WO2013042771A1 - 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
- WO2013042771A1 WO2013042771A1 PCT/JP2012/074248 JP2012074248W WO2013042771A1 WO 2013042771 A1 WO2013042771 A1 WO 2013042771A1 JP 2012074248 W JP2012074248 W JP 2012074248W WO 2013042771 A1 WO2013042771 A1 WO 2013042771A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- laminated glass
- layer
- mol
- polyvinyl acetal
- acetal resin
- Prior art date
Links
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- 239000011354 acetal resin Substances 0.000 claims abstract description 139
- 229920006324 polyoxymethylene Polymers 0.000 claims abstract description 139
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 123
- 239000004014 plasticizer Substances 0.000 claims abstract description 73
- 230000021736 acetylation Effects 0.000 claims description 57
- 238000006640 acetylation reaction Methods 0.000 claims description 57
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- 239000011347 resin Substances 0.000 claims description 45
- 239000011521 glass Substances 0.000 claims description 30
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 23
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- 238000009413 insulation Methods 0.000 abstract description 50
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- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 25
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- 125000004432 carbon atom Chemical group C* 0.000 description 7
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- 230000035484 reaction time Effects 0.000 description 6
- FRQDZJMEHSJOPU-UHFFFAOYSA-N Triethylene glycol bis(2-ethylhexanoate) Chemical compound CCCCC(CC)C(=O)OCCOCCOCCOC(=O)C(CC)CCCC FRQDZJMEHSJOPU-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
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Images
Classifications
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- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
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- B32B17/10005—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
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—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
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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
-
- 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
-
- 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
-
- 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
- Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon
Definitions
- the present invention relates to an interlayer film for laminated glass used for laminated glass for automobiles and buildings, and more particularly to an interlayer film for laminated glass containing a polyvinyl acetal resin and a plasticizer.
- the present invention also relates to a laminated glass using the interlayer film for laminated glass.
- 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.
- the interlayer film As sound for soundproofing by the interlayer film, there are air sound such as car noise or horn sound and solid sound such as sound caused by car engine vibration. In the laminated glass using the intermediate film described in Patent Document 1, the sound insulation of solid sound may not be sufficiently high.
- 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.
- An object of the present invention is to provide an interlayer film for laminated glass that can enhance sound insulation in the obtained laminated glass, and a laminated glass using the interlayer film for laminated glass. Is to provide.
- a limiting object of the present invention is to provide an interlayer film for laminated glass that can enhance sound insulation in a high frequency range in the obtained laminated glass when used for constituting laminated glass, and the laminated glass. It is to provide a laminated glass using an interlayer film.
- a first layer and a second layer laminated on the first surface of the first layer are provided, and the first layer includes a polyvinyl acetal resin and a plastic layer.
- An interlayer film for laminated glass comprising an agent and a tackifier is provided.
- the second layer includes a polyvinyl acetal resin, and the degree of acetylation of the polyvinyl acetal resin in the second layer is the first level. It is lower than the degree of acetylation of the polyvinyl acetal resin in the layer.
- the second layer contains a polyvinyl acetal resin and a plasticizer, and the above-mentioned amount relative to 100 parts by weight of the polyvinyl acetal resin in the second layer.
- the content of the plasticizer in the second layer is less than the content of the plasticizer in the first layer relative to 100 parts by weight of the polyvinyl acetal resin in the first layer.
- the second layer contains a polyvinyl acetal resin having an acetylation degree of 30 mol% or less.
- a third layer laminated on a second surface opposite to the first surface of the first layer is further provided,
- the third layer contains a polyvinyl acetal resin, and the degree of acetylation of the polyvinyl acetal resin in the third layer is lower than the degree of acetylation of the polyvinyl acetal resin in the first layer.
- the third layer includes a polyvinyl acetal resin and a plasticizer, and relative to 100 parts by weight of the polyvinyl acetal resin in the third layer.
- the plasticizer content in the third layer is less than the plasticizer content in the first layer relative to 100 parts by weight of the polyvinyl acetal resin in the first layer.
- the third layer includes a polyvinyl acetal resin having an acetylation degree of 30 mol% or less.
- the tackifier is a rosin resin.
- the laminated glass according to the present invention includes a first laminated glass member, a second laminated glass member, and an intermediate film sandwiched between the first laminated glass member and the second laminated glass member.
