WO2020158934A1 - Verre feuilleté - Google Patents

Verre feuilleté Download PDF

Info

Publication number
WO2020158934A1
WO2020158934A1 PCT/JP2020/003759 JP2020003759W WO2020158934A1 WO 2020158934 A1 WO2020158934 A1 WO 2020158934A1 JP 2020003759 W JP2020003759 W JP 2020003759W WO 2020158934 A1 WO2020158934 A1 WO 2020158934A1
Authority
WO
WIPO (PCT)
Prior art keywords
laminated glass
glass
block copolymer
adhesive layer
layer
Prior art date
Application number
PCT/JP2020/003759
Other languages
English (en)
Japanese (ja)
Inventor
小原　禎二
Original Assignee
日本ゼオン株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本ゼオン株式会社 filed Critical 日本ゼオン株式会社
Priority to JP2020568634A priority Critical patent/JPWO2020158934A1/ja
Publication of WO2020158934A1 publication Critical patent/WO2020158934A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C03C27/06—Joining glass to glass by processes other than fusing

Definitions

  • the present invention relates to a laminated glass having improved heat insulating properties and heat shielding properties.
  • Laminated glass is excellent in safety because it can prevent the penetration of colliding objects and the scattering of glass fragments even if it is damaged by impact. Therefore, the laminated glass is widely used for automobiles, railway vehicles, aircrafts, ships, buildings and the like.
  • Laminated glass is manufactured by bonding and integrating a plurality of glass plates with an interlayer film made of a resin having adhesiveness interposed therebetween.
  • PVB polyvinyl butyral
  • Resins such as polycarbonate and polyethylene terephthalate that are used have a smaller thermal conductivity than glass. Therefore, a laminated glass using an interlayer film or a sheet made of these resins has a smaller thermal conductivity as a whole laminated glass and a higher heat insulating property than a glass plate having the same thickness.
  • Patent Document 1 discloses a laminated glass in which an interlayer film made of PVB is made thick to increase synthetic thermal resistance. It is described that this makes it possible to prevent fogging of windows even when the outside temperature is low.
  • the thickness of the interlayer film is increased without changing the thickness of the glass, the rigidity of the laminated glass can be maintained, but the thickness of the laminated glass becomes thicker and the weight increases. ..
  • the laminated film made of PVB has a small elastic modulus, so that the laminated glass There was a contradictory problem that the rigidity of could not be maintained.
  • Patent Document 2 in a laminated glass having a layer structure of glass/PVB/polycarbonate/PVB/glass, by reducing the thickness of the glass layer and increasing the thickness of the polycarbonate layer, it is lightweight and has low thermal conductivity. It is disclosed that a laminated glass is obtained. However, when the thickness of glass is reduced to reduce the weight per unit area, the elastic modulus of polycarbonate is smaller than that of glass, and the elastic modulus of PVB of the adhesive layer is also smaller. Similarly, there is a problem that the rigidity of the laminated glass is lowered. Further, in order to maintain the rigidity of the laminated glass, it is necessary to increase the thickness of the entire laminated glass, which causes a problem that the lightness cannot be maintained.
  • Patent Document 3 discloses a laminated glass in which an intermediate film made of a modified block copolymer having an alkoxysilyl group introduced therein is used instead of the intermediate film made of PVB. However, Patent Document 3 does not describe a technique of reducing the thermal conductivity and improving the heat insulating property while maintaining the rigidity of the laminated glass. Further, Patent Document 3 discloses that an infrared absorber for shielding infrared rays can be blended with an intermediate film made of a hydride of a modified block copolymer.
  • Patent Document 4 discloses a laminated glass in which a hydride of a modified block copolymer having an alkoxysilyl group introduced is used for an intermediate film, and one or more heat insulating layers containing hollow particles are sandwiched between the glasses. ..
  • the hollow particles described in Patent Document 4 are produced, for example, by depositing silica generated by the hydrolysis reaction of silicon alkoxide on the surface of colloidal calcium carbonate and then dissolving the calcium carbonate by acid treatment.
  • Patent Document 5 as a laminated glass that prevents the incidence of heat rays and enhances the cooling effect in the summer, it is composed of a layer structure of glass/first interlayer film/heat ray reflection film/second interlayer film/glass.
  • a laminated glass composed of a hydride of a modified block copolymer having an alkoxysilyl group introduced therein is disclosed.
  • Patent Document 5 does not describe a technique for preventing heat rays from entering and simultaneously improving the heat insulating property by reducing the thermal conductivity while maintaining the rigidity of the laminated glass.
  • the present invention has been made in view of the above-mentioned circumstances, has rigidity and lightness equal to or higher than that of a laminated glass using an interlayer film made of conventional PVB, and has heat insulation and heat shield properties.
  • An object is to provide an improved laminated glass.
  • the present inventors have conducted intensive studies to achieve the above-mentioned object, and if an interlayer film having an adhesive layer and an infrared reflective film having specific properties is used, the heat insulating property and the heat shielding property of the laminated glass are improved.
  • the inventors have found that a laminated glass that maintains rigidity and lightweight can be manufactured even when improved, and completed the present invention.
  • a laminated glass comprising at least two glass plates and at least one interlayer film
  • the at least two glass plates include a first glass plate and a second glass plate
  • the at least one interlayer film includes an interlayer film X disposed between the first glass plate and the second glass plate
  • the intermediate film X is a laminated body having a first adhesive layer, a second adhesive layer, and an infrared reflective layer arranged between the first adhesive layer and the second adhesive layer.
  • the storage elastic modulus in the dynamic viscoelastic property of the intermediate film X is 3.0 ⁇ 10 7 Pa or more and 5.0 ⁇ 10 8 Pa or less at 40° C.
  • the ratio of ti to tg (ti/tg) is 0.7 or more, where tg is the total thickness of the at least two glass plates and ti is the total thickness of the at least one interlayer film.
  • At least one of the first adhesive layer and the second adhesive layer comprises at least two polymer blocks [A] containing a structural unit [a] derived from an aromatic vinyl compound as a main component.
  • the laminated glass as described in (1) which has a modified block copolymer hydride [E] obtained by introducing an alkoxysilyl group in a block copolymer hydride [D] obtained by hydrogenating (3)
  • a laminated glass having rigidity and lightness equal to or higher than those of a conventional laminated glass using an interlayer film made of PVB, and having improved heat insulating properties and heat shielding properties.
  • the laminated glass of the present invention is defined by the following (i) to (vii).
  • At least two glass plates and at least one interlayer film are provided as constituent members.
  • the at least two glass plates include a first glass plate and a second glass plate.
  • At least one interlayer film includes an interlayer film X arranged between the first glass plate and the second glass plate.
  • the intermediate film X is a laminated body having a first adhesive layer, a second adhesive layer, and an infrared reflective layer arranged between the first adhesive layer and the second adhesive layer. ..
  • the storage elastic modulus in the dynamic viscoelastic property of the interlayer film X is 3.0 ⁇ 10 7 Pa or more and 5.0 ⁇ 10 8 Pa or less at 40° C.
  • Vi When the total thickness of at least two glass plates is tg and the total thickness of at least one interlayer film is ti, the ratio of ti to tg (ti/tg) is 0.7. That is all.
  • the light transmittance in the thickness direction of the laminated glass is 50% or more at a wavelength of 550 nm and 20% or less at a wavelength of 2000 nm.
  • the laminated glass of the present invention will be described in detail below by classifying it into (a) glass plate, (b) intermediate film, and (c) laminated glass.
  • the thickness of the glass plate used for the laminated glass of the present invention is not particularly limited.
  • the thickness of the glass plate used in the present invention is usually 0.2 mm or more and 10 mm or less, preferably 0.3 mm or more, more preferably 0.5 mm or more, still more preferably 0.7 mm or more, and preferably It is 3 mm or less, more preferably 2.5 mm or less, and further preferably 2 mm or less.
  • the thickness of the glass plate used in the present invention can be appropriately selected according to the application of the laminated glass.
  • at least two glass plates are used. Then, the at least two glass plates include a first glass plate and a second glass plate.
  • the thickness of the plurality of glass plates used may be the same or different.
  • the thermal conductivity in the thickness direction of the glass plate used in the present invention is preferably 1.4 W/(m ⁇ K) or less, and 1.2 W/(m ⁇ K) or less at a temperature of 20° C. It is more preferably 1.1 W/(m ⁇ K) or less, further preferably 0.9 W/(m ⁇ K) or more.
  • the thermal conductivity in the thickness direction of the glass plate is a value obtained by measurement based on the ASTM E1530 method (disk heat flow meter method).
  • the material of such a glass plate include soda lime glass, silicate glass, aluminosilicate glass, borosilicate glass, aluminoborosilicate glass, borate glass, quartz glass, silica glass, white plate glass, and blue.
  • Plate glass, lead glass, barium glass, phosphosilicate glass and the like can be mentioned. Further, as the glass plate, general-purpose float glass, heat-strengthened glass, chemically-strengthened glass, etc., which are manufactured by different methods, can be used.
  • the light transmittance in the thickness direction of the glass plate used for the laminated glass of the present invention is usually 80% or more, preferably 85% or more, more preferably 90% or more at a wavelength of 550 nm. When the light transmittance is within this range, the glass plate is excellent in transparency and is therefore preferable.
  • the at least one intermediate film used for the laminated glass of the present invention includes the intermediate film X arranged between the first glass plate and the second glass plate.
  • the materials, structures, sizes and thicknesses of the interlayer films used may be the same or different.
  • only the intermediate film X may be used as the two or more intermediate films, or the intermediate films X and other than the intermediate film X. It may be used together with the intermediate film.
  • the intermediate films other than the intermediate film X are not particularly limited, and for example, a layer made of the same material as the adhesive layer of the intermediate film X can be used.
