JP7259856B2 - Laminates and laminated glass - Google Patents

Description

TECHNICAL FIELD The present invention relates to a laminate and laminated glass, and more particularly to a laminate having specific dynamic viscoelastic properties and a laminated glass comprising an intermediate film comprising the laminate.

Laminated glass is excellent in safety because even if it is damaged by an impact, it can prevent the penetration of an impacting object and the scattering of glass fragments. Therefore, laminated glass is widely used in automobiles, railroad vehicles, aircraft, ships, buildings, and the like. Laminated glass is manufactured by bonding and integrating a plurality of glass plates with an intermediate film made of an adhesive resin sandwiched therebetween.

In cold districts, it is useful to impart heat insulating properties to window glass in order to increase the heating effect in a room or in a vehicle. For example, polyvinyl butyral (hereinafter sometimes referred to as "PVB"), which is commonly used as an intermediate film for laminated glass, and a sheet-like material interposed between glass plates to increase the penetration resistance of laminated glass. Resins such as ethylene-vinyl acetate copolymers, ionomer resins, polycarbonates and polyethylene terephthalate, which are used, have lower thermal conductivity than glass. Therefore, a laminated glass using an interlayer film or sheet made of these resins has a lower thermal conductivity as a whole and a higher heat insulating property than a glass plate of the same thickness.

Patent Literature 1 discloses laminated glass in which the thickness of the intermediate film made of PVB is increased to reduce the thermal conductivity. However, if the thickness of the interlayer is increased without changing the thickness of the glass, although the rigidity of the laminated glass can be maintained, the thickness of the laminated glass increases and the mass increases. . On the other hand, if an attempt is made to maintain the thickness and mass of the laminated glass by increasing the thickness of the intermediate film and reducing the thickness of the glass, the elastic modulus of the intermediate film made of PVB is small. There was a contradictory problem that the rigidity of was not maintained.

Patent Literature 2 discloses a lightweight laminated glass with low thermal conductivity, which is composed of glass/PVB/polycarbonate/PVB/glass. However, when the thickness of the glass is reduced to reduce the mass per unit area, since the modulus of elasticity of polycarbonate is smaller than that of glass, there is a problem that the rigidity of the laminated glass is reduced similarly to the above. Moreover, when trying to maintain the rigidity of the laminated glass, it is necessary to increase the thickness of the entire laminated glass.

Patent Literature 3 discloses a laminated glass in which a hydrogenated modified block copolymer into which an alkoxysilyl group is introduced is used as an intermediate film in place of the intermediate film made of PVB. However, Patent Literature 3 does not describe a technique for improving heat insulating properties by reducing thermal conductivity while maintaining rigidity of laminated glass.

Patent Document 4 discloses a laminated glass in which a hydrogenated modified block copolymer having an alkoxysilyl group introduced therein is used as an intermediate film, and at least one heat insulating layer containing hollow particles is sandwiched between the glasses. . However, the hollow particles described in Patent Document 4 are produced, for example, by precipitating silica generated by a hydrolysis reaction of silicon alkoxide on the surface of colloidal calcium carbonate and then dissolving the calcium carbonate by acid treatment. It is not easy to obtain industrially.

Further, in recent years, in order to improve the comfort of automobiles and the like, laminated glass with improved sound insulation has been used. Glass is a material with low damping performance. For example, in a laminated glass in which glasses having a thickness of about 3 mm are bonded together, the coincidence effect reduces the amount of sound transmission loss in the mid-to-high range of frequencies in the vicinity of 2000 Hz to 3000 Hz, resulting in reduced sound insulation. For this reason, there is known a method of reducing the coincidence effect and improving the sound insulation performance by bonding glass to a resin interlayer having excellent damping performance.

Laminated glass with improved sound insulation performance includes, for example, (a) laminated glass using a laminated interlayer in which two types of polyvinyl acetal are blended with a plasticizer as a resin interlayer (see, for example, Patent Documents 5 to 7), (b) Laminated glass using an intermediate film in which an adhesive resin layer made of a polyvinyl acetal resin or the like is laminated on both sides of a sound insulation layer made of a polyvinyl acetal resin mixed with a large amount of plasticizer (see, for example, Patent Document 8). (c) Laminated glass (Patent Documents 9 and 10) using an intermediate film in which an adhesive resin layer made of a polyvinyl acetal resin or the like is laminated on both sides of a sound insulation layer mainly composed of a styrene-diene block copolymer. mentioned.

However, (b) an intermediate film in which an adhesive resin layer made of a polyvinyl acetal resin or the like is laminated on both sides of a sound insulation layer made of a polyvinyl acetal resin mixed with a large amount of plasticizer, and (c) a styrene-diene block copolymer The elastic modulus of the intermediate film, which is made by laminating adhesive resin layers made of polyvinyl acetal resin or the like on both sides of a sound insulation layer mainly composed of When manufacturing glass, there is a problem that the rigidity of the laminated glass cannot be maintained.

In Patent Documents 11 to 13, a thermoplastic elastomer composition containing a block copolymer hydride as a main component is used as a sound insulation layer, and the storage elasticity is enhanced by not containing a plasticizer or containing a small amount of plasticizer. An intermediate film using a polyvinyl acetal resin for an adhesive layer is disclosed. Laminated glass using this interlayer film is disclosed to be excellent in sound insulation and bending strength. When the thickness of the film is increased to improve the heat insulating properties of the laminated glass, there is a possibility that the rigidity of the laminated glass cannot be maintained.

Patent Literature 14 discloses that a laminated glass having excellent sound insulation can be obtained by using a block copolymer hydride as an interlayer material. However, there is no suggestion regarding techniques for maintaining the rigidity of the laminated glass to which sound insulation is imparted and improving the heat insulation. In an example of Patent Document 14, a laminated glass excellent in sound insulation is disclosed in which two sheets of glass with a thickness of 1.2 mm are laminated with an interlayer film with a thickness of 0.76 mm, and the thermal conductivity of the laminated glass is Although it is expected to be small, the thickness of the sound insulating layer made of block copolymer hydride having a low storage modulus is too thick, and there is a possibility that the rigidity of the laminated glass cannot be maintained.

JP 2006-137648 A JP-A-6-915 WO2013/176258 JP 2017-81775 A JP-A-4-254444 JP-A-6-926 JP-A-9-156967 JP-A-2005-144753 JP-A-2007-91491 JP 2011-240676 A JP 2016-107632 A JP 2016-108227 A WO2016/076338 WO2016/104740

The present invention has been made in view of the above-described circumstances, and includes a laminate capable of forming a laminated glass that achieves a high level of balance between rigidity, sound insulation, and heat insulation, and an interlayer film made of the laminate. An object of the present invention is to provide laminated glass.

The inventors of the present invention have made intensive studies to achieve the above object, and found that a specific hydrogenated block copolymer has a low thermal conductivity among resins. Furthermore, the present inventors have found that at least one resin layer (X) (sound insulation layer) made of a resin composition (X) containing a specific hydrogenated block copolymer (D) as a main component, and a specific A resin composition containing, as a main component, a hydrogenated block copolymer (H) and/or a hydrogenated modified block copolymer (J) in which an alkoxysilyl group is introduced into the specific hydrogenated block copolymer (H) By using an intermediate film made of a laminate (Z) having at least two resin layers (Y) (elastic layers) made of (Y), the balance of rigidity, sound insulation and heat insulation can be achieved at a high level. The inventors have found that it is possible to form the realized laminated glass, and have completed the present invention.
In addition, in this specification, "containing as a main component" means "containing more than 50% by mass".

Thus, according to the present invention, the following laminates (1) to (7) and the following laminated glasses (8) and (9) are provided.
(1) A laminate (Z) having at least one resin layer (X) made of the resin composition (X) and at least two resin layers (Y) made of the resin composition (Y) (a) the resin layer (X) is laminated between at least two resin layers (Y); (c) the storage elastic modulus in the dynamic viscoelastic properties of the laminate (Z) is 1.0× in the temperature range of −20° C. or higher and 40° C. or lower. A laminate having a pressure of 10 ⁷ Pa or more and 5.0×10 ⁸ Pa or less. (However, the tan δ in the dynamic viscoelastic properties of the resin layer (X) and the storage elastic modulus in the dynamic viscoelastic properties of the laminate (Z) are calculated based on JIS K7244-2 method (torsion pendulum method). Frequency: 1 rad/s, measurement temperature range: -100°C to 100°C, temperature increase rate: 5°C/min.
(2) A block in which the resin composition (X) contains a structural unit derived from an aromatic vinyl compound and a structural unit derived from a chain conjugated diene compound (linear conjugated diene compound, branched conjugated diene compound). A hydrogenated block copolymer (D) obtained by hydrogenating the copolymer (C) is contained as a main component, and the block copolymer (C) mainly contains a structural unit [a] derived from an aromatic vinyl compound. Consists of at least two polymer blocks (A) contained as components and at least one polymer block (B) containing as a main component a structural unit [b] derived from a chain conjugated diene compound, The structural unit [b] derived from the linear conjugated diene compound in the polymer block (B) includes structural units derived from 1,2-addition polymerization and 3,4-addition polymerization, and the structural unit [a ] in the block copolymer (C) is wA, and the mass fraction of the structural unit [b] in the block copolymer (C) is wB. ratio (wA/wB) is 10/90 or more and 35/65 or less, and the block copolymer hydride (D) is a main chain derived from the chain conjugated diene compound in the block copolymer (C) and 95% or more of the carbon-carbon unsaturated bonds in the side chains are hydrogenated, the laminate according to (1).
(3) The structural unit [b] in the polymer block (B) is a structural unit derived from 1,2-addition polymerization and 3,4-addition polymerization. b] The laminate according to (2), which contains 40% by mass or more and 80% by mass or less with respect to the whole.
(4) The resin composition (Y) is a block copolymer obtained by hydrogenating a block copolymer (G) containing a structural unit derived from an aromatic vinyl compound and a structural unit derived from a chain conjugated diene compound. A hydrogenated polymer (H) and/or a hydrogenated modified block copolymer (J) in which an alkoxysilyl group is introduced into the hydrogenated block copolymer (H) as a main component, and the block copolymerization The coalescence (G) comprises at least two polymer blocks (E) containing structural units [e] derived from an aromatic vinyl compound as main components, and structural units [f] derived from a chain conjugated diene compound. Consists of at least one polymer block (F) contained as a main component, wherein wE is the mass fraction of the structural unit [e] in the block copolymer (G), and the structural unit [f] is When the mass fraction occupied in the block copolymer (G) is wF, the ratio (wE/wF) of wE to wF is 40/60 or more and 60/40 or less, and the block copolymer hydride (H) is obtained by hydrogenating 95% or more of the carbon-carbon unsaturated bonds of the main chain and side chains derived from the chain conjugated diene compound in the block copolymer (G), (1) to (3 ).
(5) The laminate according to any one of (1) to (4), wherein the resin layer (X) has a thickness of 0.02 mm or more and 0.6 mm or less.
(6) The laminate according to any one of (1) to (5), wherein the resin layer (Y) has a thickness of 0.05 mm or more and 1.0 mm or less.
(7) The laminate according to any one of (1) to (6), wherein the laminate (Z) has a thickness of 0.2 mm or more and 2 mm or less.
(8) A laminated glass comprising two glass plates and an intermediate film comprising the laminate (Z) according to any one of (1) to (7) arranged between the two glass plates. and a laminated glass having a thermal conductivity of 0.5 W/(m·K) or less at 25° C. in the thickness direction of the laminated glass.
(9) The laminated glass according to (8), wherein the laminated glass has a flexural modulus of 11 GPa or more at 25°C.

ADVANTAGE OF THE INVENTION According to this invention, the laminated body which can form the laminated glass which realized rigidity, sound insulation, and thermal insulation at the high level balance, and the laminated glass provided with the intermediate film which consists of this laminated body are provided.

It is a figure which shows an example of embodiment of the laminated body of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows an example of embodiment of the laminated glass of this invention. FIG. 4 is a diagram showing another example of an embodiment of the laminate of the present invention; FIG. 4 is a diagram showing another example of an embodiment of the laminated glass of the present invention;

Hereinafter, regarding the laminate and laminated glass of the present invention, (a) resin layer (X), (b) resin layer (Y), (c) laminate (Z), (d) glass plate, (e) laminated glass will be described in detail.

(a) resin layer (X)
The resin layer (X) in the present invention is a layer made of the resin composition (X), and has a maximum value of tan δ in the dynamic viscoelastic property in the temperature range of -20°C or higher and 20°C or lower.
By arranging the laminate (Z) having at least one or more resin layers (X) between two glass plates, a laminated glass imparted with sound insulation can be formed.

The temperature range in which the maximum value of tan δ exists in the dynamic viscoelastic properties of the resin layer (X) is not particularly limited as long as it is -20°C or higher and 20°C or lower, but it is preferably -15°C or higher. , more preferably -10°C or higher, particularly preferably -9°C or higher, and preferably 15°C or lower, more preferably 10°C or lower.

As a method for adjusting the maximum value of tan δ in the dynamic viscoelastic properties of the resin layer (X) to −20° C. or higher and 20° C. or lower, for example, (i) a resin having a glass transition temperature in a temperature range of 20° C. or higher (ii) a method of using a resin having a glass transition temperature in the temperature range of -20°C or higher and 20°C or lower; and the like. Among these, (ii) using a resin having a glass transition temperature in the temperature range of -20 ° C. or higher and 20 ° C. or lower eliminates the need to add additives such as plasticizers and softeners. It is preferable because it is possible to prevent the temperature of the maximum value of tan δ from fluctuating due to additives such as elution from the resin composition. Further, using a block copolymer composed of a polymer block having a glass transition temperature in the temperature range of −20° C. or higher and 20° C. or lower and a polymer block having a glass transition temperature in a higher temperature range as the resin It is preferable in that heat resistance as an intermediate film in laminated glass can be easily maintained.

<Resin composition (X)>
The resin composition (X) contains the resin (x) as a main component and, if necessary, other components.

<<Resin (x)>>
The resin (x) is a block copolymer (C) composed of at least two predetermined polymer blocks (A) and at least one predetermined polymer block (B) from the viewpoint of light resistance and sound insulation. It is preferably a hydrogenated block copolymer hydride (D).
Specific examples of the resin (x) include polystyrene/diene block copolymers, polyolefin block copolymers, polyurethane block copolymers, polyester block copolymers, polyamide block copolymers, acrylic system block copolymers, polyvinyl acetal polymers, ethylene/vinyl acetate copolymers, and hydrogenated polymers thereof. These may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.
Among these, from the viewpoint of transparency, hydrogenated polystyrene block copolymers composed of aromatic vinyl compounds and chain conjugated diene compounds, etc., hydrogenated polyolefin block copolymers, and acrylic block copolymers Hydrides are preferred.

-Polymer block (A)-
Polymer block (A) contains structural unit [a] derived from an aromatic vinyl compound as a main component.

-- structural unit [a] --
Specific examples of the aromatic vinyl compound capable of forming the structural unit [a] derived from the aromatic vinyl compound include styrene; α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2, 4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, and other styrenes having an alkyl group having 1 to 6 carbon atoms as a substituent; styrenes having a halogen atom as a substituent, such as monochlorostyrene, dichlorostyrene, and 4-monofluorostyrene; styrenes having an alkoxy group having 1 to 6 carbon atoms as a substituent, such as 4-methoxystyrene; 4-phenyl styrenes having an aryl group as a substituent such as styrene; vinylnaphthalenes such as 1-vinylnaphthalene and 2-vinylnaphthalene; and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.
Among these, aromatic vinyl compounds containing no polar group, such as styrene and styrenes having an alkyl group having 1 to 6 carbon atoms as a substituent, are preferred from the viewpoint of hygroscopicity, and are easy to obtain industrially. From a viewpoint, styrene is more preferable.

--Other Structural Units--
The polymer block (A) may contain structural units other than the structural unit [a]. Such other structural unit may be, for example, a structural unit [b] derived from a chain conjugated diene compound (linear conjugated diene compound, branched conjugated diene compound) described later. Further, compounds capable of forming other structural units include linear vinyl compounds and cyclic vinyl compounds, more specifically having a nitrile group, an alkoxycarbonyl group, a hydroxycarbonyl group, or a halogen group. vinyl compounds, unsaturated cyclic acid anhydrides, unsaturated imide compounds, and the like. Among these, from the viewpoint of hygroscopicity, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-eicosene, chain olefins having 2 to 20 carbon atoms such as 4-methyl-1-pentene and 4,6-dimethyl-1-heptene; Those not containing a polar group, such as cyclic olefins; are preferred, chain olefins having 2 to 10 carbon atoms are more preferred, and ethylene and propylene are more preferred.

--Composition, etc.--
The content of the structural unit [a] in the polymer block (A) is preferably 90% by mass or more, more preferably 95 mass % or more, particularly preferably 98 mass % or more. If the content of the structural unit [a] in the polymer block (A) is 90% by mass or more, sufficiently high heat resistance of the resin layer (X) can be ensured.
The content of structural units other than the structural unit [a] in the polymer block (A) is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 2% by mass or less. be.
By setting the content ratio of the other structural unit in the polymer block (A) within the above range, it is possible to prevent the heat resistance of the resin layer (X) from deteriorating.

-Polymer block (B)-
The polymer block (B) contains structural units [b] derived from a chain conjugated diene compound as a main component.

