JP7563178B2 - Laminated Glass - Google Patents

Description

The present invention relates to laminated glass with improved thermal insulation and heat shielding properties.

Laminated glass is highly safe because, even if it is broken by impact, it can prevent penetration by the colliding object and scattering of glass fragments. For this reason, laminated glass is widely used in automobiles, railway vehicles, aircraft, ships, buildings, etc. Laminated glass is manufactured by bonding and integrating multiple glass sheets with an interlayer film made of adhesive resin sandwiched between them.

It is useful to impart thermal insulation to window glass in order to increase the heating effect inside a room or a company in cold regions, and to increase the cooling effect inside a room or a car in hot regions. For example, polyvinyl butyral (hereinafter sometimes referred to as "PVB"), which is commonly used as an interlayer in laminated glass, and resins such as polycarbonate and polyethylene terephthalate, which are formed into sheets and placed between glass sheets to increase the penetration resistance of laminated glass, have lower thermal conductivity than glass. Therefore, laminated glass using interlayers or sheets made of these resins has lower thermal conductivity as a whole laminated glass and higher thermal insulation than glass sheets of the same thickness.

Patent Document 1 discloses laminated glass in which the thickness of the interlayer made of PVB is increased to increase the composite thermal resistance. It is described that this makes it possible to prevent fogging of the window even when the outside temperature is low. However, if the thickness of the interlayer 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 increases and the weight increases. On the other hand, if an attempt is made to maintain the thickness and weight of the laminated glass by increasing the thickness of the interlayer while reducing the thickness of the glass, there is a contradictory problem in that the rigidity of the laminated glass cannot be maintained because the elastic modulus of the interlayer made of PVB is small.

Patent Document 2 discloses that 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, a lightweight laminated glass with low thermal conductivity can be obtained. However, when the glass thickness 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 the PVB in the adhesive layer is also small, so there is a problem that the rigidity of the laminated glass decreases as described above. In addition, if one tries 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 lightweight property cannot be maintained.

Patent Document 3 discloses laminated glass in which an interlayer film made of PVB is replaced with an interlayer film made of a modified hydrogenated block copolymer having an alkoxysilyl group introduced therein. However, Patent Document 3 does not disclose any technology for improving heat insulation by reducing the thermal conductivity while maintaining the rigidity of the laminated glass.
Also, Patent Document 3 discloses that an infrared absorbing agent for blocking infrared rays can be blended into an interlayer film made of a modified block copolymer hydrogenate. This can prevent infrared rays from penetrating the laminated glass and directly raising the internal temperature, but it cannot prevent the heat of the interlayer film that has absorbed infrared rays from being transmitted to the inside through the glass, so the heat blocking effect is not necessarily sufficient.

Patent Document 4 discloses laminated glass in which an interlayer is made of a modified hydrogenated block copolymer having an alkoxysilyl group introduced therein, and one or more insulating layers containing hollow particles are sandwiched between the glass sheets. However, the hollow particles described in Patent Document 4 are produced, for example, by precipitating silica produced by hydrolysis of silicon alkoxide on the surface of colloidal calcium carbonate, and then dissolving the calcium carbonate by acid treatment, and are not easily available industrially.

Patent Document 5 discloses laminated glass that prevents the incidence of heat rays and enhances the cooling effect in summer, and has a layer structure of glass/first interlayer film/heat ray reflective film/second interlayer film/glass, with the interlayer film being made of a modified block copolymer hydride having an alkoxysilyl group introduced therein. However, Patent Document 5 does not disclose any technology that prevents the incidence of heat rays and simultaneously maintains the rigidity of the laminated glass while lowering the thermal conductivity and improving the insulation.

JP 2006-137648 A Japanese Patent Application Publication No. 6-915 International Publication No. 2016/163409 JP 2017-81775 A International Publication No. 2016/006610

The present invention has been made in consideration of the above-mentioned circumstances, and aims to provide laminated glass that has equal or greater rigidity and lighter weight than conventional laminated glass that uses an interlayer made of PVB, and also has improved insulation and heat shielding properties.

As a result of extensive research into achieving the above-mentioned objective, the inventors discovered that by using an interlayer film having an adhesive layer with specific properties and an infrared reflective film, it is possible to produce laminated glass that maintains its rigidity and light weight even when the insulating and heat-shielding properties of the laminated glass are improved, and thus completed the present invention.

Thus, according to the present invention, there are provided laminated glasses as described below in (1) to (4).
(1) A laminated glass comprising at least two glass sheets and at least one interlayer film,
the at least two glass sheets include a first glass sheet and a second glass sheet;
The at least one interlayer film includes an interlayer film X disposed between the first glass sheet and the second glass sheet,
the intermediate film X is a laminate having a first adhesive layer, a second adhesive layer, and an infrared reflective layer disposed between the first adhesive layer and the second adhesive layer,
The storage modulus of the dynamic viscoelastic properties of the interlayer film X is 3.0×10 ⁷ Pa or more and 5.0×10 ⁸ Pa or less at 40° C.,
wherein when a total thickness of the at least two glass sheets is defined as tg and a total thickness of the at least one interlayer film is defined as ti, a ratio of ti to tg (ti/tg) is 0.7 or more,
The laminated glass has a light transmittance in a thickness direction of 50% or more at a wavelength of 550 nm and 20% or less at a wavelength of 2000 nm.
(2) The laminated glass according to (1), wherein at least one of the first adhesive layer and the second adhesive layer is mainly composed of a modified hydrogenated block copolymer [E] obtained by introducing an alkoxysilyl group into a hydrogenated block copolymer [D] obtained by hydrogenating a block copolymer [C] having at least two polymer blocks [A] mainly composed of a structural unit [a] derived from an aromatic vinyl compound and at least one polymer block [B] mainly composed of a structural unit [b] derived from a chain conjugated diene (straight-chain conjugated diene, branched-chain conjugated diene) compound.
(3) The laminated glass according to (1) or (2), wherein the thermal conductivity in a thickness direction of the laminated glass is 0.35 W/(m·K) or less at 20° C.
(4) The laminated glass according to any one of (1) to (3), which has a flexural modulus of 11 GPa or more.

According to the present invention, laminated glass is provided which has equal or greater rigidity and lighter weight than conventional laminated glass using an interlayer made of PVB, and which also has improved insulation and heat shielding properties.

The laminated glass of the present invention is defined by the following (i) to (vii).
(i) The optical fiber panel comprises at least two glass plates and at least one interlayer film as constituent members.
(ii) The at least two glass sheets include a first glass sheet and a second glass sheet.
(iii) The at least one interlayer film includes an interlayer film X disposed between the first glass sheet and the second glass sheet.
(iv) Interlayer film X is a laminate having a first adhesive layer, a second adhesive layer, and an infrared reflective layer disposed between the first adhesive layer and the second adhesive layer.
(v) The storage modulus in the dynamic viscoelastic properties 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 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, the ratio of ti to tg (ti/tg) is 0.7 or greater.
(vii) The light transmittance through the thickness 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, divided into (a) glass plate, (b) interlayer film, and (c) laminated glass.

(a) Glass plate The thickness of the glass plate used in 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, even more preferably 0.7 mm or more, and preferably 3 mm or less, more preferably 2.5 mm or less, even more 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.
In the laminated glass of the present invention, at least two glass plates are used. The at least two glass plates include a first glass plate and a second glass plate. The thicknesses of the 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, more preferably 1.2 W/(m·K) or less, even more preferably 1.1 W/(m·K) or less, and usually 0.9 W/(m·K) or more at a temperature of 20° C. Here, the thermal conductivity in the thickness direction of the glass plate is a value determined by measurement based on the ASTM E1530 method (disk heat flow meter method).
Examples of materials for such glass plates include soda-lime glass, silicate glass, aluminosilicate glass, borosilicate glass, aluminoborosilicate glass, borate glass, quartz glass, silica glass, white plate glass, blue plate glass, lead glass, barium glass, and phosphosilicate glass.
As the glass plate, general-purpose float glass, heat-strengthened glass, chemically strengthened glass, etc., which are manufactured by different methods, can also be used.

The light transmittance in the thickness direction of the glass plate used in the laminated glass of the present invention is usually 80% or more, preferably 85% or more, and more preferably 90% or more at a wavelength of 550 nm. If the light transmittance is in this range, the glass plate has excellent transparency, which is preferable.

(b) Interlayer Film At least one interlayer film is used in the laminated glass of the present invention. The at least one interlayer film used in the laminated glass of the present invention includes an interlayer film X disposed between the first glass sheet and the second glass sheet.
When two or more interlayer films are used in the laminated glass of the present invention, the interlayer films used may be the same or different in material, structure, size, thickness, etc.
Furthermore, when two or more interlayer films are used in the laminated glass of the present invention, the two or more interlayer films may be only the interlayer film X, or may be a combination of the interlayer film X and an interlayer film other than the interlayer film X. The interlayer film other than the interlayer film X is not particularly limited, and for example, a layer made of the same material as the adhesive layer of the interlayer film X can be used.
The interlayer film X used in the laminated glass of the present invention will be described in detail below.
The interlayer film X used in the laminated glass of the present invention is a laminate having a first adhesive layer, a second adhesive layer, and an infrared reflective layer disposed between the first adhesive layer and the second adhesive layer. If necessary, other functional layers can be disposed 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 bonded to the first glass plate on the side opposite to the infrared reflective layer side, and the second adhesive layer is bonded to the second glass plate on the side opposite to the infrared reflective layer side.
The interlayer film X used in the laminated glass of the present invention reflects infrared rays and at the same time reduces the thermal conductivity of the laminated glass in the lamination direction to less than half that of glass of the same thickness, thereby improving the heat insulating properties of the laminated glass.

The interlayer film X used in the laminated glass of the present invention must have a storage modulus in the dynamic viscoelastic properties at a temperature of 40° C. of 3.0×10 ⁷ Pa or more and 5.0×10 ⁸ Pa or less, preferably 4.0×10 ⁷ Pa or more, more preferably 5.0×10 ⁷ Pa or more, preferably 4.0×10 ⁸ Pa or less, and more preferably 3.0×10 ⁸ Pa or less. Here, the storage modulus in the dynamic viscoelastic properties of the interlayer film X is a value determined by measuring the viscoelasticity spectrum according to JIS K7244-2 (torsion pendulum method) under conditions of an angular frequency of 1 rad/sec, a measurement temperature range of −100 to +100° C., and a temperature rise rate of 5° C./min.
When the storage modulus of the interlayer film X is within the above range, even when the ratio (ti/tg) of the total thickness (ti) of the interlayer film to the total thickness (tg) of the glass sheets is increased to improve the thermal insulation of the laminated glass, the rigidity of the laminated glass is easily maintained, and cracks in the glass sheets are easily prevented even when subjected to a sudden temperature change.