  • the intermediate film X used in the laminated glass of the present invention will be described in detail.
  • the intermediate film X used for the laminated glass of the present invention is a first adhesive layer, a second adhesive layer, and an infrared reflective layer arranged between the first adhesive layer and the second adhesive layer. And a laminated body having. If necessary, another functional layer can be arranged between the first adhesive layer and the infrared reflective layer and/or between the second adhesive layer and the infrared reflective layer.
  • the first adhesive layer is the surface opposite to the surface on the infrared reflecting layer side, and is assumed to be bonded to the first glass plate described above, and the second adhesive layer is the surface on the infrared reflecting layer side. It is assumed that it is bonded to the above-mentioned second glass plate on the surface opposite to the above.
  • the intermediate film X used for the laminated glass of the present invention reflects infrared rays and at the same time lowers the thermal conductivity in the laminating direction of the laminated glass to less than half of that of the glass having the same thickness. The heat insulating property can be improved.
  • the intermediate film X used in the laminated glass of the present invention needs to have a storage elastic modulus in dynamic viscoelastic properties of 3.0 ⁇ 10 7 Pa or more and 5.0 ⁇ 10 8 Pa or less at a temperature of 40° C. And is preferably 4.0 ⁇ 10 7 Pa or higher, more preferably 5.0 ⁇ 10 7 Pa or higher, more preferably 4.0 ⁇ 10 8 Pa or lower, and 3.0 ⁇ It is more preferably 10 8 Pa or less.
  • the storage elastic modulus in the dynamic viscoelastic property of the intermediate film X is based on JIS K7244-2 (torsional pendulum method), angular frequency: 1 rad/sec, measurement temperature range: ⁇ 100 to +100° C., heating rate : A value obtained by measuring a viscoelastic spectrum under the condition of 5°C/min.
  • the ratio (ti/tg) of the total thickness (ti) of the intermediate film to the total thickness (tg) of the glass plate is increased to increase the heat insulation of the laminated glass. Even if the properties are improved, the rigidity of the laminated glass can be easily maintained, and the occurrence of cracks in the glass plate can be easily prevented even with a rapid temperature change.
  • the thermal conductivity in the thickness direction of the intermediate film X in the present invention at a temperature of 20° C. is preferably 0.20 W/(m ⁇ K) or less, more preferably 0.19 W/(m ⁇ K) or less, and further preferably Is 0.18 W/(m ⁇ K) or less.
  • the thermal conductivity in the thickness direction of the interlayer film is a value obtained by measurement based on the ASTM E1530 method (disk heat flow meter method).
  • the ratio (ti/tg) of the total thickness (ti) of the interlayer film is increased corresponding to the total thickness (tg) of the glass plate. By doing so, the thermal conductivity of the laminated glass can be reduced as compared with the glass plate.
  • the structure of the intermediate film X in the present invention may be a three-layer structure in which a first adhesive layer, an infrared reflective layer, and a second adhesive layer are laminated in this order.
  • the intermediate film X is a four-layer structure that includes, between the first adhesive layer and the second adhesive layer, an infrared reflective layer and, if necessary, other single layer and/or a plurality of functional layers. It may have the above-mentioned multilayer structure.
  • Other functional layers include a resin layer for improving the heat insulating properties of the laminated glass, a resin layer having a high elastic modulus for easily maintaining the rigidity of the laminated glass, and sound wave absorption for imparting sound insulation to the laminated glass.
  • each functional layer described above can be appropriately selected so that the thermal conductivity and the storage elastic modulus of the intermediate film X are within the above ranges.
  • the thickness of the intermediate film X used for the laminated glass of the present invention is usually 0.3 mm or more, preferably 0.6 mm or more, more preferably 1 mm or more, and further preferably 1.5 mm or more. Yes, it is usually 10 mm or less, preferably 7 mm or less, more preferably 5 mm or less, and further preferably 4 mm or less.
  • the thermal conductivity in the thickness direction of the laminated glass at 20° C. is about 1/3 or less of the thermal conductivity of ordinary glass.
  • the bending elastic modulus of the laminated glass is 2 mm, which is generally used as laminated glass for automobiles and has a thickness of 2 mm. It becomes easy to set the elastic modulus to 11 GPa or more, which is equal to or higher than the bending elastic modulus of the laminated glass composed of the glass plate (1) and the interlayer film containing 0.76 mm of PVB as a main component.
  • the adhesive layer which is a constituent member of the intermediate film used in the present invention, is made of a resin composition containing a resin as a main component and, if necessary, other compounding agents.
  • the resin compositions forming the first adhesive layer and the second adhesive layer may be the same or different.
  • the resin used for the adhesive layer has a thermal conductivity at a temperature of 20° C. of usually 0.1 W/(m ⁇ K) or more and 0.2 W/(m ⁇ K) or less, preferably 0.19 W/(m ⁇ K). ) Or less, more preferably 0.18 W/(m ⁇ K) or less, for example, (meth)acrylic block copolymer, polypropylene block copolymer, polyvinyl acetal resin, polyvinyl containing a plasticizer.
  • the structural unit derived from the aromatic vinyl compound [a is excellent in transparency, heat resistance, impact resistance, flexibility at low temperature, and easy adjustment of the storage elastic modulus at a temperature of 40° C. of the interlayer film to a desired value.
  • modified block copolymer hydride obtained by introducing an alkoxysilyl group into said block copolymer hydride [D] [E] is preferred.
  • the modified block copolymer hydride [E] exhibits strong adhesion to glass, and therefore the surface of the adhesive layer contains the modified block copolymer hydride [E] as a main component. More preferably, it is composed of a resin composition.
  • the modified block copolymer hydride [E] which is a suitable resin used for the adhesive layer, a polymer block [A], a polymer block [B], a block copolymer [C], and a block copolymer
  • the combined hydride [D] and the modified block copolymer hydride [E] will be described in detail in this order.
  • the polymer block [A] is a polymer block containing a structural unit [a] derived from an aromatic vinyl compound as a main component.
  • the content of the structural unit [a] derived from the aromatic vinyl compound in the polymer block [A] is usually 90% by mass or more, preferably 95% by mass or more, and more preferably 99% by mass or more.
  • the polymer block [A] may contain a component other than the structural unit [a] derived from an aromatic vinyl compound. Examples of the other component include a structural unit [b] derived from a chain conjugated diene and/or a structural unit [m] derived from another vinyl compound.
  • the content of the structural unit [b] and/or the structural unit [m] is usually 10 mass% or less, preferably 5 mass% or less, and more preferably 1 mass% or less with respect to the polymer block [A].
  • the plurality of polymer blocks [A] contained in the block copolymer [C] may be the same or different from each other as long as they satisfy the above range.
  • the polymer block [B] is a polymer block containing a structural unit [b] derived from a chain conjugated diene compound as a main component.
  • the content of the structural unit [b] derived from the chain conjugated diene compound in the polymer block [B] is usually 70% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more.
  • the polymer block [B] may contain a component other than the structural unit [b] derived from the chain conjugated diene compound. Examples of the other component include a structural unit [a] derived from an aromatic vinyl compound and/or a structural unit [m] derived from another vinyl compound.
  • the content of the structural unit [a] and/or the structural unit [m] is usually 30% by mass or less, preferably 20% by mass or less, and more preferably 10% by mass or less based on the polymer block [B]. ..
  • the content of the structural unit [b] derived from the chain conjugated diene compound in the polymer block [B] is within the above range, flexibility is imparted to the adhesive layer, which is preferable.
  • the block copolymer [C] has a plurality of polymer blocks [B]
  • the polymer blocks [B] may be the same as or different from each other.
  • Aromatic vinyl compounds include styrene; ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, Styrenes having an alkyl group having 1 to 6 carbon atoms as a substituent such as 5-t-butyl-2-methylstyrene; a halogen atom as a substituent such as 4-chlorostyrene, dichlorostyrene, 4-monofluorostyrene And styrenes such as 4-methoxystyrene and the like, styrenes having an alkoxy group having 1 to 6 carbon atoms as a substituent, 4-phenylstyrene and the like, styrenes having an aryl group as a substituent, and the like.
  • aromatic vinyl compounds containing no polar group such as styrene and styrenes having an alkyl group having 1 to 6 carbon atoms as a substituent, are preferable from the viewpoint of hygroscopicity, and they are industrially easily available.
  • Styrene is particularly preferred.
  • chain conjugated diene compound examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and the like, which does not contain a polar group from the viewpoint of hygroscopicity.
  • a chain conjugated diene compound is preferable, and 1,3-butadiene and isoprene are particularly preferable from the viewpoint of industrial availability.
  • vinyl compounds include chain vinyl compounds, cyclic vinyl compounds, unsaturated cyclic acid anhydrides, unsaturated imide compounds, and the like. These compounds may have a substituent such as a nitrile group, an alkoxycarbonyl group, a hydroxycarbonyl group and a halogen atom.
  • ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-eicosene Does not contain polar groups such as 4-methyl-1-pentene, 4,6-dimethyl-1-heptene and other chain olefins having 2 to 20 carbon atoms; vinyl cyclohexane and other cyclic olefins having 5 to 20 carbon atoms; Those having 2 to 20 carbon atoms are more preferable, and ethylene and propylene are particularly preferable.
  • the block copolymer [C] is a precursor of the block copolymer hydride [D], and is a polymer containing at least two polymer blocks [A] and at least one polymer block [B]. is there.
  • the number of polymer blocks [A] in the block copolymer [C] is usually 3 or less, preferably 2.
  • the number of polymer blocks [B] in the block copolymer [C] is usually 2 or less, preferably 1.
  • the form of the block of the block copolymer [C] is not particularly limited and may be a chain type block or a radial type block, but a chain type block is preferable because it is excellent in mechanical strength.
  • the most preferable form of the block copolymer [C] is a triblock copolymer ([A]-[B]-[A]) in which the polymer block [A] is bonded to both ends of the polymer block [B]. is there.