--Structural unit [b]--
Chain conjugated diene compounds capable of forming the structural unit [b] derived from a chain conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene. , 2-chloro-1,3-butadiene, and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.
Among these, (i) those containing no polar group (1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene) are preferred from the viewpoint of hygroscopicity, and ( ii) from the viewpoint of industrial availability, 1,3-butadiene and isoprene are more preferable; Isoprene is particularly preferable from the viewpoint of ease of control to the range of 20° C. or less.

--Other Structural Units--
In addition, the polymer block (B) may contain structural units other than the structural unit [b]. Such other structural unit may be, for example, the structural unit [a] derived from the aromatic vinyl compound described above. In addition, as compounds capable of forming other structural units, the chain olefins and cyclic olefins described above in the section “Polymer block (A)” can also be used.

--Composition, etc.--
The content of the structural unit [b] in the polymer block (B) is preferably 90% by mass or more, more preferably 95 mass % or more, particularly preferably 98 mass % or more. When the content of the structural unit [b] in the polymer block (B) is 90% by mass or more, tan δ in the viscoelastic properties of the resin layer (X) reaches a maximum value in the temperature range of −20° C. or higher and 20° C. or lower. can be easily controlled to have
The content of structural units other than the structural unit [b] in the polymer block (B) is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 2% by mass or less. be.
By setting the content ratio of the other structural units in the polymer block (B) within the above range, tan δ in the viscoelastic properties of the resin layer (X) has a maximum value in the temperature range of −20° C. or higher and 20° C. or lower. It can be easier to control to have

The structural unit [b] in the polymer block (B) contains structural units derived from 1,2-addition polymerization and 3,4-addition polymerization, and the remainder comprises structural units derived from 1,4-addition polymerization. include. The proportion of structural units derived from 1,2-addition polymerization and 3,4-addition polymerization of a chain conjugated diene compound is 40% by mass or more with respect to the total structural units [b] in the polymer block (B). It is preferably 45% by mass or more, particularly preferably 50% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less. , 65% by mass or less.
The content ratio of the structural units derived from the 1,2-addition polymerization and 3,4-addition polymerization of the chain conjugated diene compound to the total structural units [b] in the polymer block (B) is within the above range. Thus, tan δ in the viscoelastic properties of the resin layer (X) can reliably have a maximum value in the temperature range of -20°C or higher and 20°C or lower.

Here, the polymer block containing structural units derived from 1,2-addition polymerization and/or structural units derived from 3,4-addition polymerization is composed of a chain conjugated diene compound and, if necessary, Existence of a specific compound having an electron-donating atom (hereinafter sometimes referred to as a "randomizer") and a compound capable of forming other structural units such as aromatic vinyl compounds, chain olefins, and cyclic olefins. can be obtained by polymerizing under The total content of structural units derived from 1,2-addition polymerization and structural units derived from 3,4-addition polymerization can be controlled by the type and amount of the randomizer.

Compounds having electron donating atoms (eg, oxygen (O), nitrogen (N)) that can be used as randomizers include ether compounds, amine compounds, phosphine compounds, and the like. Among these, ether compounds are preferable from the viewpoint that the molecular weight distribution of the polymer block can be narrowed and the hydrogenation reaction thereof is less likely to be inhibited.

Specific examples of randomizers include diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol diisopropyl ether, ethylene glycol dibutyl ether, ethylene glycol methylphenyl ether, and propylene glycol dimethyl ether. , propylene glycol diethyl ether, propylene glycol diisopropyl ether, propylene glycol dibutyl ether, di(2-tetrahydrofuryl)methane, diethylene glycol dibutyl ether, dipropylene glycol dibutyl ether, tetramethylethylenediamine, and the like. Among them, from the viewpoint of controlling the mass fraction of structural units derived from 1,2-addition polymerization and/or structural units derived from 3,4-addition polymerization and further enhancing the sound insulation properties of the resulting resin sheet, ethylene glycol is used. Preference is given to using dibutyl ether.

The amount of these randomizing agents used during the preparation of the block copolymer (C) is preferably 0.001 parts by mass or more, preferably 0.01 parts by mass, relative to 100 parts by mass of the chain conjugated diene compound. It is more preferably 10 parts by mass or less, and more preferably 1 part by mass or less.

-Block copolymer (C)-
The block copolymer (C), which is the precursor of the block copolymer hydride (D), 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 not particularly limited as long as it is 2 or more, but it is usually 3 or less, preferably 2, and the block copolymer (C) The number of polymer blocks (B) therein is not particularly limited as long as it is one or more, but it is usually two or less, preferably one.
When the block copolymer (C) has a plurality of polymer blocks (A), the composition and block length of structural units in the polymer blocks (A) may be the same or different.
When the block copolymer (C) has a plurality of polymer blocks (B), the composition and block length of the structural units in the polymer blocks (B) may be the same or different.

The form of the blocks of the block copolymer (C) is not particularly limited, and may be a chain block or a radial block, but the chain block is preferred from the viewpoint of excellent mechanical strength. The most preferred form of the block copolymer (C) is a triblock copolymer (ABA) in which the polymer block (A) is bound to both ends of the polymer block (B).

--mass fraction--
Here, when the mass fraction of the structural unit [a] in the block copolymer (C) is wA, and the mass fraction of the structural unit [b] in the block copolymer (C) is wB, The ratio of wA to wB (wA/wB) is preferably 10/90 or more and 35/65 or less, more preferably 12/88 or more, further preferably 15/85 or more, It is particularly preferably 18/82 or more, more preferably 30/70 or less, even more preferably 25/75 or less, and particularly preferably 20/80 or less.
By setting the ratio of wA to wB (wA/wB) to the upper limit or less, it is possible to prevent the sound insulation performance of the resin layer (X) from deteriorating. On the other hand, by setting the ratio of wA to wB (wA/wB) to the lower limit or more, it is possible to prevent the heat resistance of the resin layer (X) from deteriorating.

The molecular weight of the block copolymer (C) is a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, and is 30,000 or more. is preferably 40,000 or more, particularly preferably 50,000 or more, preferably 200,000 or less, more preferably 170,000 or less, 150,000 The following are particularly preferred.
The molecular weight distribution (Mw/Mn) of the block copolymer (C) is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.8 or less.
By setting Mw and Mw/Mn within the above ranges, sufficient Melt moldability and heat resistance can be imparted.

The method for producing the block copolymer (C) is not particularly limited, and known methods can be employed. mentioned.

- Block copolymer hydride (D) -
The block copolymer hydride (D) is a high- is a molecule.
The block copolymer hydride (D) is a polymer obtained by selectively hydrogenating only the carbon-carbon unsaturated bonds of the main chain and side chains derived from the chain conjugated diene compound in the block copolymer (C). Main chain and side chain carbon-carbon unsaturated bonds derived from the chain conjugated diene compound in the block copolymer (C), and derived from the aromatic vinyl compound in the block copolymer (C) It may be a polymer obtained by hydrogenating the carbon-carbon unsaturated bond of the aromatic ring, or a mixture thereof.

When selectively hydrogenating only the carbon-carbon unsaturated bonds of the main chain and side chains derived from the chain conjugated diene compound in the block copolymer (C), the chain in the block copolymer hydride (D) The hydrogenation rate of carbon-carbon unsaturated bonds in the main chain and side chains derived from the conjugated diene compound is preferably 95% or more, more preferably 97% or more, and 99% or more. Particularly preferably, the hydrogenation rate of the carbon-carbon unsaturated bond of the aromatic ring derived from the aromatic vinyl compound in the hydrogenated block copolymer (D) is preferably 10% or less, and preferably 5% or less. is more preferable, and 3% or less is particularly preferable.
The block copolymer hydride (D) obtained by selectively hydrogenating only the carbon-carbon unsaturated bonds of the main chain and side chains derived from the chain conjugated diene compound in the block copolymer (C) is , the light resistance and heat deterioration resistance are improved as compared with the block copolymer (C).
By making the hydrogenation rate of the carbon-carbon unsaturated bonds of the main chain and side chains derived from the chain conjugated diene compound in the block copolymer (C) equal to or higher than the above lower limit, the block copolymer hydride (D ) as a main component, the light resistance and heat deterioration resistance of the resin composition (X) can be improved. Further, by setting the hydrogenation rate of the carbon-carbon unsaturated bond of the aromatic ring derived from the aromatic vinyl compound in the block copolymer (C) to the above upper limit value or less, the block copolymer hydride (D) can be obtained. It becomes easy to maintain the heat deterioration resistance of the resin composition (X) as a main component.

Main chain and side chain carbon-carbon unsaturated bonds derived from the chain conjugated diene compound in the block copolymer (C), and aromatic ring carbon derived from the aromatic vinyl compound in the block copolymer (C) - When hydrogenating carbon unsaturated bonds, the hydrogenation rate of carbon-carbon unsaturated bonds in the block copolymer hydride (D) is preferably 90% or more of the total amount of carbon-carbon unsaturated bonds. , is more preferably 95% or more, and particularly preferably 99% or more. By setting the hydrogenation rate of the carbon-carbon unsaturated bond in the hydrogenated block copolymer (D) within this range, the hydrogenated block copolymer (D) obtained is derived from a chain conjugated diene compound. Compared to the block copolymer hydride (D) obtained by selectively hydrogenating only the carbon-carbon unsaturated bonds of the main chain and side chains, the light resistance and heat deterioration resistance are further improved, and the heat distortion temperature can be raised.

The hydrogenation rate of the carbon-carbon unsaturated bond in the block copolymer hydride (D) can be determined, for example, by ¹ H-NMR of the precursor block copolymer (C) and the block copolymer hydride (D). By measuring the hydrogenation rate of the carbon-carbon unsaturated bonds of the main chain and side chains derived from the chain conjugated diene compound, and the carbon-carbon unsaturated bond of the aromatic ring derived from the aromatic vinyl compound Each hydrogenation rate can be determined.

The method for hydrogenating unsaturated bonds in the block copolymer (C), the reaction mode, and the like are not particularly limited, and the hydrogenation may be carried out according to known methods.
A method for selectively hydrogenating the carbon-carbon unsaturated bonds of the main chain and side chains derived from the chain conjugated diene compound in the block copolymer (C) is described, for example, in JP-A-2015-78090. and the known hydrogenation methods described above. In addition, the main chain and side chain carbon-carbon unsaturated bonds derived from the chain conjugated diene compound in the block copolymer (C), and the aromatic ring carbon-carbon unsaturated bonds derived from the aromatic vinyl compound Examples of hydrogenation methods include the methods described in International Publication No. 2011/096389, International Publication No. 2012/043708, and the like.

The molecular weight of the hydrogenated block copolymer (D) is a polystyrene-equivalent weight-average molecular weight (Mw) measured by GPC using THF as a solvent, and is preferably 30,000 or more, more preferably 40,000 or more. is more preferably 50,000 or more, preferably 200,000 or less, more preferably 170,000 or less, and particularly preferably 150,000 or less.
The molecular weight distribution (Mw/Mn) of the hydride block copolymer (D) is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.8 or less.
By setting Mw and Mw/Mn within the above ranges, sufficient melt moldability and mechanical strength can be imparted to the resin composition (X) mainly composed of the hydrogenated block copolymer (D). can.

<<Additives>>
The resin composition (X) containing the resin (x) as the main component may contain various additives in addition to the resin (x) as the main component.
Preferred additives include UV absorbers for blocking ultraviolet rays, infrared absorbers for blocking infrared rays, antioxidants and antiblocking agents for improving processability, and light stabilizers for improving durability. , and so on.

- Ultraviolet absorber -
Examples of ultraviolet absorbers include oxybenzophenone-based compounds, benzotriazole-based compounds, salicylic acid ester-based compounds, benzophenone-based compounds, and triazine-based compounds.

-Infrared absorber-
Examples of infrared absorbers include (i) tin oxide, aluminum-doped tin oxide, indium-doped tin oxide, antimony-doped tin oxide, zinc oxide, aluminum-doped zinc oxide, indium-doped zinc oxide, gallium-doped zinc oxide, and tin-doped oxide. Metal oxide fine particles such as zinc, silicon-doped zinc oxide, titanium oxide, niobium-doped titanium oxide, tungsten oxide, sodium-doped tungsten oxide, cesium-doped tungsten oxide, thallium-doped tungsten oxide, rubidium-doped tungsten oxide, indium oxide, and tin-doped indium oxide (ii) phthalocyanine compounds, naphthalocyanine compounds, imonium compounds, diimonium compounds, polymethine compounds, diphenylmethane compounds, anthraquinone compounds, pentadiene compounds, azomethine compounds, lanthanum hexaboride, and other particulate near-infrared absorbing dyes; .

-Antioxidant-
Antioxidants include, for example, phosphorus antioxidants, phenolic antioxidants, sulfur antioxidants, and the like.

-light stabilizer-
Light stabilizers include, for example, hindered amine light stabilizers.

Additives such as ultraviolet absorbers, infrared absorbers, antioxidants, light stabilizers, etc., which are blended in the resin (x) can be used singly or in combination of two or more at any ratio. can.
The amount of additives such as ultraviolet absorbers, infrared absorbers, antioxidants, and light stabilizers is preferably 5 parts by mass or less in total with respect to 100 parts by mass of the resin (x), and more preferably 3 parts by mass or less. Preferably, 2 parts by mass or less is particularly preferable.

As a method for blending various additives into the resin (x), generally used known methods can be applied. For example, (i) resin (x) pellets and compounding agents are uniformly mixed using a mixer such as a tumbler, ribbon blender, and Henschel type mixer, and then a continuous melt-kneader such as a twin-screw extruder is used. A method of melt-mixing and extruding into pellets, (ii) resin (x) is melt-kneaded and extruded by a twin-screw extruder equipped with a side feeder while continuously adding compounding agents from the side feeder. , a pelletizing method, or the like can be used to produce a resin composition containing resin (x) as a main component in which the compounding agents are uniformly dispersed.

By using an intermediate film containing a resin layer (X) having a temperature range of −20° C. or more and 20° C. or less in which tan δ in dynamic viscoelasticity exhibits a maximum value, the coincidence effect of the glass plate is reduced to produce a laminated glass. sound insulation performance is improved.

The thickness of the resin layer (X) is preferably 0.02 mm or more, more preferably 0.03 mm or more, still more preferably 0.04 mm or more, particularly preferably 0.08 mm or more, and preferably 0.6 mm or less. 0.5 mm or less is more preferable, and 0.4 mm or less is particularly preferable.
By making the thickness of the resin layer (X) equal to or greater than the lower limit, it is possible to impart sound insulation to the laminated glass without introducing many resin layers (X) into the interlayer film. Further, by setting the thickness of the resin layer (X) to be equal to or less than the upper limit, it is possible to prevent the rigidity of the laminated glass from decreasing.

When the thickness of the resin layer (X) is thin, a plurality of resin layers (X) can be used to enhance the sound insulation of the laminated glass. When using a plurality of resin layers (X), by laminating a plurality of resin layers (X) via a resin layer with a high elastic modulus between the plurality of resin layers (X), the rigidity of the laminated glass is reduced. can be suppressed.

(b) resin layer (Y)
The resin layer (Y) is made of the resin composition (Y), and the resin layer (X) is formed so as to obtain a laminate (Z) having a specific storage elastic modulus in dynamic viscoelastic properties in a specific temperature range. It is a layer laminated so as to sandwich the The resin layer (Y) maintains the rigidity and impact resistance of the laminated glass using the laminate (Z) as an intermediate film, and improves the heat insulating properties of the laminated glass.

<Resin composition (Y)>
The resin composition (Y) contains the resin (y) as a main component and, if necessary, other components.

<<Resin (y)>>
As the resin (y), the storage elastic modulus in the dynamic viscoelastic properties of the laminate (Z) is 1.0×10 ⁷ Pa or more and 5.0×10 ⁸ Pa or less in the temperature range of −20° C. or more and 40° C. or less. is not particularly limited as long as it is a resin having a value of .
As the resin (y), from the viewpoint of adhesion between the resin layer (Y) and the resin layer (X), a specific block copolymer hydride (H) composed of an aromatic vinyl compound, a chain conjugated diene compound, or the like. and/or a modified block copolymer hydride (J) into which an alkoxysilyl group has been introduced is preferred. Here, if the resin layer (Y) is a layer made of a resin composition (Y) containing a modified block copolymer hydride (J) as a main component, the resin layer (Y) and the glass plate form an adhesive layer. It can be strongly adhered without intervening.
Specific examples of the resin (y) include, for example, polyester-based (co)polymers, polyamide-based (co)polymers, polyolefin-based (co)polymers, polystyrene-based (co)polymers, acrylonitrile-butadiene-styrene copolymers. Polymer, polystyrene/diene block copolymer, polyolefin block copolymer, polyurethane block copolymer, polyester block copolymer, polyamide block copolymer, acrylic block copolymer, polyvinyl acetal Polymers, polyvinyl butyral polymers, ethylene-vinyl acetate copolymers, hydrogenated polymers thereof, and functional groups having adhesive properties such as acid anhydride groups, alkoxysilyl groups, hydroxyl groups, epoxy groups, etc. A modified polymer into which a group is introduced, and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.
Among these, from the viewpoint of thermal conductivity, polystyrene (co)polymer hydrides, polypropylene (co)polymer hydrides, polyurethane (co)polymer hydrides, acrylic (co)polymers Hydrogenated products of coalescence are preferable, and from the viewpoint of transparency when used as an interlayer film for laminated glass, hydrogenated products of polystyrene block copolymers composed of aromatic vinyl compounds, chain conjugated diene compounds, etc., and methyl methacrylate. and a hydrogenated acrylic block copolymer composed of long-chain alkyl methacrylate and/or a modified polymer into which an adhesive reactive group is introduced.