The thermal conductivity of the interlayer film X in the present invention in the thickness direction 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 even more preferably 0.18 W/(m·K) or less. Here, the thermal conductivity of the interlayer film in the thickness direction is a value determined by measurement based on the ASTM E1530 method (disk heat flow meter method).
When the thermal conductivity of the interlayer film in the thickness direction is within the above range, the thermal conductivity of the laminated glass can be reduced compared to that of the glass sheets by increasing the ratio (ti/tg) of the total thickness (ti) of the interlayer film to the total thickness (tg) of the glass sheets.

The structure of the interlayer 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 interlayer film X may also have a multilayer structure of four or more layers having, as necessary, other single and/or multiple functional layers in addition to the infrared reflective layer between the first adhesive layer and the second adhesive layer. Examples of the other functional layers include a resin layer for improving the heat insulating properties of the laminated glass, a resin layer with a high elastic modulus for making it easier to maintain the rigidity of the laminated glass, a sound wave absorbing layer for imparting sound insulation to the laminated glass, and an infrared absorbing layer for improving the heat insulating properties of the laminated glass.
The thickness of each of the above-mentioned functional layers can be appropriately selected so that the thermal conductivity and storage modulus of the interlayer film X fall within the above-mentioned ranges.

The thickness of the interlayer film X used in 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 even more preferably 1.5 mm or more, and is usually 10 mm or less, preferably 7 mm or less, more preferably 5 mm or less, and even more preferably 4 mm or less.
When the thickness of the interlayer film X used in the laminated glass of the present invention is within the above range, it is easy to make the thermal conductivity of the laminated glass in the thickness direction at 20° C. about ⅓ or less of the thermal conductivity of ordinary glass, that is, usually 0.35 W/(m·K) or less, preferably 0.3 W/(m·K) or less, more preferably 0.25 W/(m·K) or less. Furthermore, when the thickness of the interlayer film X used in the laminated glass of the present invention is within the above range, it is easy to make the flexural modulus of the laminated glass 11 GPa or more, which is equal to or greater than the flexural modulus of a laminated glass composed of two 2 mm thick glass sheets and a 0.76 mm thick interlayer film mainly composed of PVB, which is commonly used as laminated glass for automobiles.

(Adhesive Layer)
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 constituting the first adhesive layer and the second adhesive layer may be the same or different.

The resin used for the adhesive layer preferably has a thermal conductivity at a temperature of 20°C of typically 0.1 W/(m·K) or more and 0.2 W/(m·K) or less, preferably 0.19 W/(m·K) or less, and more preferably 0.18 W/(m·K) or less. Examples include (meth)acrylic block copolymers, polypropylene block copolymers, polyvinyl acetal resins, polyvinyl acetal resins containing plasticizers, polyurethane resins, hydrogenated styrene-butadiene-styrene block copolymers, hydrogenated styrene-isoprene-styrene block copolymers, styrene-isobutene-styrene block copolymers, hydrogenated styrene-isobutene-styrene block copolymers, and/or modified resins in which acid anhydride groups or alkoxysilyl groups have been introduced into the above resins.

Among these, preferred are hydrogenated block copolymer [D] obtained by hydrogenating block copolymer [C] having at least two polymer blocks [A] mainly composed of structural units [a] derived from an aromatic vinyl compound and at least one polymer block [B] mainly composed of structural units [b] derived from a linear conjugated diene compound, and/or modified hydrogenated block copolymer [E] obtained by introducing an alkoxysilyl group into the hydrogenated block copolymer [D], because they have excellent transparency, heat resistance, impact resistance, and flexibility at low temperatures, and the storage modulus of the interlayer film at a temperature of 40°C can be easily adjusted to a desired value.
Among the above resins, the modified hydrogenated block copolymer [E] exhibits strong adhesion to glass, and therefore it is more preferable that the surface of the adhesive layer be composed of a resin composition containing the modified hydrogenated block copolymer [E] as a main component.

The modified hydrogenated block copolymer [E], which is a suitable resin for use in the adhesive layer, will be described in detail below in the order of polymer block [A], polymer block [B], block copolymer [C], hydrogenated block copolymer [D], and modified hydrogenated block copolymer [E].
<Polymer block [A]>
Here, the polymer block [A] is a polymer block mainly composed of a structural unit [a] derived from an aromatic vinyl compound. The content of the structural unit [a] derived from an aromatic vinyl compound in the polymer block [A] is usually 90% by mass or more, preferably 95% by mass or more, more preferably 99% by mass or more. The polymer block [A] may contain components other than the structural unit [a] derived from an aromatic vinyl compound. Examples of the other components 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% by mass or less, preferably 5% by mass or less, more preferably 1% by mass or less, based on the polymer block [A].
If the content of the structural unit [a] derived from an aromatic vinyl compound in the polymer block [A] is too small, the heat resistance of the adhesive layer may decrease.
The multiple polymer blocks [A] contained in the block copolymer [C] may be the same as or different from each other, so long as they satisfy the above range.

<Polymer block [B]>
The polymer block [B] is a polymer block mainly composed of a structural unit [b] derived from a chain conjugated diene compound. The content of the structural unit [b] derived from a 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 components other than the structural unit [b] derived from a chain conjugated diene compound. Examples of the other components 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, more preferably 10% by mass or less, based on the polymer block [B].
It is preferable that the content of the structural unit [b] derived from a chain conjugated diene compound in the polymer block [B] is within the above range since flexibility is imparted to the adhesive layer.
When the block copolymer [C] has a plurality of polymer blocks [B], the polymer blocks [B] may be the same or different from each other.

Examples of aromatic vinyl compounds include styrene; styrenes having an alkyl group having 1 to 6 carbon atoms as a substituent, such as α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, and 5-t-butyl-2-methylstyrene; styrenes having a halogen atom as a substituent, such as 4-chlorostyrene, dichlorostyrene, and 4-monofluorostyrene; styrenes having an alkoxy group having 1 to 6 carbon atoms as a substituent, such as 4-methoxystyrene; and styrenes having an aryl group as a substituent, such as 4-phenylstyrene. Among these, aromatic vinyl compounds that do not contain polar groups, such as styrene and styrenes having an alkyl group having 1 to 6 carbon atoms as a substituent, are preferred from the viewpoint of hygroscopicity, and styrene is particularly preferred from the viewpoint of industrial availability.

Examples of linear conjugated diene compounds include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, etc. From the viewpoint of hygroscopicity, linear conjugated diene compounds that do not contain polar groups are preferred, and from the viewpoint of industrial availability, 1,3-butadiene and isoprene are particularly preferred.

Other vinyl compounds include linear vinyl compounds, cyclic vinyl compounds, unsaturated cyclic acid anhydrides, and unsaturated imide compounds. These compounds may have substituents such as nitrile groups, alkoxycarbonyl groups, hydroxycarbonyl groups, and halogen atoms. Among these, from the viewpoint of hygroscopicity, those that do not contain polar groups such as linear olefins having 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-eicosene, 4-methyl-1-pentene, and 4,6-dimethyl-1-heptene; cyclic olefins having 5 to 20 carbon atoms, such as vinylcyclohexane; are preferred, linear olefins having 2 to 20 carbon atoms are more preferred, and ethylene and propylene are particularly preferred.

<Block copolymer [C]>
The block copolymer [C] is a precursor of the hydrogenated block copolymer [D], and is a polymer containing at least two polymer blocks [A] and at least one polymer block [B].
The number of polymer blocks [A] in the block copolymer [C] is usually not more than 3, and preferably not more than 2. The number of polymer blocks [B] in the block copolymer [C] is usually not more than 2, and preferably not more than 1.

The block form 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 preferred because it has superior mechanical strength.
The most preferred embodiment 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].

When the weight fraction of the total amount of the structural units [a] derived from an aromatic vinyl compound in the block copolymer [C] in the entire block copolymer [C] is denoted as wa, and the weight fraction of the total amount of the structural units [b] derived from a chain conjugated diene compound in the entire block copolymer [C] is denoted as wb, the ratio of wa to wb (wa:wb) is preferably 30:70 to 60:40, more preferably 40:60 to 58:42, and even more preferably 45:55 to 55:45.
If wa is too large, the storage modulus of the adhesive layer is high, but the impact resistance of the laminated glass at low temperatures may decrease, whereas if wa is too small, the storage modulus of the adhesive layer is low, and the rigidity of the laminated glass may decrease.

The molecular weight of the block copolymer [C] is, in terms of polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, usually 35,000 to 200,000, preferably 38,000 to 150,000, more preferably 40,000 to 100,000. The molecular weight distribution (Mw/Mn) of the block copolymer [C] is preferably 3 or less, more preferably 2 or less, and even more preferably 1.7 or less.
When Mw and Mw/Mn are within the above ranges, the adhesive layer has good heat resistance and mechanical strength.
The elution curve of the sample containing the block copolymer [C] measured by gel permeation chromatography (GPC) may have a main peak and a second peak having a peak top showing a molecular weight smaller than that shown by the peak top of the main peak. The molecular weight shown by the peak top of the second peak is preferably 1000 or more. The ratio (second peak top sensitivity/main peak top sensitivity) of the RI detection sensitivity (main peak top sensitivity) (mV) shown by the peak top of the main peak to the RI detection sensitivity (main peak top sensitivity) (mV) shown by the peak top of the second peak is preferably 0.2 or less, more preferably 0.1 or less. The second peak may be generated by the deactivation of a part of the catalyst in the polymerization step. When the elution curve has a second peak, a modified hydrogenated block copolymer [E] in which an alkoxysilyl group or the like is introduced into the hydrogenated product of the block copolymer [C] can be used to obtain an adhesive layer with better adhesion.

The method for producing the block copolymer [C] is not particularly limited, and any known method can be used. Specifically, examples of the method for producing the block copolymer [C] include the methods described in WO 2003/018656 and WO 2011/096389.

<Hydrogenated block copolymer [D]>
The hydrogenated block copolymer [D] may be a polymer obtained by selectively hydrogenating only the carbon-carbon unsaturated bonds in the main chain and the side chain derived from the linear conjugated diene compound of the block copolymer [C], or may be a polymer obtained by hydrogenating the carbon-carbon unsaturated bonds in the main chain and the side chain derived from the linear conjugated diene compound of the block copolymer [C] and the carbon-carbon unsaturated bonds in the aromatic ring derived from the aromatic vinyl compound, or may be a mixture thereof.
In the adhesive layer, there is no significant difference in the storage modulus between the case where the carbon-carbon unsaturated bonds in the aromatic ring derived from the aromatic vinyl compound are hydrogenated and the case where they are not hydrogenated.