  • the total amount of the structural unit [a] derived from the aromatic vinyl compound in the block copolymer [C] is wa, which is a weight fraction of the entire block copolymer [C], and the structural unit derived from a chain conjugated diene compound.
  • the ratio of wa to wb (wa:wb) is preferably 30:70 to 60:40, It is more preferably 40:60 to 58:42, and even more preferably 45:55 to 55:45. If the wa is too large, the storage elastic modulus of the adhesive layer will be high, but the impact resistance of the laminated glass at low temperatures may be reduced. On the other hand, if the wa is too small, the storage elastic modulus of the adhesive layer may decrease, and the rigidity of the laminated glass may decrease.
  • the molecular weight of the block copolymer [C] is a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, and is usually 35,000 to 200. 2,000, preferably 38,000 to 150,000, more preferably 40,000 to 100,000.
  • Mw/Mn polystyrene-equivalent weight average molecular weight
  • Mw/Mn molecular weight distribution of the block copolymer [C] is preferably 3 or less, more preferably 2 or less, still more preferably 1.7 or less. When Mw and Mw/Mn are in the above ranges, the heat resistance and mechanical strength of the adhesive layer are good.
  • the elution curve of the sample containing the block copolymer [C] measured by gel permeation chromatography has a main peak and a peak top having a molecular weight smaller than that of the peak top of the main peak. It may have a second peak.
  • the molecular weight indicated by the peak top of the second peak is preferably 1000 or more.
  • the ratio (second peak top sensitivity/main peak top sensitivity) is preferably 0.2 or less, more preferably 0.1 or less.
  • the second peak may occur due to deactivation of a part of the catalyst in the polymerization step.
  • the above elution curve has a second peak, if a modified block copolymer hydride [E] obtained by introducing an alkoxysilyl group or the like into the hydride of the block copolymer [C] is used, the adhesive property is more excellent. Layers can be obtained.
  • the method for producing the block copolymer [C] is not particularly limited, and a known method can be adopted. Specifically, examples of the method for producing the block copolymer [C] include methods described in International Publication No. 2003/018656, International Publication No. 2011/096389 and the like.
  • the block copolymer hydride [D] is a polymer obtained by selectively hydrogenating only carbon-carbon unsaturated bonds in the main chain and side chains derived from the chain conjugated diene compound of the block copolymer [C]. May be present, carbon-carbon unsaturated bond of main chain and side chain derived from chain conjugated diene compound of block copolymer [C] and carbon-carbon unsaturated of aromatic ring derived from aromatic vinyl compound It may be a polymer having a hydrogenated bond or a mixture thereof.
  • the adhesive layer there is no significant difference in storage elastic modulus between when the carbon-carbon unsaturated bond of the aromatic ring derived from the aromatic vinyl compound is not hydrogenated and when it is hydrogenated.
  • the hydrogenation rate of is usually 95% or more, preferably 97% or more, more preferably 99% or more.
  • the hydrogenation rate of the carbon-carbon unsaturated bond of the aromatic ring derived from the aromatic vinyl compound is usually 10% or more. % Or less, preferably 5% or less, more preferably 3% or less.
  • the higher the hydrogenation rate of the carbon-carbon unsaturated bond of the main chain and the side chain derived from the chain conjugated diene compound the better the weather resistance and heat deterioration resistance of the adhesive layer. Further, by suppressing the hydrogenation of the carbon-carbon unsaturated bond of the aromatic ring derived from the aromatic vinyl compound, it becomes easier to maintain the heat deterioration resistance of the adhesive layer.
  • the hydrogenation rate is 90% or more, preferably 95% or more, and more preferably 99% or more of the total carbon-carbon unsaturated bonds.
  • the adhesive layer has excellent transparency and heat deterioration resistance, and has only carbon-carbon unsaturated bonds derived from the chain conjugated diene compound. Is particularly preferable because it has excellent light resistance and a high heat distortion temperature as compared with the adhesive layer using the block copolymer hydride [D] that is selectively hydrogenated.
  • the hydrogenation rate of the saturated bond can be determined, for example, by measuring 1 H-NMR of the block copolymer [C] and the hydride of the block copolymer [D].
  • the method for hydrogenating the unsaturated bond in the block copolymer [C], the reaction form and the like are not particularly limited, and the known method may be used.
  • a method for selectively hydrogenating carbon-carbon unsaturated bonds in the main chain and side chains derived from the chain conjugated diene compound of the block copolymer [C] is described in, for example, JP-A-2015-78090.
  • the known hydrogenation methods described may be mentioned.
  • the main chain and side chain carbon-carbon unsaturated bonds derived from the chain conjugated diene compound of the block copolymer [C] and the aromatic ring carbon-carbon unsaturated bonds derived from the aromatic vinyl compound are hydrogenated. Examples of the method include those described in International Publication No. 2011/096389 and International Publication No. 2012/043708.
  • the hydrogenation catalyst, or the hydrogenation catalyst and the polymerization catalyst are removed from the reaction solution, and then the solvent is removed from the obtained solution to recover the block copolymer hydride [D]. be able to.
  • the recovered block copolymer hydride [D] can usually be made into a pellet shape and then used for the subsequent reaction of introducing an alkoxysilyl group or the molding process of a sheet.
  • the molecular weight of the block copolymer hydride [D] is a polystyrene-equivalent weight average molecular weight (Mw) measured by GPC using THF as a solvent, and is usually 35,000 to 200,000, preferably 38,000 to 150. 1,000, more preferably 40,000 to 100,000. Further, the molecular weight distribution (Mw/Mn) of the block copolymer hydride [D] is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.7 or less. When Mw and Mw/Mn are in the above ranges, the heat resistance and mechanical strength of the adhesive layer are good.
  • the elution curve of the sample containing the block copolymer hydride [D] measured by GPC shows a main peak and a second peak having a peak top having a molecular weight smaller than that of the peak top of the main peak. May be included.
  • the molecular weight indicated by the peak top of the second peak is preferably 1000 or more.
  • the detection sensitivity (second peak top sensitivity) (mV) of RI indicated by the peak top of the second peak to the detection sensitivity (main peak top sensitivity) (mV) of the differential refractometer (RI) indicated by the peak top of the main peak is , Preferably 0.2 or less, more preferably 0.1 or less.
  • the second peak may occur due to deactivation of the catalyst in the polymerization step or partial cutting of the polymer in the hydrogenation step.
  • the above elution curve has a second peak, if a modified block copolymer hydride [E] obtained by introducing an alkoxysilyl group or the like into the block copolymer hydride [D] is used, it is more excellent in adhesiveness and filling property. An adhesive layer can be obtained.
  • the modified block copolymer hydride [E] is introduced with an alkoxysilyl group by reacting the above block copolymer hydride [D] with an ethylenically unsaturated silane compound in the presence of an organic peroxide. It was done.
  • Examples of the method for introducing an alkoxysilyl group into the hydrogenated block copolymer [D] include known methods described in International Publication No. 2012/043708, JP-A-2015-78090 and the like.
  • the modified block copolymer hydride [E] is imparted with strong adhesion to glass and metal.
  • alkoxysilyl group examples include trimethoxysilyl group and triethoxysilyl group, such as tri(C 1-6 alkoxy)silyl group; methyldimethoxysilyl group, methyldiethoxysilyl group, ethyldimethoxysilyl group, ethyldiethoxysilyl group.
  • Group, propyldimethoxysilyl group, propyldiethoxysilyl group, etc. C1-20 alkyl)di(C1-6 alkoxy)silyl group; phenyldimethoxysilyl group, phenyldiethoxysilyl group, etc. ) Di (C 1-6 alkoxy) silyl group; and the like.
  • a trimethoxysilyl group is particularly preferable from the viewpoint of providing the adhesive layer with strong adhesiveness to a glass plate.
  • the alkoxysilyl group is bonded to the block copolymer hydride [D] via a divalent organic group such as an alkylene group having 1 to 20 carbon atoms or an alkyleneoxycarbonylalkylene group having 2 to 20 carbon atoms. You can do it.
  • the introduction amount of the alkoxysilyl group into the block copolymer hydride [D] is usually 0.1 part by mass or more and 10 parts by mass or less, preferably 100 parts by mass with respect to the block copolymer hydride [D]. Is 0.2 parts by mass or more, more preferably 0.3 parts by mass or more, preferably 5 parts by mass or less, more preferably 3 parts by mass or less.
  • the introduction amount of the alkoxysilyl group is too large, the crosslinkage of the alkoxysilyl groups decomposed by a small amount of water or the like proceeds before the obtained modified block copolymer hydride [E] is melt-molded into a desired shape, Problems such as gelation and deterioration of flowability during melting and deterioration of moldability are likely to occur. Further, if the introduced amount of the alkoxysilyl group is too small, a problem that the adhesive force sufficient to bond the intermediate film to the glass plate via the adhesive layer cannot be obtained easily occurs.
  • the introduction of the alkoxysilyl group can be confirmed by IR spectrum. The introduced amount can be calculated by 1 H-NMR spectrum.
  • the ethylenically unsaturated silane compound used is not particularly limited as long as it is graft-polymerized with the block copolymer hydride [D] to introduce an alkoxysilyl group into the block copolymer hydride [D].
  • Examples of the ethylenically unsaturated silane compound include vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, p-styryltrimethoxysilane, and 3-acryl acrylate.
  • Roxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxy Silane, 3-acryloxypropyltrimethoxysilane and the like are preferably used.
  • These ethylenically unsaturated silane compounds may be used alone or in combination of two or more.
  • the amount of the ethylenically unsaturated silane compound used is usually 0.1 parts by mass or more and 10 parts by mass or less, preferably 0.2 parts by mass or more, with respect to 100 parts by mass of the block copolymer hydride [D]. It is more preferably 0.3 part by mass or more, preferably 5 parts by mass or less, and more preferably 3 parts by mass or less.
  • organic peroxide one having a one-minute half-life temperature of 170° C. or higher and 190° C. or lower is preferably used.
  • t-butylcumyl peroxide, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, di-t-butyl peroxide, Di(2-t-butylperoxyisopropyl)benzene and the like are preferably used.