In addition, from the viewpoint of reducing the thermal conductivity of the laminated glass, the thermal conductivity of the resin (y) at a temperature of 25 ° C. is preferably 0.25 W / (m K) or less, and 0.21 W / ( m·K) or less, and particularly preferably 0.17 W/(m·K) or less. Here, the thermal conductivity is a value obtained by measuring based on the ASTM E1530 method (disc heat flow meter method).

- Block copolymer hydride (H) -
The block copolymer hydride (H) comprises an aromatic vinyl compound, a chain conjugated diene compound, and the like, and includes at least two predetermined polymer blocks (E) and at least one or more predetermined polymer blocks (F ) is a polymer obtained by hydrogenating a block copolymer (G) composed of

--Polymer block (E)--
Polymer block (E) contains structural unit [e] derived from an aromatic vinyl compound as a main component.

[Structural unit [e]]
Structural unit [e] is a structural unit derived from an aromatic vinyl compound, and is the same as that described above for structural unit [a], and its preferred examples are also the same as those described above.

[Other structural units]
In addition, the polymer block (E) may contain structural units other than the structural unit [e].
Other structural units that can be contained in the polymer block (E) are the same as those described above as other structural units that can be contained in the polymer block (A), and preferred examples thereof are also the same as those described above. is.

[Composition, etc.]
The content of the structural unit [e] in the polymer block (E) is preferably 90% by mass or more when the total repeating units in the polymer block (E) is 100% by mass. It is more preferably 95% by mass or more, and particularly preferably 98% by mass or more. If the content of the structural unit [e] in the polymer block (E) is 90% by mass or more, sufficiently high heat resistance of the resin layer (Y) can be ensured.
In addition, the content of structural units other than the structural unit [e] in the polymer block (E) is preferably 10% by mass or less, more preferably 5% by mass or less, and 2% by mass. % or less is particularly preferred.
By setting the content ratio of the other structural units in the polymer block (E) to the above upper limit or less, the heat resistance of the resin composition (Y) containing the hydrogenated block copolymer (H) as a main component is improved. can be prevented from declining.

--Polymer block (F)--
The polymer block (F) contains structural units [f] derived from a chain conjugated diene compound as a main component.

[Structural unit [f]]
Structural unit [f] is a structural unit derived from a chain conjugated diene compound, and is the same as that described above for structural unit [b], and its preferred examples are also the same as those described above.

[Other structural units]
In addition, the polymer block (F) may contain structural units other than the structural unit [f].
Other structural units that can be contained in the polymer block (F) are the same as those described above as other structural units that can be contained in the polymer block (B), and preferred examples thereof are also the same as those described above. is.

[Composition, etc.]
The content of the structural unit [f] in the polymer block (F) is preferably 90% by mass or more when the total repeating units in the polymer block (F) is 100% by mass. It is more preferably 95% by mass or more, and particularly preferably 98% by mass or more. If the content of the structural unit [f] in the polymer block (F) is 90% by mass or more, flexibility can be imparted to the hydrogenated block copolymer (H), and the hydrogenated block copolymer When (H) is the main component of the resin composition (Y), the resin layer (Y) can maintain its flexibility, and the laminated body (Z) is used as an intermediate film to impart impact resistance to laminated glass. be able to.
The content of structural units other than the structural unit [f] in the polymer block (F) is preferably 10% by mass or less, more preferably 5% by mass or less, and 2% by mass. The following are particularly preferred.
By setting the content ratio of other structural units in the polymer block (F) to the upper limit or less, the flexibility of the hydrogenated block copolymer (H) can be maintained, and the hydrogenated block copolymer ( When H) is the main component of the resin composition (Y), the resin layer (Y) can maintain flexibility, and the laminated body (Z) can maintain the impact resistance of the laminated glass using the laminate (Z) as an intermediate film. can be done.

The structural unit [f] in the polymer block (F) is mainly composed of structural units derived from 1,4-addition polymerization, and the remainder is derived from 1,2-addition polymerization and/or 3,4-addition polymerization. contains structural units that The ratio of the structural units derived from 1,4-addition polymerization of the chain conjugated diene compound is preferably 70% by mass or more with respect to the total structural units [f] in the polymer block (F), and 80% by mass. It is more preferably at least 90% by mass, particularly preferably at least 90% by mass.
By setting the content ratio of the structural unit derived from 1,4-addition polymerization to the entire structural unit [f] in the polymer block (F) within the above range, the soft block copolymer hydride (H) The glass transition temperature derived from the segment can be controlled within the range of -60°C or higher and -30°C or lower. As a result, when the block copolymer hydride (H) is the main component of the resin composition (Y), the resin layer (Y) can maintain flexibility at -20 ° C. or higher and 40 ° C. or lower, and the laminate ( Z) can be used as an intermediate film to provide impact resistance in a wide temperature range of -20°C to 40°C.

As the aromatic vinyl compound as a component of the polymer block (E) and/or the polymer block (F), the same aromatics as those used for the polymer block (A) and/or the polymer block (B) group vinyl compounds can be used.

As a component of the polymer block (E) and/or the polymer block (F), a linear conjugated diene compound similar to those used for the polymer block (A) and/or the polymer block (B) Chain conjugated diene compounds can be used.

As the vinyl compound that may be contained as a component of the polymer block (E) and/or the polymer block (F), the same vinyl compounds as those used for the polymer block (A) and/or the polymer block (B) A linear vinyl compound or a cyclic vinyl compound can be used.

-- Block copolymer (G) --
The block copolymer (G), which is the precursor of the block copolymer hydride (H), is a polymer containing at least two polymer blocks (E) and at least one polymer block (F). .
The number of polymer blocks (E) in the block copolymer (G) is not particularly limited as long as it is two or more. The number of polymer blocks (F) in the polymer block (F) is not particularly limited as long as it is one or more, but it is usually two or less, preferably one.
When the block copolymer (G) has a plurality of polymer blocks (E), the composition of structural units in the polymer blocks (E) may be the same or different.
When the block copolymer (G) has a plurality of polymer blocks (F), the composition of structural units in the polymer blocks (F) may be the same or different.

[mass fraction]
Here, when the mass fraction of the structural unit [e] in the block copolymer (G) is wE, and the mass fraction of the structural unit [f] in the block copolymer (G) is wF, The ratio of wE to wF (wE/wF) is preferably 40/60 or more and 60/40 or less, more preferably 42/58 or more, and further preferably 45/55 or more, It is particularly preferably 48/52 or more, preferably 58/42 or less, more preferably 55/45 or less, and particularly preferably 52/48 or less.
By setting the ratio of wE to wF (wE/wF) to be equal to or higher than the lower limit, it is possible to prevent the elastic modulus of the resin layer (Y) from decreasing. wF) is equal to or less than the upper limit to prevent the flexibility of the resin layer (Y) from deteriorating and the impact resistance of the laminated glass using the laminate (Z) as an interlayer film to be prevented from deteriorating. can do.

The form of the block of the block copolymer (G) is not particularly limited, and may be either a chain block or a radial block, but the chain block is preferred from the viewpoint of excellent mechanical strength. The most preferred form of the block copolymer (G) is a triblock copolymer (EFE) in which the polymer block (F) is bound to both ends of the polymer block (E).

The molecular weight of the block copolymer (G) is a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, and is 30,000 or more. is preferably 40,000 or more, particularly preferably 50,000 or more, preferably 100,000 or less, more preferably 90,000 or less, 80,000 It is more preferably 70,000 or less, and particularly preferably 60,000 or less.
The molecular weight distribution (Mw/Mn) of the block copolymer (G) is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.8 or less.
By setting Mw and Mw/Mn within the above ranges, the resin composition (Y) having a hydrogenated block copolymer (H) obtained by hydrogenating the block copolymer (G) as a main component has sufficient Melt moldability and mechanical strength can be imparted.

The method for producing the block copolymer (G) is not particularly limited, and known methods can be employed. mentioned.

The hydrogenated block copolymer (H) is a polymer obtained by hydrogenating at least 95% of the carbon-carbon unsaturated bonds of the main chain and side chains derived from the chain conjugated diene compound in the block copolymer (G). is.
The block copolymer hydride (H) is a polymer obtained by selectively hydrogenating only the carbon-carbon unsaturated bonds of the main chain and side chains derived from the chain conjugated diene compound in the block copolymer (G). Main chain and side chain carbon-carbon unsaturated bonds derived from the chain conjugated diene compound in the block copolymer (G), and derived from the aromatic vinyl compound in the block copolymer (G) It may be a polymer obtained by hydrogenating the carbon-carbon unsaturated bond of the aromatic ring, or a mixture thereof.

When selectively hydrogenating only the carbon-carbon unsaturated bonds of the main chain and side chains derived from the chain conjugated diene compound in the block copolymer (G), the chain in the block copolymer hydride (H) The hydrogenation rate of carbon-carbon unsaturated bonds in the main chain and side chains derived from the conjugated diene compound is preferably 95% or more, more preferably 97% or more, and 99% or more. Particularly preferably, the hydrogenation rate of the carbon-carbon unsaturated bond of the aromatic ring derived from the aromatic vinyl compound in the block copolymer hydride (H) is preferably 10% or less, and 5% or less. is more preferable, and 3% or less is particularly preferable.
The block copolymer hydride (H) obtained by selectively hydrogenating only the carbon-carbon unsaturated bonds of the main chain and side chains derived from the chain conjugated diene compound in the block copolymer (G) is , the light resistance and heat deterioration resistance are improved as compared with the block copolymer (G).
By making the hydrogenation rate of the carbon-carbon unsaturated bonds of the main chain and side chains derived from the chain conjugated diene compound in the block copolymer (G) equal to or higher than the above lower limit, the block copolymer hydride (H ) as a main component can improve the light resistance and heat deterioration resistance of the resin composition (Y). Further, by setting the hydrogenation rate of the carbon-carbon unsaturated bond of the aromatic ring derived from the aromatic vinyl compound in the block copolymer (G) to the above upper limit value or less, the block copolymer hydride (H) can be obtained. It becomes easy to maintain the heat deterioration resistance of the resin composition (Y) as a main component.

Main chain and side chain carbon-carbon unsaturated bonds derived from the chain conjugated diene compound in the block copolymer (G), and aromatic ring carbon derived from the aromatic vinyl compound in the block copolymer (G) - When hydrogenating carbon unsaturated bonds, the hydrogenation rate of carbon-carbon unsaturated bonds in the block copolymer hydride (H) is preferably 90% or more of the total amount of carbon-carbon unsaturated bonds. , is more preferably 95% or more, and particularly preferably 99% or more. By setting the hydrogenation rate of the carbon-carbon unsaturated bond in the hydrogenated block copolymer (H) within this range, the hydrogenated block copolymer (H) obtained is derived from a chain conjugated diene compound. Compared to the block copolymer hydride (H) obtained by selectively hydrogenating only the carbon-carbon unsaturated bonds of the main chain and side chains, it has improved light resistance and heat deterioration resistance, and furthermore has a heat distortion temperature. can be raised.

The hydrogenation rate of the carbon-carbon unsaturated bond in the block copolymer hydride (H) can be determined, for example, by ¹ H-NMR of the precursor block copolymer (G) and the block copolymer hydride (H). By measuring the hydrogenation rate of the carbon-carbon unsaturated bonds of the main chain and side chains derived from the chain conjugated diene compound, and the carbon-carbon unsaturated bond of the aromatic ring derived from the aromatic vinyl compound Each hydrogenation rate can be obtained.

The method for hydrogenating the unsaturated bonds in the block copolymer (G), the reaction mode, etc. are not particularly limited, and are the same as the method for hydrogenating the unsaturated bonds, the reaction mode, etc. in the block copolymer (C) described above. It can be carried out.

The molecular weight of the hydrogenated block copolymer (H) is the weight average molecular weight (Mw) in terms of polystyrene measured by GPC using THF as a solvent, and is preferably 30,000 or more, more preferably 40,000 or more. is more preferably 50,000 or more, particularly preferably 100,000 or less, more preferably 90,000 or less, and even more preferably 80,000 or less, It is even more preferably 70,000 or less, and particularly preferably 60,000 or less.
The molecular weight distribution (Mw/Mn) of the hydride block copolymer (H) is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.8 or less.
By setting Mw and Mw/Mn within the above ranges, sufficient melt moldability and mechanical strength can be imparted to the resin composition (Y) mainly composed of the hydrogenated block copolymer (H). can.

-Modified block copolymer hydride (J)-
The modified block copolymer hydride (J) is obtained by reacting the block copolymer hydride (H) with an ethylenically unsaturated silane compound in the presence of an organic peroxide, thereby introducing an alkoxysilyl group. It is what was done.
By introducing an alkoxysilyl group into the hydrogenated block copolymer (H), the resin composition (Y) containing the hydrogenated modified block copolymer (J) as a main component maintains its elastic modulus and transparency. As a result, strong adhesion to glass and metal is imparted. Therefore, when the outermost layer of the laminate (Z) of the present invention is composed of the modified block copolymer hydride (J), an adhesive is not interposed between the laminate (Z) and the glass plate. A laminated glass using the laminate (Z) as an intermediate film can be produced.

The alkoxysilyl group to be introduced includes, for example, a tri(C1-C6 alkoxy)silyl group such as a trimethoxysilyl group and a triethoxysilyl group; a methyldimethoxysilyl group, a methyldiethoxysilyl group and an ethyldimethoxysilyl group. , an ethyldiethoxysilyl group, a propyldimethoxysilyl group, a propyldiethoxysilyl group, an (alkyl having 1 to 20 carbon atoms) di(alkoxy having 1 to 6 carbon atoms)silyl group; a phenyldimethoxysilyl group, a phenyldiethoxy (aryl)di(alkoxy having 1 to 6 carbon atoms)silyl group such as silyl group; and the like. Among these, a trimethoxysilyl group is preferable from the viewpoint of strong adhesion of the laminate (Z) to the glass plate.
The alkoxysilyl group is bonded to the hydrogenated block copolymer (H) 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. may

The amount of alkoxysilyl groups introduced into the hydrogenated block copolymer (H) is preferably 0.1 parts by mass or more, and preferably 0.2 parts by mass, relative to 100 parts by mass of the hydrogenated block copolymer (H). It is more preferably 0.3 parts by mass or more, particularly preferably 1.0 parts by mass or more, preferably 5 parts by mass or less, and 4 parts by mass or less. more preferably 3 parts by mass or less, and particularly preferably 2 parts by mass or less.
By setting the amount of the alkoxysilyl group to be introduced to the upper limit or less, the resulting hydrogenated block copolymer (J) having an alkoxysilyl group is melt-molded into a desired shape, and the alkoxy that has been decomposed with a trace amount of moisture etc. It is possible to prevent problems such as progress of cross-linking between silyl groups to produce unmelted substances, and deterioration of moldability due to deterioration of fluidity when melted. In addition, by setting the amount of the alkoxysilyl group to be introduced to the lower limit value or more, the resin layer (Y) made of the resin composition (Y) mainly composed of the hydrogenated block copolymer (H) having the alkoxysilyl group is formed. It is possible to prevent insufficient adhesive force from being obtained when adhering to a glass plate.
The introduction of alkoxysilyl groups can be confirmed by IR spectrum. Also, the introduction amount can be calculated from the ¹ H-NMR spectrum.

As the ethylenically unsaturated silane compound used for introducing the alkoxysilyl group, any compound that graft-reacts with the hydrogenated block copolymer (H) and introduces the alkoxysilyl group into the hydrogenated block copolymer (H) can be used. , is not particularly limited, and examples include vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, p-styryltrimethoxysilane, 3-acryloxypropyltrisilane. methoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3 -acryloxypropyltrimethoxysilane, and the like. Each of these may be used alone, or two or more thereof may be used in combination.

The amount of the ethylenically unsaturated silane compound used is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, relative to 100 parts by mass of the hydrogenated block copolymer (H). It is preferably 0.3 parts by mass or more, particularly preferably 1.0 parts by mass or more, and preferably 5 parts by mass or less, more preferably 4 parts by mass or less. , is more preferably 3 parts by mass or less, and particularly preferably 2.5 parts by mass or less.

As the peroxide used for the introduction reaction of the alkoxysilyl group, the one-minute half-life temperature is 170° C. in order to allow the ethylenically unsaturated silane compound to react advantageously in the molten state of the hydrogenated block copolymer (H). Above 190° C. and below are preferably used. Oxy)hexane, di-t-butyl peroxide, di(2-t-butylperoxyisopropyl)benzene, and the like are preferably used. Each of these may be used alone, or two or more thereof may be used in combination.
The amount of the peroxide used is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the block copolymer hydride (H). It is particularly preferably 2 parts by mass or more, preferably 2 parts by mass or less, more preferably 1 part by mass or less, and particularly preferably 0.5 parts by mass or less.

The method of reacting the modified block copolymer hydride (J) and the ethylenically unsaturated silane compound in the presence of a peroxide is not particularly limited. The known methods described can be mentioned.

The molecular weight of the modified block copolymer hydride (J) is almost the same as the molecular weight of the block copolymer hydride (H) used as a starting material, since the amount of alkoxysilyl groups to be introduced is small. On the other hand, since the polymer is reacted with an ethylenically unsaturated silane compound in the presence of a peroxide, cleavage reaction and cross-linking reaction of the polymer occur simultaneously, and the modified block copolymer hydride (J) has a large molecular weight distribution. Become.
The molecular weight of the hydrogenated modified block copolymer (J) is preferably 30,000 or more, more preferably 40,000 or more, as a polystyrene equivalent weight average molecular weight (Mw) measured by GPC using THF as a solvent. more preferably 50,000 or more, preferably 100,000 or less, more preferably 90,000 or less, and particularly preferably 80,000 or less. Also, the molecular weight distribution (Mw/Mn) is preferably 3.5 or less, more preferably 2.5 or less, and particularly preferably 2.0 or less.
By setting Mw and Mw/Mn within the above ranges, sufficient melt moldability and mechanical strength can be imparted to the resin composition (Y) mainly composed of the hydrogenated modified block copolymer (J). can.