When only the carbon-carbon unsaturated bonds in the main chain and the side chain derived from the linear conjugated diene compound of the block copolymer [C] are selectively hydrogenated, the hydrogenation rate of the carbon-carbon unsaturated bonds in the main chain and the side chain is usually 95% or more, preferably 97% or more, and more preferably 99% or more, and the hydrogenation rate of the carbon-carbon unsaturated bonds in the aromatic ring derived from the aromatic vinyl compound is usually 10% or less, preferably 5% or less, and more preferably 3% or less.
The higher the hydrogenation rate of the carbon-carbon unsaturated bonds in the main chain and side chain derived from the linear conjugated diene compound, the better the weather resistance and heat deterioration resistance of the adhesive layer. In addition, by suppressing the hydrogenation of the carbon-carbon unsaturated bonds in the aromatic ring derived from the aromatic vinyl compound, the heat deterioration resistance of the adhesive layer can be easily maintained.

When the carbon-carbon unsaturated bonds in the main chain and side chain derived from the linear conjugated diene compound of the block copolymer [C] and the carbon-carbon unsaturated bonds in the aromatic ring derived from the aromatic vinyl compound are hydrogenated, the hydrogenation rate is 90% or more, preferably 95% or more, and more preferably 99% or more of the total carbon-carbon unsaturated bonds.
When the hydrogenation rate of the hydrogenated block copolymer [D] is within this range, the adhesive layer has excellent transparency and heat deterioration resistance, and is particularly preferred because it has excellent light resistance and a high heat distortion temperature compared to an adhesive layer using a hydrogenated block copolymer [D] in which only the carbon-carbon unsaturated bonds derived from a chain conjugated diene compound are selectively hydrogenated.

The hydrogenation rate of the carbon-carbon unsaturated bonds in the main chain and side chain derived from the linear conjugated diene compound and the hydrogenation rate of the carbon-carbon unsaturated bonds in the aromatic ring derived from the aromatic vinyl compound of the hydrogenated block copolymer [D] can be determined, for example, by measuring ^{the 1H} -NMR of the block copolymer [C] and the hydrogenated block copolymer [D].

The method and reaction form of hydrogenating the unsaturated bonds in the block copolymer [C] are not particularly limited, and may be carried out according to a known method.
Examples of a method for selectively hydrogenating the carbon-carbon unsaturated bonds in the main chain and the side chain derived from the linear conjugated diene compound of the block copolymer [C] include known hydrogenation methods described in JP-A-2015-78090 and the like.
In addition, examples of methods for hydrogenating the carbon-carbon unsaturated bonds in the main chain and side chain derived from the linear conjugated diene compound of the block copolymer [C] and the carbon-carbon unsaturated bonds in the aromatic ring derived from the aromatic vinyl compound include the methods described in WO 2011/096389, WO 2012/043708, and the like.

After completion of the hydrogenation reaction, 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 resulting solution to recover the hydrogenated block copolymer [D].
The recovered hydrogenated block copolymer [D] is usually formed into pellets, which can then be subjected to the subsequent reaction for introducing alkoxysilyl groups or the molding process into a sheet.

The molecular weight of the hydrogenated block copolymer [D] is, in terms of polystyrene, a weight average molecular weight (Mw) measured by GPC using THF as a solvent, usually 35,000 to 200,000, preferably 38,000 to 150,000, more preferably 40,000 to 100,000. The molecular weight distribution (Mw/Mn) of the hydrogenated block copolymer [D] is preferably 3 or less, more preferably 2 or less, particularly preferably 1.7 or less.
When Mw and Mw/Mn are within the above ranges, the adhesive layer has good heat resistance and mechanical strength.
The elution curve measured by GPC of a sample containing the hydrogenated block copolymer [D] may have a main peak and a second peak having a peak top showing a molecular weight smaller than that shown by the peak top of the main peak. The molecular weight shown by the peak top of the second peak is preferably 1000 or more. The detection sensitivity of the differential refractometer (RI) shown by the peak top of the main peak (main peak top sensitivity) (mV) relative to the detection sensitivity of the RI shown by the peak top of the second peak (second peak top sensitivity) (mV) is preferably 0.2 or less, more preferably 0.1 or less. The second peak may be generated by the deactivation of the catalyst in the polymerization step, or the partial cleavage of the polymer in the hydrogenation step. When the elution curve has a second peak, an adhesive layer having excellent adhesion and filling properties can be obtained by using a modified hydrogenated block copolymer [E] in which an alkoxysilyl group or the like is introduced into the hydrogenated block copolymer [D].

<Modified hydrogenated block copolymer [E]>
The modified hydrogenated block copolymer [E] is obtained by reacting the hydrogenated block copolymer [D] with an ethylenically unsaturated silane compound in the presence of an organic peroxide to introduce an alkoxysilyl group.
Examples of a method for introducing an alkoxysilyl group into the hydrogenated block copolymer [D] include known methods described in WO 2012/043708, JP 2015-78090 A, and the like.
By introducing an alkoxysilyl group into the hydrogenated block copolymer [D], the modified hydrogenated block copolymer [E] is endowed with strong adhesiveness to glass or metal.

Examples of the alkoxysilyl group include tri(alkoxy having 1 to 6 carbon atoms)silyl groups such as trimethoxysilyl group and triethoxysilyl group; (alkyl having 1 to 20 carbon atoms)di(alkoxy having 1 to 6 carbon atoms)silyl groups such as methyldimethoxysilyl group, methyldiethoxysilyl group, ethyldimethoxysilyl group, ethyldiethoxysilyl group, propyldimethoxysilyl group, and propyldiethoxysilyl group; (aryl)di(alkoxy having 1 to 6 carbon atoms)silyl groups such as phenyldimethoxysilyl group and phenyldiethoxysilyl group; and the like. Of these, trimethoxysilyl groups are particularly preferred from the viewpoint of imparting strong adhesion to the glass plate to the adhesive layer. The alkoxysilyl group may be bonded to the hydrogenated block copolymer [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.

The amount of alkoxysilyl groups introduced into the hydrogenated block copolymer [D] is usually 0.1 parts by mass or more and 10 parts by mass or less, preferably 0.2 parts by mass or more, more preferably 0.3 parts by mass or more, and preferably 5 parts by mass or less, more preferably 3 parts by mass or less, relative to 100 parts by mass of the hydrogenated block copolymer [D]. If the amount of alkoxysilyl groups introduced is too large, crosslinking between alkoxysilyl groups decomposed by a small amount of water or the like proceeds before the obtained modified hydrogenated block copolymer [E] is melt-molded into a desired shape, and problems such as gelation or reduced fluidity during melting and reduced moldability are likely to occur. In addition, if the amount of alkoxysilyl groups introduced is too small, problems such as insufficient adhesive strength to bond the interlayer to the glass plate via the adhesive layer are likely to occur. The introduction of alkoxysilyl groups can be confirmed by IR spectroscopy. In addition, the amount introduced can be calculated by ¹ H-NMR spectroscopy.

The ethylenically unsaturated silane compound to be used is not particularly limited, so long as it is capable of graft polymerization with the hydrogenated block copolymer [D] and introducing an alkoxysilyl group into the hydrogenated block copolymer [D]. As the ethylenically unsaturated silane compound, for example, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, p-styryltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 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 typically 0.1 parts by mass or more and 10 parts by mass or less, preferably 0.2 parts by mass or more, more preferably 0.3 parts by mass or more, and preferably 5 parts by mass or less, more preferably 3 parts by mass or less, per 100 parts by mass of the hydrogenated block copolymer [D].

As the organic peroxide, one having a one-minute half-life temperature of 170° C. or more and 190° C. or less is preferably used. For example, 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, etc. are preferably used. When these organic peroxides are used, the decomposition reaction of the organic peroxide and the reaction of the ethylenically unsaturated silane compound with the hydrogenated block copolymer [D] can proceed simultaneously, which is preferable.
These organic peroxides may be used alone or in combination of two or more.
The amount of the organic peroxide used is usually 0.01 part by mass or more and 1 part by mass or less, preferably 0.03 part by mass or more, more preferably 0.05 part by mass or more, and preferably 0.5 part by mass or less, and more preferably 0.3 part by mass or less, relative to 100 parts by mass of the hydrogenated block copolymer [D].

The method of reacting the hydrogenated block copolymer [D] with the ethylenically unsaturated silane compound in the presence of an organic peroxide is not particularly limited. For example, by kneading in a twin-screw kneader at a desired temperature for a desired time, an alkoxysilyl group can be introduced into the hydrogenated block copolymer [D]. The kneading temperature in the twin-screw kneader is usually 180°C or more and 220°C or less, preferably 185°C or more, more preferably 190°C or more, preferably 210°C or less, more preferably 200°C or less. 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.
Specifically, the introduction of alkoxysilyl groups into the hydrogenated block copolymer [D] may be performed by continuously kneading and extruding the hydrogenated block copolymer [D], the ethylenically unsaturated silane compound, and the organic peroxide at a temperature and residence time within the above ranges.

The molecular weight of the modified hydrogenated block copolymer [E] is not significantly different from that of the hydrogenated block copolymer [D] used as the raw material because the amount of alkoxysilyl groups introduced is small. On the other hand, since the modified hydrogenated block copolymer [E] is reacted with an ethylenically unsaturated silane compound in the presence of an organic peroxide, crosslinking and cleavage reactions of the polymer occur simultaneously, and the molecular weight distribution value of the modified hydrogenated block copolymer [E] becomes larger than that of the hydrogenated block copolymer [D].
The molecular weight of the hydrogenated modified block copolymer [E] is, in terms of polystyrene, a weight average molecular weight (Mw) measured by GPC using THF as a solvent, usually 35,000 to 200,000, preferably 38,000 to 150,000, more preferably 40,000 to 100,000. The molecular weight distribution (Mw/Mn) is preferably 3.5 or less, more preferably 3.0 or less, particularly preferably 2.5 or less.
When Mw and Mw/Mn are within the above ranges, the heat resistance and mechanical strength of the adhesive layer are maintained.
The elution curve measured by GPC of a sample containing the modified block copolymer hydrogenated [E] may have a main peak and a second peak having a peak top showing a molecular weight smaller than that shown by the peak top of the main peak. The molecular weight shown by the peak top of the second peak is preferably 1000 or more. The detection sensitivity of the differential refractometer (RI) shown by the peak top of the main peak (main peak top sensitivity) (mV) relative to the detection sensitivity of the RI shown by the peak top of the second peak (second peak top sensitivity) (mV) is preferably 0.2 or less, more preferably 0.1 or less. When the elution curve has a second peak, an adhesive layer with better adhesion can be obtained by using the modified block copolymer hydrogenated [E].