  • organic peroxides are preferable because the decomposition reaction of the organic peroxide and the reaction of the ethylenically unsaturated silane compound and the block copolymer hydride [D] can proceed simultaneously.
  • organic peroxides may be used alone or in combination of two or more.
  • the amount of the organic peroxide used is usually 0.01 parts by mass or more and 1 part by mass or less, and preferably 0.03 parts by mass or more, with respect to 100 parts by mass of the block copolymer hydride [D].
  • the amount is more preferably 0.05 part by mass or more, preferably 0.5 part by mass or less, and more preferably 0.3 part by mass or less.
  • the method of reacting the block copolymer hydride [D] with the ethylenically unsaturated silane compound in the presence of an organic peroxide is not particularly limited.
  • an alkoxysilyl group can be introduced into the block copolymer hydride [D] by kneading with a biaxial kneader at a desired temperature for a desired time.
  • the kneading temperature by the biaxial kneader is usually 180° C. or higher and 220° C. or lower, preferably 185° C. or higher, more preferably 190° C. or higher, preferably 210° C. or lower, more preferably 200° C. or lower.
  • the heating and kneading time is usually 0.1 minutes or more and 10 minutes or less, preferably 0.2 minutes or more, more preferably 0.3 minutes or more, preferably 5 minutes or less, more preferably 2 minutes or less.
  • the introduction of the alkoxysilyl group into the block copolymer hydride [D] is performed so that the temperature and the residence time are within the above ranges so that the block copolymer hydride [D], the ethylenic unsaturated
  • the silane compound and the organic peroxide may be continuously kneaded and extruded.
  • the molecular weight of the modified block copolymer hydride [E] is not much different from the molecular weight of the block copolymer hydride [D] used as a raw material because the amount of the introduced alkoxysilyl groups is small.
  • the reaction with the ethylenically unsaturated silane compound occurs in the presence of the organic peroxide, the crosslinking reaction and the cleavage reaction of the polymer occur simultaneously, and the value of the molecular weight distribution of the modified block copolymer hydride [E] is , Which is larger than the value of the molecular weight distribution of the block copolymer hydride [D].
  • the molecular weight of the modified block copolymer hydride [E] is a polystyrene-equivalent weight average molecular weight (Mw) measured by GPC using THF as a solvent, and is usually 35,000 to 200,000, preferably 38,000 to It is 150,000, more preferably 40,000 to 100,000.
  • Mw/Mn The molecular weight distribution (Mw/Mn) is preferably 3.5 or less, more preferably 3.0 or less, and particularly preferably 2.5 or less. When Mw and Mw/Mn are in the above ranges, the heat resistance and mechanical strength of the adhesive layer are maintained.
  • the elution curve of the sample containing the modified block copolymer hydride [E] measured by GPC shows a second peak having a main peak and a peak top having a molecular weight smaller than that of the peak top of the main peak. And may have.
  • the molecular weight indicated by the peak top of the second peak is preferably 1000 or more.
  • the detection sensitivity (second peak top sensitivity) (mV) of RI indicated by the peak top of the second peak to the detection sensitivity (main peak top sensitivity) (mV) of the differential refractometer (RI) indicated by the peak top of the main peak is , Preferably 0.2 or less, more preferably 0.1 or less.
  • the resin composition forming the adhesive layer may contain various compounding agents in addition to the above resin as the main component.
  • the proportion of the resin in the resin composition forming the adhesive layer is usually 70% by mass or more and 100% by mass or less, preferably 75% by mass or more, and more preferably 80% by mass or more.
  • Preferred compounding agents include tackifiers for adjusting the adhesiveness to glass, adhesiveness imparting agents, ultraviolet absorbers for blocking ultraviolet rays, and antioxidants and antiblocking agents for enhancing processability. , And a light stabilizer for improving durability.
  • tackifier a hydrocarbon polymer having a number average molecular weight of 300 to 10,000 is preferable.
  • specific examples of the tackifier include low molecular weight substances such as polyisobutylene, polybutene, poly-4-methylpentene, poly-1-octene, ethylene/ ⁇ -olefin copolymers and hydrogenated products thereof; polyisoprene, poly Examples thereof include low molecular weight compounds such as isoprene-butadiene copolymer and styrene-isoprene copolymer, and hydrides thereof.
  • the compounding amount of the tackifier is usually 30 parts by mass or less, preferably 25 parts by mass or less, and more preferably 20 parts by mass or less with respect to 100 parts by mass of the resin as the main component. If the amount of the tackifier added is too large, the storage elastic modulus of the interlayer film may be lowered, and the rigidity of the laminated glass of the present invention may not be maintained.
  • Adhesiveness-imparting agents include petroleum resins such as 1,3-pentadiene-based petroleum resin, cyclopentadiene-based petroleum resin, styrene-indene-based petroleum resin and hydrides thereof; vinylsilane-based, epoxysilane-based, acrylsilane-based, aminosilane-based And other silane coupling agents; and the like.
  • the compounding amount of the adhesion-imparting agent is usually 10 parts by mass or less, preferably 7 parts by mass or less, and more preferably 5 parts by mass or less with respect to 100 parts by mass of the resin as the main component. If the amount of the adhesion-imparting agent blended is too large, the storage elastic modulus of the adhesive layer may be lowered, and the rigidity of the laminated glass of the present invention may not be maintained.
  • the ultraviolet absorber for example, an oxybenzophenone compound, a benzotriazole compound, a salicylic acid ester compound, a benzophenone compound, a triazine compound or the like can be used.
  • the antioxidant for example, a phosphorus-based antioxidant, a phenol-based antioxidant, a sulfur-based antioxidant and the like can be used.
  • the light stabilizer for example, a hindered amine light stabilizer or the like can be used.
  • the ultraviolet absorber, the antioxidant, the light stabilizer, and the like, which are blended with the resin as the main component, can be used alone or in combination of two or more.
  • the blending amount of the ultraviolet absorber, the antioxidant, and the light stabilizer is usually 5 parts by mass or less, preferably 3 parts by mass or less, and more preferably 2 parts by mass or less with respect to 100 parts by mass of the resin as the main component. ..
  • resin pellets and compounding ingredients are uniformly mixed using a mixer such as a tumbler, ribbon blender, and Henschel type mixer, and then melt-mixed by a continuous melt-kneader such as a twin-screw extruder and extruded.
  • a mixer such as a tumbler, ribbon blender, and Henschel type mixer
  • a continuous melt-kneader such as a twin-screw extruder and extruded.
  • Pelletizing method resin is melt-kneaded and extruded by a twin-screw extruder equipped with a side feeder while continuously adding the compounding agent from the side feeder; It is possible to produce a resin composition that is uniformly dispersed.
  • the infrared ray reflective layer of the intermediate film X used in the laminated glass of the present invention has a light transmittance in the thickness direction of usually 50% or more, preferably 60% or more, more preferably 70% or more at a wavelength of 550 nm. At a wavelength of 2000 nm, it is usually 20% or less, preferably 15% or less, more preferably 10% or less.
  • the infrared reflective layer includes (1) a film in which an infrared reflective film is formed on a transparent resin film serving as a base material, and (2) dozens of layers of thermoplastic resins having different refractive indexes alternately. It is a multilayer resin film or the like laminated above.
  • the infrared reflective layer is a film in which an infrared reflective film is formed on a transparent resin film as a base material
  • the resin film is transparent (the light transmittance at a wavelength of 600 nm is 60% or more, preferably 70%). As described above, more preferably 80% or more) and is not particularly limited as long as it is excellent in rigidity, heat resistance and the like.
  • a film made of a synthetic resin such as a polyester resin such as polyethylene terephthalate or polyethylene naphthalate; a cycloolefin polymer; a polycarbonate; a polyether sulfone; a nylon;
  • a film made of a polyester resin is preferable, and the shape of the glass having a curved surface is softened at a temperature of around 140° C. in the laminating step during the production of the laminated glass.
  • a film made of polyethylene terephthalate is particularly preferable because it can be molded in conformity with.
  • Infrared reflecting films formed by alternately laminating the above are listed.
  • the metal oxide or the like constituting the metal oxide layer and the dielectric TiO 2 , Nb 2 O 5 , Ta 2 O 5 , SiO 2 , Al 2 O 3 , ZrO 2 , In 2 O 3 and MgF are used. 2 etc.
  • metal constituting the metal layer Au, Ag, Cu, Al, Pd, Pt, Sn, In, Zn, Ti, Cd, Fe, Co, Cr, Ni, and two or more of these metals are used. Examples include alloys made of.
  • the infrared reflective layer is a film having a multilayer structure in which two or more kinds of thermoplastic resins having different refractive indexes are alternately laminated to each other in several tens of layers
  • thermoplastic resins having different refractive indexes include, for example, a polyethylene terephthalate layer and a cyclohexanedimethanol carboxy.
  • Examples thereof include a multilayer film composed of a methyl methacrylate layer, a multilayer film composed of a polyvinyl butyral layer and a polystyrene layer, and the like.
  • the laminated glass of the present invention is used for an automobile window. When used for such purposes, it does not block radio waves and does not hinder the use of devices using electromagnetic waves such as mobile phones.
  • the thickness of the infrared reflective layer is not particularly limited and is usually 20 to 200 ⁇ m, preferably 30 to 150 ⁇ m, more preferably 40 to 100 ⁇ m.
  • the infrared reflective layer used in the present invention it is also possible to use a film which is generally commercially available as an infrared reflective film, a heat shield film, a heat ray reflective film, an infrared cut film or the like.
  • the intermediate film X used in the present invention may have a functional layer in addition to the adhesive layer and the infrared reflective layer, if necessary.
  • the functional layer can preferably be arranged between the first adhesive layer and the infrared reflecting layer and/or between the second adhesive layer and the infrared reflecting layer.
  • a resin layer for further lowering the thermal conductivity of the laminated glass a resin layer having a high elastic modulus for adjusting the storage elastic modulus of the interlayer film, and a mechanical layer for increasing the penetration resistance of the laminated glass. Examples thereof include a resin layer having excellent strength and a vibration absorbing layer for imparting sound insulation to laminated glass.