- 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 and a second layer laminated on the first surface of the first layer, and the first layer is a polyvinyl acetal. Since resin, a plasticizer, and a tackifier are included, the sound insulation of the laminated glass using the intermediate film for laminated glasses which concerns on this invention can be improved.
- 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. 1 schematically shows a partially cutaway sectional view of an interlayer film for laminated glass according to an embodiment of the present invention.
- 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 member is sufficiently increased.
- the main feature of the present embodiment is that the intermediate film 1 includes a first layer 2 and a second layer 3 laminated on the first surface 2a of the first layer 2, and further the first layer 2 Includes a polyvinyl acetal resin, a plasticizer, and a tackifier.
- the sound insulation of the interlayer film for laminated glass using the interlayer film 1 can be enhanced.
- the sound insulation in the high frequency range of the laminated glass using the intermediate film 1 can also be improved. In particular, it is possible to effectively enhance sound insulation in a high frequency region exceeding 3 kHz.
- the second and third layers 3 and 4 are laminated one by one on both surfaces of the first layer 2. It is only necessary that the second layer is laminated on at least one 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. However, it is preferable that 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 first layer includes a polyvinyl acetal resin (hereinafter, may be referred to as a polyvinyl acetal resin (1)) that is a thermoplastic resin.
- the polyvinyl acetal resin (1) in the first layer is not particularly limited. As for the said polyvinyl acetal resin (1), only 1 type may be used and 2 or more types may be used together.
- the second layer preferably contains a thermoplastic resin, and more preferably contains a polyvinyl acetal resin (hereinafter sometimes referred to as a polyvinyl acetal resin (2)).
- the third layer preferably includes a thermoplastic resin, and more preferably includes a polyvinyl acetal resin (hereinafter sometimes referred to as a polyvinyl acetal resin (3)).
- the adhesive force of a 2nd, 3rd layer and a laminated glass member will become high enough.
- only one type of the thermoplastic resin may be used, or two or more types may be used in combination.
- thermoplastic resin used for the second and third layers is not particularly limited.
- polyvinyl acetal resins (2) and (3) used for the second and third layers are not particularly limited.
- thermoplastic resin examples include polyvinyl acetal resin, ethylene-vinyl acetate copolymer resin, ethylene-acrylic copolymer resin, polyurethane resin, and polyvinyl alcohol resin.
- the degree of acetylation (acetyl group amount) of the polyvinyl acetal resin (1) is preferably 0 mol% or more, preferably 50 mol% or less. From the viewpoint of further improving the sound insulation of the laminated glass, the acetylation degree (acetyl group amount) of the polyvinyl acetal resin (1) is more preferably 10 mol% or more, and more preferably 45 mol% or less.
- the polyvinyl acetal resin (1) may have a degree of acetylation of 30 mol% or less. In order to further improve the sound insulation of the laminated glass, the degree of acetylation of the polyvinyl acetal resin (1) in the first layer is preferably more than 30 mol%.
- the degree of acetylation of the polyvinyl acetal resin (1) in the first layer is 30 mol%. Is preferably exceeded. Moreover, the compatibility of polyvinyl acetal resin (1) and the plasticizer (1) mentioned later becomes high that the acetylation degree of the said polyvinyl acetal resin (1) is more than the said minimum.
- the degree of acetylation of the polyvinyl acetal resins (2) and (3) is preferably 0 mol% or more, more preferably 0.1 mol% or more, still more preferably 0.5 mol% or more, preferably 30 mol%. Below, more preferably 20 mol% or less, still more preferably 10 mol% or less, particularly preferably 5 mol% or less, and most preferably 3 mol% or less.
- the acetylation degree is not more than the above upper limit, the penetration resistance of the interlayer film and the laminated glass is increased. Furthermore, when the degree of acetylation is not more than the above upper limit, bleed out of the plasticizer can be suppressed.
- the degree of acetylation of the polyvinyl acetal resin in the polyvinyl acetal resins (2) and (3) is 3 mol% or less, the mechanical properties of the interlayer film are further improved. As a result, the penetration resistance of the laminated glass is further increased.
- the degree of acetylation of the polyvinyl acetal resin (2) is preferably lower than the degree of acetylation of the polyvinyl acetal resin (1).
- the degree of acetylation of the polyvinyl acetal resin (3) is preferably lower than the degree of acetylation of the polyvinyl acetal resin (1).