<Containing Agents>
The resin composition constituting the adhesive layer can contain various compounding agents in addition to the above-mentioned resin as the main component. The ratio of the resin in the resin composition constituting the adhesive layer is usually 70% by mass or more and 100% by mass or less, preferably 75% by mass or more, more preferably 80% by mass or more. By containing 70% by mass or more of the resin in the resin composition constituting the adhesive layer, the heat resistance and mechanical strength of the obtained adhesive layer are maintained.
Preferred compounding agents include tackifiers for adjusting adhesion to glass, adhesion imparting agents, ultraviolet absorbers for blocking ultraviolet rays, antioxidants and antiblocking agents for improving processability, etc., and light stabilizers for improving durability.

As the tackifier, a hydrocarbon polymer having a number average molecular weight of 300 to 10,000 is preferred. Specific examples of tackifiers include low molecular weight compounds such as polyisobutylene, polybutene, poly-4-methylpentene, poly-1-octene, ethylene-α-olefin copolymers, and hydrogenated products thereof; low molecular weight compounds such as polyisoprene, polyisoprene-butadiene copolymers, and styrene-isoprene copolymers, and hydrogenated products thereof. Among these, low molecular weight hydrogenated polyisobutylene, low molecular weight hydrogenated polyisoprene, and low molecular weight styrene-isoprene copolymers are preferred, in that they maintain transparency and light resistance and are excellent in the effect of imparting tack.

The amount of the tackifier to be added is usually 30 parts by mass or less, preferably 25 parts by mass or less, and more preferably 20 parts by mass or less, based on 100 parts by mass of the resin which is the main component.
If the blending amount of the tackifier is too large, the storage modulus of the interlayer film decreases, and there is a risk that the rigidity of the laminated glass of the present invention cannot be maintained.

Examples of adhesion promoters include petroleum resins such as 1,3-pentadiene-based petroleum resins, cyclopentadiene-based petroleum resins, and styrene-indene-based petroleum resins, and hydrides thereof; silane coupling agents such as vinylsilane-based, epoxysilane-based, acrylicsilane-based, and aminosilane-based silane coupling agents; and the like.
The amount of the adhesion promoter is usually 10 parts by mass or less, preferably 7 parts by mass or less, and more preferably 5 parts by mass or less, based on 100 parts by mass of the resin which is the main component.
If the amount of the adhesion promoter is too large, the storage modulus of the adhesive layer decreases, and the rigidity of the laminated glass of the present invention may not be maintained.

As the ultraviolet absorbing agent, for example, an oxybenzophenone-based compound, a benzotriazole-based compound, a salicylic acid ester-based compound, a benzophenone-based compound, a triazine-based compound, etc. can be used.
As the antioxidant, for example, phosphorus-based antioxidants, phenol-based antioxidants, sulfur-based antioxidants, etc. can be used.
As the light stabilizer, for example, a hindered amine light stabilizer can be used.
The ultraviolet absorbents, antioxidants, light stabilizers, and the like that are blended with the resin as the main component may each be used alone or in combination of two or more kinds.
The blending amount of the ultraviolet absorber, antioxidant, and 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, per 100 parts by mass of the resin which is the main component.

As a method for blending various additives with the resin, which is the main component, a commonly used known method can be applied. For example, a resin composition in which the additives are uniformly dispersed can be produced by a method in which the resin pellets and the additives are mixed evenly using a mixer such as a tumbler, ribbon blender, or Henschel type mixer, and then melt-mixed and extruded into pellets using a continuous melt kneader such as a twin-screw extruder; a resin is melt-kneaded and extruded into pellets using a twin-screw extruder equipped with a side feeder while the additives are continuously added from the side feeder; etc.

(Infrared Reflective Layer)
The infrared reflective layer of the interlayer film X used in the laminated glass of the present invention has a light transmittance in the thickness direction at a wavelength of 550 nm of usually 50% or more, preferably 60% or more, and more preferably 70% or more, and at a wavelength of 2000 nm of usually 20% or less, preferably 15% or less, and more preferably 10% or less.

Specifically, the infrared reflective layer may be (1) a film in which an infrared reflective film is formed on a transparent resin film that serves as a base material, or (2) a multilayer resin film in which several tens of layers of thermoplastic resins with different refractive indices are alternately laminated.

When the infrared reflective layer is a film in which an infrared reflective film is formed on a transparent resin film serving as a base material, the resin film is not particularly limited as long as it is transparent (light transmittance at a wavelength of 600 nm is 60% or more, preferably 70% or more, more preferably 80% or more) and has excellent rigidity, heat resistance, etc. For example, films made of synthetic resins such as polyester resins such as polyethylene terephthalate and polyethylene naphthalate; cycloolefin polymers; polycarbonate; polyethersulfone; nylon; etc. can be used. Among these, films made of polyester resins are preferred from the viewpoints of transparency, strength, economy, etc., and films made of polyethylene terephthalate are particularly preferred because they soften at a temperature of around 140 ° C. during the lamination process during the production of laminated glass and can be molded to fit the shape of glass having a curved surface.

Examples of the infrared reflective film formed on the resin film include an infrared reflective film formed by alternately laminating a metal oxide layer and a metal layer, and an infrared reflective film formed by alternately laminating high refractive index layers and low refractive index layers of a dielectric material such as a metal oxide in multiple layers.
Here, examples of metal oxides constituting the metal oxide layer and the dielectric include _TiO2 , _Nb2O5 , _{Ta2O5 , SiO2} , _Al2O3 , _ZrO2 , _In2O3 , MgF2, etc. Examples of metals constituting the metal layer include Au, Ag, Cu, Al, _Pd , Pt, Sn, In, Zn, _Ti , _Cd , Fe, Co, Cr, Ni, and alloys of _two or more of these metals.

Examples of the infrared reflective layer that is a film having a multilayer structure in which two or more types of thermoplastic resins having different refractive indexes are alternately laminated in several tens of layers include a multilayer film consisting of a polyethylene terephthalate layer and a polyester layer containing cyclohexane dimethanol carboxylate units, a multilayer film consisting of a polyethylene terephthalate layer and a polyethylene naphthalate layer, a multilayer film consisting of a polyethylene terephthalate layer and a methyl methacrylate copolymer layer, a multilayer film consisting of a polyethylene naphthalate layer and a polymethyl methacrylate layer, and a multilayer film consisting of a polyvinyl butyral layer and a polystyrene layer.
Furthermore, when the infrared reflective layer is a film having a multilayer structure in which two or more types of thermoplastic resins having different refractive indexes are alternately laminated in several tens of layers, when the laminated glass of the present invention is used for automobile windows or the like, it does not block radio waves and therefore does not interfere with the use of devices that utilize electromagnetic waves, such as mobile phones.

The thickness of the infrared reflective layer is not particularly limited and is typically 20 to 200 μm, preferably 30 to 150 μm, and more preferably 40 to 100 μm.

In addition, the infrared reflective layer used in the present invention may be a film that is generally commercially available as an infrared reflective film, heat shielding film, heat ray reflective film, infrared cut film, etc.

(Functional layer)
The interlayer 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 be preferably disposed between the first adhesive layer and the infrared reflective layer and/or between the second adhesive layer and the infrared reflective layer.
Examples of functional layers include a resin layer for further reducing the thermal conductivity of the laminated glass, a resin layer with a high elastic modulus for adjusting the storage elastic modulus of the interlayer film, a resin layer with excellent mechanical strength for increasing the penetration resistance of the laminated glass, and a vibration absorbing layer for imparting sound insulation to the laminated glass.

When the functional layer is a resin layer for reducing the thermal conductivity of the laminated glass, the resin layer may be the same layer as the first and/or second adhesive layer.
When the functional layer is a resin layer having a high elastic modulus, specific examples of the resin constituting the resin layer include layers made of resins having excellent transparency, such as hydrogenated block copolymers having a high styrene content, polymethyl methacrylate, cycloolefin polymers, polystyrene, styrene-acrylonitrile copolymers, and styrene-methyl methacrylate copolymers.
When the functional layer is a resin layer having excellent mechanical strength, specific examples of the resin constituting the resin layer include layers made of transparent resins such as polyethylene terephthalate, polynaphthalene terephthalate, and polycarbonate.
When the functional layer is a vibration absorbing layer, specific examples of the resin constituting the resin layer include a styrene-diene block copolymer and/or its hydrogenated product, an acrylic block copolymer, a polyvinyl acetal resin containing a plasticizer, and the like, which have a maximum value of loss tangent (tan δ) in the viscoelastic properties in the temperature range of -20°C to 20°C.

(Method of forming interlayer film)
Methods for forming the interlayer film X used in the laminated glass of the present invention include a method in which, prior to the production of the laminated glass, the first adhesive layer, the infrared reflective layer, the second adhesive layer, and a single-layer or multi-layer functional layer, if necessary, disposed between the first adhesive layer and the infrared reflective layer and/or between the second adhesive layer and the infrared reflective layer, are appropriately laminated, bonded, and integrated to form the interlayer film X; a method in which, in the step of producing the laminated glass, the first adhesive layer, the infrared reflective layer, the second adhesive layer, and a single-layer or multi-layer functional layer, if necessary, disposed between the first adhesive layer and the infrared reflective layer and/or between the second adhesive layer and the infrared reflective layer, which have been formed in advance, are appropriately laminated, bonded, and integrated between two glass sheets, thereby forming the interlayer film X at the same time as the laminated glass is produced; and the like.

The method for molding a single adhesive layer, a multilayer sheet consisting of a first adhesive layer/functional layer/third adhesive layer, etc. is not particularly limited, and known methods such as melt extrusion molding, multilayer coextrusion molding, extrusion lamination, thermal lamination, calendar molding, etc. can be applied.

For example, when a single-layer adhesive layer made of a resin composition containing the hydrogenated modified block copolymer [E] as a main component is molded by melt extrusion molding, the resin temperature is usually set to a range of 180 to 240°C, preferably 190 to 230°C, and more preferably 200 to 220°C, and the resin is molded into a sheet by melt extrusion molding.
If the resin temperature is too low, the fluidity is deteriorated, and the extrusion speed of the adhesive layer cannot be increased, which may be industrially disadvantageous.If the resin temperature is too high, the adhesive layer formed may have poor adhesion to the glass surface, or the storage stability of the adhesive layer may decrease, resulting in a decrease in adhesion to glass after long-term storage of the adhesive layer.
In addition, for example, when molding a multilayer sheet having a functional layer in which an outer layer is made of a resin composition mainly composed of a modified hydrogenated block copolymer [E] and an inner layer is made of a resin composition mainly composed of a hydrogenated block copolymer [D] having a high elastic modulus, a molding method using a two-kind three-layer co-extrusion molding machine or the like; a method in which single resin layers previously molded by an extrusion molding method or the like are laminated together by a method such as thermal lamination to form an adhesive layer; and the like can be applied.