  • the resin layer may be the same layer as the first and/or the second adhesive layer.
  • the functional layer is a resin layer having a high elastic modulus
  • specific examples of the resin constituting the resin layer include block copolymer hydrides having a high styrene content, polymethylmethacrylate, cycloolefin polymer, polystyrene, styrene-
  • the layer include a resin having excellent transparency such as an acrylonitrile copolymer and a styrene-methyl methacrylate copolymer.
  • the resin forming the resin layer When the functional layer is a resin layer having excellent mechanical strength, specific examples of the resin forming the resin layer include a layer made of a resin having transparency such as polyethylene terephthalate, polynaphthalene terephthalate, and polycarbonate. ..
  • a specific example of the resin forming the resin layer is styrene-having a maximum value of loss tangent (tan ⁇ ) in viscoelastic properties in a temperature range of ⁇ 20° C. to 20° C. Examples thereof include a diene block copolymer and/or a hydride thereof, an acrylic block copolymer, a polyvinyl acetal resin containing a plasticizer, and the like.
  • the first adhesive layer, the infrared reflective layer, the second adhesive layer, and the first adhesive layer as necessary may be prepared before the laminated glass is manufactured.
  • the single layer or the multilayer functional layer is appropriately laminated and integrally bonded to form the intermediate film X.
  • Method of forming preformed first adhesive layer, infrared reflecting layer, second adhesive layer, and optionally between first adhesive layer and infrared reflecting layer and/or second adhesive layer
  • a single-layer or multi-layer functional layer disposed between the infrared reflection layer and the infrared reflection layer is appropriately laminated and laminated between two glass plates in the process of manufacturing a laminated glass, and at the same time as a laminated glass is manufactured, an intermediate layer is formed.
  • the method for molding a single-layer adhesive layer, a multilayer sheet comprising a first adhesive layer/a functional layer/a third adhesive layer, etc. is not particularly limited, and there are known melt extrusion molding methods and multilayer coextrusion molding methods. Method, extrusion laminating method, thermal laminating method, calender molding method and the like can be applied.
  • the resin temperature is usually 180 to 240° C., preferably At 190 to 230° C., more preferably 200 to 220° C., and may be molded into a sheet by a melt extrusion molding method. If the resin temperature is too low, the fluidity deteriorates, the extrusion rate of the adhesive layer cannot be increased, and there is a risk of industrial disadvantage.
  • the outer layer is composed of a resin composition containing a modified block copolymer hydride [E] as a main component
  • the inner layer is composed of a resin composition containing a block copolymer hydride [D] having a high elastic modulus as a main component.
  • the laminated glass of the present invention has at least two glass plates including a first glass plate and a second glass plate, and at least one intermediate film including an intermediate film X.
  • the at least two glass plates are bonded and integrated via an intermediate film.
  • it is assumed that the first glass plate and the second glass plate are bonded and integrated via the intermediate film X.
  • the thermal conductivity of the laminated glass of the present invention in the thickness direction at 20° C. is preferably 0.35 W/(m ⁇ K) or less, more preferably 0.3 W/(m ⁇ K) or less, and particularly preferably 0. It is 0.25 W/(m ⁇ K) or less.
  • the thermal conductivity of the laminated glass of the present invention is the above value or less, it is about 1/3 or less of the thermal conductivity of the glass plate (usually about 1 W/(m ⁇ K)), and the laminated glass for automobiles
  • the thermal conductivity of the laminated glass (about 0.6 W/( about 0.6 W/( Since it is smaller than m ⁇ K)), it has excellent heat insulation.
  • the thermal conductivity in the thickness direction of the laminated glass at 20° C. was determined by using a thermal conductivity measuring device and measuring in a temperature atmosphere of 20° C. according to the ASTM E1530 method (disk heat flow meter method). It is a value.
  • the ratio of ti to tg (ti/tg) when the total thickness of at least two glasses is tg and the total thickness of at least one interlayer film is ti is , 0.7 or more, preferably 1.0 or more, and more preferably 1.3 or more.
  • the light transmittance in the thickness direction of the laminated glass of the present invention needs to be 50% or more at a wavelength of 550 nm, preferably 60% or more, more preferably 70% or more, and 20% or less at a wavelength of 2000 nm. It is necessary to be, and preferably 15% or less, more preferably 10% or less. It is a laminated glass that has a high transmittance of visible light and a low transmittance in the infrared region, and has both heat insulating properties and heat shielding properties.
  • the light transmittance is a value obtained by measurement using an integrating sphere type spectrophotometer in accordance with JIS K7375 method.
  • the laminated glass of the present invention has high rigidity.
  • the bending elastic modulus of the laminated glass which is an index of the rigidity of the laminated glass, is preferably 11 GPa or more, more preferably 15 GPa or more, and further preferably 20 GPa or more.
  • the thickness of the laminated glass of the present invention is usually 0.7 mm or more, preferably 1 mm or more, more preferably 1.5 mm or more, further preferably 2.5 mm or more, particularly preferably 4.0 mm or more, preferably 9 mm.
  • the following is more preferably 8 mm or less, still more preferably 7 mm or less, and particularly preferably 6.0 mm or less.
  • the laminated glass has a thickness within the above range, it can be suitably used as display glass, automobile glass, building glass, and the like.
  • the shape of the laminated glass may be a flat plate shape used for a building material, a display or the like, or may be a curved surface shape like a laminated glass for automobiles.
  • the method for producing the laminated glass of the present invention is not particularly limited.
  • a laminated glass having a curved shape such as a laminated glass for automobiles
  • a first glass plate/first adhesive layer/infrared reflecting film/second adhesive layer/second A glass plate is laminated in this order to form a laminate, and the laminate is placed in a degassable flexible resin bag to degas the inside, and then placed in an autoclave at a temperature of 100 to 150° C. and a pressure of 0. It can be pressure-bonded under the condition of 0.01 to 1.5 MPa.
  • a method of heating and pressurizing the above-mentioned laminate using a vacuum laminator, a heat press or the like to bond and integrate them can also be applied.
  • the laminated glass of the present invention Since the laminated glass of the present invention has excellent heat insulating properties and heat insulating properties, it is useful as a window material, wall material, roof material, floor material, partition material, etc. for automobiles, railway vehicles, ships, buildings and the like. Further, the laminated glass of the present invention, while increasing the thickness of the interlayer film without increasing the thickness of the entire laminated glass, even when the thickness of the glass plate is reduced, while maintaining the rigidity Since the heat insulating property and the heat shielding property can be improved, it contributes to the weight reduction of the laminated glass.
  • the laminated glass of the present invention as a side glass, a rear glass, a roof glass, a windshield or the like in an automobile application, and a window glass, a partition glass, a ceiling glass or the like in a building material application, energy saving of cooling and heating and fuel consumption can be achieved. It can be expected that the improvement will be effective.
  • the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.
  • “part” and “%” are based on mass unless otherwise specified.
  • the mass fraction of the structural unit derived from a compound in the entire polymer is the total mass of all compounds polymerized during the preparation of the polymer. It is calculated from the ratio (mass ratio) of the mass of the certain compound occupying the ratio and the actually measured polymerization conversion rate of the certain compound.
  • the evaluation in this example is performed by the following method.
  • (1) Weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) The molecular weights of the block copolymer [C] and the block copolymer hydride [D] were measured at 40° C. as a standard polystyrene conversion value by GPC using THF as an eluent. As a measuring device, HLC8320GPC manufactured by Tosoh Corporation was used.
  • Hydrogenation rate The hydrogenation rate of the main chain, side chains and aromatic ring of the block copolymer hydride [D] is 1 H of the block copolymer [C] and the block copolymer hydride [D].
  • -It was calculated by measuring NMR.
  • the laminated glass prepared in each of the examples and comparative examples was used as a test piece, and an integrating sphere type spectrophotometer (V-670, manufactured by JASCO Corporation) was used to measure JIS K7375 (The light transmittance in the thickness direction at wavelengths of 550 nm and 2000 nm was measured according to the method for obtaining total light transmittance and total light reflectance of plastics).
  • a light transmittance of 50% or more at a wavelength of 550 nm was evaluated as good, and a light transmittance of less than 50% was evaluated as poor.
  • the heat-shielding property of the laminated glass the case where the light transmittance at a wavelength of 2000 nm is 20% or less was evaluated as good, and the case where it exceeded 20% was evaluated as poor.
  • Block copolymer hydride [D1] Block copolymer hydride [D1]
  • a hydrogenation catalyst a diatomaceous earth supported nickel catalyst (product name "E22U", nickel supported amount 60%, manufactured by JGC Catalysts & Chemicals) ) 4.0 parts and 30 parts of dehydrated cyclohexane were added and mixed.
  • the inside of the reactor was replaced with hydrogen gas, hydrogen was supplied while stirring the solution, and a hydrogenation reaction was carried out at a temperature of 190° C. and a pressure of 4.5 MPa for 6 hours.
  • the weight average molecular weight (Mw) of the block copolymer hydride [D1] contained in the reaction solution obtained by the hydrogenation reaction was 49,900, and the molecular weight distribution (Mw/Mn) was 1.36.
  • the reaction solution was filtered to remove the hydrogenation catalyst, and then pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl) which was a phenolic antioxidant.
  • Propionate] product name "Songnox (registered trademark) 1010", manufactured by Matsubara Sangyo Co., Ltd.
  • cyclohexane, xylene and other volatile components were removed from the solution at a temperature of 260° C. and a pressure of 0.001 MPa or less using a cylindrical concentrating dryer (product name “Contro”, manufactured by Hitachi, Ltd.).