- the absolute value of the difference from the degree of acetylation is preferably 10 mol% or more, more preferably 20 mol% or more, preferably 50 mol% or less, more preferably 30 mol% or less.
- the absolute value of the difference between the degree of acetylation of the polyvinyl acetal resin (1) and the degree of acetylation of the polyvinyl acetal resins (2) and (3) is not less than the lower limit and not more than the upper limit, the interlayer film and the laminated glass The sound insulation and penetration resistance of the material are further enhanced.
- 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 ethylene group to which the acetal group is bonded can be measured, for example, according to JIS K6728 “Testing method for polyvinyl butyral”.
- the polyvinyl acetal resins (1), (2), and (3) can be produced, for example, by acetalizing polyvinyl alcohol with 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), (2), (3) is preferably 200 or more, more preferably 500 or more, still more preferably 1600 or more, particularly preferably 2600 or more. Most preferably, it is 2700 or more, preferably 5000 or less, more preferably 4000 or less, and still more preferably 3500 or less.
- the average degree of polymerization is not less than the above lower limit, the penetration resistance of the laminated glass is further enhanced.
- the average degree of polymerization is not more than the above upper limit, the intermediate film can be easily molded.
- the average polymerization degree of the polyvinyl alcohol is preferably 2600 or more, more preferably 2700 or more.
- the plate displacement refers to a phenomenon in which the other glass plate is displaced with respect to one glass plate due to the weight of the glass plate when the laminated glass is stored in a high temperature environment in a state where the laminated glass is leaned.
- the average degree of polymerization of the polyvinyl alcohol is particularly preferably 2700 or more and 5000 or less.
- the average degree of polymerization of the polyvinyl alcohol used to obtain the polyvinyl acetal resin (1) in the first layer is 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 the polyvinyl alcohol used in the above, preferably higher than 500, preferably higher than 800, more preferably higher than 1000, still more preferably higher than 1300, more preferably higher than 1800. Is particularly preferred.
- 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 resins (1), (2) and (3) are preferably polyvinyl butyral resins.
- the interlayer film for laminated glass according to the present invention preferably contains a polyvinyl butyral resin as the polyvinyl acetal resins (1), (2), and (3) in the first, second, and third layers, respectively. . 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 member. Furthermore, light resistance, weather resistance, etc. become still higher.
- the hydroxyl group content (hydroxyl group amount) of the polyvinyl acetal resin (1) is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 15 mol% or more, preferably 45 mol% or less, more preferably. Is 35 mol% or less, more preferably 30 mol% or less, and particularly preferably 25 mol% or less.
- the content of the hydroxyl group is not less than the lower limit, the mechanical properties of the interlayer film are further enhanced.
- the sound insulation of laminated glass becomes still higher that the content rate of the said hydroxyl group is below the said upper limit.
- the flexibility of the interlayer film is increased, and the handling of the interlayer film is facilitated. From the viewpoint of further improving the sound insulation 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%.
- the content of hydroxyl groups (hydroxyl content) in the polyvinyl acetal resins (2) and (3) is preferably 20 mol% or more, more preferably 25 mol% or more, still more preferably 30 mol% or more, preferably 50 mol. % Or less, more preferably 45 mol% or less, still more preferably 40 mol% or less, particularly preferably 35 mol% or less, and most preferably 32 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 in the polyvinyl acetal resin (1) in the first layer is determined by the polyvinyl acetal resin (2 in the second and third layers).
- (3) are preferably lower than the respective hydroxyl group contents.
- the content of hydroxyl groups in the polyvinyl acetal resin (1) in the first layer is determined by the polyvinyl acetal resin (2 in the second and third layers). ), (3) preferably 1 mol% or less, more preferably 3 mol% or less, still more preferably 5 mol% or less, particularly preferably 7 mol% or less. preferable.
- the hydroxyl group content of the polyvinyl acetal resins (1), (2), and (3) is the molar fraction obtained by dividing the amount of ethylene groups bonded to the hydroxyl group by the total amount of ethylene groups in the main chain. It is a value expressed in percentage (mol%).
