetalization a of the polyvinyl acetal resin A is 68 mol%, a more preferable lower limit is 70 mol%, a further preferable lower limit is 71 mol%, a particularly preferable lower limit is 72 mol%, and a preferable upper limit is 85 mol%.
- a preferred upper limit is 83 mol%, a more preferred upper limit is 81 mol%, and a particularly preferred upper limit is 79 mol%.
- the hydroxyl group content a of the polyvinyl acetal resin A is preferably 30 mol% or less, preferably 27.5 mol% or less, preferably 27 mol% or less, and 26 mol% or less. It is preferably 25 mol% or less, preferably 24 mol% or less, preferably 23 mol% or less, preferably 16 mol% or more, and 18 mol% or more. It is preferable that it is 19 mol% or more, and it is preferable that it is 20 mol% or more.
- the hydroxyl group content a is not more than the above upper limit, the sound insulation of the laminated glass can be further enhanced.
- the hydroxyl group content a is equal to or higher than the lower limit, the adhesive strength of the intermediate film can be further increased.
- the polyvinyl acetal resin A is preferably a polyvinyl butyral resin.
- the degree of acetylation b of the polyvinyl acetal resin B is 8 mol% or more, preferably 9 mol% or more, preferably 10 mol% or more, preferably 11 mol% or more, 12 It is preferably at least mol%, preferably at most 30 mol%, preferably at most 28 mol%, preferably at most 26 mol%, preferably at most 24 mol%, It is preferably at most 1 mol%, more preferably at most 19.5 mol%.
- the acetylation degree b is not less than the above lower limit, the sound insulation of the laminated glass can be further enhanced.
- the reaction time required for producing the polyvinyl acetal resin B can be shortened.
- the acetylation degree b of the said polyvinyl acetal resin B is less than 20 mol%.
- the preferable lower limit of the degree of acetalization b of the polyvinyl acetal resin B is 50 mol%, the more preferable lower limit is 52.5 mol%, the still more preferable lower limit is 54 mol%, the particularly preferable lower limit is 60 mol%, and the preferable upper limit is 80 mol%.
- a more preferred upper limit is 77 mol%, a still more preferred upper limit is 74 mol%, and a particularly preferred upper limit is 71 mol%.
- the acetalization degree b is equal to or higher than the lower limit, the sound insulation of the laminated glass can be further enhanced.
- the acetalization degree b is not more than the above upper limit, the reaction time required for producing the polyvinyl acetal resin B can be shortened.
- the hydroxyl content b of the polyvinyl acetal resin B is preferably 30 mol% or less, preferably 27.5 mol% or less, preferably 27 mol% or less, and 26 mol% or less. It is preferably 25 mol% or less, preferably 18 mol% or more, preferably 20 mol% or more, preferably 22 mol% or more, and 23 mol% or more. It is preferable.
- the hydroxyl group content b is not more than the above upper limit, the sound insulation of the laminated glass can be further enhanced.
- the hydroxyl group content b is not less than the above lower limit, the adhesive strength of the intermediate film can be further increased.
- the polyvinyl acetal resin B is preferably a polyvinyl butyral resin.
- the polyvinyl acetal resin A and the polyvinyl acetal resin B are preferably obtained by acetalizing polyvinyl alcohol having an average polymerization degree exceeding 3000 with an aldehyde.
- the aldehyde is preferably an aldehyde having 1 to 10 carbon atoms, and more preferably an aldehyde having 4 or 5 carbon atoms.
- the preferred lower limit of the average degree of polymerization of the polyvinyl alcohol is 3010, the preferred lower limit is 3050, the preferred lower limit is 3500, the preferred lower limit is 3600, the preferred lower limit is 4000, the preferred lower limit is 4050, the preferred upper limit is 7000, the preferred upper limit is 6000, and the preferred upper limit.
- the polyvinyl acetal resins A and B in the first layer are particularly preferably obtained by acetalizing polyvinyl alcohol having an average degree of polymerization of more than 3000 and less than 4000.
- the average degree of polymerization of the polyvinyl alcohol used to obtain B is preferably 3010 or more, more preferably 3020 or more, preferably 4000 or less, more preferably less than 4000, 3800 More preferably, it is more preferably 3600 or less, and most preferably 3500 or less.
- the preferred lower limit of the weight average molecular weight of the polyvinyl acetal resins (1) to (3) is 100,000, the more preferred lower limit is 300,000, the preferred upper limit is 10,000,000, and the more preferred upper limit is 5,000,000. is there.
- the weight average molecular weight of the polyvinyl acetal resin is not more than the preferable lower limit, the strength of the interlayer film may be lowered.
- the weight average molecular weight of the polyvinyl acetal resin exceeds the preferable upper limit, the strength of the obtained interlayer film may be too strong.
- the said weight average molecular weight shows the weight average molecular weight in polystyrene conversion by gel permeation chromatography (GPC) measurement.
- the said weight average molecular weight and the said number average molecular weight show the weight average molecular weight and number average molecular weight in polystyrene conversion by a gel permeation chromatography (GPC) measurement.
- GPC gel permeation chromatography
- An approximate straight line obtained by plotting the molecular weight against the elution time indicated by the peak top of each standard sample peak is used as a calibration curve.
- the surface layer (the second and third layers) and the intermediate layer (the first layer) And the peeled first layer (intermediate layer) is dissolved in tetrahydrofuran (THF) to prepare a 0.1 wt% solution.
- the obtained solution can be analyzed by a GPC apparatus, and a weight average molecular weight and a number average molecular weight can be measured.
- a GPC apparatus As a GPC apparatus, a GPC apparatus (Hitachi High-Tech "RI: L2490, autosampler: L-2200, pump: L-2130, GPC apparatus to which a GPC light scattering detector (" Model 270 (RALS + VISCO) "manufactured by VISCOTEK)" is connected. Column oven: L-2350, column: GL-A120-S and GL-A100MX-S in series ”) can be used to analyze the weight average molecular weight and the number average molecular weight.
- Method for producing a polyvinyl acetal resin containing a high molecular weight component X having an absolute molecular weight of 1 million or more or a high molecular weight component Y having a molecular weight y of 1 million or more A specific method for producing a polyvinyl acetal resin containing a high molecular weight component X having an absolute molecular weight of 1 million or more or a high molecular weight component Y having a molecular weight y of 1 million or more will be described below.
- the polyvinyl alcohol can be obtained, for example, by saponifying polyvinyl acetate.
- the saponification degree of the polyvinyl alcohol is generally in the range of 70 to 99.9 mol%, preferably in the range of 75 to 99.8 mol%, and preferably in the range of 80 to 99.8 mol%. It is more preferable.
- the preferred lower limit of the degree of polymerization of the polyvinyl alcohol is 200, the more preferred lower limit is 500, the still more preferred lower limit is 1,000, the particularly preferred lower limit is 1,500, the preferred upper limit is 3,000, the more preferred upper limit is 2,900, and further A preferred upper limit is 2,800, and a particularly preferred upper limit is 2,700.
- the said polymerization degree is too low, there exists a tendency for the penetration resistance of a laminated glass to fall. If the polymerization degree is too high, it may be difficult to mold the intermediate film.
- the polyvinyl alcohol and aldehyde are reacted using a catalyst to acetalize the polyvinyl alcohol.
- a solution containing the polyvinyl alcohol may be used. Water etc. are mentioned as a solvent used for the solution containing this polyvinyl alcohol.
- the method for producing the polyvinyl acetal resin contained in the first layer is a method for producing a polyvinyl acetal resin by reacting polyvinyl alcohol with an aldehyde using a catalyst to acetalize the polyvinyl alcohol. Is preferred.
- the manufacturing method of the said 1st layer is the process of obtaining polyvinyl acetal resin by making polyvinyl alcohol and an aldehyde react using a catalyst, and acetalizing polyvinyl alcohol, and the obtained polyvinyl acetal resin and a plasticizer, It is preferable to provide the process of obtaining the said 1st layer using the mixture which mixed.
- a second layer is laminated on the first layer, and a third layer is further laminated as necessary.
- a multilayer interlayer film can be obtained.
- a multilayer intermediate film may be produced by coextrusion of the first layer and the second layer, and the multilayer may be produced by coextrusion of the first layer, the second layer, and the third layer.
- An intermediate film may be manufactured.
- the aldehyde is not particularly limited. In general, an aldehyde having 1 to 10 carbon atoms is preferably used as the aldehyde.
- Examples of the aldehyde having 1 to 10 carbon atoms include propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, n-octylaldehyde, and n-nonylaldehyde.
- n-butyraldehyde n-hexylaldehyde or n-valeraldehyde is preferable, and n-butyraldehyde is more preferable.
- the said aldehyde only 1 type may be used and 2 or more types may be used together.
- a method of adding a crosslinking agent such as dialdehyde, a method of promoting an acetalization reaction between molecules by adding an excess of aldehyde, and a high degree of polymerization examples include a method of adding polyvinyl alcohol. Moreover, these methods may be used independently and 2 or more types may be used together.
- the catalyst is preferably an acid catalyst.
- the acid catalyst include nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, and paratoluenesulfonic acid.
- the above molecular weight in terms of polystyrene indicates the molecular weight in terms of polystyrene as measured by gel permeation chromatography (GPC).
- the proportion (%) of the high molecular weight component Y having a molecular weight y of 1 million or more in the polyvinyl acetal resin is a peak area detected by an RI detector when measuring the polystyrene-equivalent molecular weight by GPC of the polyvinyl acetal resin.
- the molecular weight y is calculated from the ratio of the area corresponding to the region of 1 million or more.
- the peak area means the area between the peak of the component to be measured and the baseline.
- the molecular weight in terms of polystyrene is measured, for example, as follows.
- GPC measurement of a polystyrene standard sample with a known molecular weight is performed.
- polystyrene standard samples (“Shodex Standard SM-105”, “Shodex Standard SH-75” manufactured by Showa Denko KK)
- An approximate straight line obtained by plotting the weight average molecular weight against the elution time indicated by the peak top of each standard sample peak is used as a calibration curve.
- the surface layer and the intermediate layer are peeled from the multi-layered intermediate film left for one month in a constant temperature and humidity chamber (humidity 30% ( ⁇ 3%), temperature 23 ° C.).
- the peeled intermediate layer is dissolved in tetrahydrofuran (THF) to prepare a 0.1% by weight solution.
- THF tetrahydrofuran
- an area corresponding to a region where the polystyrene-equivalent molecular weight of the polyvinyl acetal resin in the intermediate layer is 1 million or more is calculated.
- the value obtained by dividing the area corresponding to the region where the polystyrene conversion molecular weight of the polyvinyl acetal resin in the intermediate layer is 1 million or more by the peak area of the polyvinyl acetal resin in the intermediate layer as a percentage (%) the above polyvinyl acetal The ratio (%) of the high molecular weight component Y in which the molecular weight y is 1 million or more can be calculated.
- GPC Gel Permeation Chromatography
- the first layer includes a plasticizer (hereinafter may be 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)).
- the plasticizer (1) contains a first plasticizer.
- the plasticizer (1) may contain only the first plasticizer.
- the plasticizer (1) preferably includes a second plasticizer different from the first plasticizer. Therefore, the said plasticizer (1) may contain 2 or more types of plasticizers, and may contain 3 or more types of plasticizers.
- the chemical formula of the second plasticizer is different from the chemical formula of the first plasticizer.
- Each of the plasticizers (2) and (3) may be used alone or in combination of two or more.
- the plasticizer (1) contained in the first layer is not particularly limited as long as it contains the first plasticizer that satisfies the cloud point. From the viewpoint of further enhancing the sound insulation in the high frequency range of the laminated glass, the SP value of the plasticizer (1) is preferably 13.5 to 14.5, and the SP value of the first plasticizer is More preferably, it is 13.5 to 14.5, and the SP value of the second plasticizer is more preferably 13.5 to 14.5.
