WO2020009064A1 - Stratifié et verre feuilleté - Google Patents

Stratifié et verre feuilleté Download PDF

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Publication number
WO2020009064A1
WO2020009064A1 PCT/JP2019/026121 JP2019026121W WO2020009064A1 WO 2020009064 A1 WO2020009064 A1 WO 2020009064A1 JP 2019026121 W JP2019026121 W JP 2019026121W WO 2020009064 A1 WO2020009064 A1 WO 2020009064A1
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Prior art keywords
block copolymer
resin layer
laminated glass
laminate
resin
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PCT/JP2019/026121
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English (en)
Japanese (ja)
Inventor
竜太 栗原
洋平 小出
小原　禎二
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Zeon Corp
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Zeon Corp
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Priority to JP2020528854A priority Critical patent/JP7259856B2/ja
Publication of WO2020009064A1 publication Critical patent/WO2020009064A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin

Definitions

  • the present invention relates to a laminated body and a laminated glass, and more particularly to a laminated body having a specific dynamic viscoelastic property and a laminated glass provided with an intermediate film composed of the laminated body.
  • Laminated glass is excellent in safety because even if it is damaged by an impact, penetration of a collision object and scattering of glass fragments can be prevented. Therefore, laminated glass is widely used for automobiles, railway vehicles, aircraft, ships, buildings, and the like.
  • the laminated glass is manufactured by bonding and integrating a plurality of glass plates with an interlayer made of an adhesive resin interposed therebetween.
  • polyvinyl butyral which is generally used as an interlayer film of laminated glass, or a sheet-like material for improving the penetration resistance of laminated glass, is interposed between glass plates.
  • Resins such as ethylene-vinyl acetate copolymer, ionomer resin, polycarbonate, and polyethylene terephthalate have lower thermal conductivity than glass. Therefore, a laminated glass using an interlayer film or a sheet made of such a resin has a lower thermal conductivity as a whole of the laminated glass and a higher heat insulating property than a glass plate having the same thickness.
  • Patent Document 1 discloses a laminated glass in which the thickness of an intermediate film made of PVB is increased to reduce the thermal conductivity.
  • the thickness of the interlayer is increased without changing the thickness of the glass, the rigidity of the laminated glass can be maintained, but the thickness of the laminated glass is increased, and a problem that the mass is increased occurs.
  • the thickness and the mass of the laminated glass are to be maintained by reducing the thickness of the glass while increasing the thickness of the intermediate film, the elastic modulus of the PVB intermediate film is small. There is a contradictory problem that the rigidity of the steel cannot be maintained.
  • Patent Document 2 discloses a lightweight laminated glass having a low thermal conductivity, which is composed of glass / PVB / polycarbonate / PVB / glass.
  • the elastic modulus of the polycarbonate is smaller than that of the glass, so that the rigidity of the laminated glass is reduced as described above.
  • Patent Document 3 discloses a laminated glass in which a modified block copolymer hydride having an alkoxysilyl group introduced therein is used for an intermediate film instead of an intermediate film made of PVB.
  • Patent Literature 3 does not disclose a technique for improving the heat insulating property by lowering the thermal conductivity while maintaining the rigidity of the laminated glass.
  • Patent Document 4 discloses a laminated glass in which a hydride of a modified block copolymer into which an alkoxysilyl group is introduced is used for an interlayer, and one or more heat insulating layers including hollow particles are sandwiched between the glasses.
  • 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 calcium carbonate by acid treatment. It is not easy to obtain industrially.
  • Examples of the laminated glass having improved sound insulation performance include (a) a laminated glass using a laminated interlayer in which a plastic interlayer is blended with two types of polyvinyl acetal in a resin interlayer (for example, see Patent Documents 5 to 7).
  • the interlayer with an adhesive resin layer made of polyvinyl acetal resin or the like laminated on both sides of a sound insulation layer containing as a main component has a low elastic modulus.
  • thermoplastic elastomer composition containing a hydride of a block copolymer as a main component is used as a sound insulation layer, and storage elasticity containing no plasticizer or containing a small amount of plasticizer is enhanced.
  • An interlayer using a polyvinyl acetal-based resin for an adhesive layer is disclosed. It is disclosed that a laminated glass using this interlayer film is excellent in sound insulation and bending strength, but the interlayer film including the sound insulation layer shown here cannot be said to have a high storage elastic modulus, When the thickness of the film is increased to improve the heat insulation of the laminated glass, the rigidity of the laminated glass may not be maintained.