- the degree of acetalization of the polyvinyl acetal resin (1) is preferably 20 mol% or more, more preferably 25 mol% or more, still more preferably 30 mol% or more, preferably 65 The mol% or less, more preferably 60 mol% or less, and still more preferably 55 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 is increased, and bleeding out of the plasticizer 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 (degree of butyralization in the case of polyvinyl butyral resin) of the polyvinyl acetal resins (2) and (3) is preferably 55 mol% or more, more preferably 60 mol% or more, and still more preferably 63 mol%. As mentioned above, Preferably it is 85 mol% or less, More preferably, it is 75 mol% or less, More preferably, it is 70 mol% or less.
- the degree of acetalization is not less than the above lower limit, the compatibility between the polyvinyl acetal resins (2) and (3) and the plasticizer is increased.
- the degree of acetalization is less than or equal to the above upper limit, the reaction time required for producing a polyvinyl acetal resin is shortened.
- the degree of acetalization is 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 was determined by measuring the degree of acetylation (degree of acetylation) and the content of hydroxyl groups (vinyl alcohol content) by a method in accordance with JIS K6728 “Testing methods for polyvinyl butyral”. It can be calculated by calculating the fraction and then subtracting the degree of acetylation and the hydroxyl content from 100 mol%.
- the degree of acetalization (degree of butyralization) and the degree of acetylation are measured by a method based on JIS K6728 “Testing methods for polyvinyl butyral” or ASTM D1396-92. Can be calculated from the results. It is preferable to measure by a method based on ASTM D1396-92.
- the polyvinyl acetal resin (1) in the first layer is a polyvinyl acetal resin (hereinafter referred to as “polyvinyl acetal resin” having an acetylation degree of less than 8 mol%. A ”) or a polyvinyl acetal resin having an acetylation degree of 8 mol% or more (hereinafter also referred to as“ polyvinyl acetal resin B ”).
- the polyvinyl acetal resin (1) is preferably the polyvinyl acetal resin A, and is preferably the polyvinyl acetal resin B.
- 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 A 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 a polyvinyl alcohol resin 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 resin 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, and the preferred upper limit is 6000, preferred.
- the upper limit is 5000, the preferred upper limit is 4900, and the preferred upper limit is 4500.
- the polyvinyl acetal resins A and B in the first layer are particularly preferably obtained by acetalizing a polyvinyl alcohol resin having an average degree of polymerization of more than 3000 and less than 4000.
- the average degree of polymerization of the polyvinyl alcohol resin used for obtaining B is preferably 3010 or more, more preferably 3020 or more, preferably 4000 or less, more preferably less than 4000, It is more preferably 3800 or less, particularly preferably 3600 or less, and most preferably 3500 or less.
- 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)).
- a plasticizer (1), (2), and (3) may be used alone or in combination of two or more.
- plasticizers (1), (2), and (3) examples include organic ester plasticizers such as monobasic organic acid esters and polybasic organic acid esters, and organic phosphate plasticizers and organic phosphorous acids. Examples thereof include organic phosphate plasticizers such as plasticizers. Of these, organic ester plasticizers are preferred.
- the plasticizers (1), (2) and (3) are preferably liquid plasticizers.
- 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) in the first layer is preferably a diester plasticizer represented by the following formula (1).
- the plasticizers (2) and (3) in the second and third layers are each a diester plasticizer represented by the following formula (1). preferable.
- R1 and R2 each represents an organic group having 5 to 10 carbon atoms
- R3 represents an ethylene group, an isopropylene group or an n-propylene group
- p represents an integer of 3 to 10 .
- the plasticizers (1), (2) and (3) are each at least one of triethylene glycol di-2-ethylhexanoate (3GO) and triethylene glycol di-2-ethylbutyrate (3GH). It preferably contains a species and more preferably contains triethylene glycol di-2-ethylhexanoate.
- the content of the plasticizer (1) is preferably 25 parts by weight or more and preferably 80 parts by weight or less with respect to 100 parts by weight of the polyvinyl acetal resin (1).
- the content of the plasticizer (1) in the first layer is more preferably 30 weights with respect to 100 parts by weight of the polyvinyl acetal resin (1).
- the content of the plasticizer (1) is not less than the above lower limit, the flexibility of the interlayer film is increased, the handling of the interlayer film is facilitated, and the penetration resistance of the laminated glass is further increased.
- the content of the plasticizer (1) is not more than the above upper limit, the transparency of the interlayer film is further increased.