  • the molten polymer was extruded from the die in a strand shape, and after cooling, 95 parts of pellets of the block copolymer hydride [D1] were prepared by a pelletizer.
  • the obtained pellet-shaped block copolymer hydride [D1] had a weight average molecular weight (Mw) of 49,500, a molecular weight distribution (Mw/Mn) of 1.40, and a main chain and side chains derived from a chain conjugated diene.
  • Mw weight average molecular weight
  • Mw/Mn molecular weight distribution
  • the hydrogenation rate of the carbon-carbon unsaturated bond in the chain and the hydrogenation rate of the carbon-carbon unsaturated bond derived from the aromatic ring derived from the aromatic vinyl compound were both about 100%.
  • Modified block copolymer hydride [E1] To 100 parts of the pellets of the obtained block copolymer hydride [D1], 2.0 parts of vinyltrimethoxysilane and 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (product 0.1 part of the name "Perhexa (registered trademark) 25B" manufactured by NOF CORPORATION was added. This mixture was kneaded using a twin-screw extruder at a resin temperature of 200° C. and a residence time of 60 to 70 seconds, extruded in a strand form, air-cooled, and then cut with a pelletizer to obtain a modified block co-polymer having an alkoxysilyl group. 96 parts of pellets of the combined hydride [E1] were obtained.
  • T-die type film melt extrusion molding machine T die width 400 mm
  • an extrusion sheet molding machine equipped with a cast roll (with an emboss pattern) and a sheet take-up device a molten resin temperature of 200° C.
  • a T-die temperature 200° C.
  • an adhesive layer [G1-1] thickness 0.76 mm, width 330 mm
  • one surface of the extruded sheet was pressed against an embossing roll with a nip roll to transfer an embossing pattern.
  • the obtained adhesive layers [G1-1] and [G1-2] were wound around a roll and collected.
  • the thermal conductivity of the adhesive layers [G1-1] and [G1-2] in the thickness direction was measured according to ASTM E1530, and as a result, both were 0.15 W/(m ⁇ K).
  • the polymerization conversion rate at this time was 99.5%.
  • 60.0 parts of dehydrated isoprene was continuously added to the reaction solution over 150 minutes, and after the addition was completed, stirring was continued for 30 minutes as it was.
  • the reaction liquid was analyzed by GC, and as a result, the polymerization conversion rate was 99.5%.
  • 20.0 parts of dehydrated styrene was continuously added to the reaction liquid over 50 minutes, and after the addition was completed, the mixture was stirred for 60 minutes as it was.
  • the reaction liquid was analyzed by GC and as a result, the polymerization conversion rate was about 100%.
  • the obtained pellet-shaped block copolymer hydride [D2] had a weight average molecular weight (Mw) of 62,300, a molecular weight distribution (Mw/Mn) of 1.35, a main chain derived from a chain conjugated diene compound, and The hydrogenation rate of the carbon-carbon unsaturated bond of the side chain was 99%, and the hydrogenation rate of the carbon-carbon unsaturated bond of the aromatic ring derived from the aromatic vinyl compound was less than 5%.
  • Modified block copolymer hydride [E2] Modified block copolymer hydrogen having an alkoxysilyl group, in the same manner as in Production Example 1 except that pellets of the block copolymer hydride [D2] were used in place of the pellets of the block copolymer hydride [D1]. 96 parts of a pellet of compound [E2] was obtained.
  • the obtained modified block copolymer hydride [E2] was analyzed in the same manner as in Production Example 1, and as a result, 1.8 parts of vinyltrimethoxysilane was bonded to 100 parts of the block copolymer hydride [D2]. Was confirmed.
  • Adhesive layers [G2-1] and [G2-2] The modified block copolymer hydride [E2] was used as the main component in the same manner as in Production Example 1 except that the modified block copolymer hydride [E2] was used in place of the modified block copolymer hydride [E1].
  • Adhesive layers [G2-1] (thickness 0.76 mm, width 330 mm) and [G2-2] (thickness 0.38 mm, width 330 mm) were obtained.
  • the thermal conductivity of the adhesive layers [G2-1] and [G2-2] in the thickness direction was measured according to ASTM E1530, and as a result, both were 0.15 W/(m ⁇ K).
  • infrared reflective layer [H1] 40 cm in length and 40 cm in width of polyethylene terephthalate film (trade name: Lumirror, thickness 50 ⁇ m, manufactured by Toray Industries, Inc.) was coated with In 2 O 3 by a DC magnetron sputtering method. (30 nm)/Ag (10 nm))/In 2 O 3 (60 nm)/Ag (10 nm)/In 2 O 3 (30 nm) The infrared reflective film having a layered structure is laminated to produce an infrared reflective layer [H1]. did.
  • the light transmittance in the thickness direction of the infrared reflective layer [H1] was 78% at a wavelength of 550 nm and 5% at a wavelength of 2000 nm.
  • an integrating sphere type spectrophotometer V-670, manufactured by JASCO Corporation was used, and the JIS K7375 method (plastic total light transmittance and total light transmittance) was used. It was measured in accordance with the method for obtaining reflectance).
  • Example 1 (Laminated glass [K1-1] for heat insulation evaluation) Between two sheets of blue sheet glass (diameter 50 mm, thickness 1.1 mm, thermal conductivity: 1.0 W/(mK), light transmittance: 91% (550 nm, 2000 nm)) that were cut into a circle, Two adhesive layers [G1-1] (diameter 50 mm, thickness 0.76 mm) produced in Production Example 1 and infrared reflection layer [H1] (diameter 50 mm, thickness 0) produced in Production Example 3 were cut into a circle. .05 mm) was placed one on top of another in the order of glass plate/[G1-1]/[H1]/[G1-1]/glass plate.
  • This laminate was placed in a resin bag having a layer structure of nylon/polypropylene and having a thickness of 75 ⁇ m, and the inside of the bag was degassed by using a sealed pack device (BH-951, manufactured by Panasonic). Was heat-sealed to hermetically package the laminate. Then, the hermetically sealed laminate was put into an autoclave and treated at a temperature of 140° C. and a pressure of 0.8 MPa for 30 minutes to prepare a glass plate/[G1-1]/[H1]/[G1-1]/glass plate. A laminated glass [K1-1] having a layer structure was produced. The appearance of the obtained laminated glass [K1-1] was good with no defects such as bubbles observed. The ratio (ti/tg) of the total thickness (ti) of the interlayer film to the total thickness (tg) of the glass plate was 0.71.
  • laminated glass [K1-2] for evaluation of transparency, heat shield and rigidity
  • two sheets of soda lime glass (length 100 mm, width 20 mm, thickness 1.1 mm), adhesive layer [G1-1] (length 100 mm, width 20 mm, thickness) 0.76 mm) and one infrared reflection layer [H1] (length 100 mm, width 20 mm, thickness 0.05 mm) are used, and a glass plate/[G1-1]/[H1]/[G1-1 ]/Glass plates were stacked in this order to prepare laminated glass [K1-2].
  • Interlayer film [J1] for measuring storage elastic modulus A PET film (manufactured by Toray Industries, Inc., product name “Lumirror (registered trademark) R75”, thickness 75 ⁇ m) as a release film is further used to form a glass plate and an adhesive layer [G1-1] at the time of producing a laminate.
  • a laminated glass [K1-3] was produced in the same manner as the laminated glass [K1-2] except that the PET film was placed therebetween.
  • the obtained laminated glass [K1-3] was peeled off from the PET film surface, and an intermediate film [J1] having a three-layer structure of [G1-1]/[H1]/[G1-1] was taken out.
  • a test piece having a length of 70 mm and a width of 10 mm was cut out from this interlayer film to obtain a test piece for measuring viscoelasticity.
  • the storage elastic modulus of the produced intermediate film [J1] was 8.8 ⁇ 10 7 Pa.
  • the light transmittance in the thickness direction of the produced laminated glass [K1-2] was 77% at 550 nm and 5% at 2000 nm, and the transparency evaluation was good and the heat shielding property evaluation was good.
  • the manufactured laminated glass [K1-1] had a thermal conductivity in the thickness direction of 0.30 W/(m ⁇ K), and the heat insulation was evaluated well.
  • the bending elastic modulus of the produced laminated glass [K1-2] was 31 GPa, and the evaluation of the rigidity of the laminated glass was good. The results are shown in Table 1.
  • Example 2 In addition to using two adhesive layers [G1-1] and one infrared reflecting layer [H1], the same resin layer as the adhesive layer [G1] is used as a functional layer to reduce the thermal conductivity of laminated glass. -1] is further used, and the layer structure is laminated in the order of glass plate/[G1-1]/[H1]/[G1-1]/[G1-1]/glass plate.
  • the storage elastic modulus of the produced intermediate film [J2] was 8.6 ⁇ 10 7 Pa.
  • the light transmittance in the thickness direction of the produced laminated glass [K2-2] was 74% at 550 nm and 5% at 2000 nm, and the transparency was evaluated good and the heat shield property was evaluated good.
  • the thermal conductivity of the produced laminated glass [K2-1] in the thickness direction was 0.23 W/(m ⁇ K), and the evaluation of the heat insulating property was good.
  • the bending elastic modulus of the manufactured laminated glass [K2-2] was 22 GPa, and the evaluation of the rigidity of the laminated glass was good. The results are shown in Table 1.
  • An intermediate film [J3] having a 5-layer structure of [-1]/[G3]/[G1-1] was produced.
  • the ratio (ti/tg) of the total thickness (ti) of the interlayer film to the total thickness (tg) of the glass plates of laminated glass [K3-1] and [K3-2] was 1.40. ..
  • the thermal conductivity in the thickness direction of the laminated glass interlayer film sheet [G3] used above was 0.17 W/(m ⁇ K) when measured in accordance with ASTM E1530.
  • the storage elastic modulus of the produced interlayer film [J3] was 0.58 ⁇ 10 7 Pa, which did not satisfy the requirements of the present invention.
  • the light transmittance in the thickness direction of the manufactured laminated glass [K3-2] was 74% at 550 nm and 5% at 2000 nm, and the transparency was evaluated good and the heat shield property was evaluated good.
  • the produced laminated glass [K3-1] had a thermal conductivity in the thickness direction of 0.25 W/(m ⁇ K), and the evaluation of the heat insulating property was good.
  • the flexural modulus of the produced laminated glass [K3-2] was as low as 3 GPa, and the evaluation of rigidity was poor. The results are shown in Table 1.
  • the ratio (ti/tg) of the total thickness (ti) of the interlayer film to the total thickness (tg) of the glass plates of the laminated glasses [K4-1] and [K4-2] was 0.37, It did not meet the requirements of the invention.
  • the storage elastic modulus of the produced interlayer film [J4] was 9.0 ⁇ 10 7 Pa.
  • the light transmittance in the thickness direction of the produced laminated glass [K4-2] was 77% at 550 nm and 5% at 2000 nm, and the transparency was evaluated good and the heat shield property was evaluated good.
  • the thermal conductivity of the produced laminated glass [K4-1] in the thickness direction was a large value of 0.41 W/(m ⁇ K), and the evaluation of the heat insulating property was poor.
  • the bending elastic modulus of the produced laminated glass [K4-2] was 42 GPa, and the evaluation of the rigidity of the laminated glass was good. The results are shown in Table 1.