<<Additives>>
The resin composition (Y) containing the resin (y) as the main component may contain various additives in addition to the resin (y) as the main component.
Preferable additives include plasticizers and softeners for adjusting the storage elastic modulus in the dynamic viscoelastic properties of the laminate (Z) containing the resin layer (X) and the resin layer (Y) to a desired value, UV absorbers for shielding ultraviolet rays, infrared absorbers for shielding infrared rays, antioxidants and antiblocking agents for improving processability, light stabilizers for improving durability, and the like.

-Plasticizer-
The plasticizer is not particularly limited as long as it can be blended with the resin (y) containing many polar groups and the storage elastic modulus in the dynamic viscoelastic properties of the laminate (Z) can be set to a desired value. organic plasticizers such as monobasic organic acid esters and polybasic organic acid esters; phosphoric acid plasticizers such as organic phosphoric acid compounds and organic phosphorous acid compounds; and the like.
Specific examples of the plasticizer include diethylene glycol-di-2-ethylbutyrate, diethylene glycol-di-n-heptanoate, diethylene glycol-di-2-ethylhexanoate, and triethylene glycol-di-2-ethylbutyrate. , triethylene glycol-di-n-heptanoate, triethylene glycol-di-2-ethylhexanoate, tetraethylene glycol-di-2-ethylbutyrate, tetraethylene glycol-di-n-heptanoate, tetraethylene glycol- di-2-ethylhexanoate, and the like.

The amount of the plasticizer to be blended can be appropriately selected depending on the resin (y), the thickness structure of the resin layer (X) and the resin layer (Y), etc., so that the storage elastic modulus of the laminate (Z) becomes a desired value. However, it is preferably 30 parts by mass or less with respect to 100 parts by mass of the resin (y).

- softener -
The softening agent is a hydrocarbon-based resin containing no polar group, or is added to the resin (y) so long as the storage elastic modulus in the dynamic viscoelastic properties of the laminate (Z) can be set to a desired value. , without any particular limitation, for example, polyisobutylene, polybutene, poly-4-methylpentene, poly-1-octene, ethylene/α-olefin copolymer, and other olefinic low-molecular-weight compounds and their hydrides; polyisoprene, conjugated diene-based low-molecular-weight materials such as polyisoprene-butadiene copolymers and hydrides thereof; and paraffin-based low-molecular-weight materials such as liquid paraffin.
Among these, from the viewpoint of easy adjustment of the storage elastic modulus while maintaining the transparency of the laminate (Z), the above-mentioned low molecular weight substances having a number average molecular weight of 300 or more and 5,000 or less are preferable, and further excellent A low-molecular-weight polyisobutylene hydride and a low-molecular-weight polyisoprene hydride are more preferable from the viewpoint of maintaining transparency and light resistance and being excellent in the effect of adjusting the storage elastic modulus.

The blending amount of the softening agent is appropriately selected so that the storage elastic modulus of the laminate (Z) becomes a desired value depending on the resin (y), the thickness structure of the resin layer (X) and the resin layer (Y), etc. Although possible, it is preferably 30 parts by mass or less with respect to 100 parts by mass of the resin (y).

Additives other than plasticizers and softeners (e.g., ultraviolet absorbers, infrared absorbers, antioxidants, light stabilizers, etc.) include the same additives as those blended in the above resin composition (X). can be used. These can each be used individually by 1 type or in combination of 2 or more types.
The total amount of additives other than the plasticizer and the softener is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and 2 parts by mass with respect to 100 parts by mass of the resin (y). Part or less is particularly preferred.

As a method of blending various additives into resin (y), the same method as the method of blending various additives into resin (x) can be applied.

The resin layer (Y) adjusts the storage elastic modulus in the viscoelastic properties of the laminate (Z) to a desired value. The resin layer (Y) imparts sufficient heat insulating properties to the laminated glass when the laminate (Z) is used as an intermediate film for the laminated glass. Therefore, the thickness of the resin layer (Y) is preferably 0.05 mm or more, more preferably 0.1 mm or more, particularly preferably 0.15 mm or more, and 1.0 mm or less. is preferably 0.8 mm or less, and particularly preferably 0.6 mm or less.
By setting the thickness of the resin layer (Y) to the lower limit or more, the elastic modulus of the laminate (Z) is prevented from becoming insufficient, and the laminated glass having the laminate (Z) as an intermediate film is heat-insulated. Insufficient quality can be prevented. In addition, by setting the thickness of the resin layer (Y) to be equal to or less than the upper limit, it is possible to prevent the laminate (Z) from being difficult to store in a rolled form, and to prevent the work during the production of the laminated glass from becoming difficult. It is possible to prevent deterioration of the properties.

(c) Laminate (Z)
In the laminate (Z) of the present invention, at least one resin layer (X) having the properties described above is laminated between at least two resin layers (Y).
The storage elastic modulus in the dynamic viscoelastic properties of the laminate (Z) must be 1.0×10 7 Pa or more and 1.5× ^{10 7} Pa in the temperature range of −20° C. or higher and 40° C. or lower. is preferably 1.7×10 ⁷ Pa or more, more preferably 1.7×10 7 Pa or more, even more preferably 2.0×10 ⁷ Pa or more, and particularly 2.4×10 ⁷ Pa or more. preferably 5.0×10 ⁸ Pa or less, preferably 4.5×10 ⁸ Pa or less, more preferably 4.0×10 ⁸ Pa or less, and 3.0 It is particularly preferable that the pressure is ×10 ⁸ Pa or less.
The laminate (Z) has the above laminate structure and has the above dynamic viscoelastic properties, so that when used as an intermediate film for laminated glass, the laminate (Z) maintains the rigidity of the laminated glass and has sound insulating properties. and a laminated glass having excellent heat insulating properties can be obtained.

The thickness of the laminate (Z) is preferably 0.2 mm or more, more preferably 0.3 mm or more, particularly preferably 0.4 mm or more, and 2 mm or less. It is preferably 1.5 mm or less, more preferably 1.0 mm or less. By making the thickness of the laminate (Z) equal to or more than the lower limit, it is possible to prevent the heat insulating effect of the laminated glass from becoming insufficient, and the thickness of the laminate (Z) is made equal to or less than the upper limit. Therefore, it is possible to prevent difficulty in winding and storing the laminate (Z) in a roll, and to prevent deterioration of workability in manufacturing the laminated glass.

FIG. 1 is a diagram showing an example of an embodiment of the laminate (Z) of the present invention.
In the laminate (Z) 3a of FIG. 1, one resin layer (X) 1a is sandwiched between two resin layers (Y) 2a and 2b, namely resin layer (Y)/resin layer (X)/resin layer It has a three-layer structure consisting of (Y).
FIG. 3 is a diagram showing another example of an embodiment of the laminate of the present invention.
In the laminate (Z) 3b of FIG. 3, one resin layer (X) 1a is sandwiched between two resin layers (Y) 2a and 2b, and further, between the two resin layers (Y) 2b and 2c It has a five-layer structure consisting of resin layer (Y)/resin layer (X)/resin layer (Y)/infrared reflective film/resin layer (Y) with an infrared reflective film 4 sandwiched between them.
Here, the resin layers (Y) 2a, 2b and 2c may have the same or different compositions and thicknesses.

The laminate structure of the laminate (Z) can be appropriately selected depending on the purpose, and examples thereof include the structures illustrated in FIGS. 1 and 3 and the following lamination structures (i) to (x).
(i): resin layer (Y)/resin layer (X)/resin layer (Y)/resin layer (Y),
(ii): resin layer (Y)/resin layer (X)/resin layer (Y)/resin layer (X)/resin layer (Y),
(iii): resin layer (Y)/resin layer (X)/resin layer (Y)/resin layer (X)/resin layer (Y)/resin layer (X)/resin layer (Y),
(iv): resin layer (Y)/resin layer (X)/resin layer (Y)/resin layer (Y)/resin layer (X)/resin layer (Y),
(v): resin layer (Y)/resin layer (X)/resin layer (Y)/resin layer (Y)/resin layer (X)/resin layer (Y)/resin layer (Y)/resin layer (X )/resin layer (Y),
(vi): resin layer (Y)/resin layer (X)/resin layer (Y)/resin layer (Y)/resin layer (X)/resin layer (Y)/resin layer (Y)/resin layer (X )/resin layer (Y)/resin layer (Y)/resin layer (X)/resin layer (Y),
(vii): resin layer (Y)/infrared reflective film/resin layer (Y)/resin layer (X)/resin layer (Y)/resin layer (Y),
(viii): resin layer (Y)/light control sheet/resin layer (Y)/resin layer (X)/resin layer (Y),
(ix): resin layer (Y)/adhesive layer/resin layer (X)/adhesive layer/resin layer (Y),
(x): resin layer (Y)/other resin layer/resin layer (Y)/resin layer (X)/resin layer (Y)
When the laminate (Z) has a plurality of resin layers (X), each resin layer (X) may have the same or different composition and thickness. In addition, the laminate (Z) includes (i) another resin film for improving the penetration resistance of the laminated glass, (ii) a colored resin film for forming a light shielding portion in the laminated glass, and (iii) the laminated glass. It may also be a laminate structure in which another resin film layer is laminated to impart a desired function, such as a highly elastic resin film for increasing the rigidity of the film.
When the resin layer (Y) does not have adhesiveness to glass, it may have an adhesive layer on the outside of the resin layer (Y).
In this case, the laminate (Z) is, for example,
(i): adhesive layer/resin layer (Y)/resin layer (X)/resin layer (Y)/adhesive layer,
(ii): A laminated structure such as adhesive layer/resin layer (Y)/resin layer (X)/resin layer (Y)/resin layer (Y)/adhesive layer may be employed.

A production method for producing the laminate (Z) of the present invention is not particularly limited. The resin composition (X) and/or the resin composition (Y) are formed into the resin layer (X) and/or the resin composition (Y) by a known manufacturing method such as an extrusion molding method, a calendar molding method, a press molding method, a casting molding method, and an inflation molding method. Each layer of the resin layer (Y) is prepared in advance, and the resin layer (X), the resin layer (Y) and, if necessary, another functional resin layer are laminated and heat-pressed to form a laminate (Z). can be manufactured. In addition, the resin composition (X) is melt-extruded onto the film by extrusion lamination molding or the like on one side of the resin layer (Y) that has been molded in advance by the molding method or the like, and the resin layer (X) is bonded and laminated. Body (Z) can also be produced. Furthermore, the resin composition (X), the resin composition (Y), and, if necessary, another functional resin can be co-extruded to produce a laminate (Z) having a desired layer structure. .

A plurality of the same or different resin layers (Y) can also be used to enhance the heat insulating properties of the laminated glass. In the case of using a plurality of resin layers (Y), for example, (i) the penetration resistance of laminated glass such as polyethylene terephthalate film, polycarbonate film, ionomer resin film, etc. is placed between the plurality of resin layers (Y). A functional film such as a resin film that enhances, (ii) a polyethylene terephthalate film vapor-deposited with an infrared reflective layer, etc. can also be arranged.

The laminate (Z) of the present invention may have an embossed shape on its surface. Specific examples of the embossed shape include JP-A-6-198809, WO 1995/19885, JP-A-9-40444, JP-A-9-241045, JP-A-9-295839, JP-A-9-295839, 10-17338, JP-A-10-167773, JP-A-10-231150, JP-A-11-35347, JP-A-11-147735, JP-A-2000-7390, JP-A-2000- 44295, JP 2000-203902, JP 2000-203900, JP 2000-203901, JP 2000-256043, JP 2000-290046, JP 2000-319045 Publications, JP-A-2001-19499, JP-A-2001-26468, JP-A-2001-48599, JP-A-2001-114538, JP-A-2001-130931, JP-A-2001-150540, JP 2001-163641, JP 2001-192244, JP 2001-261385, JP 2001-220182, WO 2001/072509, JP 2002-037648, JP 2002-104846, JP 2003-128442, JP 2003-048762, JP 2003-212614, JP 2003-238218, WO 2014/021459, WO 2015 /016361, International Publication No. 2015/016358, International Publication No. 2015/016366, etc., the satin finish shape, the continuous groove shape, the quadrangular pyramid-shaped concave shape, the quadrangular pyramid-shaped convex shape, A combination of these shapes and the like are included.

When the resin (y), which is the main component of the resin layer (Y), does not have an adhesive functional group to glass, for example, when it is a block copolymer hydride (H) having no functional group, When manufacturing laminated glass by bonding the resin layer (Y) to a glass plate, an adhesive layer can be arranged on the side of the resin layer (Y) facing the glass plate. Examples of adhesives include polyurethane-based adhesives, silicone resin-based adhesives, modified polyolefin-based adhesives, modified block copolymer-based adhesives, and the like. Among these, from the viewpoint of excellent adhesion to both the resin layer (Y) and the glass plate, a modified polyolefin adhesive having an alkoxysilyl group and a modified block copolymer hydride adhesive having an alkoxysilyl group are used. preferable.

(d) Glass Plate The thickness of the glass plate used for the laminated glass of the present invention is not particularly limited. The thickness of the glass plate used in the present invention is usually 0.1 mm or more and 10 mm or less, preferably 0.2 mm or more, more preferably 0.5 mm or more, and 0.7 mm or more. It is particularly preferably 3 mm or less, more preferably 2.5 mm or less, and particularly preferably 2 mm or less. The thickness of the glass plate used in the present invention can be appropriately selected according to the use of the laminated glass (for example, window materials for automobiles and buildings, wall materials, partition materials, floor materials, etc.).
In the laminated glass of the present invention, two glass plates are usually used, and three or more glass plates are used as necessary. The thickness of the multiple glass sheets used may be the same or different.

The material of the glass plate is not particularly limited. Materials for the glass plate include, for example, aluminosilicate glass, borosilicate glass, aluminoborosilicate glass, barium goosilicate glass, silicate glass, crystallized glass, germanium glass, quartz glass, soda lime glass, white plate glass, and lead glass. , uranium glass, potash glass, alkali-free glass, and the like.
Moreover, the thermal conductivity in the thickness direction of the glass plate used in the present invention is usually about 0.9 W/(m·K) or more and 1.3 W/(m·K) or less. Here, the thermal conductivity in the thickness direction of the glass plate is a value determined by measurement based on the ASTM E1530 method (disc heat flow meter method).

A heat ray reflective film, an infrared reflective film, or the like may be formed on the glass plate. A glass plate having, on its surface, a heat ray reflective film or infrared ray reflective film made of an ultrathin metal film or metal oxide film, or the like is provided with heat shielding properties. Therefore, a laminated glass including the glass plate is preferable because heat transfer through the glass plate can be reduced. 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.

(e) Laminated glass The laminated glass of the present invention comprises two glass plates and an intermediate film composed of a laminate (Z) disposed between the two glass plates, and usually the glass plates. are bonded and integrated via an intermediate film.

In addition, the thermal conductivity in the thickness direction (laminating direction) of the laminated glass must be 0.5 W/(mK) or less, preferably 0.4 W/(mK) or less. , 0.3 W/(m·K) or less, and particularly preferably 0.25 W/(m·K) or less.
Compared to the thermal conductivity of a glass plate, which is usually about 1 W/(m·K), the thermal conductivity of the laminated glass of the present invention is about 1/2 or less and is excellent in heat insulation.
The thermal conductivity in the thickness direction (laminating direction) of the laminated glass is obtained by measuring in a temperature atmosphere of 60 ° C. using a thermal conductivity measuring device in accordance with the ASTM E1530 method (disc heat flow meter method). value.

The laminated glass of the present invention preferably has a flexural modulus at 25° C. of 11 GPa (11×10 ⁹ Pa) or more, more preferably 12 GPa or more, and particularly preferably 13 GPa or more.
The flexural modulus of laminated glass, which is generally used as laminated glass for automobiles, is about 11 GPa and is composed of two sheets of glass with a thickness of 2 mm and an interlayer film mainly composed of polyvinyl butyral with a thickness of 0.76 mm. On the other hand, the laminated glass of the present invention has a bending elastic modulus equal to or higher than that of the laminated glass, and provides a laminated glass excellent in rigidity.
The flexural modulus of the laminated glass was measured using an Autograph (manufactured by Instron, INSTRON5582) and using a rotating 4-point bending test jig based on the JIS R1602 method (4-point bending test method). , distance between fulcrums: top = 27 mm, bottom = 81 mm, support rod diameter 6 mm, temperature 25°C.

^The laminated ^glass of the present invention is a laminate (Z ) as an intermediate film, the above flexural modulus can be obtained, and both heat insulation and rigidity can be achieved.

The thickness and shape of the laminated glass of the present invention are not particularly limited, but are usually 0.3 mm or more and 20 mm or less, preferably 1 mm or more, more preferably 2 mm or more, and particularly 3 mm or more. It is preferably 15 mm or less, more preferably 10 mm or less, and particularly preferably 7 mm or less. If the thickness is within this range, it can be suitably used as glass for displays, glass for automobiles, glass for railway vehicles, glass for building materials, and the like.
Further, the shape of the laminated glass may be a flat plate shape used for building materials, displays, etc., or may be a curved shape such as laminated glass for automobiles, laminated glass for railway vehicles, and the like.