- the content of the plasticizer (2) is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, further preferably 100 parts by weight of the polyvinyl acetal resin (2). 15 parts by weight or more, preferably 50 parts by weight or less, more preferably 45 parts by weight or less, and still more preferably 40 parts by weight or less.
- the content of the plasticizer (3) is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, further preferably 100 parts by weight of the polyvinyl acetal resin (3). 15 parts by weight or more, preferably 50 parts by weight or less, more preferably 45 parts by weight or less, and still more preferably 40 parts by weight or less.
- the content of the plasticizers (2) and (3) is not less than the above lower limit, the flexibility of the interlayer film is increased and the handling of the interlayer film is facilitated.
- the content of the plasticizers (2) and (3) is not more than the above upper limit, the penetration resistance of the laminated glass is further enhanced.
- the content of the plasticizer (2) in the second layer relative to 100 parts by weight of the polyvinyl acetal resin (2) in the second layer (hereinafter sometimes referred to as content (2)) is The content of the plasticizer (1) in the first layer relative to 100 parts by weight of the polyvinyl acetal resin (1) in the first layer (hereinafter sometimes referred to as content (1)) Is preferably less.
- the content of the plasticizer (3) in the third layer relative to 100 parts by weight of the polyvinyl acetal resin (3) in the third layer (hereinafter sometimes referred to as content (3)). ) May be described as the content of the plasticizer (1) in the first layer relative to 100 parts by weight of the polyvinyl acetal resin (1) in the first layer (hereinafter referred to as content (1)). Less).
- the absolute value of the difference between the content (1) and the content (2) and the absolute value of the difference between the content (1) and the content (3) are each preferably 10 parts by weight or more.
- the amount is preferably 15 parts by weight or more, more preferably 20 parts by weight or more, preferably 40 parts by weight or less, more preferably 35 parts by weight or less, and still more preferably 30 parts by weight or less.
- the first layer includes a tackifier.
- the adhesion of the first layer to the second and third layers is further improved, and the penetration resistance of the laminated glass is further enhanced.
- the present inventors have found that the sound insulation of the laminated glass can be enhanced by the first layer containing a tackifier.
- the said 1st layer can also improve the sound-insulating property in the high frequency range of a laminated glass because a tackifier is included.
- tackifier examples include rosin resin, terpene resin and petroleum resin. As for the said tackifier, only 1 type may be used and 2 or more types may be used together. Each of the second and third layers may or may not contain the tackifier.
- the tackifier is preferably a rosin resin.
- the rosin resin is a resin based on rosin or a rosin derivative.
- the rosin resin include rosin, acid-modified rosin, rosin-containing diol, rosin ester, hydrogenated rosin ester and maleic acid-modified rosin ester.
- the acid-modified rosin include acrylic acid-modified rosin.
- the content of the tackifier is preferably 10 parts by weight or more, more preferably 20 parts by weight or more, still more preferably 25 parts by weight with respect to 100 parts by weight of the polyvinyl acetal resin (1) in the first layer. Above, particularly preferably 30 parts by weight or more, most preferably 50 parts by weight or more, preferably 500 parts by weight or less, more preferably 300 parts by weight or less, still more preferably 100 parts by weight or less, particularly preferably 90 parts by weight or less. .
- the content of the tackifier is not less than the above lower limit, the sound insulating property of the laminated glass is further enhanced.
- content of the said tackifier exceeds the said upper limit, a tackifier may become excess in order to improve sound-insulating property.
- Each of the first, second, and third layers is, if necessary, an ultraviolet absorber, an antioxidant, a light stabilizer, a flame retardant, an antistatic agent, a pigment, a dye, an adhesive force adjusting agent, a moisture resistant agent, Additives such as fluorescent brighteners and infrared absorbers may be included. As for these additives, only 1 type may be used and 2 or more types may be used together.
- the 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 preferably 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 preferably 1.15 or more, more preferably 1.25. That's it.
- 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 0.50 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 is preferably performed after the interlayer film for laminated glass is stored in an environment of 23 ° C. for one month.
- the thickness of the first layer is preferably 0.02 mm or more, more preferably 0.05 mm or more, preferably 1.8 mm or less, more preferably 0.5 mm or less.
- the thickness of the first layer 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 laminated glass are further enhanced.
- the thicknesses of the second and third layers are each preferably 0.1 mm or more, more preferably 0.2 mm or more, preferably 1 mm or less, more preferably 0.5 mm or less.