- the “SP value” can be calculated using the Fedors method (R. F. Fedors, Polym. Eng. Sci., 14, 147 (1974)). If the SP value is within the above range, the compatibility between the plasticizer (1) and the polyvinyl acetal resin (1), the compatibility between the first plasticizer and the polyvinyl acetal resin (1), and the second The compatibility between the plasticizer and the polyvinyl acetal resin (1) is good.
- the plasticizers (2) and (3) contained in the second and third layers are not particularly limited. Conventionally known plasticizers can be used as the plasticizers (2) and (3).
- plasticizers (1) to (3) examples include organic ester plasticizers such as monobasic organic acid esters and polybasic organic acid esters, and organic phosphate plasticizers and organic phosphorous acid plasticizers. A phosphoric acid plasticizer etc. are mentioned. Of these, organic ester plasticizers are preferred.
- the plasticizers (1) to (3) are preferably liquid plasticizers.
- the interlayer film preferably contains the same plasticizer as the first plasticizer and the plasticizer (2) because the sound insulation is further improved.
- the first plasticizer, the plasticizer (2), and the plasticizer are preferable. It is more preferable that the same plasticizer is included as the agent (3).
- the monobasic organic acid ester is not particularly limited.
- examples include esters.
- Examples of the glycol include triethylene glycol, tetraethylene glycol, and tripropylene glycol.
- Examples of the monobasic organic acid include butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptylic acid, n-octylic acid, 2-ethylhexylic acid, n-nonylic acid, and decylic acid.
- the polybasic organic acid ester is not particularly limited, and examples thereof include an ester compound of a polybasic organic acid and an alcohol having a linear or branched structure having 4 to 8 carbon atoms.
- Examples of the polybasic organic acid include adipic acid, sebacic acid, and azelaic acid.
- the organic ester plasticizer is not particularly limited, and triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol dicaprylate, triethylene glycol di-n- Octanoate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate, ethylene glycol di-2-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 Rudi-2-ethylbutyrate, triethylene glycol di-2-ethylpentanoate, te
- the organic phosphate plasticizer is not particularly limited, and examples thereof include tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphate, and the like.
- the plasticizer (1) contained in the first layer is preferably a diester plasticizer represented by the following formula (1). .
- R1 and R2 each represent an organic group having 1 to 10 carbon atoms
- R3 represents an ethylene group, an isopropylene group or an n-propylene group
- p represents an integer of 2 to 10
- P in the above formula (1) is preferably 3 or more, preferably 8 or less, more preferably 5 or less, and still more preferably 4 or less.
- the organic group may be a hydrocarbon group or an organic group having at least one ether bond. When the organic group does not have an ether bond, p is preferably 3 to 10, and when the organic group has an ether bond, p is preferably 2 to 8.
- the first plasticizer contained in the plasticizer (1) is preferably a diester plasticizer represented by the following formula (1A). .
- R1 and R2 each represent an organic group having 2 to 5 carbon atoms
- R3 represents an ethylene group, an isopropylene group or an n-propylene group
- p represents an integer of 2 to 10
- R1 and R2 in the above formula (1A) are each preferably an organic group having 2 to 4 carbon atoms.
- P in the formula (1A) is preferably 3 or more, preferably 8 or less, more preferably 5 or less, and still more preferably 4 or less.
- the first plasticizer is preferably a diester plasticizer represented by the following formula (2). Therefore, the first plasticizer is preferably a diester plasticizer represented by the above formula (1) or a diester plasticizer represented by the following formula (2).
- R1 and R2 each represents an organic group having at least one ether bond, and n represents an integer of 2 to 8.
- R1 and R2 each represent at least an ether bond structural unit represented by the following formula (11) or the following formula (12). It is preferable to have one.
- the first plasticizer is preferably a diester plasticizer represented by the following formula (2A).
- R21 and R26 each represent an alkyl group having 1 to 10 carbon atoms
- R22 and R27 each represent an alkylene group having 1 to 10 carbon atoms
- m1 and m2 each represent 1 to 5 carbon atoms.
- n represents an integer of 2 to 8.
- R1 and R2 in the case of an organic group having at least one ether bond include 2-butoxyethyl group, 2- (2-butoxyethoxy) ethyl group, 2- [2- (2-butoxyethoxy) ) Ethoxy] ethyl group and the like.
- R1 and R2 may be groups other than these.
- the second plasticizer contained in the first layer is a diester plasticizer represented by the following formula (1B). It is preferable.
- R1 and R2 each represents an organic group having 6 to 10 carbon atoms
- R3 represents an ethylene group, an isopropylene group or an n-propylene group
- p represents an integer of 2 to 10 .
- the number of carbon atoms of R1 and R2 in the above formula (1B) is preferably 8 or less.
- P in the formula (1B) is preferably 3 or more, preferably 8 or less, more preferably 5 or less, and still more preferably 4 or less.
- the plasticizers (2) and (3) are each preferably a diester plasticizer represented by the above formula (1), more preferably a diester plasticizer represented by the above formula (1A), More preferably, it is a diester plasticizer represented by the above formula (1B), and further comprises a diester plasticizer represented by the above formula (1A) and a diester plasticizer represented by the above formula (1B). preferable.
- the plasticizers (2) and (3) contain at least one of triethylene glycol di-2-ethylhexanoate (3GO) and triethylene glycol di-2-ethylbutyrate (3GH). Preferably, it contains triethylene glycol di-2-ethylhexanoate.
- the total content of all the plasticizers (1) is preferably 25 parts by weight or more, preferably 80 parts by weight or less. is there. From the viewpoint of further improving the sound insulation in the high frequency range of the laminated glass, the total content of all the plasticizers (1) in 100 parts by weight of the polyvinyl acetal resin (1) in the first layer.
- the amount is more preferably 30 parts by weight or more, more preferably 70 parts by weight or less, still more preferably 60 parts by weight or less.
- the penetration resistance of a laminated glass becomes still higher that content of the said plasticizer (1) is more than the said minimum.
- the transparency of the interlayer film is further increased.
- the content of the first plasticizer is preferably 1% by weight or more, more preferably 3% by weight or more, out of a total of 100% by weight of all the plasticizers (1) contained in the first layer. , 100% by weight or less.
- the total amount of the plasticizer (1) may be the first plasticizer.
- the first plasticizer in the total 100% by weight of all the plasticizers (1) contained in the first layer.
- the content of the plasticizer is preferably 1% by weight or more, more preferably 3% by weight or more, further preferably 5% by weight or more, particularly preferably 50% by weight or more, preferably 99% by weight or less, more preferably 97% by weight. % Or less, still more preferably 95% by weight or less, still more preferably 90% by weight or less, particularly preferably 80% by weight or less, and most preferably 50% by weight or less.
- the content of the first plasticizer is not less than the above lower limit and not more than the above upper limit, the sound insulation in the high frequency region of the interlayer film and the laminated glass is further enhanced.
- the content of the second plasticizer is preferably 99% by weight or less, more preferably 97% by weight or less, in a total of 100% by weight of all the plasticizers (1) contained in the first layer. It is. In a total of 100% by weight of all the plasticizers (1) contained in the first layer, the content of the second plasticizer may be 0% by weight, and the plasticizer (1 ) May be the first plasticizer. When the content of the second plasticizer is not more than the above upper limit, the sound insulating properties in the high frequency region of the intermediate film and the laminated glass are further enhanced.
- the second plasticizer is contained in 100% by weight of the total of all the plasticizers (1) contained in the first layer.
- the content of the plasticizer is preferably 1% by weight or more, more preferably 5% by weight or more, further preferably 10% by weight or more, preferably 99% by weight or less, and more preferably 97% by weight or less.
- the content of the second plasticizer is not less than the above lower limit and not more than the above upper limit, the sound insulation in the high frequency region of the interlayer film and the laminated glass is further enhanced.
- the total content of all the plasticizers (2) is preferably 5 parts by weight or more, preferably 50 parts by weight or less with respect to 100 parts by weight of the polyvinyl acetal resin (2). is there.
- the total content of all the plasticizers (3) is preferably 5 parts by weight or more and preferably 50 parts by weight or less with respect to 100 parts by weight of the polyvinyl acetal resin (3). is there. From the viewpoint of further enhancing the sound insulation in the high frequency range of the laminated glass, all the plasticizers in the second and third layers with respect to 100 parts by weight of the polyvinyl acetal resins (2) and (3).
- the total content of (2) and (3) is more preferably 10 parts by weight or more, and more preferably 45 parts by weight or less.
- the content of the plasticizers (2) and (3) is not less than the above lower limit, the penetration resistance of the laminated glass is further enhanced.
- the content of the plasticizers (2) and (3) is not more than the above upper limit, the transparency of the interlayer film is further increased.
- the content of the plasticizer (2) with respect to 100 parts by weight of the polyvinyl acetal resin (2) in the second layer (hereinafter sometimes referred to as content (2)) is the same as that in the first layer.
- the total content of all the plasticizers (1) relative to 100 parts by weight of the polyvinyl acetal resin (1) (hereinafter sometimes referred to as “content (1)”) is preferably less.
- the content of the plasticizer (3) (hereinafter sometimes referred to as content (3)) relative to 100 parts by weight of the polyvinyl acetal resin (3) in the third layer is the first layer.
- the total content of all the plasticizers (1) with respect to 100 parts by weight of the polyvinyl acetal resin (1) is preferably less than the total content (hereinafter sometimes referred to as content (1)).
- a preferred lower limit of the difference between the content (1) and the contents (2) and (3) is 5 parts by weight, a more preferred lower limit is 10 parts by weight, a still more preferred lower limit is 12 parts by weight, and a particularly preferred lower limit is 15 parts by weight. Parts, the most preferred lower limit is 20 parts by weight, the preferred upper limit is 40 parts by weight, the more preferred upper limit is 35 parts by weight, and the still more preferred upper limit is 30 parts by weight.
- the difference between the content (1) and the contents (2) and (3) is not less than the above lower limit, the sound insulating property of the laminated glass is further enhanced. The penetrability becomes even higher.
- the difference between the content (1) and the contents (2) and (3) is a value obtained by subtracting the contents (2) and (3) from the content (1).
- Each of the above first to third layers is, if necessary, an ultraviolet absorber, an antioxidant, a light stabilizer, a flame retardant, an antistatic agent, a pigment, a dye, an adhesion modifier, a moisture-resistant agent, and a fluorescent whitening agent.
- Additives such as an agent and an infrared absorber may be included. As for these additives, only 1 type may be used and 2 or more types may be used together.
- the peak temperature of tan ⁇ appearing on the lowest temperature side measured at a frequency of 1 Hz of the interlayer film for laminated glass according to the present invention is 0 ° C. or less. It is preferable.
- the maximum value of tan ⁇ at the peak temperature of tan ⁇ appearing on the lowest temperature side measured at a frequency of 1 Hz is preferably 1.15 or more.
- the maximum value of tan ⁇ at the peak temperature of tan ⁇ appearing on the highest temperature side measured at a frequency of 1 Hz is preferably 0.55 or more.
- the maximum value of tan ⁇ at the peak temperature of tan ⁇ that appears on the lowest temperature side, and the maximum value of tan ⁇ on the peak temperature of tan ⁇ that appears on the highest temperature side It is preferable to measure immediately after storing the interlayer film for laminated glass in an environment of 23 ° C. for one month.
- the thickness of the first layer is preferably within a range of 0.02 to 1.8 mm.
- the thickness of the first layer is more preferably 0.05 mm or more, further preferably 0.08 mm, more preferably 0.5 mm or less, and still more preferably 0.15 mm or less.