  • Example 3 Example 1 except that two 2.1 mm-thick glass plates and one laminated glass interlayer film sheet [G3] were used, and the layer structure was laminated in the order of glass plate/[G3]/glass plate. Similarly, a laminated glass [K5-1] for evaluating heat insulating properties and a laminated glass [K5-2] for evaluating transparency, heat shielding properties and rigidity were produced. Further, the interlayer film [J5] obtained by cutting the glass interlayer film sheet [G3] into a length of 70 mm and a width of 10 mm was used as a test piece for viscoelasticity measurement. The ratio (ti/tg) of the total thickness (ti) of the interlayer film to the total thickness (tg) of the glass plates of the laminated glasses [K5-1] and [K5-2] was 0.18, It did not meet the requirements of the invention.
  • the storage elastic modulus of the produced interlayer film [J5] was 0.15 ⁇ 10 7 Pa, which did not satisfy the requirements of the present invention.
  • the light transmittance in the thickness direction of the produced laminated glass [K5-2] was 78% at 550 nm and 88% at 2000 nm, and the transparency was evaluated as good and the heat shielding property was evaluated as poor.
  • the thermal conductivity in the thickness direction of the manufactured laminated glass [K5-1] was a large value of 0.60 W/(m ⁇ K), and the evaluation of the heat insulating property was poor.
  • the bending elastic modulus of the manufactured laminated glass [K5-2] was 11 GPa, and the evaluation of the rigidity of the laminated glass was good. The results are shown in Table 1.
  • Laminated glass [K6-1] for heat insulation evaluation was performed in the same manner as in Example 1 except that the adhesive layer [G2-1] produced in Production Example 2 was used instead of the adhesive layer [G1-1].
  • a laminated glass [K6-2] for evaluating transparency, heat shielding property and rigidity, and an intermediate film [J6] having a three-layer structure of [G2-1]/[H1]/[G2-1] were prepared. ..
  • the ratio (ti/tg) of the total thickness (ti) of the interlayer film to the total thickness (tg) of the glass plates of the laminated glasses [K6-1] and [K6-2] was 0.71. ..
  • the storage elastic modulus of the produced interlayer film [J6] was 4.3 ⁇ 10 7 Pa.
  • the light transmittance in the thickness direction of the produced laminated glass [K6-2] was 77% at 550 nm and 5% at 2000 nm, and the transparency was evaluated good and the heat shield property was evaluated good.
  • the thermal conductivity of the produced laminated glass [K6-1] in the thickness direction was 0.30 W/(m ⁇ K), and the evaluation of the heat insulating property was good.
  • the bending elastic modulus of the produced laminated glass [K6-2] was 16 GPa, and the evaluation of the rigidity of the laminated glass was good. The results are shown in Table 2.
  • Example 4 A laminate for heat insulation evaluation as in Example 2, except that the adhesive layer [G2-1] produced in Production Example 2 was used as the adhesive layer and the functional layer instead of the adhesive layer [G1-1].
  • Glass [K7-1], laminated glass [K7-2] for evaluation of transparency, heat shielding property and rigidity, and [G2-1]/[H1]/[G2-1]/[G2-1]/[ An intermediate film [J7] having a 5-layer structure of G2-1] was produced.
  • the ratio (ti/tg) of the total thickness (ti) of the interlayer film to the total thickness (tg) of the glass plates of laminated glass [K7-1] and [K7-2] was 1.40. ..
  • the storage elastic modulus of the produced interlayer film [J7] was 4.3 ⁇ 10 7 Pa.
  • the light transmittance in the thickness direction of the produced laminated glass [K7-2] was 74% at 550 nm and 5% at 2000 nm, and the transparency was evaluated good and the heat shielding property was evaluated good.
  • the produced laminated glass [K7-1] had a thermal conductivity in the thickness direction of 0.23 W/(m ⁇ K), and the evaluation of the heat insulating property was good.
  • the bending elastic modulus of the produced laminated glass [K7-2] was 11 GPa, and the evaluation of the rigidity of the laminated glass was good. The results are shown in Table 2.
  • the produced intermediate film [J8] had a storage elastic modulus of 0.55 ⁇ 10 7 Pa, which did not satisfy the requirements of the present invention.
  • the light transmittance in the thickness direction of the produced laminated glass [K8-2] was 74% at 550 nm and 5% at 2000 nm, and the transparency was evaluated good and the heat shield property was evaluated good.
  • the manufactured laminated glass [K8-1] had a thermal conductivity in the thickness direction of 0.25 W/(m ⁇ K), and the evaluation of the heat insulating property was good.
  • the bending elastic modulus of the manufactured laminated glass [K8-2] was a low value of 3 GPa, and the evaluation of rigidity was poor. The results are shown in Table 2.
  • a laminated glass [K9-1] for heat insulation evaluation was prepared in the same manner as in Comparative Example 2 except that the adhesive layer [G2-2] produced in Production Example 2 was used instead of the adhesive layer [G1-2].
  • Laminated glass [K9-2] for evaluating transparency, heat shielding property and rigidity, and an intermediate film [J9] having a three-layer structure of [G2-2]/[H1]/[G2-2] were prepared. ..
  • the ratio (ti/tg) of the total thickness (ti) of the interlayer film to the total thickness (tg) of the glass plates of the laminated glasses [K9-1] and [K9-2] was 0.37, It did not meet the requirements of the invention.
  • the storage elastic modulus of the produced interlayer film [J9] was 4.5 ⁇ 10 7 Pa.
  • the light transmittance in the thickness direction of the produced laminated glass [K9-2] was 77% at 550 nm and 5% at 2000 nm, and the transparency was evaluated good and the heat shield property was evaluated good.
  • the thermal conductivity of the produced laminated glass [K9-1] in the thickness direction was a large value of 0.41 W/(m ⁇ K), and the evaluation of the heat insulating property was poor.
  • the manufactured laminated glass [K9-2] had a bending elastic modulus of 25 GPa, and the evaluation of the rigidity of the laminated glass was good. The results are shown in Table 2.
  • an adhesive layer [G4-1] (thickness 0.76 mm, width 330 mm) containing a modified block copolymer hydride [E1] as a main component was produced.
  • the thermal conductivity of the adhesive layer [G4-1] in the thickness direction was measured according to ASTM E1530, and it was 0.16 W/(m ⁇ K).
  • Laminated glass [K10] and interlayer film [J10] Laminated glass [K10-1] for heat insulation evaluation, transparency and shielding were obtained in the same manner as in Example 1 except that the above adhesive layer [G4-1] was used in place of the adhesive layer [G1-1].
  • a laminated glass [K10-2] for evaluating thermal properties and rigidity and an intermediate film [J10] having a three-layer structure of [G4-1]/[H1]/[G4-1] were prepared.
  • the ratio (ti/tg) of the total thickness (ti) of the interlayer film to the total thickness (tg) of the glass plates of laminated glass [K10-1] and [K10-2] was 0.71. ..
  • the produced intermediate film [J10] had a storage elastic modulus of 2.8 ⁇ 10 7 Pa, which did not satisfy the requirements of the present invention.
  • the light transmittance in the thickness direction of the produced laminated glass [K10-2] was 77% at 550 nm and 5% at 2000 nm, and the transparency was evaluated good and the heat shield property was evaluated good.
  • the manufactured laminated glass [K10-1] had a thermal conductivity in the thickness direction of 0.32 W/(m ⁇ K), and the evaluation of the heat insulating property was good.
  • the flexural modulus of the produced laminated glass [K10-2] was a low value of 10 GPa, and the evaluation of rigidity was poor.
  • Example 5 Laminated glass [K11-1] for heat insulation evaluation, transparency, and shielding in the same manner as in Example 1 except that the thickness of the glass plate (blue plate glass) used was changed from 1.1 mm to 0.7 mm.
  • a laminated glass [K11-2] for evaluating thermal properties and rigidity, and an intermediate film [J11] having a three-layer structure of [G1-1]/[H1]/[G1-1] were prepared.
  • the ratio (ti/tg) of the total thickness (ti) of the interlayer film to the total thickness (tg) of the glass plates of laminated glass [K11-1] and [K11-2] was 1.12. ..
  • the storage elastic modulus of the produced intermediate film [J11] was 8.8 ⁇ 10 7 Pa.
  • the light transmittance in the thickness direction of the produced laminated glass [K11-2] was 77% at 550 nm and 5% at 2000 nm, and the transparency was evaluated good and the heat shield property was evaluated good.
  • the produced laminated glass [K11-1] had a thermal conductivity in the thickness direction of 0.25 W/(m ⁇ K), and the evaluation of the heat insulating property was good.
  • the bending elastic modulus of the manufactured laminated glass [K11-2] was 29 GPa, and the evaluation of the rigidity of the laminated glass was good. The results are shown in Table 2.
  • Laminated glass [K12-1] for heat insulation evaluation, transparency, and shielding in the same manner as in Example 2 except that the thickness of the glass plate (blue plate glass) used was changed from 1.1 mm to 2.0 mm.
  • Laminated glass [K12-2] for evaluating heat resistance and rigidity, and an intermediate layer composed of five layers of [G1-1]/[H1]/[G1-1]/[G1-1]/[G1-1] A film [J12] was prepared.
  • the ratio (ti/tg) of the total thickness (ti) of the interlayer film to the total thickness (tg) of the glass plates of laminated glass [K12-1] and [K12-2] was 0.77. ..
  • the storage elastic modulus of the produced intermediate film [J12] was 8.6 ⁇ 10 7 Pa.
  • the light transmittance in the thickness direction of the produced laminated glass [K12-2] was 74% at 550 nm and 5% at 2000 nm, and the transparency was evaluated good and the heat shield property was evaluated good.
  • the thermal conductivity of the produced laminated glass [K12-1] in the thickness direction was 0.29 W/(m ⁇ K), and the evaluation of the heat insulating property was good.
  • the flexural modulus of the produced laminated glass [K12-2] was 26 GPa, and the evaluation of the rigidity of the laminated glass was good. The results are shown in Table 2.
  • An intermediate film having an infrared reflective layer and having a storage elastic modulus at 40° C. of 3.0 ⁇ 10 7 Pa or more is used, and the total thickness of the intermediate film with respect to the total thickness (tg) of the glass plate (( By setting the ratio (ti/tg) of ti) to 0.7 or more, the thermal conductivity in the thickness direction of the laminated glass is 0.35 W/(m ⁇ K) or less, and the heat shielding property and heat insulating property are improved. Moreover, it is possible to manufacture a laminated glass having a flexural modulus of elasticity of 11 GPa or more (Examples 1 to 6).
  • a PVB-based interlayer film that has been conventionally generally used as a laminated glass interlayer film has a storage elastic modulus at 40° C. of significantly less than 3 ⁇ 10 7 Pa and a bending elastic modulus of 11 GPa.
  • the laminated glass of the present invention has improved heat insulating properties and heat shielding properties, and also maintains rigidity and light weight. Therefore, when used as a window material for automobiles, railway vehicles, ships, buildings, etc., it has a cooling and heating effect. It is useful because it can increase