- the thickness of the second and third layers are not less than the above lower limit and not more than the above upper limit, the thickness of the intermediate film is not excessively increased, and the sound insulation of the laminated glass is further enhanced, and further, the plasticizer bleed out. Can be suppressed.
- the thickness of the interlayer film for laminated glass according to the present invention is preferably 0.1 mm or more, more preferably 0.25 mm or more, preferably 3 mm or less, more preferably 1.5 mm or less.
- the thickness of the interlayer film is not less than the above lower limit, the penetration resistance of the laminated glass is sufficiently increased.
- the thickness of the interlayer film is not more than the above upper limit, the transparency of the interlayer film is further improved.
- 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 More preferably, the same plasticizer is contained, and the second and third layers are more preferably 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.
- the laminated glass 11 shown in FIG. 2 includes an intermediate film 1 and first and second laminated glass members 21 and 22.
- the intermediate film 1 is sandwiched between the first and second laminated glass members 21 and 22.
- a first laminated glass member 21 is laminated on the first surface 1 a of the intermediate film 1.
- a second laminated glass member 22 is laminated on a second surface 1 b opposite to the first surface 1 a of the intermediate film 1.
- a first laminated glass member 21 is laminated on the outer surface 3 a of the second layer 3.
- a second laminated glass member 22 is laminated on the outer surface 4 a of the third layer 4.
- the laminated glass according to the present invention includes the first laminated glass member, the second laminated glass member, and the intermediate film sandwiched between the first and second laminated glass members.
- the interlayer film for laminated glass of the present invention is used as the interlayer film.
- first and second laminated glass 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 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 intermediate film is 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, thereby the first and second laminated glasses.
- the air remaining between the member and the intermediate film is deaerated. 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 is 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 laminated glass for vehicles.
- the said intermediate film and the said laminated glass can be used besides these uses.
- 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.
- Laminated glass can be used for a windshield, side glass, rear glass, roof glass, or the like of an automobile.
- Polyvinyl butyral resin a A polyvinyl butyral resin (average polymerization degree 3000) having an acetylation degree of 0.5 mol%, a butyralization degree of 40 mol%, and a hydroxyl group content of 59.5 mol% was dissolved in pyridine. A molar equivalent of acetic anhydride was added, and the mixture was 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 a (average polymerization degree 3000). The obtained polyvinyl butyral resin a had an acetylation degree of 30.5 mol%, a butyralization degree of 40 mol%, and a hydroxyl group content of 29.5 mol%.
- Polyvinyl butyral resin b A polyvinyl butyral resin (average polymerization degree 3000) having an acetylation degree of 0.5 mol%, a butyralization degree of 55 mol%, and a hydroxyl group content of 44.5 mol% was dissolved in pyridine. 0.5 molar equivalent of acetic anhydride was added, and the mixture was 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 b (average polymerization degree 3000). The obtained polyvinyl butyral resin b had an acetylation degree of 20.5 mol%, a butyralization degree of 55 mol%, and a hydroxyl group content of 24.5 mol%.
- Polyvinyl acetal resin c Degree of acetylation 12.8 mol%, degree of butyral 63.5 mol%, hydroxyl group content 23.7 mol%
- Polyvinyl acetal resin d acetylation degree 1 mol%, butyralization degree 68.5 mol%, hydroxyl group content 30.5 mol%
- Polyvinyl acetal resin e Degree of acetylation 7.1 mol%, degree of butyral 72.5 mol%, hydroxyl group content 20.4 mol%
- Polyvinyl acetal resin f Degree of acetylation 1.0 mol%, degree of butyral 81.2 mol%, hydroxyl group content 17.8 mol%
- Example 1 100 parts by weight of the obtained polyvinyl butyral resin a (degree of acetylation 30.5 mol%), 50 parts by weight of triethylene glycol di-2-ethylhexanoate as a plasticizer, and a rosin resin (tackifier) 50 parts by weight of “Pine Crystal KE-311” manufactured by Arakawa Chemical Co., Ltd.) was 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 0.35 mm) / intermediate layer A (thickness 0.1 mm) / protective layer B (thickness) An intermediate film (thickness 0.8 mm) having a laminated structure of 0.35 mm) was produced.
- the obtained multilayer intermediate film was cut into a length of 30 mm and a width of 320 mm.