FIG. 2 is a diagram showing an example of an embodiment of the laminated glass of the present invention.
In the laminated glass 6a of FIG. 2, one resin layer (X) 1a is sandwiched between two resin layers (Y) 2a and 2b, namely resin layer (Y)/resin layer (X)/resin layer (Y). ) is used as an intermediate film, and the laminate (Z) 3a as the intermediate film is arranged between two glass plates 5a and 5b.
FIG. 4 is a diagram showing another example of an embodiment of the laminated glass of the present invention.
In the laminated glass 6b of FIG. 4, one resin layer (X) 1a is sandwiched between two resin layers (Y) 2a and 2b, and an infrared reflecting layer is formed between the two resin layers (Y) 2b and 2c. A laminate (Z) 3b having a five-layer structure consisting of a resin layer (Y)/resin layer (X)/resin layer (Y)/infrared reflective film/resin layer (Y) sandwiching a film 4 is placed in the middle. A laminate (Z) 3b as an intermediate film is arranged between two glass plates 5a and 5b.
Here, the resin layers (Y) 2a, 2b, and 2c may have the same composition and thickness, or may have different compositions. The glass plates 5a and 5b may be the same or different in material and thickness.

The laminated structure of the laminated glass of the present invention can be appropriately selected depending on the purpose. Examples thereof include the structures illustrated in FIGS. 2 and 4 and the following laminated structures (i) to (xiii).
(i): glass/laminate (Z)/glass/laminate (Z)/glass,
(ii): glass/resin layer (Y)/resin layer (X)/resin layer (Y)/resin layer (Y)/glass,
(iii): glass/resin layer (Y)/resin layer (X)/resin layer (Y)/resin layer (X)/resin layer (Y)/glass,
(iv): glass/resin layer (Y)/resin layer (X)/resin layer (Y)/resin layer (X)/resin layer (Y)/resin layer (X)/resin layer (Y)/glass,
(v): glass/resin layer (Y)/resin layer (X)/resin layer (Y)/resin layer (Y)/resin layer (X)/resin layer (Y)/glass,
(vi): glass/resin layer (Y)/resin layer (X)/resin layer (Y)/resin layer (Y)/resin layer (X)/resin layer (Y)/resin layer (Y)/resin layer (X)/resin layer (Y)/glass,
(vii): glass/resin layer (Y)/resin layer (X)/resin layer (Y)/resin layer (Y)/resin layer (X)/resin layer (Y)/resin layer (Y)/resin layer (X)/resin layer (Y)/resin layer (Y)/resin layer (X)/resin layer (Y)/glass,
(viii): glass/resin layer (Y)/infrared reflective film/resin layer (Y)/resin layer (X)/resin layer (Y)/resin layer (Y)/glass,
(ix): glass/resin layer (Y)/light control sheet/resin layer (Y)/resin layer (X)/resin layer (Y)/glass,
(x): glass/resin layer (Y)/adjusting adhesive layer/resin layer (X)/adhesive layer/resin layer (Y)/glass,
(xi): glass/resin layer (Y)/other resin layer/resin layer (Y)/resin layer (X)/resin layer (Y)/glass,
(xii): glass/adhesive layer/resin layer (Y)/resin layer (X)/resin layer (Y)/adhesive layer/glass,
(xiii): glass/adhesive layer/resin layer (Y)/resin layer (X)/resin layer (Y)/resin layer (Y)/adhesive layer/glass

The method for producing the laminated glass of the present invention is not particularly limited. As a general method for producing curved laminated glass such as laminated glass for automobiles, for example, a laminate obtained by laminating glass plate/laminate (Z)/glass plate in this order is formed, and this laminate is degassed. After degassing the inside by putting it in a flexible resin bag that can be used, put it in an autoclave and crimp it under the conditions of temperature: 100 ° C. or higher and 150 ° C. or lower and pressure: 0.5 MPa or higher and 1.5 MPa or lower. can be done.
When the resin layer (Y) constituting the laminate (Z) does not have adhesiveness to the glass plate, an adhesive is interposed between the laminate (Z) and the glass plate, for example, glass plate/adhesive/laminate ( Z)/adhesive/glass plate can be stacked in this order to form a laminated glass in the same manner as described above.
In the case of laminated glass having a planar shape such as laminated glass for buildings, a method of bonding and integrating the laminate by heating using a vacuum laminator, a heat press, or the like can also be applied.

In the laminated glass of the present invention, the laminate (Z) used as an interlayer film has a specific resin layer (X) having a maximum value of tan δ in the dynamic viscoelastic property in the temperature range of −20° C. or more and 20° C. or less. Therefore, in addition to the heat insulating properties, the coincidence effect of the glass is reduced and the sound insulation performance is improved, so it is particularly useful as a laminated glass for automobiles.
Further, in the laminated glass of the present invention, the rigidity is maintained even when the thickness of the glass plate is reduced by increasing the thickness of the intermediate film without increasing the thickness of the entire laminated glass. It also contributes to the weight reduction of the laminated glass because it can improve the heat insulating property. For this reason, especially in automobile applications, it can be expected to show an effect of improving fuel consumption by using it as side glass, rear glass, roof glass, windshield, and the like.

EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not limited to these examples. In the following description, "%" and "parts" representing amounts are based on mass unless otherwise specified. Measurements and evaluations in the examples were carried out by the following methods.

(1) Weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn)
The molecular weights of block copolymer (C), block copolymer hydride (D), block copolymer (G), and block copolymer hydride (H) were determined at 38°C using tetrahydrofuran (THF) as an eluent. Measured in and calculated the standard polystyrene conversion value. As a measuring device, a gel permeation chromatography (GPC) device (HLC8320GPC, manufactured by Tosoh Corporation) was used.
(2) Hydrogenation rate The hydrogenation rate of the main chain, side chain and aromatic ring of the hydrogenated block copolymer (D) and the hydrogenated block copolymer (H) is It was calculated by measuring ¹ H-NMR of the hydrogenated polymer (D), the block copolymer (G), and the hydrogenated block copolymer (H).

(3) tan δ of resin layer (X)
A required number of the resin layers (X) thus produced were stacked and press-molded to prepare a sheet having a thickness of 1 mm or more and 1.5 mm or less. A test piece having a length of 70 mm and a width of 10 mm was produced from this sheet.
Using this test piece, using a viscoelasticity measuring device (TA Instrument Japan Co., Ltd., ARES), JIS K7244-2 method (Plastics-Dynamic mechanical property test method-Part 2: Torsion pendulum method), angular frequency: 1 rad / s, measurement temperature range: -100 ° C. or higher and 100 ° C. or lower, temperature increase rate: 5 ° C./min. The temperature showing the maximum value was measured.

(4) Storage modulus (G') of laminate (Z)
A test piece having a length of 70 mm and a width of 10 mm was produced from the produced laminate (Z).
Using this test piece, using the viscoelasticity measuring device, based on JIS K7244-2 method (Plastics-Test method for dynamic mechanical properties-Part 2: Torsion pendulum method), angular frequency: 1 rad / s , Measurement temperature range: -100 ° C. or higher and 150 ° C. or lower, temperature increase rate: 5 ° C./min. Storage modulus (G') was measured.

(5) Heat Insulation of Laminated Glass At least one laminate (Z) and, if necessary, two sheets of circular soda plate glass (50 mm in diameter and 0.5 mm to 1.5 mm in thickness) are placed between them. Another resin layer, an adhesive layer, and the like were placed and bonded together to form a laminated glass, which was used as a test piece.
Using a thermal conductivity measuring device (product name: Unithermo Model 2021, manufactured by Antar), this test piece was measured for thermal conductivity in a temperature atmosphere of 25 ° C. in accordance with the ASTM E1530 method (disc heat flow meter method). did
The heat insulating property of the laminated glass was evaluated as good when the thermal conductivity of the laminated glass was 0.5 W/(m·K) or less, and was evaluated as poor when it exceeded 0.5 W (m·K).

(6) Rigidity of laminated glass Between two sheets of soda lime glass (length 100 mm, width 20 mm, thickness 0.5 mm or more and 1.5 mm or less), at least one laminate (Z) and if necessary Another resin layer, an adhesive layer, etc. were placed and bonded together to form a laminated glass, which was used as a test piece.
Using an autograph (INSTRON 5582, manufactured by Instron) equipped with a heating oven, this test piece was tested using a rotary 4-point bending test jig based on the JIS R1602 method (4-point bending test method). , distance between fulcrums: upper part = 27 mm, lower part = 81 mm, support rod diameter 6 mm, temperature 25°C, a bending test was performed, and the bending elastic modulus was measured.
The rigidity of the laminated glass was evaluated as good when the bending elastic modulus of the laminated glass was 11 GPa (11×10 ⁹ Pa) or more, and was evaluated as poor when it was less than 11 GPa (11×10 ⁹ Pa).

(7) Sound insulation At least one laminate (Z) and, if necessary, other A resin layer, an adhesive layer, and the like were arranged and bonded together to form a laminated glass, which was used as a test piece.
Based on the JIS-K7391 method, this laminated glass test piece was used to measure the loss factor corresponding to the frequency using a vibration damping tester (manufactured by Rion Co., Ltd.) by the central excitation method. From the ratio of the loss factor obtained here and the resonance frequency of the laminated glass test piece, the sound transmission loss corresponding to the frequency was obtained.
The sound insulation was evaluated as good when there was no area where the sound transmission loss value was less than 35 dB in the frequency range of 2000 Hz or more and 4000 Hz or less, and it was evaluated as poor when there was an area where the sound transmission loss value was less than 35 dB.

[Production Example 1]
<Production of block copolymer hydride (D1)>
Block copolymer hydride (D1) was prepared by the following procedure.
300 parts of dehydrated cyclohexane, 5 parts of dehydrated styrene, and 0.53 parts of ethylene glycol dibutyl ether were introduced into a reactor equipped with a stirrer and the interior of which was sufficiently purged with nitrogen. While stirring the whole volume at 60° C., 0.47 part of n-butyllithium (15% cyclohexane solution) was added to initiate polymerization. Subsequently, while stirring the entire volume at 60°C, 5 parts of dehydrated styrene was continuously added to the reactor over 15 minutes to proceed with the polymerization reaction. was stirred. The reaction solution was measured by gas chromatography (GC), and the polymerization conversion rate at this point was 99.5%.
Next, 80 parts of dehydrated isoprene was continuously added to the reaction solution over 100 minutes, and after the addition was completed, stirring was continued for 20 minutes. At this point, the reaction solution was analyzed by GC, and the polymerization conversion rate was 99.5%.
After that, 10 parts of dehydrated styrene was continuously added to the reaction solution over 60 minutes, and the mixture was stirred for 30 minutes after the addition. At this point, the reaction solution was analyzed by GC, and the polymerization conversion rate was almost 100%.

Here, 0.5 part of isopropyl alcohol was added to the reaction liquid to stop the reaction, and a polymer solution was obtained. The block copolymer (C1) contained in the polymer solution is a polymer block (A)-polymer block (B)-polymer block (A) type triblock copolymer, and has a weight average molecular weight (Mw ) is 83,900, the molecular weight distribution (Mw / Mn) is 1.03, wA: wB = 20: 80, 1,2-addition polymerization of all isoprene-derived structural units in the block copolymer (C1) and The ratio of structural units derived from 3,4-addition polymerization (the ratio of vinyl-bonded conjugated dienes) was 58%.
In the above "wA:wB", the mass fraction of the structural unit [a] derived from the aromatic vinyl compound (styrene in Production Example 1) in the block copolymer (C1) is wA, and the linear conjugated diene is The ratio (wA:wB) between wA and wB, where wB is the mass fraction of the structural unit [b] derived from the compound (isoprene in Production Example 1) in the block copolymer (C1), is shown below. Production Examples 2 and 3 are the same.

Next, the above polymer solution was transferred to a pressure-resistant reactor equipped with a stirrer, and 0.042 parts of bis(cyclopentadienyl)titanium dichloride and diethyl were added in 1.0 parts of toluene as hydrogenation catalysts. A solution containing 0.122 parts of aluminum chloride was added and mixed.
The inside of the reactor was replaced with hydrogen gas, hydrogen was supplied while stirring the solution, and a hydrogenation reaction was carried out at a temperature of 90° C. and a pressure of 1.0 MPa for 5 hours.
The hydrogenated block copolymer (D1) contained in the reaction solution obtained by the hydrogenation reaction had a weight average molecular weight (Mw) of 88,700 and a molecular weight distribution (Mw/Mn) of 1.04.

After completion of the hydrogenation reaction, 0.10 part of water was added to the reaction solution and stirred at 60° C. for 60 minutes. After that, it is cooled to 30 ° C. or less, activated clay (product name “Galeon Earth (registered trademark)”, manufactured by Mizusawa Chemical Industry Co., Ltd.) 1.5 parts, and talc (product name “Micro Ace (registered trademark)”, Japan Talc Co., Ltd.) was added, and the reaction solution was filtered to remove insoluble matter. Pentaerythrityl tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (manufactured by SONGWON, product name "Songnox1010"), a phenolic antioxidant, was added to the filtered solution. 1.0 part of a xylene solution in which .1 part was dissolved was added and dissolved.

Next, the above solution is filtered through a metal fiber filter (pore size 0.4 μm, manufactured by Nichidai Co., Ltd.) to remove minute solids, and then a cylindrical concentration dryer (product name “Kontoro” manufactured by Hitachi, Ltd.) ) was used to remove cyclohexane, xylene and other volatile components from the solution at a temperature of 260° C. and a pressure of 0.001 MPa or less. A molten resin was extruded from a die directly connected to a concentration dryer, cooled with water, and then 91 parts of block copolymer hydride (D1) pellets were produced by an underwater cutter. About 100 ppm of finely divided ethylene bisstearic acid amide was added to the pellets as an antiblocking agent. The obtained pellet-shaped hydrogenated block copolymer (D1) had a weight average molecular weight (Mw) of 87,800 and a molecular weight distribution (Mw/Mn) of 1.09. The hydrogenation rate of double bonds derived from chain conjugated dienes (main chain and side chains) was 99%, and the hydrogenation rate of double bonds derived from aromatic rings was less than 3%.
Table 1 shows the physical properties of the produced block copolymer (C1) and block copolymer hydride (D1).

[Production Example 2]
<Production of block copolymer hydride (D2)>
Block copolymer hydride (D2) was prepared by the following procedure.
300 parts of dehydrated cyclohexane, 5 parts of dehydrated styrene, and 0.53 parts of ethylene glycol dibutyl ether were charged into the same reactor as in Production Example 1. While stirring the whole volume at 60° C., 0.5 part of n-butyllithium (15% cyclohexane solution) was added to initiate polymerization. Subsequently, while stirring the entire volume at 60°C, 4 parts of dehydrated styrene was continuously added to the reactor over 15 minutes to proceed with the polymerization reaction. was stirred. The reaction solution was measured by gas chromatography (GC), and the polymerization conversion rate at this point was 99.5%.
Next, 82 parts of dehydrated isoprene was continuously added to the reaction liquid over 100 minutes, and after the addition was completed, stirring was continued for 20 minutes. At this point, the reaction solution was analyzed by GC, and the polymerization conversion rate was 99.5%.
After that, 9 parts of dehydrated styrene was continuously added to the reaction solution over 60 minutes, and the mixture was stirred for 30 minutes after the addition. At this point, the reaction solution was analyzed by GC, and the polymerization conversion rate was almost 100%.

Here, 0.5 part of isopropyl alcohol was added to the reaction liquid to stop the reaction, and a polymer solution was obtained. The block copolymer (C2) contained in the polymer solution is a polymer block (A)-polymer block (B)-polymer block (A) type triblock copolymer, and has a weight average molecular weight (Mw ) is 78,600, molecular weight distribution (Mw / Mn) is 1.03, wA:wB = 18:82, 1,2-addition polymerization of all isoprene-derived structural units in block copolymer (C2) and The proportion of structural units derived from 3,4-addition polymerization was 58%.

Next, the above polymer solution is transferred to the same pressure-resistant reactor as in Production Example 1, and a diatomaceous earth-supported nickel catalyst (product name “E22U”, nickel loading 60%, JGC Catalyst Kasei Co., Ltd.) and 80 parts of dehydrated cyclohexane were added and mixed. The inside of the reactor is replaced with hydrogen gas, hydrogen is supplied while stirring the solution, hydrogenation reaction is carried out at a temperature of 150° C. and a pressure of 3.0 MPa for 1 hour, followed by a temperature of 190° C. and a pressure of 4.5 MPa. The temperature was elevated to 100°C and the hydrogenation reaction was carried out for 6 hours.
The hydrogenated block copolymer (D2) contained in the reaction solution obtained by the hydrogenation reaction had a weight average molecular weight (Mw) of 83,100 and a molecular weight distribution (Mw/Mn) of 1.04.

After completion of the hydrogenation reaction, the reaction solution was filtered to remove the hydrogenation catalyst, and pentaerythrityl tetrakis[3-(3,5-di-t-butyl 2.0 parts of a xylene solution in which 0.1 part of 4-hydroxyphenyl)propionate] was dissolved was added and dissolved.
Then, the above solution was treated in the same manner as in Production Example 1 to produce 93 parts of pellets of hydrogenated block copolymer (D2).
The produced pellet-shaped block copolymer hydride (D2) has a weight average molecular weight (Mw) of 82,700, a molecular weight distribution (Mw/Mn) of 1.09, and a chain conjugated diene (main chain and side chain). Both the hydrogenation rate of the double bond derived from and the hydrogenation rate of the double bond derived from the aromatic ring were almost 100%.
Table 1 shows the physical properties of the produced block copolymer (C2) and block copolymer hydride (D2).