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

Le verre feuilleté de l'invention est équipé d'au moins deux plaques de verre, et d'au moins un film intermédiaire. Le ou les films intermédiaires incluent au moins un film intermédiaire (X). Ce film intermédiaire (X) consiste en un stratifié possédant une première couche adhésive, une seconde couche adhésive, et une couche réfléchissante dans l'infrarouge disposée entre la première et la seconde couche adhésive. Le module d'élasticité de conservation du film intermédiaire (X) à 40°C est supérieur ou égal à ３,０×１０7Ｐａ et inférieur ou égal à ５,０×１０8Ｐａ. Le rapport （ｔｉ／ｔｇ） du total (ti) de l'épaisseur du ou des films intermédiaires, vis-à-vis du total (tg) de l'épaisseur des plaques de verre au nombre de deux ou plus, est supérieur ou égal à 0,7. La transmittance lumineuse du verre feuilleté de l'invention dans la direction de son épaisseur, est supérieure ou égale à 50% à une longueur d'onde de 550nm, et inférieure ou égale à 20% à une longueur d'onde de 2000nm.
PCT/JP2020/003759 2019-01-31 2020-01-31 Verre feuilleté WO2020158934A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2020568634A JPWO2020158934A1 (ja) 2019-01-31 2020-01-31 合わせガラス

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019-016054 2019-01-31
JP2019016054 2019-01-31

Publications (1)

Publication Number Publication Date
WO2020158934A1 true WO2020158934A1 (fr) 2020-08-06

Family

ID=71841129

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/003759 WO2020158934A1 (fr) 2019-01-31 2020-01-31 Verre feuilleté

Country Status (2)

Country Link
JP (1) JPWO2020158934A1 (fr)
WO (1) WO2020158934A1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014224921A (ja) * 2013-05-16 2014-12-04 日本化薬株式会社 赤外線遮蔽シート及びその製造方法
JP2016108227A (ja) * 2014-11-10 2016-06-20 株式会社クラレ 遮音性および曲げ強度に優れる積層体及び合わせガラス
WO2016163409A1 (fr) * 2015-04-09 2016-10-13 日本ゼオン株式会社 Composition de résine et son utilisation
WO2016171068A1 (fr) * 2015-04-22 2016-10-27 日本ゼオン株式会社 Verre feuilleté
JP2017071143A (ja) * 2015-10-08 2017-04-13 王子ホールディングス株式会社 遮熱フィルムおよび遮熱合わせガラス
JP2017081775A (ja) * 2015-10-26 2017-05-18 日本ゼオン株式会社 合わせガラス
JP2017122025A (ja) * 2016-01-07 2017-07-13 王子ホールディングス株式会社 自動車用遮熱合わせガラス
JP2018199602A (ja) * 2017-05-29 2018-12-20 日本ゼオン株式会社 合わせガラスおよびその製造方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014224921A (ja) * 2013-05-16 2014-12-04 日本化薬株式会社 赤外線遮蔽シート及びその製造方法
JP2016108227A (ja) * 2014-11-10 2016-06-20 株式会社クラレ 遮音性および曲げ強度に優れる積層体及び合わせガラス
WO2016163409A1 (fr) * 2015-04-09 2016-10-13 日本ゼオン株式会社 Composition de résine et son utilisation
WO2016171068A1 (fr) * 2015-04-22 2016-10-27 日本ゼオン株式会社 Verre feuilleté
JP2017071143A (ja) * 2015-10-08 2017-04-13 王子ホールディングス株式会社 遮熱フィルムおよび遮熱合わせガラス
JP2017081775A (ja) * 2015-10-26 2017-05-18 日本ゼオン株式会社 合わせガラス
JP2017122025A (ja) * 2016-01-07 2017-07-13 王子ホールディングス株式会社 自動車用遮熱合わせガラス
JP2018199602A (ja) * 2017-05-29 2018-12-20 日本ゼオン株式会社 合わせガラスおよびその製造方法

Also Published As

Publication number Publication date
JPWO2020158934A1 (ja) 2021-12-02

Similar Documents

Publication Publication Date Title
CN108638614B (zh) 夹层玻璃的制造方法
JP7249926B2 (ja) 合わせガラス
JP2017081775A (ja) 合わせガラス
JP6287040B2 (ja) 合わせガラス
US10532636B2 (en) Laminated glass for vehicle
JPWO2016163409A1 (ja) 樹脂組成物及びその利用
JP2017186229A (ja) 車両用合わせガラス
WO2018097146A1 (fr) Feuille d'adhésif, et verre feuilleté
JP6658743B2 (ja) 合わせガラス
JP2017186179A (ja) 合わせガラス
JP6907946B2 (ja) 酸無水物基を有するブロック共重合体水素化物及びその利用
WO2020158934A1 (fr) Verre feuilleté
JP7010241B2 (ja) 合わせガラス
JPWO2019044267A1 (ja) 合わせガラス
JP7259856B2 (ja) 積層体および合わせガラス
JP6229460B2 (ja) 薄膜ガラス積層体
WO2019058953A1 (fr) Feuille de résine thermoplastique et stratifié

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20749715

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2020568634

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20749715

Country of ref document: EP

Kind code of ref document: A1