- the thicknesses of the second and third layers are each preferably in the range of 0.1 mm to 1 mm.
- the thickness of the second and third layers is more preferably 0.2 mm or more, further preferably 0.3 mm or more, more preferably 0.5 mm or less, and further preferably 0.4 mm or less.
- the thickness of the second and third layers is not less than the above lower limit and not more than the above upper limit, the thickness of the intermediate film does not become too thick, and the sound insulating properties of the intermediate film and the laminated glass are further increased, and the plasticizer Bleed-out can be suppressed.
- the ratio of the thickness of the first layer to the thickness of the intermediate film ((first layer thickness) / (intermediate film thickness)) is small.
- the content of the plasticizer contained in the first layer increases, foaming in the laminated glass occurs and the foam tends to grow.
- the ratio in the intermediate film is 0.05 or more and 0.35 or less, the total content of all the plasticizers with respect to 100 parts by weight of the polyvinyl acetal resin in the first layer is large.
- the occurrence of foaming and the growth of foaming in the laminated glass can be sufficiently suppressed, and the sound insulation of the laminated glass can be further enhanced.
- the ratio ((the thickness of the first layer) / (the thickness of the intermediate film)) is preferably 0.06 or more, more preferably 0.07 or more, still more preferably 0.08 or more, and particularly preferably 0.1 or more. , Preferably 0.3 or less, more preferably 0.25 or less, still more preferably 0.2 or less, particularly preferably 0.15 or less.
- the thickness of the interlayer film for laminated glass according to the present invention is preferably in the range of 0.1 to 3 mm.
- the thickness of the intermediate film is more preferably 0.25 mm or more, and more preferably 1.5 mm or less.
- the thickness of the intermediate film is not less than the above lower limit, the penetration resistance of the intermediate film and the laminated glass is sufficiently high.
- the thickness of the interlayer film is not more than the above upper limit, the transparency of the interlayer film is further improved.
- the thickness of the intermediate film indicates the thickness of the first layer.
- the method for producing the interlayer film for laminated glass according to the present invention is not particularly limited.
- a conventionally known method can be used as a method for producing the intermediate film.
- the manufacturing method etc. which knead
- the method of kneading is not particularly limited. Examples of this method include a method using an extruder, a plastograph, a kneader, a Banbury mixer, a calendar roll, or the like. Especially, since it is suitable for continuous production, a method using an extruder is preferable, and a method using a twin screw extruder is more preferable.
- the interlayer film for laminated glass according to the present invention the first layer and the second and third layers are separately manufactured, and then the first layer and the second and third layers are laminated. A multilayer interlayer film may be obtained, or the interlayer may be obtained by laminating the first layer and the second and third layers by coextrusion.
- the second and third layers contain the same polyvinyl acetal resin, and the second and third layers contain the same polyvinyl acetal resin and It is more preferable that the same plasticizer is contained, and it is further preferable that the second and third layers are formed of the same resin composition.
- FIG. 2 An example of the laminated glass using the intermediate film for laminated glasses which concerns on one Embodiment of this invention is shown with sectional drawing.
- a laminated glass 11 shown in FIG. 2 includes an intermediate film 1 and first and second laminated glass constituent members 21 and 22.
- the intermediate film 1 is sandwiched between the first and second laminated glass constituent members 21 and 22.
- a first laminated glass constituting member 21 is laminated on the first surface 1 a of the intermediate film 1.
- a second laminated glass constituting member 22 is laminated on a second surface 1b opposite to the first surface 1a of the intermediate film 1.
- a first laminated glass constituting member 21 is laminated on the outer surface 3 a of the second layer 3.
- a second laminated glass constituent member 22 is laminated on the outer surface 4 a of the third layer 4.
- the laminated glass according to the present invention includes a first laminated glass constituent member, a second laminated glass constituent member, and an intermediate film sandwiched between the first and second laminated glass constituent members.
- the interlayer film for laminated glass of the present invention is used as the interlayer film.
- first and second laminated glass constituent members include glass plates and PET (polyethylene terephthalate) films.
- the laminated glass includes not only laminated glass in which an intermediate film is sandwiched between two glass plates, but also laminated glass in which an intermediate film is sandwiched between a glass plate and a PET film or the like.
- Laminated glass is a laminated body provided with a glass plate, and preferably at least one glass plate is used.
- the glass plate examples include inorganic glass and organic glass.
- the inorganic glass examples include float plate glass, heat ray absorbing plate glass, heat ray reflecting plate glass, polished plate glass, mold plate glass, mesh plate glass, wire plate glass, and green glass.
- the organic glass is a synthetic resin glass substituted for inorganic glass.
- the organic glass examples include polycarbonate plates and poly (meth) acrylic resin plates.
- the poly (meth) acrylic resin plate include a polymethyl (meth) acrylate plate.
- the thickness of the first and second laminated glass constituent members is not particularly limited, but is preferably in the range of 1 to 5 mm.
- the thickness of the glass plate is preferably in the range of 1 to 5 mm.
- the thickness of the PET film is preferably in the range of 0.03 to 0.5 mm.
- the method for producing the laminated glass is not particularly limited.
- the first and second laminated glass constituent members are sandwiched between the first and second laminated glass members, passed through a pressing roll, or put in a rubber bag and sucked under reduced pressure.
- the air remaining between the glass component and the intermediate film is degassed. Thereafter, it is pre-adhered at about 70 to 110 ° C. to obtain a laminate.
- the laminate is put in an autoclave or pressed and pressed at about 120 to 150 ° C. and a pressure of 1 to 1.5 MPa. In this way, a laminated glass can be obtained.
- the laminated glass can be used for automobiles, railway vehicles, aircraft, ships, buildings, and the like. Laminated glass can be used for other purposes.
- the intermediate film is preferably an architectural or vehicle intermediate film, and more preferably a vehicle intermediate film.
- the laminated glass is preferably laminated glass for buildings or vehicles, and more preferably an interlayer film for vehicles.
- the interlayer film and the laminated glass are suitably used for an electric vehicle using an electric motor and a hybrid electric vehicle using an internal combustion engine and an electric motor.
- the laminated glass can be used for an automobile windshield, side glass, rear glass, roof glass, or the like.
- the following polyvinyl acetal resins and plasticizers were used.
- the degree of acetalization (degree of butyralization), the degree of acetylation, and the hydroxyl group content of the polyvinyl acetal resin were measured by a method based on ASTM D1396-92.
- JIS K6728 “Testing method for polyvinyl butyral” the same numerical values as those in the method based on ASTM D1396-92 were shown.
- Polyvinyl acetal resin Polyvinyl acetal resin a (polyvinyl butyral resin, using n-butyraldehyde, butyralization degree 63.5 mol%, acetylation degree 12.8 mol%, hydroxyl group content 23.7 mol%)
- Polyvinyl acetal resin b polyvinyl butyral resin, using n-butyraldehyde, butyralization degree 54 mol%, acetylation degree 22.5 mol%, hydroxyl group content 23.5 mol%)
- Polyvinyl acetal resin c polyvinyl butyral resin, using n-butyraldehyde, butyralization degree 68.5 mol%, acetylation degree 1 mol%, hydroxyl group content 30.5 mol%)
- Polyvinyl acetal resin d1 polyvinyl butyral resin (synthesized in Synthesis Example 1 below), using n-butyraldehyde, buty
- the obtained polyvinyl butyral resin e1 had an acetylation degree of 0.8 mol%, a butyralization degree of 78 mol%, and a hydroxyl group content of 21.2 mol%.
- the proportion of the high molecular weight component X (polyvinyl butyral resin) having an absolute molecular weight of 1 million or more in the obtained polyvinyl butyral resin e1 was 17.3%.
- the proportion of the high molecular weight component Y (polyvinyl butyral resin) having a molecular weight y of 1,000,000 or more in the obtained polyvinyl butyral resin Z was 20.4%.
- Polyvinyl acetal resin e2 (polyvinyl butyral resin (average polymerization degree 3300), using n-butyraldehyde, butyralization degree 73 mol%, acetylation degree 7 mol%, hydroxyl group content 20 mol%)
- the obtained polyvinyl butyral resin f1 had an acetylation degree of 7 mol%, a butyral degree of 71 mol%, and a hydroxyl group content of 22 mol%.
- Polyvinyl acetal resin f2 (polyvinyl butyral resin (average polymerization degree 3300), using n-butyraldehyde, butyralization degree 80 mol%, acetylation degree 4 mol%, hydroxyl group content 16 mol%)
- polyvinyl butyral resin g had an acetylation degree of 20.5 mol%, a butyralization degree of 54.5 mol%, and a hydroxyl group content of 25 mol%.
- polyvinyl butyral resin i had an acetylation degree of 1.2 mol%, a butyralization degree of 72.4 mol%, and a hydroxyl group content of 26.4 mol%.
- (Synthesis Example 8) Synthesis of polyvinyl butyral resin j: A polyvinyl butyral resin (average polymerization degree 3050) having an acetylation degree of 20 mol%, a butyralization degree of 55 mol% and a hydroxyl group content of 25 mol% was dissolved in pyridine, and 10.5 mol equivalent to the dissolved polyvinyl butyral resin. Of acetic anhydride was added and stirred at 80 ° C. for 120 minutes. Pyridine was removed, and the polyvinyl butyral resin was washed with water and dried to obtain polyvinyl butyral resin j. The obtained polyvinyl butyral resin j had an acetylation degree of 30.5 mol%, a butyralization degree of 55 mol%, and a hydroxyl group content of 14.5 mol%.
- the obtained polyvinyl butyral resin k had a degree of acetylation of 1.8 mol%, a degree of butyralization of 68.5 mol%, and a hydroxyl group content of 29.7 mol%.
- the obtained polyvinyl butyral resin 1 had an acetylation degree of 21.7 mol%, a butyralization degree of 52.3 mol%, and a hydroxyl group content of 26 mol%.
- the obtained polyvinyl butyral resin m had an acetylation degree of 20.5 mol%, a butyralization degree of 52.8 mol%, and a hydroxyl group content of 26.7 mol%.
- the obtained polyvinyl butyral resin n had an acetylation degree of 23 mol%, a butyralization degree of 51.8 mol%, and a hydroxyl group content of 25.2 mol%.
- the obtained polyvinyl butyral resin o had a degree of acetylation of 23.2 mol%, a degree of butyralization of 49.6 mol%, and a hydroxyl group content of 27.2 mol%.
- the obtained polyvinyl butyral resin p had an acetylation degree of 18.4 mol%, a butyralization degree of 57.6 mol%, and a hydroxyl group content of 24 mol%.
- Polyvinyl acetal resin q polyvinyl butyral resin, using n-butyraldehyde, butyralization degree 68.4 mol%, acetylation degree 0.7 mol%, hydroxyl group content 30.9 mol%)
- Polyvinyl acetal resin r polyvinyl butyral resin, using n-butyraldehyde, degree of butyralization 69.9 mol%, degree of acetylation 1.2 mol%, hydroxyl group content 28.9 mol%)
- Plasticizer Triethylene glycol di-n-butanoate (3 GB) (SP value: 9.45) Triethylene glycol di-n-propanoate (3GE) (SP value: 9.56) Hexanoic acid bis (2- (2-butoxyethoxyethyl) ester) (EDENOL 422) (SP value: 13.85) Bis (2-butoxyethyl) adipate (D931) (SP value: 13.56) Triethylene glycol
- Example 1 Production of Intermediate Film 100 parts by weight of polyvinyl acetal resin a and 55 parts by weight of the first plasticizer (3GB) were sufficiently kneaded with a mixing roll to obtain an intermediate layer composition.