[Production Example 3]
<Production of block copolymer hydride (D3)>
Block copolymer hydride (D3) was prepared by the following procedure.
In Production Example 1, the amount of ethylene glycol dibutyl ether was 0.55 parts, the amount of n-butyllithium (15% cyclohexane solution) was 0.55 parts, and the monomers used for polymerization were 15 parts of dehydrated styrene and 15 parts of dehydrated isoprene. Polymerization was carried out in the same manner as in Production Example 1 except that 70 parts and 15 parts of dehydrated styrene were used to obtain a polymer solution containing the block copolymer (C3). The block copolymer (C3) has a weight average molecular weight (Mw) of 73,400, a molecular weight distribution (Mw/Mn) of 1.04, wA:wB = 30:70, and total isoprene in the block copolymer (C3). The ratio of structural units derived from 1,2-addition polymerization and 3,4-addition polymerization among the derived structural units was 50%.

Next, the polymer solution was hydrogenated in the same manner as in Production Example 2. Thereafter, in the same manner as in Production Example 2, 94 parts of pellets of hydrogenated block copolymer (D3) were obtained. The resulting block copolymer hydride (D3) has a weight average molecular weight (Mw) of 76,900, a molecular weight distribution (Mw/Mn) of 1.07, and is derived from a chain conjugated diene (main chain and side chain). Both the hydrogenation rate of the double bond of and the hydrogenation rate of the double bond derived from the aromatic ring were almost 100%.
Table 1 shows the physical properties of the produced block copolymer (C3) and block copolymer hydride (D3).

[Production Example 4]
<Production of modified block copolymer hydride (J1)>
A modified block copolymer hydride (J1) was prepared by the following procedure.
400 parts of dehydrated cyclohexane, 10 parts of dehydrated styrene, and 0.475 parts of dibutyl ether were charged into the same reactor as in Production Example 1. While stirring the whole volume at 60° C., 0.90 part 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 was continuously added to the reactor over 40 minutes to proceed with the polymerization reaction. was stirred. The reaction solution was measured by gas chromatography (GC), and the polymerization conversion rate at this point was 99.5%.
Next, 50 parts of dehydrated isoprene was continuously added to the reaction solution over 130 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 99.5%.
After that, 25 parts of dehydrated styrene was continuously added to the reaction solution over 70 minutes, and the mixture was stirred for 60 minutes after the addition. At this point, the reaction solution was analyzed by gas chromatography (GC), and the polymerization conversion rate was almost 100%.

Here, 0.5 part of isopropyl alcohol was added to the reaction liquid to stop the reaction, and a polymer solution was obtained. The block copolymer (G1) contained in the polymer solution is a polymer block (E)-polymer block (F)-polymer block (E) type triblock copolymer, and has a weight average molecular weight (Mw ) is 45,300, the molecular weight distribution (Mw/Mn) is 1.04, wE:wF = 50:50, and 1,4-addition polymerization of all isoprene-derived structural units in the block copolymer (G1) The ratio of derived structural units was 91%.
In the above "wE:wF", the mass fraction of the structural unit [e] derived from the aromatic vinyl compound (styrene in Production Example 4) in the block copolymer (G1) is wE, and the linear conjugated diene is The ratio (wE:wF) between wE and wF, where wF is the mass fraction of the structural unit [f] derived from the compound (isoprene in Production Example 1) in the block copolymer (G1), is shown below. Production Examples 5 and 6 are the same.

Next, the above polymer solution was hydrogenated in the same manner as in Production Example 2.
The hydrogenated block copolymer (H1) contained in the reaction solution obtained by the hydrogenation reaction had a weight average molecular weight (Mw) of 47,900 and a molecular weight distribution (Mw/Mn) of 1.06.

After completion of the hydrogenation reaction, the reaction solution was filtered to remove the hydrogenation catalyst, and pentaerythrityl tetrakis[3-(3,5-di-t-butyl -4-Hydroxyphenyl)propionate] (product name “AO60”, manufactured by ADEKA) dissolved in 2.0 parts of a xylene solution was added and dissolved.
Next, the above solution was treated in the same manner as in Production Example 1 to obtain 95 parts of pellets composed of hydrogenated block copolymer (H1).
The resulting pellet-shaped hydrogenated block copolymer (H1) has a weight average molecular weight (Mw) of 47,400, a molecular weight distribution (Mw/Mn) of 1.10, and a chain conjugated diene (main chain and side chain ) and the hydrogenation rate of the double bond derived from the aromatic ring were both approximately 100%.

2.0 parts of vinyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., product name “KBM-1003”) and 2,5-dimethyl 0.1 part of -2,5-di(t-butylperoxy)hexane (product name “Perhexa (registered trademark) 25B” manufactured by NOF Corporation) was added. This mixture was kneaded using a twin-screw extruder (product name “TEM37B”, manufactured by Toshiba Machine Co., Ltd.) at a resin temperature of 210° C. and a residence time of 60 seconds or more and 70 seconds or less. The resulting kneaded product was extruded into strands, air-cooled, and then cut with a pelletizer to obtain 96 parts of pellets of hydrogenated modified block copolymer (J1) having an alkoxysilyl group.

After dissolving 0.00001 parts of pellets of the hydrogenated modified block copolymer (J1) in 0.001 parts of cyclohexane, the resulting solution was poured into 0.004 parts of dehydrated methanol to obtain hydrogenated modified block copolymers. Compound (J1) was coagulated and the coagulate was collected by filtration. The filtrate was vacuum-dried at 25° C. to obtain 0.000009 parts of purified hydrogenated modified block copolymer (J1).
In the FT-IR spectrum of the modified block copolymer hydride (J1), there are new absorption bands derived from Si—OCH ₃ groups at 1090 cm ⁻¹ and Si—CH ₂ groups at 825 cm ⁻¹ and 739 cm ⁻¹ , It was observed at positions different from the absorption bands (1075 cm ⁻¹ , 808 cm ⁻¹ and 766 cm ⁻¹ ) derived from Si—OCH ₃ groups and Si—CH groups of vinyltrimethoxysilane.
Further, when the ¹ H-NMR spectrum (in deuterated chloroform) of the hydrogenated modified block copolymer (J1) was measured, a peak due to protons of methoxy groups was observed at 3.6 ppm. From the peak area ratio, it was confirmed that 1.8 parts of vinyltrimethoxysilane were bonded to 100 parts of hydrogenated block copolymer (H1).
Table 1 shows the physical properties of the produced block copolymer (G1), hydrogenated block copolymer (H1), and hydrogenated modified block copolymer (J1).

[Production Example 5]
<Production of block copolymer hydride (H2)>
A block copolymer hydride (H2) was prepared by the following procedure.
400 parts of dehydrated cyclohexane, 10 parts of dehydrated styrene, and 0.475 parts of dibutyl ether were charged into the same reactor as in Production Example 1. While stirring the whole volume at 60° C., 0.80 part of n-butyllithium (15% cyclohexane solution) was added to initiate polymerization. Subsequently, while stirring the entire volume at 60°C, 20 parts of dehydrated styrene was continuously added to the reactor over 40 minutes to proceed with the polymerization reaction. was stirred. The reaction solution was measured by gas chromatography (GC), and the polymerization conversion rate at this point was 99.5%.
Next, 40 parts of dehydrated isoprene was continuously added to the reaction solution over 110 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 99.5%.
After that, 30 parts of dehydrated styrene was continuously added to the reaction solution over 70 minutes, and after the addition was completed, the mixture was stirred for 60 minutes. At this point, the reaction solution was analyzed by gas chromatography (GC), and the polymerization conversion rate was almost 100%.

Here, 0.5 part of isopropyl alcohol was added to the reaction liquid to stop the reaction, and a polymer solution was obtained. The block copolymer (G2) contained in the polymer solution is a polymer block (E)-polymer block (F)-polymer block (E) type triblock copolymer, and has a weight average molecular weight (Mw ) is 52,100, the molecular weight distribution (Mw/Mn) is 1.04, wE:wF = 60:40, and 1,4-addition polymerization of all isoprene-derived structural units in the block copolymer (G2) The proportion of derived structural units was 91%.

Next, the above polymer solution was hydrogenated in the same manner as in Production Example 2.
The hydrogenated block copolymer (H2) contained in the reaction solution obtained by the hydrogenation reaction had a weight average molecular weight (Mw) of 55,200 and a molecular weight distribution (Mw/Mn) of 1.06.

After the completion of the hydrogenation reaction, the reaction solution was filtered to remove the hydrogenation catalyst, and then pentaerythrityl tetrakis[3-(3,5 -Di-t-butyl-4-hydroxyphenyl)propionate] (product name “AO60”, manufactured by ADEKA) dissolved in 2.0 parts of xylene solution was added and dissolved.
Then, the above solution was treated in the same manner as in Production Example 1 to obtain 94 parts of pellets composed of hydrogenated block copolymer (H2).
The obtained pellet-shaped hydrogenated block copolymer (H2) has a weight average molecular weight (Mw) of 54,600, a molecular weight distribution (Mw/Mn) of 1.10, and a chain conjugated diene (main chain and side chain ) and the hydrogenation rate of the double bond derived from the aromatic ring were both approximately 100%.
Table 1 shows the physical properties of the produced block copolymer (G2) and block copolymer hydride (H2).

[Production Example 6]
<<Production of modified block copolymer hydride (J3)>>
A modified block copolymer hydride (J3) was prepared by the following procedure.
Polymerization was carried out in the same manner as in Production Example 4, except that the amount of n-butyllithium (15% cyclohexane solution) was changed from 0.90 parts to 0.80 parts to obtain a block copolymer ( A polymer solution containing G3) was obtained. The block copolymer (G3) has a weight average molecular weight (Mw) of 51,900, a molecular weight distribution (Mw/Mn) of 1.04, wE:wF = 50:50, and total isoprene in the block copolymer (G3). The proportion of structural units derived from 1,4-addition polymerization among the derived structural units was 91%.

Next, the above polymer solution was hydrogenated in the same manner as in Production Example 1. The hydrogenated block copolymer (H3) contained in the reaction solution obtained by the hydrogenation reaction had a weight average molecular weight (Mw) of 55,000 and a molecular weight distribution (Mw/Mn) of 1.05.

After completion of the hydrogenation reaction, the reaction solution was treated in the same manner as in Production Example 1 to remove the hydrogenation catalyst, and then pentaerythrityl tetrakis [3-(3,5 2.0 parts of a xylene solution in which 0.1 part of [-di-t-butyl-4-hydroxyphenyl)propionate] was dissolved was added and dissolved.
Then, the above solution was treated in the same manner as in Production Example 1 to produce 96 parts of pellets of hydrogenated block copolymer (H3).
The produced pellet-shaped hydrogenated block copolymer (H3) had a weight average molecular weight (Mw) of 54,400 and a molecular weight distribution (Mw/Mn) of 1.08. The hydrogenation rate of double bonds derived from chain conjugated dienes (main chain and side chains) was 99%, and the hydrogenation rate of double bonds derived from aromatic rings was less than 3%.

Using pellets of the produced block copolymer hydride (H3), in the presence of 2,5-dimethyl-2,5-di(t-butylperoxy)hexane in the same manner as in Production Example 4, Methoxysilane was reacted to produce 93 parts of pellets of modified block copolymer hydride (J3) having alkoxysilyl groups.

It was confirmed that 1.8 parts of vinyltrimethoxysilane were bonded to 100 parts of the hydrogenated block copolymer (H3) in the obtained hydrogenated block copolymer (J3).
Table 1 shows physical properties of the produced block copolymer (G3), hydrogenated block copolymer (H3) and hydrogenated modified block copolymer (J3).

(Example 1)
<Resin composition (X1)>
2-(5-Chloro-2H-benzotriazol-2-yl)-6-tert-butyl-p, which is an ultraviolet absorber, was added to 100 parts of the block copolymer hydride (D1) pellets produced in Production Example 1. - 0.2 part of cresol (product name "SUMISORB (registered trademark) 300", manufactured by Sumitomo Chemical Co., Ltd.) was added and uniformly mixed to obtain a mixture. The obtained mixture is kneaded at a resin temperature of 200° C. using a twin-screw extruder (trade name: “TEM37B”, manufactured by Toshiba Machine Co., Ltd.), and the molten polymer is extruded through a die, cooled with water, and then cut with an underwater cutter. , 94 parts of pellets of the resin composition (X1) were produced.

<Resin composition (Y1)>
2-(5-Chloro-2H-benzotriazol-2-yl)-6-tert, which is the same UV absorber as above, was added to 100 parts of the hydrogenated modified block copolymer (J1) pellets produced in Production Example 4. 0.2 part of -butyl-p-cresol was added and uniformly mixed to obtain a mixture. The resulting mixture is kneaded at a resin temperature of 210° C. using a twin-screw extruder (trade name: “TEM37B”, manufactured by Toshiba Machine Co., Ltd.), extruded into strands, air-cooled, and then cut with a pelletizer to obtain a resin composition. 97 parts of pellets of product (Y1) were produced.

<Multilayer sheet (W1)>
2 types consisting of 2 single-screw extruders with 20 mm diameter screws, a feed block, a T-die (400 mm width), and a sheet take-up machine equipped with a cast roll (400 mm width) with a satin embossed pattern on the surface3 Using a layer co-extrusion film molding machine (trade name: "SZW20-25MG", manufactured by Technobell), the resin composition (X1) is the inner layer (resin layer (X)), and the resin composition (Y1) is the outer layer ( A multilayer sheet (W1) to be a resin layer (Y)) was produced.
Here, the extrusion conditions are as follows: resin composition (X1) extruder temperature 200° C., resin composition (Y1) extruder temperature 210° C., cast roll temperature 50° C., edge of sheet cut off, width 320 mm. A multilayer sheet (W1) was obtained.
The obtained multilayer sheet (W1) has three layers of resin layer (Y1)/resin layer (X1)/resin layer (Y1) in which one resin layer (X1) is sandwiched between two resin layers (Y1). The total thickness of the multilayer sheet (W1) is 0.80 mm, and the thickness of each layer is resin layer (Y1): 0.35 mm/resin layer (X1): 0.10 mm/resin layer ( Y1): 0.35 mm.

<Single layer resin composition (X1) sheet>
Using the two-kind three-layer coextrusion film forming machine, the resin composition (Y1) is not supplied to the extruder, only the resin composition (X1) is supplied to one extruder, and the extruder temperature is 200. C. and a cast roll temperature of 50.degree. The sheet of the resin composition (X1) was collected by winding a release PET film (manufactured by Toray Industries, Inc., product name “Lumirror (registered trademark) S10”, thickness 50 μm, thickness 0.050 mm) and winding it into a roll. .

<Single layer resin composition (Y1) sheet>
Using the two kinds of three-layer coextrusion film molding machine described above, the resin composition (X1) is not supplied to the extruder, the resin composition (Y1) is supplied to one extruder, and the extruder temperature is 210 ° C. , a single-layer resin composition (Y1) sheet (thickness: 0.10 mm, width: 320 mm) composed of the resin composition (Y1) was prepared under conditions of a cast roll temperature of 50°C.

<Laminated glass (LG1)>
One multilayer sheet (W1) (thickness 0.80 mm) and a resin composition (Y1) sheet (thickness 0.10 mm) are placed between two circular soda lime glass (diameter 50 mm, thickness 1.1 mm). ) were sandwiched and placed in the order of glass plate/multilayer sheet (W1)/sheet of resin composition (Y1)/glass plate.
This laminate is placed in a resin bag with a thickness of 75 μm having a layer structure of nylon / adhesive layer / polypropylene, and the inside of the bag is degassed using a sealed packer (BH-951, manufactured by Panasonic). The laminate was hermetically packaged by heat-sealing the opening. After that, the sealed laminated laminate was placed in an autoclave and treated at a temperature of 140 ° C. and a pressure of 0.8 MPa for 30 minutes to form a layer of glass plate/multilayer sheet (W1)/sheet of resin composition (Y1)/glass plate. A structured laminated glass (LG1-1) was produced.
The thickness of the laminated glass (LG1-1) was 3.1 mm. The thickness configuration of the laminated glass (LG1-1) is glass plate (1.1 mm) / resin layer (Y1) (0.35 mm) / resin layer (X1) (0.10 mm) / resin layer (Y1) ( 0.35 mm)/resin layer (Y1) (0.10 mm)/glass plate (1.1 mm). The appearance of the obtained laminated glass (LG1-1) was good with no defects such as air bubbles observed.

Using two sheets of soda plate glass (length 100 mm, width 20 mm, thickness 1.1 mm), in the same manner as above, glass plate / multilayer sheet (W1) / resin composition (Y1) sheet / glass plate A laminated glass (LG1-2) having a layer structure was produced. The thickness configuration of the laminated glass (LG1-2) is the same as above: glass plate (1.1 mm)/resin layer (Y1) (0.35 mm)/resin layer (X1) (0.10 mm)/resin layer (Y1) (0.35 mm)/resin layer (Y1) (0.10 mm)/glass plate (1.1 mm). The appearance of the obtained laminated glass (LG1-2) was good with no defects such as air bubbles observed.