(c) Laminated Glass The laminated glass of the present invention comprises at least two glass plates including a first glass plate and a second glass plate, and at least one interlayer film including an interlayer film X, and the at least two glass plates are bonded together via the interlayer film. Here, the first glass plate and the second glass plate are bonded together via the interlayer 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, particularly preferably 0.25 W/(m·K) or less. If 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 a glass plate (usually about 1 W/(m·K)), and is smaller than the thermal conductivity (about 0.6 W/(m·K)) of a laminated glass composed of two glass plates with a thickness of 2 mm and an interlayer film mainly composed of PVB with a thickness of 0.76 mm, which is commonly used as a laminated glass for automobiles, and therefore has excellent heat insulation. The thermal conductivity of the laminated glass in the thickness direction at 20°C is a value obtained by measuring in a temperature atmosphere of 20°C using a thermal conductivity measuring device in accordance with the ASTM E1530 method (disk heat flow meter method).

In the laminated glass of the present invention, when the total thickness of at least two sheets of glass is tg and the total thickness of at least one interlayer is ti, the ratio of ti to tg (ti/tg) must be 0.7 or more, preferably 1.0 or more, and more preferably 1.3 or more.
By making the ratio of ti to tg (ti/tg) equal to or greater than the above value, it becomes easy to make the thermal conductivity in the thickness direction of the laminated glass of the present invention equal to or less than the above-mentioned predetermined value.
The ratio of ti to tg (ti/tg) is usually 3.0 or less.

The light transmittance in the thickness direction of the laminated glass of the present invention must 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, preferably 15% or less, more preferably 10% or less. This laminated glass has a high visible light transmittance and a low infrared transmittance, and has both heat insulation and heat shielding properties. In this specification, the light transmittance is a value determined by measurement in accordance with JIS K7375 using an integrating sphere spectrophotometer.

In addition, it is desirable that the laminated glass of the present invention has high rigidity. The flexural 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 even more preferably 20 GPa or more. The flexural modulus of the laminated glass is a value obtained by measuring the flexural modulus of the laminated glass using an autograph equipped with a heating oven for temperature control, with reference to JIS R1602 (four-point bending test method), using a rotating four-point bending test jig under the following conditions: support distance: upper = 10-27 mm, lower = 30-80 mm, support rod diameter 6 mm, and temperature 40°C.

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, even more preferably 2.5 mm or more, particularly preferably 4.0 mm or more, preferably 9 mm or less, more preferably 8 mm or less, even more preferably 7 mm or less, particularly preferably 6.0 mm or less. If the thickness of the laminated glass is within the above range, it can be suitably used as display glass, automotive glass, building glass, etc.
The shape of the laminated glass may be a flat plate shape used for building materials, displays, etc., or a curved shape such as laminated glass for automobiles.

The method for producing the laminated glass of the present invention is not particularly limited.
For example, a general method for producing curved laminated glass such as laminated glass for automobiles can include laminating a first glass plate/a first adhesive layer/an infrared reflective film/a second adhesive layer/a second glass plate in this order to produce a laminate, placing this laminate in a degassable flexible resin bag to degas the inside, and then placing the bag in an autoclave and bonding the laminate under conditions of a temperature of 100 to 150° C. and a pressure of 0.01 to 1.5 MPa.
In the case of flat laminated glass such as laminated glass for buildings, the laminated glass may be bonded and integrated by heating and pressurizing the above-mentioned laminate using a vacuum laminator or a heat press.

The laminated glass of the present invention has excellent heat insulating and heat shielding properties, and is therefore useful as a window material, wall material, roof material, floor material, partition material, etc. for automobiles, railway vehicles, ships, buildings, etc. In addition, the laminated glass of the present invention can improve heat insulating and heat shielding properties while maintaining rigidity even when the thickness of the interlayer is increased and the thickness of the glass plate is reduced without increasing the thickness of the entire laminated glass, which also contributes to reducing the weight of the laminated glass. For this reason, by using the laminated glass of the present invention as side glass, rear glass, roof glass, windshield, etc. in automobile applications, and as window glass, partition glass, ceiling glass, etc. in building material applications, it is expected that the laminated glass of the present invention will be effective in saving energy in heating and cooling, improving fuel efficiency, etc.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. In addition, "parts" and "%" are based on mass unless otherwise specified.
In a polymer prepared by copolymerizing a plurality of compounds, the mass fraction of a structural unit derived from a certain compound in the entire polymer is calculated from the mass ratio (feed ratio) of the certain compound to the total mass of all compounds polymerized during the preparation of the polymer and the measured polymerization conversion rate of the certain compound.

The evaluation in this example is carried out 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 hydrogenated block copolymer [D] were measured in terms of standard polystyrene by GPC using THF as an eluent at 40° C. The measuring device used was a Tosoh HLC8320GPC.
(2) Hydrogenation Rate The hydrogenation rates of the main chain, side chain and aromatic ring of the hydrogenated block copolymer [D] were calculated by measuring ¹ H-NMR of the block copolymer [C] and the hydrogenated block copolymer [D].

(3) Storage modulus of interlayer (G')
For the test pieces of the interlayer film produced in each Example and Comparative Example, a viscoelasticity measuring device (ARES, manufactured by TA Instruments Japan) was used to measure the viscoelasticity spectrum based on JIS K7244-2 method (torsion pendulum method) under conditions of angular frequency: 1 rad/sec, measurement temperature range: -100 to +100°C, and heating rate: 5°C/min. From the obtained viscoelasticity spectrum, the storage modulus G' of the interlayer film at 40°C was determined.

(4) Transparency and heat shielding property of laminated glass Each of the laminated glasses produced in the respective Examples and Comparative Examples was used as a test piece, and the light transmittance in the thickness direction at wavelengths of 550 nm and 2000 nm was measured using an integrating sphere spectrophotometer (V-670, manufactured by JASCO Corporation) in accordance with JIS K7375 (Determination of total light transmittance and total light reflectance for plastics).
Regarding the transparency of the laminated glass, 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 properties of the laminated glass were evaluated as good when the light transmittance at a wavelength of 2000 nm was 20% or less, and as poor when it exceeded 20%.

(5) Thermal insulation property of laminated glass The laminated glass produced in each of the Examples and Comparative Examples was used as a test piece, and thermal conductivity in the thickness direction was measured in a temperature atmosphere of 20° C. in accordance with the ASTM E1530 method (disk heat flow meter method) using a thermal conductivity measuring device (product name: Unithermo 2021 type, manufactured by Antar Corporation).
Regarding the heat insulating properties of the laminated glass, a thermal conductivity of the laminated glass in the thickness direction of the glass was rated as good when it was 0.35 W/(m·K) or less, and a thermal conductivity of the laminated glass in the thickness direction of the glass was rated as poor when it exceeded 0.35 W/(m·K).

(6) Rigidity of Laminated Glass Using each of the laminated glasses produced in the respective Examples and Comparative Examples as test pieces, bending tests were performed using an autograph equipped with a heating oven (INSTRON 5582, manufactured by Instron Corp.) and a rotary four-point bending test jig under the conditions of support distance: upper part = 10 to 27 mm, lower part = 30 to 80 mm, support rod diameter 6 mm, and temperature 40° C., with reference to JIS R1602 method (four-point bending test method), to measure the bending modulus.
Regarding the rigidity of the laminated glass, a flexural modulus of the laminated glass of 11 GPa or more was evaluated as good, and a flexural modulus of the laminated glass of less than 11 GPa was evaluated as poor.

[Production Example 1] Production of adhesive layer [G1] (block copolymer [C1])
In a reactor equipped with a stirrer and the inside of which was sufficiently replaced with nitrogen, 400 parts of dehydrated cyclohexane, 10 parts of dehydrated styrene, and 0.475 parts of dibutyl ether were placed. While stirring the entire volume at 60°C, 0.88 parts of n-butyllithium (15% cyclohexane solution) was added to initiate polymerization. Subsequently, while stirring the entire volume at 60°C, 15 parts of dehydrated styrene were continuously added to the reactor over 40 minutes to advance the polymerization reaction, and after the addition was completed, the entire volume was stirred for another 20 minutes at 60°C. When the reaction liquid was measured by gas chromatography (GC), the polymerization conversion at this point was 99.5%.
Next, 50.0 parts of dehydrated isoprene was continuously added to the reaction solution over a period of 130 minutes, and stirring was continued for 30 minutes after the completion of the addition. At this point, the reaction solution was analyzed by GC, and the polymerization conversion rate was found to be 99.5%.
Thereafter, 25.0 parts of dehydrated styrene was continuously added to the reaction solution over a period of 70 minutes, and the mixture was stirred for 60 minutes after the completion of the addition. At this point, the reaction solution was analyzed by gas chromatography (GC), and the polymerization conversion rate was found to be almost 100%.

At this point, 0.5 parts of isopropyl alcohol was added to stop the reaction, yielding a polymer solution containing an [A]-[B]-[A] type block copolymer [C1]. The weight average molecular weight (Mw) of the block copolymer [C1] was 47,200, the molecular weight distribution (Mw/Mn) was 1.34, and wa:wb = 50:50.

(Hydrogenated block copolymer [D1])
Next, the above polymer solution was transferred to a pressure-resistant reactor equipped with a stirrer, and 4.0 parts of a diatomaceous earth-supported nickel catalyst (product name "E22U", nickel loading 60%, manufactured by JGC Catalysts and Chemicals) as a hydrogenation catalyst and 30 parts of dehydrated cyclohexane were added and mixed. The inside of the reactor was replaced with hydrogen gas, and hydrogen was further 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 hydrogenated block copolymer [D1] contained in the reaction solution obtained by the hydrogenation reaction had a weight average molecular weight (Mw) of 49,900 and a molecular weight distribution (Mw/Mn) of 1.36.

After completion of the hydrogenation reaction, the reaction solution was filtered to remove the hydrogenation catalyst, and then 2.0 parts of a xylene solution in which 0.1 part of a phenolic antioxidant, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (product name: Songnox (registered trademark) 1010, manufactured by Matsubara Sangyo Co., Ltd.), was dissolved was added and dissolved.
Next, cyclohexane, xylene and other volatile components were removed from the solution using a cylindrical concentrating dryer (product name "CONTROL", manufactured by Hitachi, Ltd.) at a temperature of 260° C. and a pressure of 0.001 MPa or less. The molten polymer was extruded in the form of a strand from a die and cooled, and then 95 parts of pellets of the hydrogenated block copolymer [D1] were produced using a pelletizer.
The resulting pellet-like hydrogenated block copolymer [D1] had a weight average molecular weight (Mw) of 49,500 and a molecular weight distribution (Mw/Mn) of 1.40. The hydrogenation rates of the carbon-carbon unsaturated bonds in the main chain and side chain derived from the linear conjugated diene and the carbon-carbon unsaturated bonds derived from the aromatic ring derived from the aromatic vinyl compound were all approximately 100%.