- the obtained intermediate layer composition and protective layer composition were molded using a co-extruder, and protective layer B (thickness 0.33 mm) / intermediate layer A (thickness 0.1 mm) / protective layer B (thickness)
- a multilayer intermediate film (thickness 0.76 mm) having a laminated structure of 0.33 mm) was produced.
- a multilayer intermediate film having a through hole was sandwiched between two transparent float glasses (length 30 cm ⁇ width 15 cm ⁇ thickness 2.5 mm) to obtain a laminate.
- the outer peripheral edge of the laminate was sealed with a width of 2 cm from the end by heat sealing, thereby enclosing the air remaining in the emboss and the air remaining in the through hole.
- the laminated body was pressure-bonded at 135 ° C. and a pressure of 1.2 MPa for 20 minutes, so that the remaining air was dissolved in the multilayer interlayer film to obtain a laminated glass used for foaming tests A and B.
- the laminated glass used for the foam tests A and B was prepared using the multilayer interlayer films of Examples 9-11.
- Examples 2 to 11 and Comparative Example 1 In the same manner as in Example 1 except that the types and contents of the polyvinyl butyral resin and the plasticizer used in the intermediate layer A and the protective layer B were set as shown in Tables 1 and 2 below, the multilayer intermediate film and the laminate Glass was obtained. In Comparative Example 1, only the plasticizer (3GO) was used as the second plasticizer without using the first plasticizer.
- Example 12 (1) Production of intermediate film Mixing roll of 100 parts by weight of polyvinyl acetal resin a, 15 parts by weight of plasticizer (3GB) as the first plasticizer, and 45 parts by weight of plasticizer (3GO) as the second plasticizer The mixture was sufficiently kneaded to obtain an intermediate layer composition.
- the obtained intermediate layer composition and protective layer composition were molded using a co-extruder, and protective layer B (thickness 0.33 mm) / intermediate layer A (thickness 0.1 mm) / protective layer B (thickness)
- a multilayer intermediate film (thickness 0.76 mm) having a laminated structure of 0.33 mm) was produced.
- a multilayer intermediate film having a through hole was sandwiched between two transparent float glasses (length 30 cm ⁇ width 15 cm ⁇ thickness 2.5 mm) to obtain a laminate.
- the outer peripheral edge of the laminate was sealed with a width of 2 cm from the end by heat sealing, thereby enclosing the air remaining in the emboss and the air remaining in the through hole.
- the laminated body was pressure-bonded at 135 ° C. and a pressure of 1.2 MPa for 20 minutes, so that the remaining air was dissolved in the multilayer interlayer film to obtain a laminated glass used for foaming tests A and B.
- the laminated glass used in the foam tests A and B was produced using the multilayer interlayer films of Examples 19 to 27.
- Example 13 to 31 In the same manner as in Example 12, except that the types and contents of the polyvinyl acetal resin and the plasticizer used in the intermediate layer A and the protective layer B were set as shown in Tables 3 to 6 below, the multilayer intermediate film and the laminate Glass was obtained.
- the test tube was left in an atmosphere of ⁇ 20 ° C. to lower the temperature of the solution to ⁇ 15 ° C. At this time, the temperature at which clouding began to occur in a part of the solution was visually observed, and this temperature was taken as the cloud point.
- the solution is cooled to the pour point of the first plasticizer in an atmosphere of -196 ° C using liquid nitrogen, and the temperature is lowered. I let you. At this time, the temperature at which clouding began to occur in a part of the solution was visually observed, and this temperature was taken as the cloud point.
- Tables 1 to 6 below cloud points according to the first cloud point determination method are shown.
- haze meter The maximum temperature at which haze was 10% or more was taken as the cloud point.
- the haze was measured according to JIS K6714 using a haze meter (“TC-HIIIDPK” manufactured by Tokyo Denshoku Co., Ltd.).
- Example 6 the haze showed 10% or more after the test tube was left in a constant temperature room at 0 ° C. for 1 hour.
- Example 3 the haze was 10% or more after the test tube was left in a thermostatic chamber at ⁇ 5 ° C. for 1 hour.
- Examples 1, 2, 5, 7, 8, and 10 to 31 even after the test tube was left in a thermostatic chamber at ⁇ 5 ° C. for 1 hour, the haze did not show 10% or more.
- the test tube was left in an atmosphere of ⁇ 20 ° C. to lower the temperature of the solution to ⁇ 15 ° C. At this time, the temperature at which clouding began to occur in a part of the solution was visually observed, and this temperature was taken as the cloud point.
- the temperature is lowered by cooling the solution to the pour point of the second plasticizer in an atmosphere of ⁇ 196 ° C. using liquid nitrogen. I let you. At this time, the temperature at which clouding began to occur in a part of the solution was visually observed, and this temperature was taken as the cloud point.
- Tables 1 to 6 below cloud points according to the first cloud point determination method are shown.
- haze meter The maximum temperature at which haze was 10% or more was taken as the cloud point.
- the haze was measured according to JIS K6714 using a haze meter (“TC-HIIIDPK” manufactured by Tokyo Denshoku Co., Ltd.).
- Example 12 to 15, 28, 29 and Comparative Example 1 the haze showed 10% or more after leaving the test tube in a constant temperature room at 5 ° C. for 1 hour.
- the haze was 10% or more after the test tube was left in a thermostatic chamber at ⁇ 5 ° C. for 1 hour.
- the haze did not show 10% or more.
- the laminated glass used for the measurement of the loss coefficient was stored for one month in an environment of 20 ° C.
- the loss factor was measured by the central vibration method under the condition of 20 ° C. using a measuring apparatus “SA-01” (manufactured by Rion).
- SA-01 manufactured by Rion
- the loss factor (20 ° C. loss factor) in the fourth-order mode (around 3150 Hz) of the resonance frequency of the obtained loss factor was evaluated.
- the loss factor was measured by the central vibration method under the condition of 30 ° C. using a measuring device “SA-01” (manufactured by Rion).
- SA-01 manufactured by Rion
- the loss factor (30 ° C. loss factor) in the sixth-order mode (around 6300 Hz) of the resonance frequency of the obtained loss factor was evaluated.
- Foam test A Foaming state
- Five laminated glasses used in the foaming test A were prepared for the multilayer interlayer films of Examples 9 to 11 and 19 to 27, and left in an oven at 50 ° C. for 100 hours.
- the presence or absence of foaming and the size of foaming were visually observed in plan view, and the state of foaming was judged according to the following criteria.
- Foam test B (foaming state) 30 laminated glasses used in the foam test B were prepared for the multilayer interlayer films of Examples 9 to 11 and 19 to 27, and left in an oven at 50 ° C. for 24 hours. In the laminated glass after being allowed to stand, the number of laminated glasses in which foaming was visually observed was confirmed and judged according to the following criteria.
- X The laminated glass in which foaming was observed visually was 16 sheets or more.
- the press-molded intermediate layer was placed in a hand press set in advance at 20 ° C. and cooled by pressing at 10 MPa for 10 minutes. Subsequently, one PET film was peeled from the mold placed between the two PET films to obtain a resin film B. After the resin film B was stored for 24 hours in a constant temperature and humidity chamber (humidity 30% ( ⁇ 3%), temperature 23 ° C.), viscoelasticity was measured using ARES-G2 manufactured by TAINSTRUMENTS. As a jig, a parallel plate having a diameter of 8 mm was used. The measurement was performed under the condition of decreasing the temperature from 100 ° C. to ⁇ 10 ° C.
- the peak temperature of the loss tangent was defined as the glass transition temperature Tg (° C.). Further, from the obtained measurement result and the glass transition temperature Tg, the value of the elastic modulus G ′ (Tg + 30) at (Tg + 30) ° C. and the value of the elastic modulus G ′ (Tg + 80) at (Tg + 80) ° C. are read. It was. Further, the ratio (G ′ (Tg + 80) / G ′ (Tg + 30)) was determined.
- the multilayer intermediate film was left in a constant temperature and humidity chamber (humidity 30% ( ⁇ 3%), temperature 23 ° C.) for 1 month. After standing for 1 month, the surface layer and the intermediate layer were peeled from the multilayer intermediate film. The peeled intermediate layer was dissolved in tetrahydrofuran (THF) to prepare a 0.1% by weight solution.
- GPC Gel Permeation Chromatography
- a GPC light scattering detector (“Model 270 (RALS + VISCO)” manufactured by VISCOTEK) is connected to the GPC apparatus, and chromatogram analysis can be performed by each detector.
- chromatogram analysis can be performed by each detector.
- the absolute molecular weight at each elution time of the polyvinyl acetal resin was determined.
- the ratio of the area of the area where the absolute molecular weight of the polyvinyl acetal resin is 1 million or more to the peak area of the polyvinyl acetal resin detected by the RI detector was expressed as a percentage (%).
- a RI c ⁇ (dn / dc) ⁇ K RI Expression (1)
- a RALS c ⁇ M ⁇ (dn / dc) 2 ⁇ K RALS (2)
- c the polymer concentration in the solution
- (dn / dc) the refractive index increment
- M the absolute molecular weight
- K the device constant.
- the peeled intermediate layer is dissolved in THF to prepare a THF solution.
- the absolute molecular weight M of the polyvinyl acetal resin was determined from the GPC measurement result of the obtained polyvinyl acetal resin solution.
- the concentration of the polyvinyl acetal resin in the polyvinyl acetal resin solution was calculated from the results of measurement of the content of the following plasticizer.
- plasticizer content Plasticize the THF so that the plasticizer content is 10%, 15%, 20%, 25%, 30%, 35%, 35%, 40%, 45% and 50% by weight.
- the agent was dissolved to prepare a plasticizer-THF solution.
- the obtained plasticizer-THF solution was subjected to GPC measurement to determine the peak area of the plasticizer.
- the peak area of the plasticizer was plotted against the concentration of the plasticizer to obtain an approximate line.
- the THF solution in which the intermediate layer was dissolved in THF was measured by GPC, and the content of the plasticizer was determined by using an approximate line from the peak area of the plasticizer.
- the polystyrene-equivalent molecular weight is measured by gel permeation chromatography (GPC), and the molecular weight of the peak area (GPC measurement result) detected by the RI detector is 1,000,000. From the proportion of the area corresponding to the above region, the proportion (%) of the high molecular weight component Y having a molecular weight y of 1,000,000 or more in the polyvinyl acetal resin was calculated.
- GPC measurement of a polystyrene standard sample with a known molecular weight is performed.
- polystyrene standard samples (“Shodex Standard SM-105”, “Shodex Standard SH-75” manufactured by Showa Denko KK)
- An approximate straight line obtained by plotting the weight average molecular weight against the elution time indicated by the peak top of each standard sample peak was used as a calibration curve.
- the surface layer and the intermediate layer were peeled from the multilayer intermediate film that was left in a constant temperature and humidity chamber (humidity 30% ( ⁇ 3%), temperature 23 ° C.) for one month.
- the peeled intermediate layer was dissolved in tetrahydrofuran (THF) to prepare a 0.1% by weight solution.
- THF tetrahydrofuran
- the obtained solution was analyzed by a GPC apparatus, and the peak area of the polyvinyl acetal resin in the intermediate layer was measured.
- the polyvinyl acetal By expressing the value obtained by dividing the area corresponding to the area of polystyrene equivalent molecular weight of the polyvinyl acetal resin in the intermediate layer by 1 million or more by the peak area of the polyvinyl acetal resin in the intermediate layer as a percentage (%), the polyvinyl acetal The ratio (%) of the high molecular weight component Y in which the molecular weight y is 1 million or more in the resin was calculated.