Using two sheets of soda plate glass (length 300 mm, width 25 mm, thickness 1.1 mm), in the same manner as above, glass plate / multilayer sheet (W1) / resin composition (Y1) sheet / glass plate A laminated glass (LG1-3) having a layer structure was produced. The thickness configuration of the laminated glass (LG1-3) is the same as above: glass plate (1.1 mm)/resin layer (Y1) (0.35 mm)/resin layer (X1) (0.10 mm)/resin layer (Y1) (0.35 mm)/resin layer (Y1) (0.10 mm)/glass plate (1.1 mm). The appearance of the obtained laminated glass (LG1-3) was good with no defects such as air bubbles observed.

<Laminate (Z1)>
Between two PET films (manufactured by Toray Industries, Inc., product name “Lumirror (registered trademark) R75”, thickness 75 μm) as a release film, one multilayer sheet (W1) and a sheet 1 of the resin composition (Y1) were placed. The sheets were overlapped and sandwiched, and arranged in the order of PET film/multilayer sheet (W1)/resin composition (Y1) sheet/PET film. This laminate is sealed and packaged in the same manner as above, 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 PET film/multilayer sheet (W1)/resin composition (Y1). A laminate having a layer structure of sheet/PET film was produced. A laminate (Z1) was produced by peeling the PET film from the laminate. The thickness of the laminate (Z1) is as follows: resin layer (Y1) (0.35 mm)/resin layer (X1) (0.10 mm)/resin layer (Y1) (0.35 mm)/resin layer (Y1) (0.10 mm). In addition, the appearance of the obtained laminate (Z1) was good with no defects such as air bubbles observed.

<Temperature at which tan δ of resin layer (X1) exhibits maximum value>
Three sheets (thickness: 0.50 mm) of the resin composition (X1) prepared above were stacked and press-molded to prepare a sheet with a thickness of 1.5 mm. A test piece having a length of 70 mm and a width of 10 mm prepared from this sheet was used to measure dynamic viscoelastic properties.
As a result, the temperature at which tan δ showed the maximum value was -9°C.

<Storage elastic modulus of laminate (Z1)>
A test piece having a length of 70 mm and a width of 10 mm was cut out from the laminate (Z1) produced above. Dynamic viscoelastic properties were measured using this test piece.
As a result, the storage elastic modulus (G′) is 0.011 GPa (1.1×10 ⁷ Pa) or more and 0.16 GPa (1.6×10 ⁸ Pa) or less in the temperature range of −20° C. or more and 40° C. or less. was in the range.

<Characteristic evaluation of laminated glass>
<<Insulation>>
The thermal conductivity of the laminated glass (LG1-1) was 0.38 W/(m·K) at 25° C., and the thermal insulation was evaluated as good.
<<Rigidity>>
The flexural modulus of the laminated glass (LG1-2) was 12 GPa (12×10 ⁹ Pa) at 25° C., and the rigidity of the laminated glass was evaluated as good.
<<Sound insulation>>
The sound transmission loss value of the laminated glass (LG1-3) did not fall below 35 dB in the frequency range of 2000 Hz to 4000 Hz, indicating that the laminated glass had good sound insulation.
These results are shown in Table 2.

(Example 2)
<Resin composition (X2)>
In the same manner as in Example 1, 2-(5-chloro-2H-benzotriazol-2-yl), which is an ultraviolet absorber, was added to 100 parts of the block copolymer hydride (D2) pellets produced in Production Example 2. 0.2 part of -6-tert-butyl-p-cresol was added to produce 95 parts of pellets of resin composition (X2).

<Resin composition (Y2)>
2-(5-Chloro-2H-benzotriazol-2-yl)-6-tert-butyl-p, which is an ultraviolet absorber, was added to 100 parts of the block copolymer hydride (H2) pellets produced in Production Example 5. - 0.4 part of cresol was added. This mixture was kneaded at a resin temperature of 220° C. using a twin-screw extruder, extruded into strands, cooled with water, and cut with a pelletizer to produce 95 parts of pellets of the resin composition (Y2).

<Multilayer sheet (W2)>
In the same manner as in Example 1, except that the resin composition (X2) was used instead of the resin composition (X1), the resin composition (X2) was used as the inner layer (resin layer (X2)), the resin composition (Y1) ) was produced as an outer layer (resin layer (Y1)).
The obtained multilayer sheet (W2) has three layers of resin layer (Y1)/resin layer (X2)/resin layer (Y1) in which one resin layer (X2) is sandwiched between two resin layers (Y1). The total thickness of the multilayer sheet (W2) is 0.80 mm, and the thickness of each layer is resin layer (Y1): 0.35 mm/resin layer (X2): 0.10 mm/resin layer ( Y1): 0.35 mm.

<Single layer resin composition (X2) sheet>
A sheet of a single-layer resin composition (X2) composed of the resin composition (X2) ( thickness of 0.50 mm and width of 320 mm).

<Single layer resin composition (Y2) sheet>
A sheet of a single-layer resin composition (Y2) composed of the resin composition (Y2) ( thickness of 0.80 mm and width of 320 mm).

<Laminated glass (LG2)>
Instead of one multilayer sheet (W1) and one sheet of resin composition (Y1), one sheet of multilayer sheet (W2) (thickness: 0.80 mm) and one sheet of resin composition (Y2) (thickness: 0.80 mm) were used. 80 mm) and one sheet (thickness 0.10 mm) of the resin composition (Y1) prepared in Example 1 were used to prepare a glass plate/multilayer sheet (W2)/resin composition (Y2) sheet. Laminated glasses (LG2-1, LG2-2, LG2-3) were produced in the same manner as in Example 1, except that the sheets of resin composition (Y1)/glass plate were laminated in this order.
The thickness of the laminated glass (LG2-1, LG2-2, LG2-3) was 3.9 mm. The thickness of laminated glass (LG2-1, LG2-2, LG2-3) is composed of glass plate (1.1 mm)/resin layer (Y1) (0.35 mm)/resin layer (X2) (0.10 mm). /resin layer (Y1) (0.35 mm)/resin layer (Y2) (0.80 mm)/resin layer (Y1) (0.10 mm)/glass plate (1.1 mm). In addition, the appearance of the obtained laminated glasses (LG2-1, LG2-2, LG2-3) was good with no defects such as air bubbles observed.

<Laminate (Z2)>
Instead of the multilayer sheet (W1) and the sheet of the resin composition (Y1), the multilayer sheet (W2), the sheet of the resin composition (Y2), and the sheet of the resin composition (Y1) are used, and the PET film/multilayer A laminate (Z2) was produced in the same manner as in Example 1, except that the sheets (W2)/sheet of resin composition (Y2)/sheet of resin composition (Y1)/PET film were stacked in this order. The thickness of the laminate (Z2) is as follows: resin layer (Y1) (0.35 mm)/resin layer (X2) (0.10 mm)/resin layer (Y1) (0.35 mm)/resin layer (Y2) (0.8 mm)/resin layer (Y1) (0.10 mm). In addition, the appearance of the obtained laminate (Z2) was good with no defects such as air bubbles observed.

<Temperature at which tan δ of resin layer (X2) exhibits maximum value>
The resin composition (X2) sheet was moved in the same manner as in Example 1, except that the resin composition (X2) sheet (thickness: 0.50 mm) was used instead of the resin composition (X1) sheet. viscoelastic properties were measured.
As a result, the temperature at which tan δ showed the maximum value was -10°C.

<Storage modulus of laminate (Z2)>
The dynamic viscoelastic properties of the laminate (Z2) were measured in the same manner as in Example 1, except that the laminate (Z2) was used instead of the laminate (Z1).
As a result, the storage elastic modulus (G′) was 0.017 GPa (1.7×10 ⁷ Pa) or more and 0.31 GPa (3.1×10 ⁸ Pa) or less in the temperature range of −20° C. or more and 40° C. or less. was in the range.

<Characteristic evaluation of laminated glass>
<<Insulation>>
The thermal conductivity of the laminated glass (LG2-1) was 0.29 W/(m·K) at 25° C., and the heat insulating property was evaluated as good.
<<Rigidity>>
The flexural modulus of the laminated glass (LG2-2) was 11 GPa (11×10 ⁹ Pa) at 25° C., and the rigidity of the laminated glass was evaluated as good.
<<Sound insulation>>
The value of the sound transmission loss of the laminated glass (LG2-3) did not fall below 35 dB in the frequency range of 2000 Hz to 4000 Hz, indicating good sound insulation of the laminated glass.
These results are shown in Table 2.

(Example 3)
<Resin composition (Y3)>
2-(5-Chloro-2H-benzotriazol-2-yl)-6-tert-butyl-p, which is an ultraviolet absorber, was added to 100 parts of the block copolymer hydride (H1) pellets produced in Production Example 4. - 0.4 part of cresol was added. This mixture was kneaded using a twin-screw extruder at a resin temperature of 220° C., extruded into strands, and cut with a pelletizer to produce 95 parts of pellets of the resin composition (Y3).

<Single layer resin composition (Y3) sheet>
A single-layer resin composition (Y3) sheet (thickness: 0.80 mm, width: 320 mm) was prepared in the same manner as in Example 1, except that the resin composition (Y3) was used instead of the resin composition (Y1). made.

<Laminated glass (LG3)>
Instead of one multilayer sheet (W1) and one sheet of resin composition (Y1), one sheet of multilayer sheet (W2) (thickness: 0.80 mm) and one sheet of resin composition (Y3) (thickness: 0.80 mm) were used. 80 mm) and one sheet (thickness 0.10 mm) of the resin composition (Y1) prepared in Example 1 were used to form a glass plate/multilayer sheet (W2)/resin composition (Y3) sheet. Laminated glass (LG3-1, LG3-2, LG3-3) in the same manner as in Example 1, except that /sheet of resin composition (Y3)/sheet of resin composition (Y1)/glass plate are laminated in this order. was made.
The thickness of the laminated glass (LG3-1, LG3-2, LG3-3) was 4.7 mm. The thickness of laminated glass (LG3-1, LG3-2, LG3-3) is composed of glass plate (1.1 mm)/resin layer (Y1) (0.35 mm)/resin layer (X2) (0.10 mm). /resin layer (Y1) (0.35 mm)/resin layer (Y3) (1.60 mm)/resin layer (Y1) (0.10 mm)/glass plate (1.1 mm). In addition, the appearance of the obtained laminated glasses (LG3-1, LG3-2, LG3-3) was good with no defects such as air bubbles observed.

<Laminate (Z3)>
Instead of the multilayer sheet (W1) and the sheet of the resin composition (Y1), the multilayer sheet (W2), the sheet of the resin composition (Y3), and the sheet of the resin composition (Y1) are used, and the PET film/multilayer In the same manner as in Example 1, except that the sheet (W2)/the sheet of the resin composition (Y3)/the sheet of the resin composition (Y3)/the sheet of the resin composition (Y1)/the PET film are stacked in this order. A laminate (Z3) was produced. The thickness configuration of the laminate (Z3) is resin layer (Y1) (0.35 mm)/resin layer (X2) (0.10 mm)/resin layer (Y1) (0.35 mm)/resin layer (Y3). (1.60 mm)/resin layer (Y1) (0.10 mm). In addition, the appearance of the obtained laminate (Z3) was good with no defects such as air bubbles observed.

<Storage elastic modulus of laminate (Z3)>
The dynamic viscoelastic properties of the laminate (Z3) were measured in the same manner as in Example 1, except that the laminate (Z3) was used instead of the laminate (Z1).
As a result, the storage elastic modulus (G′) is 0.024 GPa (2.4×10 ⁷ Pa) or more and 0.45 GPa (4.5×10 ⁸ Pa) or less in the temperature range of −20° C. or higher and 40° C. or lower. was in the range.

<Characteristic evaluation of laminated glass>
<<Insulation>>
The thermal conductivity of the laminated glass (LG3-1) was 0.25 W/(m·K) at 25° C., and the heat insulating property was evaluated as good.
<<Rigidity>>
The flexural modulus of the laminated glass (LG3-2) was 12 GPa (12×10 ⁹ Pa) at 25° C., and the rigidity of the laminated glass was evaluated as good.
<<Sound insulation>>
The sound transmission loss value of the laminated glass (LG3-3) did not fall below 35 dB in the frequency range of 2000 Hz to 4000 Hz, indicating that the laminated glass had good sound insulation.
These results are shown in Table 2.

(Example 4)
<Resin composition (Y4)>
2-(5-Chloro-2H-benzotriazol-2-yl)-6-tert-butyl-, which is an ultraviolet absorber, was added to 100 parts of the modified block copolymer hydride (J3) pellets produced in Production Example 6. 0.2 part of p-cresol was added. This mixture was kneaded using a twin-screw extruder at a resin temperature of 220° C., extruded into strands, and cut by a pelletizer to produce 95 parts of pellets of the resin composition (Y4).

<Multilayer sheet (W4)>
In Example 1, the resin composition (X1) was used as an inner layer (resin layer (X1)) in the same manner as in Example 1, except that the resin composition (Y4) was used instead of the resin composition (Y1). A multilayer sheet (W4) in which the resin composition (Y4) serves as an outer layer (resin layer (Y4)) was produced.
The resulting multilayer sheet (W4) has three layers of resin layer (Y4)/resin layer (X1)/resin layer (Y4) in which one resin layer (X1) is sandwiched between two resin layers (Y4). The total thickness of the multilayer sheet (W4) is 0.80 mm, and the thickness of each layer is resin layer (Y4): 0.35 mm/resin layer (X1): 0.10 mm/resin layer ( Y4): 0.35 mm.

<Single layer resin composition (Y4) sheet>
A sheet of a single-layer resin composition (Y4) composed of the resin composition (Y4) in the same manner as in Example 1, except that the resin composition (Y4) was used instead of the resin composition (Y1). (thickness 0.10 mm, width 320 mm).

<Laminated glass (LG4)>
Instead of one multi-layer sheet (W1) and one sheet of resin composition (Y1), one multi-layer sheet (W4) (thickness: 0.80 mm) and one sheet of resin composition (Y4) (thickness: 0.80 mm) were used. 10 mm), and laminated in the order of glass plate/multilayer sheet (W4)/resin composition (Y4) sheet/glass plate in the same manner as in Example 1 (LG4-1, LG4 -2, LG4-3) were prepared.
The thickness of the laminated glass (LG4-1, LG4-2, LG4-3) was 3.1 mm. Laminated glass (LG4-1, LG4-2, LG4-3) has a thickness structure of glass plate (1.1 mm) / resin layer (Y4) (0.35 mm) / resin layer (X1) (0.10 mm) /resin layer (Y4) (0.35 mm)/resin layer (Y4) (0.10 mm)/glass plate (1.1 mm). In addition, the appearance of the obtained laminated glasses (LG4-1, LG4-2, LG4-3) was good with no defects such as air bubbles observed.

<Laminate (Z4)>
Instead of the multilayer sheet (W1) and the sheet of the resin composition (Y1), the multilayer sheet (W4) and the sheet of the resin composition (Y4) are used, and the PET film/multilayer sheet (W4)/resin composition (Y4) is used. A laminate (Z4) was produced in the same manner as in Example 1, except that the sheet/PET film of ) were stacked in this order. The thickness of the laminate (Z4) is as follows: resin layer (Y4) (0.35 mm)/resin layer (X1) (0.10 mm)/resin layer (Y4) (0.35 mm)/resin layer (Y4) (0.10 mm). In addition, the appearance of the obtained laminate (Z4) was good with no defects such as air bubbles observed.

<Storage modulus of laminate (Z4)>
The dynamic viscoelastic properties of the laminate (Z4) were measured in the same manner as in Example 1, except that the laminate (Z4) was used instead of the laminate (Z1).
As a result, the storage elastic modulus (G′) is 0.011 GPa (1.1×10 ⁷ Pa) or more and 0.17 GPa (1.7×10 ⁸ Pa) or less in the temperature range of −20° C. or more and 40° C. or less. was in the range of

<Characteristic evaluation of laminated glass>
<<Insulation>>
The thermal conductivity of the laminated glass (LG4-1) was 0.38 W/(m·K) at 25° C., and the heat insulating property was evaluated as good.
<<Rigidity>>
The flexural modulus of the laminated glass (LG4-2) was 12 GPa (12×10 ⁹ ) Pa at 25° C., and the rigidity of the laminated glass was evaluated as good.
<<Sound insulation>>
The value of the sound transmission loss of the laminated glass (LG4-3) did not fall below 35 dB in the frequency range of 2000 Hz to 4000 Hz, indicating good sound insulation of the laminated glass.
These results are shown in Table 2.

(Comparative example 1)
Instead of one multilayer sheet (W1) and one sheet of the resin composition (Y1), only one multilayer sheet (W1) (thickness: 0.80 mm) was used, and the glass plate/multilayer sheet (W1)/ Laminated glasses (LG5-1, LG5-2, LG5-3) were produced in the same manner as in Example 1, except that the glass plates were laminated in order.
The thickness of the laminated glass (LG5-1, LG5-2, LG5-3) was 3.0 mm. The thickness of laminated glass (LG5-1, LG5-2, LG5-3) consists of glass plate (1.1 mm)/resin layer (Y1) (0.35 mm)/resin layer (X1) (0.10 mm). /resin layer (Y1) (0.35 mm)/glass plate (1.1 mm). In addition, the appearance of the obtained laminated glasses (LG5-1, LG5-2, LG5-3) was good with no defects such as air bubbles observed.

<Storage modulus of laminate (Z5)>
In Comparative Example 1, the laminate (Z5) used for bonding two sheets of glass is the same as the multilayer sheet (W1).
The dynamic viscoelastic properties of the multilayer sheet (W1) were measured in the same manner as in Example 1, except that the multilayer sheet (W1) was used instead of the laminate (Z1).
As a result, the storage modulus (G') was in the range of 0.85×10 ⁷ Pa or more and 1.4×10 ⁸ Pa or less in the temperature range of -20° C. or more and 40° C. or less.