  • Patent Document 14 discloses that a laminated glass having excellent sound insulation properties can be obtained by using a hydride of a block copolymer as an interlayer material. However, there is no suggestion about a technique for maintaining the rigidity of the laminated glass provided with the sound insulation and increasing the heat insulation.
  • a laminated glass having excellent sound insulation properties in which two sheets of glass having a thickness of 1.2 mm are bonded together with an intermediate film having a thickness of 0.76 mm, is disclosed. Although it is expected to be small, there is a possibility that the rigidity of the laminated glass cannot be maintained because the thickness of the sound insulating layer made of a block copolymer hydride having a low storage elastic modulus is large.
  • JP 2006-137648 A JP-A-6-915 International Publication No. WO 2013/176258 JP-A-2017-81775 JP-A-4-254444 JP-A-6-926 JP-A-9-156967 JP 2005-144753 A JP 2007-91491 A JP 2011-240676 A JP 2016-107632 A JP 2016-108227 A International Publication No. WO 2016/076338 International Publication No. WO 2016/104740
  • the present invention has been made in view of the above-described circumstances, and includes a laminate capable of forming a laminated glass having a high level of rigidity, sound insulation, and heat insulation balance, and an intermediate film including the laminate.
  • the purpose is to provide laminated glass.
  • a specific hydride of a block copolymer has a low thermal conductivity among resins. Further, the present inventors have developed a resin composition (X) containing at least one resin layer (X) (sound insulation layer) composed of a specific block copolymer hydride (D) as a main component, Resin composition containing block copolymer hydride (H) and / or modified block copolymer hydride (J) obtained by introducing an alkoxysilyl group into said specific block copolymer hydride (H) By using an intermediate film composed of a laminate (Z) having at least two or more resin layers (Y) (elastic layers) composed of (Y), rigidity, sound insulation and heat insulation can be balanced at a high level. They have found that it is possible to form a realized laminated glass, and have completed the present invention.
  • "containing as a main component” means "containing more than 50% by
  • tan ⁇ in dynamic viscoelastic characteristics of the resin layer (X) is ⁇ 20.
  • C) a storage elastic modulus in the dynamic viscoelastic properties of the laminate (Z) is 1.0 ⁇ in a temperature range of ⁇ 20 ° C. to 40 ° C.
  • the tan ⁇ 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 the JIS K7244-2 method (torsional pendulum method).
  • the structural unit [b] derived from the chain conjugated diene compound in the polymer block (B) includes a structural unit derived from 1,2-addition polymerization and 3,4-addition polymerization, and the structural unit [a Is wA, the mass fraction occupying the block copolymer (C) in the block copolymer (C) is wA, and the mass fraction occupying the block copolymer (C) in the block copolymer (C) is wB.
  • the ratio (wA / wB) is 10/90 or more and 35/65 or less
  • the block copolymer hydride (D) contains a main chain derived from the chain conjugated diene compound in the block copolymer (C) and The laminate according to (1), wherein 95% or more of the side chain carbon-carbon unsaturated bonds are hydrogenated.
  • 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 structural unit in the polymer block (B) [ b] The laminate according to (2), which contains 40% by mass or more and 80% by mass or less based on the whole.
  • the united product (G) is composed of at least two polymer blocks (E) each containing a structural unit [e] derived from an aromatic vinyl compound as a main component and a structural unit [f] derived from a chain conjugated diene compound.
  • the structural unit [f] is composed of at least one polymer block (F) contained as a main component, the mass fraction of the structural unit [e] in the block copolymer (G) is wE, and the structural unit [f] is When the mass fraction in the block copolymer (G) is wF, the ratio of wE to wF (wE / wF) is 40/60 or more and 60/40 or less, and the hydride of the block copolymer is used. (H) is 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), from (1) to (3). )).
  • the laminated glass having a thermal conductivity in a thickness direction of the laminated glass of not more than 0.5 W / (m ⁇ K) at 25 ° C. (9)
  • a laminate capable of forming a laminated glass realizing a balance of rigidity, sound insulation and heat insulation at a high level, and a laminated glass including an interlayer film composed of the laminated body.
  • the resin layer (X) in the present invention is a layer composed of the resin composition (X), and has a maximum value of tan ⁇ in dynamic viscoelastic properties in a temperature range from ⁇ 20 ° C. to 20 ° C.
  • a laminate (Z) having at least one or more resin layers (X) between two glass plates a laminated glass provided with sound insulation can be formed.