- the polyvinyl acetal resin constituting the first layer and the plasticizer constituting the first layer Using the resin film B (first layer) containing the content of Table 2 above, the plasticizer is transferred between the layers of the multilayer intermediate film, and then the elastic modulus of the resin film B (first layer)
- the ratio of the resin film B (G ′ (Tg + 80) / G ′ (Tg + 30)) includes 100 parts by weight of polyvinyl acetal resin and 60 parts by weight of 3GO contained in the first layer. The ratio was almost the same as the ratio of resin film A (G ′ (Tg + 80) / G ′ (Tg + 30)).
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Abstract
Description
本発明に係る合わせガラス用中間膜のさらに他の特定の局面では、周波数1Hzで測定した最も低温側に現れるtanδのピーク温度におけるtanδの最大値が1.15以上である。
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)を含むことが好ましい。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)~(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、上記第1の層が2種以上のポリビニルアセタール樹脂を含む場合に、上記曇点を測定する際の「ポリビニルアセタール樹脂8重量部」は、2種以上のポリビニルアセタール樹脂を、上記第1の層に含まれている重量比で合計8重量部となるように配合して得られる。
絶対分子量100万以上の高分子量成分X又は分子量yが100万以上である高分子量成分Yを含むポリビニルアセタール樹脂の具体的な製造方法を以下説明する。
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)を含む。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。上記可塑剤(1)は、第1の可塑剤を含有する。上記可塑剤(1)は、上記第1の可塑剤のみを含有していてもよい。上記可塑剤(1)は、上記第1の可塑剤とは異なる第2の可塑剤を含むことが好ましい。従って、上記可塑剤(1)は、2種以上の可塑剤を含有していてもよく、3種以上の可塑剤を含有していてもよい。上記第2の可塑剤の化学式は、上記第1の可塑剤の化学式と異なる。上記可塑剤(2),(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~第3の層はそれぞれ、必要に応じて、紫外線吸収剤、酸化防止剤、光安定剤、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。
合わせガラスの低温及び高周波域での遮音性をより一層高める観点からは、本発明に係る合わせガラス用中間膜の周波数1Hzで測定した最も低温側に現れるtanδのピーク温度は、0℃以下であることが好ましい。
また、中間膜が2層以上の積層構造を有する場合に、上記第1の層の厚みの上記中間膜の厚みに対する比((第1の層の厚み)/(中間膜の厚み))が小さく、上記第1の層に含まれる可塑剤の含有量が多いほど、合わせガラスにおける発泡が発生し、発泡が成長する傾向にある。特に、中間膜における上記比が0.05以上、0.35以下である場合には、上記第1の層中の上記ポリビニルアセタール樹脂100重量部に対する全ての上記可塑剤の合計の含有量が多くても、合わせガラスにおける発泡の発生及び発泡の成長を十分に抑制し、かつ合わせガラスの遮音性をより一層高めることができる。上記比((第1の層の厚み)/(中間膜の厚み))は好ましくは0.06以上、より好ましくは0.07以上、更に好ましくは0.08以上、特に好ましくは0.1以上、好ましくは0.3以下、より好ましくは0.25以下、更に好ましくは0.2以下、特に好ましくは0.15以下である。
図2に、本発明の一実施形態に係る合わせガラス用中間膜を用いた合わせガラスの一例を断面図で示す。
ポリビニルアセタール樹脂a(ポリビニルブチラール樹脂、n-ブチルアルデヒドを使用、ブチラール化度63.5モル%、アセチル化度12.8モル%、水酸基の含有率23.7モル%)
ポリビニルアセタール樹脂b(ポリビニルブチラール樹脂、n-ブチルアルデヒドを使用、ブチラール化度54モル%、アセチル化度22.5モル%、水酸基の含有率23.5モル%)
ポリビニルアセタール樹脂c(ポリビニルブチラール樹脂、n-ブチルアルデヒドを使用、ブチラール化度68.5モル%、アセチル化度1モル%、水酸基の含有率30.5モル%)
ポリビニルアセタール樹脂d1(ポリビニルブチラール樹脂(下記の合成例1で合成)、n-ブチルアルデヒドを使用、ブチラール化度40モル%、アセチル化度30.5モル%、水酸基の含有率は29.5モル%)
ポリビニルアセタール樹脂d1の合成:
アセチル化度0.5モル%、ブチラール化度40モル%、水酸基の含有率59.5モル%のポリビニルブチラール樹脂(平均重合度3000)をピリジンに溶解し、溶解したポリビニルブチラール樹脂に対し、30モル当量の無水酢酸を加え、80℃の環境下で120分間攪拌した。ピリジンを除去し、ポリビニルブチラール樹脂を水洗し、乾燥させることにより、ポリビニルブチラール樹脂d1(平均重合度3000)を得た。得られたポリビニルブチラール樹脂d1のブチラール化度は40モル%、アセチル化度は30.5モル%、水酸基の含有率は29.5モル%であった。
ポリビニルアセタール樹脂d2の合成:
アセチル化度0.5モル%、ブチラール化度40モル%、水酸基の含有率59.5モル%のポリビニルブチラール樹脂(平均重合度3000)をピリジンに溶解し、溶解したポリビニルブチラール樹脂に対し、33モル当量の無水酢酸を加え、80℃の環境下で120分間攪拌した。ピリジンを除去し、ポリビニルブチラール樹脂を水洗し、乾燥させることにより、ポリビニルブチラール樹脂d2(平均重合度3000)を得た。得られたポリビニルブチラール樹脂d2のブチラール化度は40モル%、アセチル化度は33.5モル%、水酸基の含有率は26.5モル%であった。
ポリビニルアセタール樹脂e1の合成:
純水2890gに、重合度2500、ケン化度99.2モル%のポリビニルアルコール95.5gと、重合度3500、ケン化度99.2モル%のポリビニルアルコール100gとを加えて加熱し、溶解させた溶液を、12℃に温度調節し、35重量%塩酸220gとn-ブチルアルデヒド160gを加えて、ポリビニルブチラール樹脂を析出させた。その後、温度50℃で3時間保持し、反応を完了させた。過剰の水での洗浄により、未反応のn-ブチルアルデヒドを洗浄し、塩酸触媒を中和し、塩を除去した後、乾燥させ、ポリビニルブチラール樹脂e1を得た。得られたポリビニルブチラール樹脂e1のアセチル化度は0.8モル%、ブチラール化度は78モル%、水酸基の含有率は21.2モル%であった。得られたポリビニルブチラール樹脂e1に占める、絶対分子量100万以上の高分子量成分X(ポリビニルブチラール樹脂)の割合は17.3%であった。得られたポリビニルブチラール樹脂Zに占める、分子量yが100万以上である高分子量成分Y(ポリビニルブチラール樹脂)の割合は20.4%であった。
ポリビニルアセタール樹脂f1の合成:
純水2890gに、重合度3200、ケン化度93モル%のポリビニルアルコール194gを加えて加熱し、溶解させた溶液を、12℃に温度調節し、35重量%塩酸210gとn-ブチルアルデヒド145gを加えて、ポリビニルブチラール樹脂を析出させた。その後、温度50℃で3時間保持し、反応を完了させた。過剰の水での洗浄により、未反応のn-ブチルアルデヒドを洗浄し、塩酸触媒を中和し、塩を除去した後、乾燥させ、ポリビニルブチラール樹脂f1を得た。得られたポリビニルブチラール樹脂f1のアセチル化度は7モル%、ブチラール化度は71モル%、水酸基の含有率は22モル%であった。
ポリビニルアセタール樹脂gの合成:
純水2890gに、重合度3050、ケン化度79.5モル%のポリビニルアルコール191gを加えて加熱し、溶解させた溶液を、12℃に温度調節し、35重量%塩酸201gとn-ブチルアルデヒド150gを加えて、ポリビニルブチラール樹脂を析出させた。その後、温度50℃で3時間保持し、反応を完了させた。過剰の水での洗浄により、未反応のn-ブチルアルデヒドを洗浄し、塩酸触媒を中和し、塩を除去した後、乾燥させ、ポリビニルブチラール樹脂gを得た。得られたポリビニルブチラール樹脂gのアセチル化度は20.5モル%、ブチラール化度は54.5モル%、水酸基の含有率は25モル%であった。
ポリビニルブチラール樹脂hの合成:
アセチル化度30モル%、ブチラール化度45モル%、水酸基の含有率25モル%のポリビニルブチラール樹脂(平均重合度3200)をピリジンに溶解し、溶解したポリビニルブチラール樹脂に対し、10モル当量の無水酢酸を加え、80℃の環境下で120分間攪拌した。ピリジンを除去し、ポリビニルブチラール樹脂を水洗し、乾燥させることにより、ポリビニルブチラール樹脂hを得た。得られたポリビニルブチラール樹脂hのアセチル化度は40モル%、ブチラール化度は45モル%、水酸基の含有率は15モル%であった。
ポリビニルブチラール樹脂iの合成:
純水3000gに、ケン化度98.8%、重合度1700のポリビニルアルコール190gを加えて加熱し、溶解させた溶液を、12℃に温度調節し、35重量%塩酸206gとn-ブチルアルデヒド142gを加えて、ポリビニルブチラール樹脂を析出させた。その後、温度50℃で4時間保持し、反応を完了させた。過剰の水での洗浄により、未反応のn-ブチルアルデヒドを洗浄し、塩酸触媒を中和し、塩を除去した後、乾燥させ、ポリビニルブチラール樹脂iを得た。得られたポリビニルブチラール樹脂iのアセチル化度は1.2モル%、ブチラール化度は72.4モル%、水酸基の含有率は26.4モル%であった。
ポリビニルブチラール樹脂jの合成:
アセチル化度20モル%、ブチラール化度55モル%、水酸基の含有率25モル%のポリビニルブチラール樹脂(平均重合度3050)をピリジンに溶解し、溶解したポリビニルブチラール樹脂に対し、10.5モル当量の無水酢酸を加え、80℃の環境下で120分間攪拌した。ピリジンを除去し、ポリビニルブチラール樹脂を水洗し、乾燥させることにより、ポリビニルブチラール樹脂jを得た。得られたポリビニルブチラール樹脂jのアセチル化度は30.5モル%、ブチラール化度は55モル%、水酸基の含有率は14.5モル%であった。
ポリビニルブチラール樹脂kの合成:
純水3000gに、ケン化度98.2%、重合度1700のポリビニルアルコール190gを加えて加熱し、溶解させた溶液を、12℃に温度調節し、35重量%塩酸212gとn-ブチルアルデヒド136gを加えて、ポリビニルブチラール樹脂を析出させた。その後、温度50℃で4時間保持し、反応を完了させた。過剰の水での洗浄により、未反応のn-ブチルアルデヒドを洗浄し、塩酸触媒を中和し、塩を除去した後、乾燥させ、ポリビニルブチラール樹脂kを得た。得られたポリビニルブチラール樹脂kのアセチル化度は1.8モル%、ブチラール化度は68.5モル%、水酸基の含有率は29.7モル%であった。
ポリビニルブチラール樹脂lの合成:
純水2890gに、重合度3050、ケン化度78.3モル%のポリビニルアルコール191gを加えて加熱し、溶解させた溶液を、12℃に温度調節し、35重量%塩酸201gとn-ブチルアルデヒド150gを加えて、ポリビニルブチラール樹脂を析出させた。その後、温度50℃で3時間保持し、反応を完了させた。過剰の水での洗浄により、未反応のn-ブチルアルデヒドを洗浄し、塩酸触媒を中和し、塩を除去した後、乾燥させ、ポリビニルブチラール樹脂lを得た。得られたポリビニルブチラール樹脂lのアセチル化度は21.7モル%、ブチラール化度は52.3モル%、水酸基の含有率は26モル%であった。
ポリビニルブチラール樹脂mの合成:
純水2890gに、重合度3200、ケン化度79.5モル%のポリビニルアルコール191gを加えて加熱し、溶解させた溶液を、12℃に温度調節し、35重量%塩酸201gとn-ブチルアルデヒド150gを加えて、ポリビニルブチラール樹脂を析出させた。その後、温度50℃で1.5時間保持し、反応を完了させた。過剰の水での洗浄により、未反応のn-ブチルアルデヒドを洗浄し、塩酸触媒を中和し、塩を除去した後、乾燥させ、ポリビニルブチラール樹脂mを得た。得られたポリビニルブチラール樹脂mのアセチル化度は20.5モル%、ブチラール化度は52.8モル%、水酸基の含有率は26.7モル%であった。
ポリビニルブチラール樹脂nの合成:
純水2890gに、重合度3050、ケン化度77モル%のポリビニルアルコール191gを加えて加熱し、溶解させた溶液を、12℃に温度調節し、35重量%塩酸201gとn-ブチルアルデヒド150gを加えて、ポリビニルブチラール樹脂を析出させた。その後、温度50℃で3時間保持し、反応を完了させた。過剰の水での洗浄により、未反応のn-ブチルアルデヒドを洗浄し、塩酸触媒を中和し、塩を除去した後、乾燥させ、ポリビニルブチラール樹脂nを得た。得られたポリビニルブチラール樹脂nのアセチル化度は23モル%、ブチラール化度は51.8モル%、水酸基の含有率は25.2モル%であった。
ポリビニルブチラール樹脂oの合成:
純水2890gに、重合度3050、ケン化度76.8モル%のポリビニルアルコール191gを加えて加熱し、溶解させた溶液を、12℃に温度調節し、35重量%塩酸201gとn-ブチルアルデヒド150gを加えて、ポリビニルブチラール樹脂を析出させた。その後、温度50℃で2時間保持し、反応を完了させた。過剰の水での洗浄により、未反応のn-ブチルアルデヒドを洗浄し、塩酸触媒を中和し、塩を除去した後、乾燥させ、ポリビニルブチラール樹脂oを得た。得られたポリビニルブチラール樹脂oのアセチル化度は23.2モル%、ブチラール化度は49.6モル%、水酸基の含有率は27.2モル%であった。
ポリビニルブチラール樹脂pの合成:
純水2890gに、重合度3050、ケン化度81.6モル%のポリビニルアルコール191gを加えて加熱し、溶解させた溶液を、12℃に温度調節し、35重量%塩酸201gとn-ブチルアルデヒド150gを加えて、ポリビニルブチラール樹脂を析出させた。その後、温度50℃で3時間保持し、反応を完了させた。過剰の水での洗浄により、未反応のn-ブチルアルデヒドを洗浄し、塩酸触媒を中和し、塩を除去した後、乾燥させ、ポリビニルブチラール樹脂pを得た。得られたポリビニルブチラール樹脂pのアセチル化度は18.4モル%、ブチラール化度は57.6モル%、水酸基の含有率は24モル%であった。
ポリビニルアセタール樹脂r(ポリビニルブチラール樹脂、n-ブチルアルデヒドを使用、ブチラール化度69.9モル%、アセチル化度1.2モル%、水酸基の含有率は28.9モル%)
(可塑剤)
トリエチレングリコールジ-n-ブタノエート(3GB)(SP値:9.45)
トリエチレングリコールジ-n-プロパノエート(3GE)(SP値:9.56)
ヘキサン酸ビス(2-(2-ブトキシエトキシエチル)エステル)(EDENOL422)(SP値:13.85)
アジピン酸ビス(2-ブトキシエチル)(D931)(SP値:13.56)
トリエチレングリコールジ-2-エチルヘキサノエート(3GO)(SP値:9.06)
(1)中間膜の作製
ポリビニルアセタール樹脂a100重量部と、第1の可塑剤(3GB)55重量部とをミキシングロールで充分に混練し、中間層用組成物を得た。
得られた中間膜を、縦30mm×横320mmに切り出した。次に、2枚の透明なフロートガラス(縦25mm×横305mm×厚み2.0mm)の間に中間膜を挟み込み、真空ラミネーターにて90℃で30分間保持し、真空プレスし、積層体を得た。積層体において、ガラスからはみ出た中間膜部分を切り落とし、損失係数の測定に用いる合わせガラスを得た。
得られた多層中間膜を縦30cm×横15cmの大きさに切断し、温度23℃の環境下にて、10時間保管した。なお、得られた多層中間膜の両面にはエンボスが形成されており、そのエンボスの十点平均粗さは30μmであった。切断された多層中間膜において、多層中間膜の端部から縦方向にそれぞれ内側に向かって8cmの位置と、多層中間膜の端部から横方向にそれぞれ内側に向かって5cmの位置との交点4箇所に、直径6mmの貫通孔を作製した。
中間層A及び保護層Bに用いたポリビニルブチラール樹脂及び可塑剤の種類及び含有量を下記の表1,2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、多層中間膜及び合わせガラスを得た。なお、比較例1では、第1の可塑剤を用いずに、第2の可塑剤として可塑剤(3GO)のみを用いた。
(1)中間膜の作製
ポリビニルアセタール樹脂a100重量部と、第1の可塑剤として可塑剤(3GB)15重量部と、第2の可塑剤として可塑剤(3GO)45重量部とをミキシングロールで充分に混練し、中間層用組成物を得た。
得られた中間膜を、縦30mm×横320mmに切り出した。次に、2枚の透明なフロートガラス(縦25mm×横305mm×厚み2.0mm)の間に中間膜を挟み込み、真空ラミネーターにて90℃で30分間保持し、真空プレスし、積層体を得た。積層体において、ガラスからはみ出た中間膜部分を切り落とし、損失係数の測定に用いる合わせガラスを得た。
得られた多層中間膜を縦30cm×横15cmの大きさに切断し、温度23℃の環境下にて、10時間保管した。なお、得られた多層中間膜の両面にはエンボスが形成されており、そのエンボスの十点平均粗さは30μmであった。切断された多層中間膜において、多層中間膜の端部から縦方向にそれぞれ内側に向かって8cmの位置と、多層中間膜の端部から横方向にそれぞれ内側に向かって5cmの位置との交点4箇所に、直径6mmの貫通孔を作製した。
中間層A及び保護層Bに用いたポリビニルアセタール樹脂及び可塑剤の種類及び含有量を下記の表3~6に示すように設定したこと以外は実施例12と同様にして、多層中間膜及び合わせガラスを得た。
(1)中間層に含まれているポリビニルアセタール樹脂及び第1の可塑剤を用いて測定された曇点
(1-1)第1の曇点の判定方法による曇点
実施例の中間層で用いた各第1の可塑剤3.5g(100重量部)と、実施例の中間層で用いた各ポリビニルアセタール樹脂0.28g(8重量部)とを用意した。試験管(直径2cm)内で、該第1の可塑剤3.5g(100重量部)と、該ポリビニルアセタール樹脂0.28g(8重量部)とを混合し、該第1の可塑剤に該ポリビニルアセタール樹脂を溶解させた溶液を得た。この試験管内の溶液を150℃に加熱した後、試験管を-20℃の雰囲気下に放置して溶液の温度を-15℃まで降下させた。このときに、溶液の一部に曇りが発生し始める温度を目視で観察し、該温度を曇点とした。
実施例の中間層で用いた各第1の可塑剤3.5g(100重量部)と、実施例の中間層で用いた各ポリビニルアセタール樹脂0.28g(8重量部)とを用意した。試験管(直径2cm)内で、該第1の可塑剤3.5g(100重量部)と、該ポリビニルアセタール樹脂0.28g(8重量部)とを混合し、該第1の可塑剤に該ポリビニルアセタール樹脂を溶解させた溶液を得た。この試験管内の溶液を150℃に加熱し、5℃、0℃及び-5℃の恒温室内に試験管を1時間放置した後、該恒温室の温度を保持して試験管内の溶液のヘーズをヘーズメーターで測定した。ヘーズが10%以上を示した最大温度を曇点とした。なお、ヘーズは、ヘーズメーター(東京電色社製「TC-HIIIDPK」)を用いて、JIS K6714に準拠して測定した。
(2-1)第1の曇点の判定方法による曇点
実施例及び比較例の中間層で用いた各第2の可塑剤3.5g(100重量部)と、実施例及び比較例の中間層で用いた各ポリビニルアセタール樹脂0.28g(8重量部)とを用意した。試験管(直径2cm)内で、該第2の可塑剤3.5g(100重量部)と、該ポリビニルアセタール樹脂0.28g(8重量部)とを混合し、該第2の可塑剤に該ポリビニルアセタール樹脂を溶解させた溶液を得た。この試験管内の溶液を150℃に加熱した後、試験管を-20℃の雰囲気下に放置して溶液の温度を-15℃まで降下させた。このときに、溶液の一部に曇りが発生し始める温度を目視で観察し、該温度を曇点とした。
実施例及び比較例の中間層で用いた各第2の可塑剤3.5g(100重量部)と、実施例の中間層で用いた各ポリビニルアセタール樹脂0.28g(8重量部)とを用意した。試験管(直径2cm)内で、該第2の可塑剤3.5g(100重量部)と、該ポリビニルアセタール樹脂0.28g(8重量部)とを混合し、該第2の可塑剤に該ポリビニルアセタール樹脂を溶解させた溶液を得た。この試験管内の溶液を150℃に加熱し、5℃、0℃及び-5℃の恒温室内に試験管を1時間放置した後、該恒温室の温度を保持して試験管内の溶液のヘーズをヘーズメーターで測定した。ヘーズが10%以上を示した最大温度を曇点とした。なお、ヘーズは、ヘーズメーター(東京電色社製「TC-HIIIDPK」)を用いて、JIS K6714に準拠して測定した。
得られた中間膜を23℃の環境下にて1ヶ月保管した直後に、中間膜を直径8mmの円形に切り抜き、粘弾性測定装置(レオメトリックス社製「ARES」)を用いて、せん断法にて、歪み量1.0%及び周波数1Hzの条件で、昇温速度5℃/分で動的粘弾性の温度分散測定を行うことにより、最も低温側に現れるtanδのピーク温度、最も低温側に現れるtanδのピーク温度におけるtanδの最大値、及び、最も高温側に現れるtanδのピーク温度におけるtanδの最大値を測定した。
損失係数の測定に用いる合わせガラスを20℃の環境下にて1ヶ月保管した。20℃の環境下にて1ヶ月保管した合わせガラスについて、測定装置「SA-01」(リオン社製)を用いて、20℃の条件で中央加振法により損失係数を測定した。得られた損失係数の共振周波数の4次モード(3150Hz付近)での損失係数(20℃損失係数)を評価した。
発泡試験Aに用いる合わせガラスを、実施例9~11,19~27の多層中間膜について5枚作製し、50℃のオーブン内に100時間放置した。放置後の合わせガラスにおいて、発泡の有無及び発泡の大きさを平面視にて目視で観察し、発泡の状態を下記の判定基準で判定した。
5枚の合わせガラスに発生した発泡を、楕円で近似し、その楕円面積を発泡面積とした。5枚の合わせガラスにて観察された楕円面積の平均値を求め、合わせガラスの面積(30cm×15cm)に対する楕円面積の平均値(発泡面積)の割合(百分率)を求めた。
○○:5枚全ての合わせガラスに発泡が観察されなかった
○:楕円面積の平均値(発泡面積)の割合が5%未満であった
△:楕円面積の平均値(発泡面積)の割合が5%以上、10%未満であった
×:楕円面積の平均値(発泡面積)の割合が10%以上であった
発泡試験Bに用いる合わせガラスを、実施例9~11,19~27の多層中間膜について30枚作製し、50℃のオーブン内に24時間放置した。放置後の合わせガラスにおいて、目視で発泡が観察された合わせガラスの枚数を確認し、下記の判定基準で判定した。
[発泡試験Bによる発泡の状態の判定基準]
○○:目視で発泡が観察された合わせガラスは5枚以下であった
○:目視で発泡が観察された合わせガラスは6枚以上、10枚以下であった
△:目視で発泡が観察された合わせガラスは11枚以上、15枚以下であった
×:目視で発泡が観察された合わせガラスは16枚以上であった
実施例9~11,19~27の合わせガラス用中間膜の第1の層に含まれる各ポリビニルアセタール樹脂(第1の層に用いるポリビニルアセタール樹脂)100重量部と、可塑剤としてトリエチレングリコールジ-2-エチルヘキサノエート(3GO)60重量部とを充分に混練し、混練物を得た。得られた混練物をプレス成型機でプレス成型して、平均厚さが0.35mmの樹脂膜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社製の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-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。また、得られた測定結果とガラス転移温度Tgとから、(Tg+30)℃での弾性率G’(Tg+30)の値と、(Tg+80)℃での弾性率G’(Tg+80)の値とを読み取った。また、比(G’(Tg+80)/G’(Tg+30))を求めた。
実施例9~11,19~27の合わせガラス用中間膜を恒温恒湿室(湿度30%(±3%)、温度23℃)に1ヶ月間保管した。1ヶ月間保管した後すぐに、表面層と中間層と表面層とを剥離することにより、中間層を取り出した。2枚のポリエチレンテレフタレート(PET)フィルムの間に配置された型枠(縦2cm×横2cm×厚み0.76mm)内に、剥離された中間層1gを置き、温度150℃、プレス圧0kg/cm2で10分間予熱した後、80kg/cm2で15分間プレス成型した。予め20℃に設定したハンドプレス機に、プレス成型された中間層を配置し、10MPaで10分間プレスすることにより冷却した。次いで、2枚のPETフィルムの間に配置された型枠から、1枚のPETフィルムを剥離し、樹脂膜Bを得た。樹脂膜Bを、恒温恒湿室(湿度30%(±3%)、温度23℃)で24時間保管した後、TAINSTRUMENTS社製の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-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。また、得られた測定結果とガラス転移温度Tgとから、(Tg+30)℃での弾性率G’(Tg+30)の値と、(Tg+80)℃での弾性率G’(Tg+80)の値とを読み取った。また、比(G’(Tg+80)/G’(Tg+30))を求めた。
(絶対分子量の測定)
上述した合成例3に記載の高分子量成分X,Yの割合を求めるための絶対分子量及びポリスチレン換算分子量は、得られた多層中間膜から表面層と中間層とを剥離して、以下のようにして求めた値である。
ARI=c×(dn/dc)×KRI ・・・式(1)
ARALS=c×M×(dn/dc)2×KRALS ・・・式(2)
ここで、cは溶液中のポリマー濃度、(dn/dc)は屈折率増分、Mは絶対分子量、Kは装置定数である。
可塑剤の含有量が、10重量%、15重量%、20重量%、25重量%、30重量%、35重量%、40重量%、45重量%及び50重量%となるように、THFに可塑剤を溶解させ、可塑剤-THF溶液を調製した。得られた可塑剤-THF溶液をGPC測定し、可塑剤のピーク面積を求めた。可塑剤の濃度に対し可塑剤のピーク面積をプロットし、近似直線を得た。次に、中間層をTHFに溶解させたTHF溶液をGPC測定し、可塑剤のピーク面積から近似直線を用いることにより、可塑剤の含有量を求めた。
上記絶対分子量の測定方法と同様にして、ゲルパーミエーションクロマトグラフィー(GPC)によるポリスチレン換算分子量を測定して、RI検出器で検出されるピーク面積(GPCの測定結果)のうち、分子量が100万以上の領域に相当する面積の割合から、ポリビニルアセタール樹脂に占める、分子量yが100万以上である高分子量成分Yの割合(%)を算出した。
1a…第1の表面
1b…第2の表面
2…第1の層
2a…第1の表面
2b…第2の表面
3…第2の層
3a…外側の表面
4…第3の層
4a…外側の表面
11…合わせガラス
21…第1の合わせガラス構成部材
22…第2の合わせガラス構成部材
Claims (27)
- 1層の構造又は2層以上の積層構造を有する合わせガラス用中間膜であって、
ポリビニルアセタール樹脂と可塑剤とを含む第1の層を備え、
前記第1の層に含まれている前記可塑剤は、第1の可塑剤を含有し、