<Characteristic evaluation of laminated glass>
<<Insulation>>
The thermal conductivity of the laminated glass (LG5-1) was 0.40 W/(m·K) at 25° C., and the heat insulating property was evaluated as good.
<<Rigidity>>
The bending elastic modulus of the laminated glass (LG5-2) was 10 GPa (10×10 ⁹ Pa) at 25° C., and the evaluation of the rigidity of the laminated glass was poor.
<<Sound insulation>>
The value of the sound transmission loss of the laminated glass (LG5-3) did not fall below 35 dB in the frequency range of 2000 Hz to 4000 Hz, and the sound insulation of the laminated glass was good.
These results are shown in Table 2.

(Comparative example 2)
<Laminated glass (LG6)>
Instead of one multilayer sheet (W1) and one sheet of the resin composition (Y1), one multilayer sheet (W2) (thickness 0.80 mm), a plasticizer-blended PVB sheet (Y5) ( Solucia Co., Ltd., product name "Saflex (registered trademark) RF41", thickness 0.76 mm), and one sheet of the resin composition (Y1) prepared in Example 1 (thickness: 0.10 mm) are used. Laminated glass (LG6-1, LG6-2, LG6-3) were produced.
The thickness of the laminated glass (LG6-1, LG6-2, LG6-3) was 3.86 mm. Laminated glass (LG6-1, LG6-2, LG6-3) has a thickness structure of glass plate (1.1 mm) / resin layer (Y1) (0.35 mm) / resin layer (X2) (0.10 mm) /resin layer (Y1) (0.35 mm)/PVB sheet (0.76 mm)/resin layer (Y1) (0.10 mm)/glass plate (1.1 mm). In addition, the appearance of the obtained laminated glasses (LG6-1, LG6-2, LG6-3) was good with no defects such as air bubbles observed.

<Laminate (Z6)>
Instead of the multilayer sheet (W1) and the sheet of the resin composition (Y1), the multilayer sheet (W2), the PVB sheet (Y5) and the sheet of the resin composition (Y1) are used, and the PET film/multilayer sheet (W2 )/PVB sheet (Y5)/resin composition (Y1) sheet/PET film were stacked in this order to prepare a laminate (Z6) in the same manner as in Example 1. The laminate (Z6) has a thickness configuration of resin layer (Y1) (0.35 mm)/resin layer (X2) (0.10 mm)/resin layer (Y1) (0.35 mm)/PVB sheet (Y5 ) (0.76 mm)/resin layer (Y1) (0.10 mm). The appearance of the obtained laminate (Z6) was good with no defects such as air bubbles observed.

<Storage modulus of laminate (Z6)>
The dynamic viscoelastic properties of the laminate (Z6) were measured in the same manner as in Example 1, except that the laminate (Z6) was used instead of the laminate (Z1).
As a result, the storage elastic modulus (G′) is 0.0028 GPa (0.28×10 ⁷ Pa) or more and 0.3 GPa (3.0×10 ⁸ Pa) or less in the temperature range of −20° C. or higher and 40° C. or lower. was in the range.

<Characteristic evaluation of laminated glass>
<<Insulation>>
The thermal conductivity of the laminated glass (LG6-1) was 0.29 W/(m·K) at 25° C., and the heat insulating property was evaluated as good.
<<Rigidity>>
The bending elastic modulus of the laminated glass (LG6-2) was 2 GPa (2×10 ⁹ Pa) at 25° C., and the evaluation of the rigidity of the laminated glass was poor.
<<Sound insulation>>
The value of the sound transmission loss of the laminated glass (LG6-3) did not fall below 35 dB in the frequency range of 2000 Hz to 4000 Hz, and the sound insulation of the laminated glass was good.
These results are shown in Table 2.

(Comparative Example 3)
<Single layer resin composition (Y1) sheet>
Using the same two-kind three-layer coextrusion device as used in Example 1, the resin composition (X1) is not supplied to the extruder, and the resin composition (Y1) is supplied to one extruder, Under conditions of an extruder temperature of 210° C. and a cast roll temperature of 50° C., a single-layer resin composition (Y1) sheet (thickness: 0.80 mm, width: 320 mm) composed of the resin composition (Y1) was prepared. made.

<Laminated glass (LG7)>
A sheet of the resin composition (Y1) (thickness: 0.80 mm) was used instead of the multilayer sheet (W1), and one sheet of the resin composition (Y1) (thickness: 0.80 mm) was used. Using two sheets (0.80 mm thick) of the resin composition (Y3) prepared in and one sheet (0.10 mm thick) of the resin composition (Y1) prepared in Example 1, glass Plate/sheet of resin composition (Y1) (thickness 0.80 mm)/sheet of resin composition (Y3) (thickness 0.80 mm)/sheet of resin composition (Y3) (thickness 0.80 mm)/ Laminated glasses (LG7-1, LG7-2, LG7-3) were produced in the same manner as in Example 1, except that the resin composition (Y1) sheet (thickness 0.10 mm)/glass plate were laminated in this order. .
The thickness of the laminated glass (LG7-1, LG7-2, LG7-3) was 4.7 mm. The thickness of laminated glass (LG7-1, LG7-2, LG7-3) is composed of glass plate (1.1 mm)/resin layer (Y1) (0.80 mm)/resin layer (Y3) (0.8 mm). /resin layer (Y3) (0.80 mm)/resin layer (Y1) (0.10 mm)/glass plate (1.1 mm). The laminated glass (LG7) did not have the resin layer (X). In addition, the appearance of the obtained laminated glasses (LG7-1, LG7-2, LG7-3) was good with no defects such as air bubbles observed.

<Laminate (Z7)>
A sheet of the resin composition (Y1) (thickness: 0.80 mm) was used instead of the multilayer sheet (W2), and a PET film/sheet of the resin composition (Y1) (thickness: 0.80 mm)/resin composition (Y3) sheet (thickness 0.80 mm)/resin composition (Y3) sheet (thickness 0.80 mm)/resin composition (Y1) sheet (thickness 0.10 mm)/PET film stacked in this order A laminate (Z7) was produced in the same manner as in Example 3, except that the layers were arranged in the same manner as in Example 3. The thickness of the laminate (Z7) is as follows: resin layer (Y1) (0.80 mm)/resin layer (Y3) (0.80 mm)/resin layer (Y3) (0.80 mm)/resin layer (Y1) (0.10 mm). The appearance of the obtained laminate (Z7) was good with no defects such as air bubbles observed.

<Storage elastic modulus of laminate (Z7)>
The dynamic viscoelastic properties of the laminate (Z7) were measured in the same manner as in Example 1, except that the laminate (Z7) was used instead of the laminate (Z1).
As a result, the storage elastic modulus (G′) is 0.091 GPa (9.1×10 ⁷ Pa) or more and 0.41 GPa (4.1×10 ⁸ Pa) or less in the temperature range of −20° C. or more and 40° C. or less. was in the range.

<Characteristic evaluation of laminated glass>
<<Insulation>>
The thermal conductivity of the laminated glass (LG7-1) was 0.25 W/(m·K) at 25° C., and the heat insulating property was evaluated as good.
<<Rigidity>>
The flexural modulus of the laminated glass (LG7-2) was 20 GPa (20×10 ⁹ Pa) at 25° C., and the rigidity of the laminated glass was evaluated as good.
<<Sound insulation>>
The value of the sound transmission loss of the laminated glass (LG7-3) had a region below 35 dB in the frequency range of 2000 Hz or more and 4000 Hz or less, indicating that the sound insulation of the laminated glass was poor.
These results are shown in Table 2.

(Comparative Example 4)
<Resin composition (X3)>
In the same manner as in Example 1, 2-(5-chloro-2H-benzotriazol-2-yl), which is an ultraviolet absorber, was added to 100 parts of the block copolymer hydride (D3) pellets produced in Production Example 3. 0.2 part of -6-tert-butyl-p-cresol was added to produce 95 parts of pellets of resin composition (X3).

<Multilayer sheet (W8)>
Example 1 except that the resin composition (X3) is used instead of the resin composition (X1), and the same two-kind three-layer coextrusion film forming machine as used in Example 1 is used, except that the extrusion ratio is changed. In the same manner as above, a multilayer sheet (W8) having an inner layer (resin layer (X3)) of the resin composition (X3) and an outer layer (resin layer (Y1)) of the resin composition (Y1) was produced.
The obtained multilayer sheet (W8) has three layers of resin layer (Y1)/resin layer (X3)/resin layer (Y1) in which one resin layer (X3) is sandwiched between two resin layers (Y1). The total thickness of the multilayer sheet (W8) is 0.76 mm, and the thickness of each layer is resin layer (Y1): 0.08 mm/resin layer (X3): 0.60 mm/resin layer ( Y1): 0.08 mm.

<Single layer resin composition (X3) sheet>
A single-layer resin composition (X3) sheet ( thickness of 0.60 mm and width of 320 mm).

<Laminated glass (LG8)>
Instead of one multilayer sheet (W1) and one sheet of the resin composition (Y1), only one multilayer sheet (W8) (thickness 0.76 mm) was used, and a glass plate with a thickness of 1.1 mm was used. Laminated glass (LG8-1, LG8-2, LG8-1, LG8-2, LG8-3) was produced.
The thickness of the laminated glass (LG8-1, LG8-2, LG8-3) was 3.16 mm. The thickness of laminated glass (LG8-1, LG8-2, LG8-3) consists of glass plate (1.2 mm)/resin layer (Y1) (0.08 mm)/resin layer (X3) (0.60 mm). /resin layer (Y1) (0.08 mm)/glass plate (1.2 mm). In addition, the appearance of the obtained laminated glasses (LG8-1, LG8-2, LG8-3) was good with no defects such as air bubbles observed.

<Temperature at which tan δ of resin layer (X3) exhibits maximum value>
The resin composition (X3) sheet was moved in the same manner as in Example 1, except that the resin composition (X3) sheet (thickness: 0.60 mm) was used instead of the resin composition (X1) sheet. viscoelastic properties were measured.
As a result, the temperature at which tan δ showed the maximum value was -14°C.

<Storage modulus of laminate (Z8)>
In Comparative Example 4, the laminate (Z8) used for bonding two sheets of glass is the same as the multilayer sheet (W8).
The dynamic viscoelastic properties of the multilayer sheet (W8) were measured in the same manner as in Example 1, except that the multilayer sheet (W8) was used instead of the laminate (Z1).
As a result, the storage elastic modulus (G′) is 0.0094 GPa (0.94×10 ⁷ Pa) or more and 0.31 GPa (3.1×10 ⁸ Pa) or less in the temperature range of −20° C. or more and 40° C. or less. was in the range.

<Characteristic evaluation of laminated glass>
<<Insulation>>
The thermal conductivity of the laminated glass (LG8-1) was 0.42 W/(m·K) at 25° C., and the heat insulating property was evaluated as good.
<<Rigidity>>
The bending elastic modulus of the laminated glass (LG8-2) was 10 GPa (10×10 ⁹ Pa) at 25° C., and the evaluation of the rigidity of the laminated glass was poor.
<<Sound insulation>>
The sound transmission loss value of the laminated glass (LG8-3) did not fall below 35 dB in the frequency range of 2000 Hz to 4000 Hz, indicating that the laminated glass had good sound insulation.
These results are shown in Table 2.

The results of this example and comparative example reveal the following.
The resin layer (X) has a maximum value of tan δ in dynamic viscoelastic properties in the range of −20° C. or higher and 20° C. or lower, and the storage elastic modulus in dynamic viscoelastic properties is 0 at −20° C. or higher and 40° C. or lower. By using the laminate (Z) having a thermal conductivity of 0.01 GPa (1.0 × 10 ⁷ Pa) or more and 0.5 GPa (5.0 × 10 ⁸ Pa) or less as an intermediate film of laminated glass, the thermal conductivity is reduced to that of glass. It is 1/2 or less (0.5 W/m·K or less) and has excellent heat insulation properties, maintains rigidity equivalent to that of conventional laminated glass, and can provide laminated glass with excellent sound insulation (Examples 1 to 4). .
If the storage elastic modulus in the dynamic viscoelastic properties of the laminate (Z) has a range of less than 0.01 GPa (1.0 × 10 ⁷ Pa) at -20 ° C or higher and 40 ° C or lower, the laminate (Z) is The rigidity of the laminated glass used as the interlayer film cannot be maintained (Comparative Examples 1, 2 and 4).
When the laminate (Z) does not have a resin layer (X) having a maximum value of tan δ in the dynamic viscoelastic property range of −20° C. or higher and 20° C. or lower, the laminate (Z) is used as an intermediate film. The sound insulation of the laminated glass that has been laminated cannot be maintained (Comparative Example 3).

When the laminate (Z) of the present invention is used as an interlayer film for laminated glass, it improves the heat insulation properties of the laminated glass, enhances the cooling and heating effect, and imparts sound insulation. When the laminated glass of the present invention is used as a window material for automobiles, railroad vehicles, ships, buildings, etc., it is useful because it can enhance the cooling and heating effect as well as the sound insulation.
In addition, the laminated glass of the present invention is useful as window material for automobiles, window material for buildings, roof material, window material for ships and aircraft, and the like, from the viewpoint of energy saving.

1a resin layer (X)
2a resin layer (Y)
2b resin layer (Y)
2c resin layer (Y)
3a Laminate (Z)
3b Laminate (Z)
4 Infrared reflective film 5a Glass plate 5b Glass plate 6a Laminated glass 6b Laminated glass

Claims (6)

A laminate (Z) having at least one resin layer (X) made of the resin composition (X) and at least two resin layers (Y) made of the resin composition (Y),
The laminate (Z) has a thickness of 0.2 mm or more and 2 mm or less,
(a) the laminate (Z) has a laminate structure of resin layer (Y)/resin layer (X)/resin layer (Y)/resin layer (Y);
(b) tan δ in the dynamic viscoelastic properties of the resin layer (X) has a maximum value in a temperature range of −20° C. or higher and 20° C. or lower;
(c) the laminate (Z) has a storage elastic modulus in dynamic viscoelastic properties of 1.0×10 ⁷ Pa or more and 5.0×10 ⁸ Pa or less in a temperature range of −20° C. or more and 40° C. or less; ,
The resin composition (X) is obtained by hydrogenating a block copolymer (C) containing a structural unit [a] derived from an aromatic vinyl compound and a structural unit [b] derived from a chain conjugated diene compound. A block copolymer hydride (D) as a main component, and the block copolymer (C) contains as a main component a structural unit [a] derived from an aromatic vinyl compound, at least two polymers It consists of a block (A) and at least one polymer block (B) containing as a main component a structural unit [b] derived from a chain conjugated diene compound, and the chain in the polymer block (B) The structural unit [b] derived from a conjugated diene compound includes structural units derived from 1,2-addition polymerization and 3,4-addition polymerization, and the structural unit [a] is the block copolymer (C). where wA is the mass fraction occupied in the block copolymer (C), and wB is the mass fraction occupied by the structural unit [b] in the block copolymer (C), the ratio of wA to wB (wA/wB) is 10/ 90 or more and 35/65 or less,
The block copolymer hydride (D) is obtained by hydrogenating 95% or more of the carbon-carbon unsaturated bonds in the main chain and side chains derived from the chain conjugated diene compound in the block copolymer (C). ,
The resin composition (Y) hydrogenates a block copolymer (G) containing a structural unit [e] derived from an aromatic vinyl compound and a structural unit [f] derived from a chain conjugated diene compound. and/or a modified block copolymer hydride (J) in which an alkoxysilyl group is introduced into the block copolymer hydride (H) as a main component, The block copolymer (G) comprises at least two polymer blocks (E) containing structural units [e] derived from an aromatic vinyl compound as main components and structural units [e] derived from a chain conjugated diene compound. f] as a main component and at least one polymer block (F), wherein wE is the mass fraction of the structural unit [e] in the block copolymer (G), and the structural unit [ where wF is the mass fraction of f] in the block copolymer (G), the ratio of wE to wF (wE/wF) is 40/60 or more and 60/40 or less, and the block copolymer The combined hydride (H) is a laminate obtained by hydrogenating 95% or more of the carbon-carbon unsaturated bonds in the main chain and side chains derived from the chain conjugated diene compound in the block copolymer (G). (Z) .
(However, the tan δ in the dynamic viscoelastic properties of the resin layer (X) and the storage elastic modulus in the dynamic viscoelastic properties of the laminate (Z) are calculated based on JIS K7244-2 method (torsion pendulum method). Frequency: 1 rad/s, measurement temperature range: -100°C to 100°C, temperature increase rate: 5°C/min. The structural unit [b] in the polymer block (B) is a structural unit derived from 1,2-addition polymerization and 3,4-addition polymerization. The laminate (Z) according to claim 1 , containing 40% by mass or more and 80% by mass or less of the The laminate (Z) according to claim 1 or 2 , wherein the resin layer (X) has a thickness of 0.02 mm or more and 0.6 mm or less. The laminate ( Z ) according to any one of claims 1 to 3 , wherein each of the resin layers (Y) independently has a thickness of 0.05 mm or more and 1.0 mm or less. A laminated glass comprising two glass plates and an intermediate film composed of the laminate (Z) according to any one of claims 1 to 4 , which is arranged between the two glass plates,
A laminated glass having a thermal conductivity of 0.5 W/(m·K) or less at 25° C. in the thickness direction of the laminated glass. The laminated glass according to claim 5 , wherein the laminated glass has a bending elastic modulus of 11 GPa or more at 25°C.

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