(Modified hydrogenated block copolymer [E1])
To 100 parts of the obtained pellets of the hydrogenated block copolymer [D1], 2.0 parts of vinyltrimethoxysilane and 0.1 part of 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (product name "Perhexa (registered trademark) 25B", manufactured by NOF Corporation) were 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 into a strand shape, air-cooled, and then cut with a pelletizer to obtain 96 parts of pellets of a modified hydrogenated block copolymer [E1] having alkoxysilyl groups.

10 parts of the resulting modified hydrogenated block copolymer [E1] pellets were dissolved in 100 parts of cyclohexane, and then poured into 400 parts of dehydrated methanol to coagulate the modified hydrogenated block copolymer [E1], and the coagulated product was filtered off. The filtrate was vacuum dried at 25° C. to isolate 9.0 parts of crumbs of the modified hydrogenated block copolymer [E1].
When the FT-IR spectrum of the modified hydrogenated block copolymer [E1] was measured, new absorption bands due to the Si- _OCH3 group at 1090 cm ^-1 and the Si- _CH2 group at 825 cm ^-1 and 739 cm ^-1 were observed at positions different from the absorption bands (1075 cm ^-1 , 808 cm ^- 1, and 766 cm ^-1 ) due to the Si- _OCH3 group and the Si-CH group of vinyltrimethoxysilane.
In addition, when the ^1H -NMR spectrum (in deuterated chloroform) of the modified hydrogenated block copolymer [E1] was measured, a peak due to the protons of the methoxy group was observed at 3.6 ppm, and it was confirmed from the peak area ratio that 1.8 parts of vinyltrimethoxysilane were bonded to 100 parts of the hydrogenated block copolymer [D1].

(Adhesive layers [G1-1] and [G1-2])
100 parts of the pellets of the modified hydrogenated block copolymer [E1] obtained above was mixed with 0.3 parts of an ultraviolet absorber, 2-(5-chloro-2H-benzotriazol-2-yl)-6-tert-butyl-p-cresol (manufactured by Sumitomo Chemical Co., Ltd., product name "SUMISORB (registered trademark) 300"), and the resulting mixture was extrusion-molded under the conditions of a molten resin temperature of 200 ° C., a T-die temperature of 200 ° C., and a cast roll temperature of 60 ° C. using a twin-screw kneader (manufactured by Toshiba Machine Co., Ltd., TEM37B) equipped with a 37 mm φ screw, a T-die type film melt extrusion molding machine (T-die width 400 mm), a cast roll (with embossed pattern) and an extrusion sheet molding machine equipped with a sheet take-up device, to obtain adhesive layers [G1-1] (thickness 0.76 mm, width 330 mm) and [G1-2] (thickness 0.38 mm, width 330 mm) mainly composed of the modified hydrogenated block copolymer [E1].
The adhesive layers [G1-1] and [G1-2] were each formed by pressing one side of the extruded sheet against an embossing roll with a nip roll to transfer the embossed pattern. The resulting adhesive layers [G1-1] and [G1-2] were each wound up on a roll and collected.
The thermal conductivity of the adhesive layers [G1-1] and [G1-2] in the thickness direction was measured in accordance with ASTM E1530 and was found to be 0.15 W/(m·K) for both.

[Production Example 2] Production of adhesive layer [G2] (block copolymer [C2])
The same reactor as in Production Example 1 was used, and 400 parts of dehydrated cyclohexane, 10 parts of dehydrated styrene, and 0.475 parts of dibutyl ether were added. While stirring the entire volume at 60°C, 0.68 parts of n-butyllithium (15% cyclohexane solution) was added to initiate polymerization. Subsequently, while stirring the entire volume at 60°C, 10.0 parts of dehydrated styrene was continuously added to the reactor over 25 minutes to advance the polymerization reaction, and after the addition was completed, the entire volume was stirred for another 20 minutes at 60°C. The reaction liquid was measured by gas chromatography (GC), and the polymerization conversion at this point was 99.5%.
Next, 60.0 parts of dehydrated isoprene was continuously added to the reaction solution over a period of 150 minutes, and after the addition was completed, stirring was continued for 30 minutes. At this point, the reaction solution was analyzed by GC, and the polymerization conversion rate was found to be 99.5%.
Thereafter, 20.0 parts of dehydrated styrene was continuously added to the reaction solution over a period of 50 minutes, and the mixture was stirred for 60 minutes after the addition was completed. At this point, the reaction solution was analyzed by GC, and the polymerization conversion rate was found to be almost 100%.

At this point, 0.5 parts of isopropyl alcohol was added to stop the reaction, yielding a polymer solution containing the [A]-[B]-[A] type block copolymer [C2]. The weight average molecular weight (Mw) of the block copolymer [C2] was 61,600, the molecular weight distribution (Mw/Mn) was 1.35, and wa:wb = 40:60.

(Hydrogenated block copolymer [D2])
Next, the polymer solution obtained as described above was transferred to a pressure-resistant reactor equipped with a stirrer, and a solution of 0.042 parts of bis(cyclopentadienyl)titanium dichloride and 0.122 parts of diethylaluminum chloride in 1.0 part of toluene was added as a hydrogenation catalyst and mixed in. The inside of the reactor was replaced with hydrogen gas, and hydrogen was further supplied while stirring the solution, and a hydrogenation reaction was carried out at a temperature of 90° C. and a pressure of 1.0 MPa for 5 hours.
The hydrogenated block copolymer [D2] after the hydrogenation reaction had a weight average molecular weight (Mw) of 62,900 and a molecular weight distribution (Mw/Mn) of 1.35.

After the hydrogenation reaction was completed, 0.10 parts of water was added to the reaction solution, and the mixture was stirred at 60° C. for 60 minutes. The mixture was then cooled to 30° C. or less, and 1.5 parts of activated clay (product name: Galleon Earth (registered trademark), manufactured by Mizusawa Chemical Industries, Ltd.) and 1.5 parts of talc (product name: Microace (registered trademark), manufactured by Nippon Talc Co., Ltd.) were added, and the reaction solution was filtered to remove insoluble matter. 1.0 part of a xylene solution in which 0.1 part of a phenolic antioxidant, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], was dissolved, was added to the filtered solution to dissolve it.
Next, in the same manner as in Production Example 1, 92 parts of pellets of the hydrogenated block copolymer [D2] were prepared.
The resulting pellet-like hydrogenated block copolymer [D2] had a weight average molecular weight (Mw) of 62,300 and a molecular weight distribution (Mw/Mn) of 1.35. The hydrogenation rate of the carbon-carbon unsaturated bonds in the main chain and side chain derived from the linear conjugated diene compound was 99%, and the hydrogenation rate of the carbon-carbon unsaturated bonds in the aromatic ring derived from the aromatic vinyl compound was less than 5%.

(Modified hydrogenated block copolymer [E2])
96 parts of pellets of a modified hydrogenated block copolymer [E2] having an alkoxysilyl group were obtained in the same manner as in Production Example 1, except that the pellets of the hydrogenated block copolymer [D2] were used instead of the pellets of the hydrogenated block copolymer [D1].

The resulting modified hydrogenated block copolymer [E2] was analyzed in the same manner as in Production Example 1, and it was confirmed that 1.8 parts of vinyltrimethoxysilane were bonded to 100 parts of hydrogenated block copolymer [D2].

(Adhesive layers [G2-1] and [G2-2])
Except for using the hydrogenated modified block copolymer [E2] instead of the hydrogenated modified block copolymer [E1], the same procedure as in Production Example 1 was repeated to obtain adhesive layers [G2-1] (thickness 0.76 mm, width 330 mm) and [G2-2] (thickness 0.38 mm, width 330 mm) mainly composed of the hydrogenated modified block copolymer [E2].
The thermal conductivity of the adhesive layers [G2-1] and [G2-2] in the thickness direction was measured in accordance with ASTM E1530 and was found to be 0.15 W/(m·K) for both.

[Production Example 3] Production of infrared reflective layer [H1] An infrared reflective film having a layer structure of In ₂ O ₃ (30 nm)/Ag (10 nm)/In ₂ O ₃ (60 nm)/Ag (10 nm)/In ₂ O ₃ (30 nm) was laminated on one side of a polyethylene terephthalate film (trade name: Lumirror, thickness 50 μm, manufactured by Toray Industries, Inc.) measuring 40 cm in length and 40 cm in width by a DC magnetron sputtering method, to produce an infrared reflective layer [H1]. 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. The light transmittance in the thickness direction of the infrared reflective layer [H1] was measured using an integrating sphere spectrophotometer (V-670, manufactured by JASCO Corporation) in accordance with JIS K7375 (Method of determining total light transmittance and total light reflectance of plastics).

[Example 1]
(Laminated glass for evaluating thermal insulation properties [K1-1])
Between two circular cut pieces of blue plate glass (diameter 50 mm, thickness 1.1 mm, thermal conductivity: 1.0 W/(m·K), light transmittance: 91% (550 nm, 2000 nm)), two adhesive layers [G1-1] (diameter 50 mm, thickness 0.76 mm) produced in Production Example 1 and one infrared reflective layer [H1] (diameter 50 mm, thickness 0.05 mm) produced in Production Example 3, which were also cut into circles, were placed in the order of glass plate/[G1-1]/[H1]/[G1-1]/glass plate. This laminate was placed in a 75 μm thick resin bag having a layer structure of nylon/polypropylene, and the opening was heat-sealed while degassing the inside of the bag using a sealing packer (BH-951, manufactured by Panasonic Corporation) to hermetically package the laminate.
The sealed laminate was then placed in an autoclave and treated at a temperature of 140° C. and a pressure of 0.8 MPa for 30 minutes to produce a laminated glass [K1-1] having a layer structure of glass plate/[G1-1]/[H1]/[G1-1]/glass plate.
The appearance of the obtained laminated glass [K1-1] was good, with no defects such as air bubbles being observed. In addition, the ratio (ti/tg) of the total thickness of the interlayer film (ti) to the total thickness of the glass plates (tg) was 0.71.

(Laminated glass for evaluating transparency, heat shielding properties and rigidity [K1-2])
In the same manner as in the preparation of the laminated glass [K1-1], two sheets of blue plate glass (length 100 mm, width 20 mm, thickness 1.1 mm), two sheets of adhesive layers [G1-1] (length 100 mm, width 20 mm, thickness 0.76 mm) and one sheet of infrared reflective layer [H1] (length 100 mm, width 20 mm, thickness 0.05 mm) were used and arranged in the following order: glass plate/[G1-1]/[H1]/[G1-1]/glass plate, to prepare laminated glass [K1-2].