前記第1の層に含まれている前記ポリビニルアセタール樹脂及び前記第1の可塑剤は、前記第1の可塑剤100重量部に前記ポリビニルアセタール樹脂8重量部を溶解させた液を用いて測定される曇点が5℃以下であるポリビニルアセタール樹脂及び第1の可塑剤である、合わせガラス用中間膜。 - 前記第1の層に含まれている前記ポリビニルアセタール樹脂及び前記第1の可塑剤は、前記第1の可塑剤100重量部に前記ポリビニルアセタール樹脂8重量部を溶解させた液を用いて測定される曇点が0℃以下であるポリビニルアセタール樹脂及び第1の可塑剤である、請求項1に記載の合わせガラス用中間膜。
- 前記第1の層に含まれている前記可塑剤は、前記第1の可塑剤とは異なる第2の可塑剤をさらに含有する、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の層に含まれている前記ポリビニルアセタール樹脂及び前記第2の可塑剤は、前記第2の可塑剤100重量部に前記ポリビニルアセタール樹脂8重量部を溶解させた液を用いて測定される曇点が5℃を超えるポリビニルアセタール樹脂及び第2の可塑剤である、請求項3に記載の合わせガラス用中間膜。
- 前記第1の層に含まれている前記可塑剤が、前記第1の可塑剤とは異なる第2の可塑剤を含まないか又は含み、
前記第1の層に含まれている全ての前記可塑剤の合計100重量%中、前記第1の可塑剤の含有量が1重量%以上であり、かつ前記第2の可塑剤の含有量が99重量%以下である、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の層に含まれている前記可塑剤が、前記第1の可塑剤とは異なる第2の可塑剤を含み、
前記第1の層に含まれている全ての前記可塑剤の合計100重量%中、前記第1の可塑剤の含有量が1重量%以上、99重量%以下であり、かつ前記第2の可塑剤の含有量が1重量%以上、99重量%以下である、請求項1~4のいずれか1項に記載の合わせガラス用中間膜。 - 周波数1Hzで測定した最も低温側に現れるtanδのピーク温度が0℃以下である、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。
- 周波数1Hzで測定した最も低温側に現れるtanδのピーク温度におけるtanδの最大値が1.15以上である、請求項1~7のいずれか1項に記載の合わせガラス用中間膜。
- 周波数1Hzで測定した最も高温側に現れるtanδのピーク温度におけるtanδの最大値が0.55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の層に含まれている前記ポリビニルアセタール樹脂のアセチル化度が30モル%を超える、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。
- 前記第1の層に含まれている前記ポリビニルアセタール樹脂のアセチル化度が10~45モル%であり、かつ水酸基の含有率が35モル%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。
- 前記第1の層に含まれている前記第1の可塑剤のSP値が13.5~14.5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。
- 2層以上の積層構造を有する合わせガラス用中間膜であって、
前記第1の層の第1の表面に積層されており、かつポリビニルアセタール樹脂と可塑剤とを含む第2の層をさらに備え、
前記第1の層中の前記ポリビニルアセタール樹脂100重量部に対する全ての前記可塑剤の合計の含有量が50重量部以上であり、
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、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低く、
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と前記第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との差が、9.2モル%以下であり、
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と前記第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との差が、8.5モル%を超え、9.2モル%以下である場合には、前記第1の層中の前記ポリビニルアセタール樹脂のアセチル化度が8モル%以下である、請求項1~15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の層中の前記ポリビニルアセタール樹脂が絶対分子量100万以上の高分子量成分を含み、かつ前記第1の層中の前記ポリビニルアセタール樹脂に占める、前記高分子量成分の割合が7.4%以上であるか、又は、前記第1の層中の前記ポリビニルアセタール樹脂がポリスチレン換算分子量100万以上の高分子量成分を含み、かつ前記第1の層中の前記ポリビニルアセタール樹脂に占める、前記高分子量成分の割合が9%以上である、請求項1~16のいずれか1項に記載の合わせガラス用中間膜。
- 前記第1の層を樹脂膜として用いて、該樹脂膜の粘弾性を測定した場合に、該樹脂膜のガラス転移温度をTg(℃)としたときに、(Tg+80)℃での弾性率G’(Tg+80)の(Tg+30)℃での弾性率G’(Tg+30)に対する比(G’(Tg+80)/G’(Tg+30))が、0.65以上である、請求項1~17のいずれか1項に記載の合わせガラス用中間膜。
- 前記第1の層に含まれる前記ポリビニルアセタール樹脂100重量部と、可塑剤としてトリエチレングリコールジ-2-エチルヘキサノエート(3GO)60重量部とを含む樹脂膜を用いて、該樹脂膜の粘弾性を測定した場合に、該樹脂膜のガラス転移温度をTg(℃)としたときに、(Tg+80)℃での弾性率G’(Tg+80)の(Tg+30)℃での弾性率G’(Tg+30)に対する比(G’(Tg+80)/G’(Tg+30))が、0.65以上である、請求項1~18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の層中の前記ポリビニルアセタール樹脂は、平均重合度が3000を超えるポリビニルアルコールをアセタール化することにより得られている、請求項1~19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の層中の前記ポリビニルアセタール樹脂のアセチル化度が8モル%以上であるか、又は前記第1の層中の前記ポリビニルアセタール樹脂のアセチル化度が8モル%未満であり、かつアセタール化度が68モル%以上である、請求項1~20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の層中の前記ポリビニルアセタール樹脂のアセチル化度が8モル%以上である、請求項21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アセチル化度が8モル%未満であり、かつアセタール化度が68モル%以上である、請求項21に記載の合わせガラス用中間膜。
- 前記第1の層と、
前記第1の層の第1の表面に積層されており、かつポリビニルアセタール樹脂と可塑剤とを含む第2の層と、
前記第1の層の前記第1の表面とは反対の第2の表面に積層されており、かつポリビニルアセタール樹脂と可塑剤とを含む第3の層をさらに備える、請求項1~23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,第3の層に含まれている前記ポリビニルアセタール樹脂のアセタール基の炭素数がそれぞれ3又は4であり、アセタール化度がそれぞれ60~75モル%であり、アセチル化度が10モル%以下である、請求項24に記載の合わせガラス用中間膜。
- 前記第2,第3の層における前記ポリビニルアセタール樹脂100重量部に対する前記可塑剤の含有量がそれぞれ5~50重量部である、請求項24又は25に記載の合わせガラス用中間膜。
- 第1の合わせガラス構成部材と、
第2の合わせガラス構成部材と、
前記第1,第2の合わせガラス構成部材の間に挟み込まれた中間膜とを備え、
前記中間膜が、請求項1~26のいずれか1項に記載の合わせガラス用中間膜である、合わせガラス。
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WO2012141002A1 (ja) * | 2011-04-14 | 2012-10-18 | 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 |
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US9809009B2 (en) | 2014-12-08 | 2017-11-07 | Solutia Inc. | Multiple layer interlayer having improved optical and sound insulation properties |
EP3279160A4 (en) * | 2015-03-31 | 2018-12-19 | Sekisui Chemical Co., Ltd. | Intermediate film for laminated glass, and laminated glass |
RU2017128467A (ru) * | 2015-03-31 | 2019-02-12 | Секисуй Кемикал Ко., Лтд. | Межслойная пленка для многослойного стекла и многослойное стекло |
US10350861B2 (en) * | 2015-07-31 | 2019-07-16 | Corning Incorporated | Laminate structures with enhanced damping properties |
EP3348531A4 (en) * | 2015-09-11 | 2019-05-08 | Sekisui Chemical Co., Ltd. | INTERMEDIATE LAYER FOR LAMINATED GLASS, AND LAMINATED GLASS |
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US10589495B2 (en) | 2016-06-21 | 2020-03-17 | Solutia Inc. | Polymeric interlayers and multiple layer panels made therefrom exhibiting enhanced properties and performance |
US20180117883A1 (en) | 2016-10-28 | 2018-05-03 | Kuraray America, Inc. | Wedge-shaped multilayer interlayer and glass laminate |
KR102473252B1 (ko) * | 2017-01-25 | 2022-12-05 | 쿠라라이 유럽 게엠베하 | 슬러리 조성물, 세라믹 그린 시트 및 도공 시트 |
KR101936085B1 (ko) * | 2017-06-15 | 2019-04-03 | 에스케이씨 주식회사 | 합판 유리용 수지 필름, 이를 포함하는 합판 유리 및 이의 제조방법 |
KR102589141B1 (ko) | 2017-07-31 | 2023-10-13 | 쿠라레이 아메리카 인코포레이티드 | 향상된 접착 특성을 갖는 아이오노머 중간층 |
CN111655647B (zh) | 2018-02-02 | 2023-06-20 | 积水化学工业株式会社 | 夹层玻璃用中间膜和夹层玻璃 |
US12017443B2 (en) | 2020-05-22 | 2024-06-25 | Kuraray Europe Gmbh | Interlayer and laminate with controlled debonding zone treatments with enhanced performance |
EP4263739A2 (en) | 2020-12-16 | 2023-10-25 | Kuraray Europe GmbH | Laminated structures with composite adhesive polymeric interlayer comprising cohesive debonding zones for enhanced performance |
WO2023096879A1 (en) | 2021-11-23 | 2023-06-01 | Kuraray Europe Gbmh | Interlayer and laminate with controlled debonding zone treatments |
US20230182448A1 (en) * | 2021-12-10 | 2023-06-15 | Chang Chun Petrochemical Co., Ltd. | Polymer film |
WO2023249853A1 (en) | 2022-06-22 | 2023-12-28 | Kuraray America, Inc. | Ionomer resin composition |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06926A (ja) * | 1992-04-23 | 1994-01-11 | Sekisui Chem Co Ltd | 合わせガラス用中間膜 |
JP2001048600A (ja) * | 1999-08-10 | 2001-02-20 | Sekisui Chem Co Ltd | 合わせガラス用中間膜及び合わせガラス |
JP2004067427A (ja) * | 2002-08-05 | 2004-03-04 | Sekisui Chem Co Ltd | 合わせガラス用中間膜および合わせガラス |
JP2007070200A (ja) | 2005-09-09 | 2007-03-22 | Asahi Glass Co Ltd | 合わせガラス |