  • the temperature range where the maximum value of tan ⁇ in the dynamic viscoelastic properties of the resin layer (X) exists is not particularly limited as long as it is ⁇ 20 ° C. or more and 20 ° C. or less, but is preferably ⁇ 15 ° C. or more. -10 ° C or higher, particularly preferably -9 ° C or higher, more preferably 15 ° C or lower, more preferably 10 ° C or lower.
  • the method of adjusting the maximum value of tan ⁇ in the dynamic viscoelastic properties of the resin layer (X) to -20 ° C. or more and 20 ° C. or less includes, for example, (i) a resin having a glass transition temperature in a temperature range of 20 ° C. or more.
  • a resin having a glass transition temperature in a temperature range of 20 ° C. or more There are a method of blending additives such as a plasticizer and a softener, and a method of (ii) using a resin having a glass transition temperature in a temperature range of ⁇ 20 ° C. to 20 ° C.
  • a resin a block copolymer composed of a polymer block having a glass transition temperature in a temperature region of ⁇ 20 ° C. or more and 20 ° C. or less, and a polymer block having a glass transition temperature in a higher temperature region. This is preferable because the heat resistance of the laminated glass as an intermediate film is easily maintained.
  • the resin composition (X) contains the resin (x) as a main component, and if necessary, other components.
  • the resin (x) is made of 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 (D) obtained by hydrogenation.
  • the resin (x) include, for example, polystyrene / diene-based block copolymer, polyolefin-based block copolymer, polyurethane-based block copolymer, polyester-based block copolymer, polyamide-based block copolymer, acrylic Block copolymer, polyvinyl acetal polymer, ethylene / vinyl acetate copolymer, and hydrogenated polymers thereof. These may be used alone or in combination of two or more at an arbitrary ratio.
  • hydrides of polystyrene block copolymers composed of aromatic vinyl compounds and chain conjugated diene compounds hydrides of polyolefin block copolymers, acrylic block copolymers Hydrides are preferred.
  • the polymer block (A) contains a structural unit [a] derived from an aromatic vinyl compound as a main component.
  • aromatic vinyl compound capable of forming the structural unit [a] derived from the aromatic vinyl compound include styrene; ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, Styrenes having an alkyl group having 1 to 6 carbon atoms as substituents, such as 4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene; Styrenes having a halogen atom as a substituent, such as monochlorostyrene, dichlorostyrene, 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
  • aromatic vinyl compounds not containing a polar group such as styrene and styrenes having an alkyl group having 1 to 6 carbon atoms as substituents, are preferred. From the viewpoint, styrene is more preferred.
  • the polymer block (A) may include other structural units other than the structural unit [a].
  • Such another 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 below.
  • the compound capable of forming another structural unit include a chain vinyl compound and a cyclic vinyl compound, and more specifically, a compound having a nitrile group, an alkoxycarbonyl group, a hydroxycarbonyl group, or a halogen group. And unsaturated cyclic acid anhydrides and unsaturated imide compounds.
  • the content ratio of the structural unit [a] in the polymer block (A) is preferably 90% by mass or more, more preferably 90% by mass, when all the repeating units in the polymer block (A) are 100% by mass. It is at least 95% by mass, particularly preferably at least 98% by mass. When the content of the structural unit [a] in the polymer block (A) is at least 90% by mass, the heat resistance of the resin layer (X) can be sufficiently high.
  • the content ratio of other 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. is there. By setting the content ratio of other structural units in the polymer block (A) within the above range, it is possible to prevent the heat resistance of the resin layer (X) from being lowered.
  • the polymer block (B) contains a structural unit [b] derived from a chain conjugated diene compound as a main component.
  • chain conjugated diene compound capable of forming the structural unit [b] derived from the 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 alone or in combination of two or more at an arbitrary ratio. Among them, (i) those which do not contain a polar group (1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene) are preferred from the viewpoint of hygroscopicity.
  • the glass transition temperature derived from the soft segment of the hydrogenated block copolymer (D) is -20 ° C. or higher. Isoprene is particularly preferred from the viewpoint of easy control in the range of 20 ° C. or lower.
  • polymer block (B) may include other structural units other than the structural unit [b].
  • Such another structural unit may be, for example, the structural unit [a] derived from the above-mentioned aromatic vinyl compound.
  • the chain olefin and the cyclic olefin described in the section of “polymerized block (A)” can also be used.
  • the content ratio of the structural unit [b] in the polymer block (B) is preferably 90% by mass or more, more preferably 90% by mass, when all the repeating units in the polymer block (B) are 100% by mass. It is at least 95% by mass, particularly preferably at least 98% by mass.