(Interlayer film for measuring storage modulus [J1])
A laminated glass [K1-3] was produced in the same manner as the laminated glass [K1-2], except that a PET film (manufactured by Toray Industries, product name "Lumirror (registered trademark) R75", thickness 75 μm) was further used as a release film, and the PET film was placed between the glass plate and the adhesive layer [G1-1] when the laminate was produced. The obtained laminated glass [K1-3] was peeled off from the PET film surface, and an interlayer 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 prepare a test piece for viscoelasticity measurement.

(Storage modulus of interlayer film)
The storage modulus of the produced interlayer film [J1] was 8.8×10 ⁷ Pa.
(Evaluation of transparency and heat shielding properties)
The produced laminated glass [K1-2] had a light transmittance in the thickness direction of 77% at 550 nm and 5% at 2000 nm, and was evaluated as having good transparency and good heat insulation properties.
(Evaluation of Thermal Insulation)
The thermal conductivity of the produced laminated glass [K1-1] in the thickness direction was 0.30 W/(m·K), and the heat insulating property was evaluated as good.
(Rigidity evaluation)
The prepared laminated glass [K1-2] had a flexural modulus of 31 GPa, and the rigidity of the laminated glass was evaluated as good.
The results are shown in Table 1.

[Example 2]
A laminated glass [K2-1] for evaluating thermal insulation property, a laminated glass [K2-2] for evaluating transparency, heat shielding property, and rigidity, and an interlayer film [J2] consisting of a five-layer structure of [G1-1]/[H1]/[G1-1]/[G1-1]/[G1-1]/[G1-1] were prepared in the same manner as in Example 1, except that two adhesive layers [G1-1] and one infrared reflective layer [H1] were used, and two more sheets of the same [G1-1] as the adhesive layers were used as functional layers to reduce the thermal conductivity of the laminated glass, and the layers were arranged in the following order: glass plate/[G1-1]/[H1]/[G1-1]/[G1-1]/[G1-1]/glass plate.
The ratio (ti/tg) of the total thickness (ti) of the interlayers to the total thickness (tg) of the glass plates of the laminated glasses [K2-1] and [K2-2] was 1.40.

(Storage modulus of interlayer film)
The storage modulus of the produced interlayer film [J2] was 8.6×10 ⁷ Pa.
(Evaluation of transparency and heat shielding properties)
The produced laminated glass [K2-2] had a light transmittance in the thickness direction of 74% at 550 nm and 5% at 2000 nm, and was evaluated as having good transparency and good heat insulation properties.
(Evaluation of Thermal Insulation)
The thermal conductivity of the produced laminated glass [K2-1] in the thickness direction was 0.23 W/(m·K), and the heat insulating property was evaluated as good.
(Rigidity evaluation)
The prepared laminated glass [K2-2] had a flexural modulus of 22 GPa, and the rigidity of the laminated glass was evaluated as good.
The results are shown in Table 1.

[Comparative Example 1]
In addition to using two adhesive layers [G1-1] and one infrared reflective layer [H1], one functional layer, which is the same as the adhesive layer [G1-1] as a resin layer for reducing the thermal conductivity of the laminated glass, and one laminated glass interlayer film sheet [G3] (manufactured by Solutia, product name "Saflex (registered trademark) RF41", thickness 0.76 mm) mainly composed of polyvinyl butyral resin, were used, and the layer structure of the laminated glass was arranged in the order of glass plate/[G1-1]/[H1]/[G1-1]/[G3]/[G1-1]/glass plate. Except for this, a laminated glass [K3-1] for evaluating thermal insulation property, a laminated glass [K3-2] for evaluating transparency, heat shielding property, and rigidity, and an interlayer film [J3] having a five-layer structure of [G1-1]/[H1]/[G1-1]/[G3]/[G1-1] were prepared in the same manner as in Example 1.
The ratio (ti/tg) of the total thickness (ti) of the interlayers to the total thickness (tg) of the glass plates of the laminated glasses [K3-1] and [K3-2] was 1.40.
The thermal conductivity of the laminated glass interlayer sheet [G3] used above in the thickness direction was measured in accordance with ASTM E1530 and was found to be 0.17 W/(m·K).

(Storage modulus of interlayer film)
The storage modulus of the produced interlayer film [J3] was 0.58×10 ⁷ Pa, which did not satisfy the requirements of the present invention.
(Evaluation of transparency and heat shielding properties)
The produced laminated glass [K3-2] had a light transmittance in the thickness direction of 74% at 550 nm and 5% at 2000 nm, and was evaluated as having good transparency and good heat insulation properties.
(Evaluation of Thermal Insulation)
The thermal conductivity in the thickness direction of the produced laminated glass [K3-1] was 0.25 W/(m·K), and the heat insulating property was evaluated as good.
(Rigidity evaluation)
The prepared laminated glass [K3-2] had a flexural modulus of elasticity of only 3 GPa, which was a low value, and was evaluated as having poor rigidity.
The results are shown in Table 1.

[Comparative Example 2]
A laminated glass [K4-1] for evaluating thermal insulation property, a laminated glass [K4-2] for evaluating transparency, heat shielding property, and rigidity, and an interlayer film [J4] having a three-layer structure of [G1-2]/[H1]/[G1-2] were prepared in the same manner as in Example 1, except that two glass plates with a thickness of 1.1 mm and two adhesive layers [G1-2] were used and the layers were arranged in the following order: glass plate/[G1-2]/[H1]/[G1-2]/glass plate.
The ratio (ti/tg) of the sum of the thicknesses of the interlayers (ti) to the sum of the thicknesses of the glass plates (tg) of the laminated glasses [K4-1] and [K4-2] was 0.37, which did not satisfy the requirements of the present invention.

(Storage modulus of interlayer film)
The storage modulus of the produced interlayer film [J4] was 9.0×10 ⁷ Pa.
(Evaluation of transparency and heat shielding properties)
The produced laminated glass [K4-2] had a light transmittance in the thickness direction of 77% at 550 nm and 5% at 2000 nm, and was evaluated as having good transparency and good heat insulation properties.
(Evaluation of Thermal Insulation)
The thermal conductivity in the thickness direction of the produced laminated glass [K4-1] was a large value of 0.41 W/(m·K), and the heat insulation property was evaluated as poor.
(Rigidity evaluation)
The prepared laminated glass [K4-2] had a flexural modulus of 42 GPa, and the rigidity of the laminated glass was evaluated as good.
The results are shown in Table 1.

[Comparative Example 3]
A laminated glass [K5-1] for evaluating heat insulation and a laminated glass [K5-2] for evaluating transparency, heat shielding properties and rigidity were produced in the same manner as in Example 1, except that two glass plates with a thickness of 2.1 mm and one sheet of the sheet [G3] for laminated glass interlayer were used and the layers were arranged in the order of glass plate/[G3]/glass plate. The sheet [G3] for glass interlayer was cut into a length of 70 mm and a width of 10 mm to produce an interlayer [J5], which was used as a test piece for measuring viscoelasticity.
The ratio (ti/tg) of the total thickness of the interlayer (ti) to the total thickness of the glass plates (tg) of the laminated glasses [K5-1] and [K5-2] was 0.18, which did not satisfy the requirements of the present invention.

(Storage modulus of interlayer film)
The storage modulus of the produced interlayer film [J5] was 0.15×10 ⁷ Pa, which did not satisfy the requirements of the present invention.
(Evaluation of transparency and heat shielding properties)
The produced laminated glass [K5-2] had a light transmittance in the thickness direction of 78% at 550 nm and 88% at 2000 nm, and the transparency was evaluated as good, while the heat insulation property was evaluated as poor.
(Evaluation of Thermal Insulation)
The thermal conductivity in the thickness direction of the produced laminated glass [K5-1] was a large value of 0.60 W/(m·K), and the heat insulation property was evaluated as poor.
(Rigidity evaluation)
The prepared laminated glass [K5-2] had a flexural modulus of 11 GPa, and the rigidity of the laminated glass was evaluated as good.
The results are shown in Table 1.

[Example 3]
A laminated glass [K6-1] for evaluating thermal insulation property, a laminated glass [K6-2] for evaluating transparency, heat shielding property, and rigidity, and an interlayer film [J6] having a three-layer structure of [G2-1]/[H1]/[G2-1] were prepared 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].
The ratio (ti/tg) of the total thickness (ti) of the interlayers to the total thickness (tg) of the glass plates of the laminated glasses [K6-1] and [K6-2] was 0.71.

(Storage modulus of interlayer film)
The storage modulus of the produced interlayer film [J6] was 4.3×10 ⁷ Pa.
(Evaluation of transparency and heat shielding properties)
The produced laminated glass [K6-2] had a light transmittance in the thickness direction of 77% at 550 nm and 5% at 2000 nm, and was evaluated as having good transparency and good heat insulation properties.
(Evaluation of Thermal Insulation)
The thermal conductivity of the produced laminated glass [K6-1] in the thickness direction was 0.30 W/(m·K), and the heat insulating property was evaluated as good.
(Rigidity evaluation)
The prepared laminated glass [K6-2] had a flexural modulus of 16 GPa, and the rigidity of the laminated glass was evaluated as good.
The results are shown in Table 2.

[Example 4]
A laminated glass [K7-1] for evaluating thermal insulation property, a laminated glass [K7-2] for evaluating transparency, heat shielding property and rigidity, and an interlayer film [J7] having a five-layer structure of [G2-1]/[H1]/[G2-1]/[G2-1]/[G2-1] were prepared in the same manner 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].
The ratio (ti/tg) of the total thickness (ti) of the interlayers to the total thickness (tg) of the glass plates of the laminated glasses [K7-1] and [K7-2] was 1.40.

(Storage modulus of interlayer film)
The storage modulus of the produced interlayer film [J7] was 4.3×10 ⁷ Pa.
(Evaluation of transparency and heat shielding properties)
The produced laminated glass [K7-2] had a light transmittance in the thickness direction of 74% at 550 nm and 5% at 2000 nm, and was evaluated as having good transparency and good heat insulation properties.
(Evaluation of Thermal Insulation)
The thermal conductivity of the produced laminated glass [K7-1] in the thickness direction was 0.23 W/(m·K), and the heat insulating property was evaluated as good.
(Rigidity evaluation)
The prepared laminated glass [K7-2] had a flexural modulus of 11 GPa, and the rigidity of the laminated glass was evaluated as good.
The results are shown in Table 2.

[Comparative Example 4]
A laminated glass [K8-1] for evaluating thermal insulation properties, a laminated glass [K8-2] for evaluating transparency, heat shielding properties and rigidity, and an interlayer film [J8] having a five-layer structure of [G2-1]/[H1]/[G2-1]/[G3]/[G2-1] were prepared in the same manner as in Comparative Example 1, except that the adhesive layer [G2-1] was used as the adhesive layer and the functional layer instead of the adhesive layer [G1-1].
The ratio (ti/tg) of the total thickness (ti) of the interlayers to the total thickness (tg) of the glass plates of the laminated glasses [K8-1] and [K8-2] was 1.40.