Family Cites Families (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5340654A (en) * | 1992-04-23 | 1994-08-23 | Sekisui Kagaku Kogyo Kabushiki Kaisha | Interlayer film for laminated glass |
JPH06115979A (ja) * | 1992-09-29 | 1994-04-26 | Sekisui Chem Co Ltd | 遮音性合わせガラス用中間膜 |
JPH08109048A (ja) * | 1994-10-11 | 1996-04-30 | Sekisui Chem Co Ltd | 合わせガラス用中間膜および合わせガラス |
JP4986312B2 (ja) | 1999-03-25 | 2012-07-25 | 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 |
JP2001048601A (ja) * | 1999-08-17 | 2001-02-20 | Sekisui Chem Co Ltd | 合わせガラス用中間膜及び合わせガラス |
KR100458923B1 (ko) * | 2000-03-02 | 2004-12-03 | 세키스이가가쿠 고교가부시키가이샤 | 합판 유리용 중간막 및 합판 유리 |
JP4555855B2 (ja) | 2000-03-02 | 2010-10-06 | 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 |
KR100871775B1 (ko) | 2001-07-26 | 2008-12-05 | 세키스이가가쿠 고교가부시키가이샤 | 적층 유리용 중간막 및 적층 유리 |
JP2003252656A (ja) * | 2002-02-27 | 2003-09-10 | Sekisui Chem Co Ltd | 合わせガラス用中間膜及び合わせガラス |
JP2003252657A (ja) * | 2002-02-27 | 2003-09-10 | Sekisui Chem Co Ltd | 合わせガラス用中間膜及び合わせガラス |
JP2003252655A (ja) * | 2002-02-27 | 2003-09-10 | Sekisui Chem Co Ltd | 合わせガラス用中間膜及び合わせガラス |
US7491440B2 (en) | 2003-12-26 | 2009-02-17 | Sekisui Chemical Co., Ltd. | Interlayer film for laminate glass and laminate glass |
CA2567792A1 (en) | 2004-07-06 | 2006-01-12 | Sekisui Chemical Co., Ltd. | Interlayer laminated glass and laminated glass |
DE102004000023A1 (de) | 2004-08-17 | 2006-02-23 | Kuraray Specialities Europe Gmbh | Verfahren zur Herstellung von Folienlaminaten für Verbundverglasungen aus Teilfolien unterschiedlicher Zusammensetzung |
KR101211211B1 (ko) | 2004-09-02 | 2012-12-11 | 세키스이가가쿠 고교가부시키가이샤 | 유리 라미네이트용 중간막 및 유리 라미네이트 |
DE102004043907A1 (de) * | 2004-09-10 | 2006-03-16 | Kuraray Specialities Europe Gmbh | Weichmacherhaltige PVB-Folien mit Etherbindungen enthaltenden Carbonsäureestern als Co-Weichmacher |
BRPI0710907A2 (pt) * | 2006-04-25 | 2012-01-10 | Sekisui Chemical Co Ltd | pelìcula intermediária para vidro laminado e vidro laminado |
US8129027B2 (en) * | 2006-05-31 | 2012-03-06 | Sekisui Chemical Co., Ltd. | Interlayer film for laminated glass and laminated glass |
EP2053167B1 (en) | 2006-08-02 | 2018-10-31 | Komatsu Ltd. | Hybrid working vehicle |
KR101777536B1 (ko) | 2008-09-30 | 2017-09-11 | 세키스이가가쿠 고교가부시키가이샤 | 합판 유리용 중간막, 및 합판 유리 |
JP5258542B2 (ja) * | 2008-12-24 | 2013-08-07 | 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 |
KR20170086695A (ko) * | 2009-12-28 | 2017-07-26 | 세키스이가가쿠 고교가부시키가이샤 | 합판 유리용 중간막 및 합판 유리 |
EP2623474B1 (en) | 2010-09-30 | 2018-06-27 | Sekisui Chemical Co., Ltd. | Laminated glass interlayer and laminated glass |
US8795821B2 (en) * | 2011-04-14 | 2014-08-05 | Sekisui Chemical Co., Ltd. | Interlayer for laminated glass and laminated glass |
-
2011
- 2011-09-30 EP EP11829372.9A patent/EP2623474B1/en active Active
- 2011-09-30 CN CN201510390881.7A patent/CN104987638B/zh active Active
- 2011-09-30 JP JP2012504592A patent/JP5903378B2/ja active Active
- 2011-09-30 US US13/876,145 patent/US8741439B2/en active Active
- 2011-09-30 CN CN201180047671.8A patent/CN103140451B/zh active Active
- 2011-09-30 WO PCT/JP2011/072616 patent/WO2012043819A1/ja active Application Filing
- 2011-09-30 EP EP18172832.0A patent/EP3381680A1/en active Pending
-
2012
- 2012-02-01 JP JP2012019503A patent/JP4961059B1/ja active Active
- 2012-02-01 JP JP2012019504A patent/JP4961060B1/ja active Active
-
2014
- 2014-04-21 US US14/256,997 patent/US9764534B2/en active Active
-
2016
- 2016-03-02 JP JP2016039728A patent/JP6170582B2/ja active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06926A (ja) * | 1992-04-23 | 1994-01-11 | Sekisui Chem Co Ltd | 合わせガラス用中間膜 |
JP2001048600A (ja) * | 1999-08-10 | 2001-02-20 | Sekisui Chem Co Ltd | 合わせガラス用中間膜及び合わせガラス |
JP2004067427A (ja) * | 2002-08-05 | 2004-03-04 | Sekisui Chem Co Ltd | 合わせガラス用中間膜および合わせガラス |
JP2007070200A (ja) | 2005-09-09 | 2007-03-22 | Asahi Glass Co Ltd | 合わせガラス |
Non-Patent Citations (1)
Title |
---|
See also references of EP2623474A4 |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012141002A1 (ja) * | 2011-04-14 | 2012-10-18 | 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 |
US8795821B2 (en) | 2011-04-14 | 2014-08-05 | Sekisui Chemical Co., Ltd. | Interlayer for laminated glass and laminated glass |
CN105658595A (zh) * | 2014-01-15 | 2016-06-08 | 积水化学工业株式会社 | 夹层玻璃用中间膜及夹层玻璃 |
CN105658595B (zh) * | 2014-01-15 | 2019-04-12 | 积水化学工业株式会社 | 夹层玻璃用中间膜及夹层玻璃 |
US10946620B2 (en) | 2014-01-15 | 2021-03-16 | Sekisui Chemical Co., Ltd. | Interlayer film for laminated glass, and laminated glass |
US11826988B2 (en) | 2014-01-15 | 2023-11-28 | Sekisui Chemical Co., Ltd. | Interlayer film for laminated glass, and laminated glass |
JP2018501125A (ja) * | 2014-12-08 | 2018-01-18 | ソルティア・インコーポレーテッド | 向上した特性を有するポリ(ビニルアセタール)樹脂組成物、層、及び中間膜 |
JP2016188371A (ja) * | 2015-03-27 | 2016-11-04 | 株式会社クラレ | ポリビニルアセタール組成物、該組成物からなるシートおよびその用途 |
EP3248577A1 (en) * | 2016-05-25 | 2017-11-29 | Elacin International B.V. | Method for determining a measure for the sound attenuation provided by a hearing protector ear plug as well as a related computing device |
NL2016825A (en) * | 2016-05-25 | 2017-11-30 | Elacin Int B V | A method for determining a measure for the sound attenuation provided by a hearing protector ear plug as well as a related computing device. |
WO2023100928A1 (ja) * | 2021-12-01 | 2023-06-08 | 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 |
WO2024122513A1 (ja) * | 2022-12-05 | 2024-06-13 | 積水化学工業株式会社 | ポリビニルアセタール樹脂、合わせガラス用中間膜、積層体及び合わせガラス |
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CN104987638A (zh) | 2015-10-21 |
JP2016145149A (ja) | 2016-08-12 |
JP6170582B2 (ja) | 2017-07-26 |
US20140227537A1 (en) | 2014-08-14 |
US20130183532A1 (en) | 2013-07-18 |
JP2013032260A (ja) | 2013-02-14 |
EP2623474A1 (en) | 2013-08-07 |
JP4961060B1 (ja) | 2012-06-27 |
JPWO2012043819A1 (ja) | 2014-02-24 |
CN103140451B (zh) | 2015-08-05 |
US8741439B2 (en) | 2014-06-03 |
EP3381680A1 (en) | 2018-10-03 |
US9764534B2 (en) | 2017-09-19 |
CN103140451A (zh) | 2013-06-05 |
JP4961059B1 (ja) | 2012-06-27 |
CN104987638B (zh) | 2017-11-14 |
JP5903378B2 (ja) | 2016-04-13 |
JP2013032261A (ja) | 2013-02-14 |
EP2623474B1 (en) | 2018-06-27 |
EP2623474A4 (en) | 2015-01-21 |
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