- the multilayer intermediate film is sandwiched between two transparent float glasses (length 25 mm ⁇ width 305 mm ⁇ thickness 2.0 mm), held at 90 ° C. for 30 minutes with a vacuum laminator, vacuum pressed, Obtained.
- the intermediate film portion protruding from the glass was cut off to obtain a laminated glass.
- Examples 2 to 15 and Comparative Example 1 Except that the types and contents of the polyvinyl butyral resin used for the intermediate layer A and the protective layer B, the contents of the plasticizer, and the types and contents of the tackifying resin are set as shown in Tables 1 and 2 below. In the same manner as in Example 1, an interlayer film and a laminated glass were obtained.
- tackifiers shown in Tables 1 and 2 below are as follows. Rosin resin ("Pine Crystal KE-311” manufactured by Arakawa Chemical Co., Ltd.) Acrylic acid modified rosin ("Pine Crystal KE-604" manufactured by Arakawa Chemical Co., Ltd.) Rosin-containing diol (“Pine Crystal D-6011” manufactured by Arakawa Chemical Co., Ltd.) Rosin resin ("Pine Crystal KR-120” manufactured by Arakawa Chemical Co., Ltd.) Rosin resin (“Pine Crystal KR-614” manufactured by Arakawa Chemical Co., Ltd.) Rosin resin (“Pine Crystal KR-85” manufactured by Arakawa Chemical Co., Ltd.)
- the peak temperature of tan ⁇ appearing at the lowest temperature side By measuring the temperature dispersion of dynamic viscoelasticity, the peak temperature of tan ⁇ appearing at the lowest temperature side, the maximum value of tan ⁇ at the peak temperature of tan ⁇ appearing at the lowest temperature side, and the peak temperature of tan ⁇ appearing at the highest temperature side. The maximum value of tan ⁇ was measured.
- the obtained laminated glass was stored in an environment of 20 ° C. for 1 month. With respect to the laminated glass 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). 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.
Landscapes
- Joining Of Glass To Other Materials (AREA)
Abstract
Description
上記第1の層は、熱可塑性樹脂である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1の層中のポリビニルアセタール樹脂(1)は特に限定されない。上記ポリビニルアセタール樹脂(1)は1種のみが用いられてもよく、2種以上が併用されてもよい。
上記第1の層は、可塑剤(以下、可塑剤(1)と記載することがある)を含む。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),(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の層は粘着付与剤を含む。上記第1の層が粘着付与剤を含むことにより、上記第1の層の上記第2,第3の層に対する接着性がより一層良好になり、合わせガラスの耐貫通性がより一層高くなる。さらに、本発明者らは、上記第1の層が粘着付与剤を含むことにより、合わせガラスの遮音性をも高めることができることを見出した。さらに、上記第1の層が粘着付与剤を含むことにより、合わせガラスの高周波域での遮音性も高めることができる。
上記第1,第2,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、好ましくは0℃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。
ポリビニルブチラール樹脂a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a(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aのアセチル化度は30.5モル%、ブチラール化度は40モル%、水酸基の含有率は29.5モル%であった。
ポリビニルブチラール樹脂bの合成:
アセチル化度0.5モル%、ブチラール化度55モル%、水酸基の含有率44.5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、39.5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b(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bのアセチル化度は20.5モル%、ブチラール化度は55モル%、水酸基の含有率は24.5モル%であった。
ポリビニルアセタール樹脂d:アセチル化度1モル%、ブチラール化度68.5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e:アセチル化度7.1モル%、ブチラール化度72.5モル%、水酸基の含有率20.4モル%