(Storage modulus of interlayer film)
The storage modulus of the produced interlayer film [J8] was 0.55×10 ⁷ Pa, which did not satisfy the requirements of the present invention.
(Evaluation of transparency and heat shielding properties)
The produced laminated glass [K8-2] had a light transmittance in the thickness direction of 74% at 550 nm and 5% at 2000 nm, and was evaluated as having good transparency and good heat insulation properties.
(Evaluation of Thermal Insulation)
The thermal conductivity of the produced laminated glass [K8-1] in the thickness direction was 0.25 W/(m·K), and the heat insulating property was evaluated as good.
(Rigidity evaluation)
The produced laminated glass [K8-2] had a flexural modulus of elasticity of 3 GPa, which was a low value, and was evaluated as having poor rigidity.
The results are shown in Table 2.

[Comparative Example 5]
A laminated glass [K9-1] for evaluating thermal insulation property, a laminated glass [K9-2] for evaluating transparency, heat shielding property, and rigidity, and an interlayer film [J9] having a three-layer structure of [G2-2]/[H1]/[G2-2] were 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].
The ratio (ti/tg) of the total thickness of the interlayer (ti) to the total thickness of the glass plates (tg) of the laminated glasses [K9-1] and [K9-2] was 0.37, which did not satisfy the requirements of the present invention.

(Storage modulus of interlayer film)
The storage modulus of the produced interlayer film [J9] was 4.5×10 ⁷ Pa.
(Evaluation of transparency and heat shielding properties)
The produced laminated glass [K9-2] had a light transmittance in the thickness direction of 77% at 550 nm and 5% at 2000 nm, and was evaluated as having good transparency and good heat insulation properties.
(Evaluation of Thermal Insulation)
The thermal conductivity in the thickness direction of the produced laminated glass [K9-1] was a large value of 0.41 W/(m·K), and the heat insulation property was evaluated as poor.
(Rigidity evaluation)
The produced laminated glass [K9-2] had a flexural modulus of 25 GPa, and the rigidity of the laminated glass was evaluated as good.
The results are shown in Table 2.

[Comparative Example 6]
(Adhesive layer [G4-1])
An adhesive layer [G4-1] (thickness 0.76 mm, width 330 mm) mainly composed of the modified hydrogenated block copolymer [E1] was produced in the same manner as in Production Example 1, except that 100 parts of the pellets of the modified hydrogenated block copolymer [E1] obtained in Production Example 1 were blended with 0.3 parts of 2-(5-chloro-2H-benzotriazol-2-yl)-6-tert-butyl-p-cresol as an ultraviolet absorber, and 20 parts of hydrogenated polyisobutene (manufactured by NOF Corporation, product name "PARLEAM (registered trademark) 18") as a tackifier was fed from a side feeder.
The thermal conductivity of the adhesive layer [G4-1] in the thickness direction was measured in accordance with ASTM E1530 and was found to be 0.16 W/(m·K).

(Laminated glass [K10] and interlayer film [J10])
A laminated glass [K10-1] for evaluating thermal insulation property, a laminated glass [K10-2] for evaluating transparency, heat shielding property and rigidity, and an interlayer film [J10] having a three-layer structure of [G4-1]/[H1]/[G4-1] were prepared in the same manner as in Example 1, except that the adhesive layer [G4-1] was used instead of the adhesive layer [G1-1].
The ratio (ti/tg) of the total thickness (ti) of the interlayers to the total thickness (tg) of the glass plates of the laminated glasses [K10-1] and [K10-2] was 0.71.

(Storage modulus of interlayer film)
The storage modulus of the produced interlayer film [J10] was 2.8×10 ⁷ Pa, which did not satisfy the requirements of the present invention.
(Evaluation of transparency and heat shielding properties)
The produced laminated glass [K10-2] had a light transmittance in the thickness direction of 77% at 550 nm and 5% at 2000 nm, and was evaluated as having good transparency and good heat insulation properties.
(Evaluation of Thermal Insulation)
The thermal conductivity of the produced laminated glass [K10-1] in the thickness direction was 0.32 W/(m·K), and the heat insulating property was evaluated as good.
(Rigidity evaluation)
The produced laminated glass [K10-2] had a flexural modulus of elasticity of only 10 GPa, which was a low value, and was evaluated as having poor rigidity.

[Example 5]
A laminated glass [K11-1] for evaluating thermal insulation property, a laminated glass [K11-2] for evaluating transparency, heat shielding property and rigidity, and an interlayer film [J11] having a three-layer structure of [G1-1]/[H1]/[G1-1] were prepared in the same manner as in Example 1, except that the thickness of the glass plate (limestone blue plate glass) used was changed from 1.1 mm to 0.7 mm.
The ratio (ti/tg) of the total thickness (ti) of the interlayers to the total thickness (tg) of the glass plates of the laminated glasses [K11-1] and [K11-2] was 1.12.

(Storage modulus of interlayer film)
The storage modulus of the produced interlayer film [J11] was 8.8×10 ⁷ Pa.
(Evaluation of transparency and heat shielding properties)
The produced laminated glass [K11-2] had a light transmittance in the thickness direction of 77% at 550 nm and 5% at 2000 nm, and was evaluated as having good transparency and good heat insulation properties.
(Evaluation of Thermal Insulation)
The thermal conductivity in the thickness direction of the produced laminated glass [K11-1] was 0.25 W/(m·K), and the heat insulating property was evaluated as good.
(Rigidity evaluation)
The produced laminated glass [K11-2] had a flexural modulus of 29 GPa, and the rigidity of the laminated glass was evaluated as good.
The results are shown in Table 2.

[Example 6]
A laminated glass [K12-1] for evaluating thermal insulation property, a laminated glass [K12-2] for evaluating transparency, heat shielding property and rigidity, and an interlayer film [J12] having a five-layer structure of [G1-1]/[H1]/[G1-1]/[G1-1]/[G1-1] were prepared in the same manner as in Example 2, except that the thickness of the glass plate (limestone glass) used was changed from 1.1 mm to 2.0 mm.
The ratio (ti/tg) of the total thickness (ti) of the interlayers to the total thickness (tg) of the glass plates of the laminated glasses [K12-1] and [K12-2] was 0.77.

(Storage modulus of interlayer film)
The storage modulus of the produced interlayer film [J12] was 8.6×10 ⁷ Pa.
(Evaluation of transparency and heat shielding properties)
The produced laminated glass [K12-2] had a light transmittance in the thickness direction of 74% at 550 nm and 5% at 2000 nm, and was evaluated as having good transparency and good heat insulation properties.
(Evaluation of Thermal Insulation)
The thermal conductivity of the produced laminated glass [K12-1] in the thickness direction was 0.29 W/(m·K), and the heat insulating property was evaluated as good.
(Rigidity evaluation)
The produced laminated glass [K12-2] had a flexural modulus of 26 GPa, and the rigidity of the laminated glass was evaluated as good.
The results are shown in Table 2.

The results of the Examples and Comparative Examples show the following.
By using an interlayer having an infrared reflective layer and a storage modulus at 40°C of 3.0 x ¹⁰⁷ Pa or more, and by setting the ratio (ti/tg) of the total thickness of the interlayer (ti) to the total thickness of the glass plates (tg) to be 0.7 or more, it is possible to produce laminated glass having a thermal conductivity of 0.35 W/(m·K) or less in the thickness direction of the laminated glass, improved heat insulation and thermal insulation properties, and a rigidity with a flexural modulus of 11 GPa or more (Examples 1 to 6).
When an interlayer film with a storage modulus of less than 3.0 × ¹⁰ Pa at 40°C is used, if the thermal conductivity in the thickness direction of the laminated glass is set to 0.35 W/(m·K) or less, the flexural modulus of the laminated glass will be less than 11 GPa, and the rigidity of the laminated glass will not be maintained (Comparative Example 1, Comparative Example 4, Comparative Example 6).
Interlayer films mainly composed of PVB, which have been conventionally used as interlayer films for laminated glass, have a storage modulus at 40°C that is significantly lower than 3 x ¹⁰ Pa. For laminated glass with a flexural modulus of 11 GPa, it is not possible to produce laminated glass with a thermal conductivity in the thickness direction of 0.35 W/(m·K) or less (Comparative Example 3).
Even if the storage modulus of the interlayer film at 40°C is 3 x ¹⁰ Pa or more, if the thickness of the interlayer film is thin compared to the thickness of the glass, the rigidity of the laminated glass will be sufficiently high, but the thermal conductivity may not be able to be reduced to 0.35 W/(m·K) or less (Comparative Example 2 and Comparative Example 5).

The laminated glass of the present invention has improved insulation and heat shielding properties while maintaining rigidity and light weight, making it useful for enhancing the heating and cooling effect when used as a window material for automobiles, railway vehicles, ships, buildings, etc.

Claims (4)

A laminated glass comprising at least two glass sheets and at least one interlayer film,
the at least two glass sheets include a first glass sheet and a second glass sheet;
the at least one interlayer film includes an interlayer film X disposed between the first glass sheet and the second glass sheet;
the intermediate film X is a laminate having a first adhesive layer, a second adhesive layer, and an infrared reflective layer disposed between the first adhesive layer and the second adhesive layer,
The storage modulus of the dynamic viscoelastic properties of the interlayer film X is 3.0×10 ⁷ Pa or more and 5.0×10 ⁸ Pa or less at 40° C.,
wherein when a total thickness of the at least two glass sheets is defined as tg and a total thickness of the at least one interlayer film is defined as ti, a ratio of ti to tg (ti/tg) is 0.7 or more,
The laminated glass has a light transmittance in the thickness direction of 50% or more at a wavelength of 550 nm and 20% or less at a wavelength of 2000 nm (excluding laminated glass in which at least one interlayer film made of a resin composition mainly composed of a modified hydrogenated block copolymer having an alkoxysilyl group introduced therein and at least one heat insulating layer made of hollow particles and a binder resin are sandwiched and bonded together between a plurality of glass sheets) . The laminated glass according to claim 1, wherein at least one of the first adhesive layer and the second adhesive layer is mainly composed of a modified hydrogenated block copolymer [E] obtained by introducing an alkoxysilyl group into a hydrogenated block copolymer [D] obtained by hydrogenating a block copolymer [C] having at least two polymer blocks [A] mainly composed of structural units [a] derived from an aromatic vinyl compound and at least one polymer block [B] mainly composed of structural units [b] derived from a chain-like conjugated diene compound. The laminated glass according to claim 1 or 2, wherein the thermal conductivity of the laminated glass in the thickness direction is 0.35 W/(m·K) or less at 20°C. The laminated glass according to any one of claims 1 to 3, having a flexural modulus of 11 GPa or more.