ポリビニルアセタール樹脂f:アセチル化度1.0モル%、ブチラール化度81.2モル%、水酸基の含有率17.8モル%
得られたポリビニルブチラール樹脂a(アセチル化度30.5モル%)100重量部と、可塑剤であるトリエチレングリコールジ-2-エチルヘキサノエート50重量部と、粘着付与剤であるロジン樹脂(荒川化学社製「パインクリスタルKE-311」)50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。
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の種類及び含有量、可塑剤の含有量、並びに粘着付与樹脂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、中間膜及び合わせガラスを得た。
ロジン樹脂(荒川化学社製「パインクリスタルKE-311」)
アクリル酸変性ロジン(荒川化学社製「パインクリスタルKE-604」)
ロジン含有ジオール(荒川化学社製「パインクリスタルD-6011」)
ロジン樹脂(荒川化学社製「パインクリスタルKR-120」)
ロジン樹脂(荒川化学社製「パインクリスタルKR-614」)
ロジン樹脂(荒川化学社製「パインクリスタルKR-85」)
(1)低温側のtanδのピーク温度、低温側のtanδのピーク最大値、高温側のtanδのピーク最大値
得られた中間膜を23℃の環境下にて1ヶ月保管した後に、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。
得られた合わせガラスを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。
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の合わせガラス部材
22…第2の合わせガラス部材
Claims (9)
- 第1の層と、
前記第1の層の第1の表面に積層された第2の層とを備え、
前記第1の層が、ポリビニルアセタール樹脂と、可塑剤と、粘着付与剤とを含む、合わせガラス用中間膜。 - 前記第2の層が、ポリビニルアセタール樹脂を含み、
前記第2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よりも低い、請求項1に記載の合わせガラス用中間膜。 - 前記第2の層が、ポリビニルアセタール樹脂と可塑剤とを含み、
前記第2の層中の前記ポリビニルアセタール樹脂100重量部に対する前記第2の層中の前記可塑剤の含有量が、前記第1の層中の前記ポリビニルアセタール樹脂100重量部に対する前記第1の層中の前記可塑剤の含有量よりも少ない、請求項1又は2に記載の合わせガラス用中間膜。 - 前記第2の層は、アセチル化度が30モル%以下であるポリビニルアセタール樹脂を含む、請求項1~3のいずれか1項に記載の合わせガラス用中間膜。
- 前記第1の層の前記第1の表面とは反対の第2の表面に積層された第3の層をさらに備え、
前記第3の層が、ポリビニルアセタール樹脂を含み、
前記第3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よりも低い、請求項1~4のいずれか1項に記載の合わせガラス用中間膜。 - 前記第3の層が、ポリビニルアセタール樹脂と可塑剤とを含み、
前記第3の層中の前記ポリビニルアセタール樹脂100重量部に対する前記第3の層中の前記可塑剤の含有量が、前記第1の層中の前記ポリビニルアセタール樹脂100重量部に対する前記第1の層中の前記可塑剤の含有量よりも少ない、請求項5に記載の合わせガラス用中間膜。 - 前記第3の層は、アセチル化度が30モル%以下であるポリビニルアセタール樹脂を含む、請求項5又は6に記載の合わせガラス用中間膜。
- 前記粘着付与剤がロジン樹脂である、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。
- 第1の合わせガラス部材と、
第2の合わせガラス部材と、
前記第1の合わせガラス部材と第2の合わせガラス部材と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1~8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。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/346,166 US20140349124A1 (en) | 2011-09-21 | 2012-09-21 | Interlayer for laminated glass and laminated glass |
EP12834169.0A EP2759527B1 (en) | 2011-09-21 | 2012-09-21 | Interlayer for laminated glass and laminated glass |
CN201280045425.3A CN103796967A (zh) | 2011-09-21 | 2012-09-21 | 夹层玻璃用中间膜及夹层玻璃 |
JP2012553526A JP5286452B1 (ja) | 2011-09-21 | 2012-09-21 | 合わせガラス用中間膜及び合わせガラス |
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EP (1) | EP2759527B1 (ja) |
JP (1) | JP5286452B1 (ja) |
CN (2) | CN109263197A (ja) |
WO (1) | WO2013042771A1 (ja) |
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WO2018061861A1 (ja) | 2016-09-27 | 2018-04-05 | 株式会社クラレ | 合わせガラス用中間膜 |
WO2019022000A1 (ja) | 2017-07-24 | 2019-01-31 | 積水化学工業株式会社 | 樹脂膜及びガラス板含有積層体 |
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Also Published As
Publication number | Publication date |
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CN103796967A (zh) | 2014-05-14 |
JP5286452B1 (ja) | 2013-09-11 |
EP2759527A4 (en) | 2015-03-18 |
EP2759527B1 (en) | 2018-01-24 |
CN109263197A (zh) | 2019-01-25 |
US20140349124A1 (en) | 2014-11-27 |
EP2759527A1 (en) | 2014-07-30 |
JPWO2013042771A1 (ja) | 2015-03-26 |
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