  • the tan ⁇ in the viscoelastic properties of the resin layer (X) is a maximum value in a temperature range of -20 ° C to 20 ° C. Can be easily controlled.
  • the content ratio of other 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. is there.
  • the tan ⁇ in the viscoelastic properties of the resin layer (X) reaches a maximum value in a temperature range of ⁇ 20 ° C. to 20 ° C. It can be easily controlled to have.
  • the structural unit [b] in the polymer block (B) contains a structural unit derived from 1,2-addition polymerization and 3,4-addition polymerization, and the remainder is a structural unit derived from 1,4-addition polymerization. Including.
  • the ratio of the structural units derived from the 1,2-addition polymerization and 3,4-addition polymerization of the chain conjugated diene compound is at least 40% by mass based on the entire structural units [b] in the polymer block (B). Is preferably 45% by mass or more, more preferably 50% by mass or more, and further preferably 80% by mass or less, and more preferably 70% by mass or less. , 65% by mass or less.
  • the content ratio of the structural unit derived from the 1,2-addition polymerization and the 3,4-addition polymerization of the chain conjugated diene compound to the entire structural unit [b] in the polymer block (B) is within the above range. Thereby, it is possible to ensure that the tan ⁇ in the viscoelastic properties of the resin layer (X) has a maximum value in a temperature range of ⁇ 20 ° C. or more and 20 ° C. or less.
  • the above-mentioned polymer block containing a structural unit derived from the 1,2-addition polymerization and / or a structural unit derived from the 3,4-addition polymerization comprises a chain conjugated diene compound and, if necessary, Compounds that can form other structural units, such as aromatic vinyl compounds, chain olefins, and cyclic olefins, are present in the presence of a specific compound having an electron donating atom (hereinafter sometimes referred to as a “randomizing agent”). It can be obtained by polymerizing under the following conditions.
  • the total content of the structural units derived from 1,2-addition polymerization and the structural units derived from 3,4-addition polymerization can be controlled by the type and amount of the randomizing agent.
  • Examples of the compound having an electron donating atom (for example, oxygen (O) or nitrogen (N)) that can be used as a randomizing agent include an ether compound, an amine compound, and a phosphine compound.
  • ether compounds are preferred from the viewpoint that the molecular weight distribution of the polymer block can be reduced and the hydrogenation reaction is hardly inhibited.
  • randomizing agent examples include, for example, 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 methyl phenyl ether, 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, tetramethylethylene diamine, and the like.
  • ethylene glycol is preferred from the viewpoint of controlling the mass fraction of the structural unit derived from 1,2-addition polymerization and / or the structural unit derived from 3,4-addition polymerization to further enhance the sound insulation of the obtained resin sheet. It is preferred to use dibutyl ether.
  • the amount of these randomizing agents used during the preparation of the block copolymer (C) is preferably at least 0.001 part by mass, and more preferably 0.01 part by mass, based on 100 parts by mass of the chain conjugated diene compound. It is more preferably at least 10 parts by mass, more preferably at most 1 part by mass.
  • the block copolymer (C) which is a 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 the polymer blocks (A) in the block copolymer (C) is not particularly limited as long as it is two or more, but is usually three or less, preferably two, and the block copolymer (C)
  • the number of polymer blocks (B) in the polymer is not particularly limited as long as it is one or more, but is usually two or less, preferably one.
  • the composition and the block length of the structural units in the polymer block (A) may be the same or different.
  • the block copolymer (C) has a plurality of polymer blocks (B) the composition and the block length of the structural units in the polymer block (B) may be the same or different.
  • the form of the block of the block copolymer (C) is not particularly limited, and may be a chain-type block or a radial-type block, but is preferably a chain-type block 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 bonded to both ends of the polymer block (B).
  • the ratio (wA / wB) of wA and wB is preferably 10/90 or more and 35/65 or less, more preferably 12/88 or more, even more preferably 15/85 or more, The ratio is particularly preferably 18/82 or more, more preferably 30/70 or less, further preferably 25/75 or less, particularly preferably 20/80 or less.
  • the ratio of wA and wB (wA / wB) equal to or less than the upper limit, it is possible to prevent the sound insulation performance of the resin layer (X) from lowering.
  • the ratio of wA and wB (wA / wB) to a lower limit or more, it is possible to prevent the heat resistance of the resin layer (X) from lowering.
  • the molecular weight of the block copolymer (C) is 30,000 or more in terms of polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent. Is preferably 40,000 or more, more preferably 50,000 or more, particularly preferably 200,000 or less, more preferably 170,000 or less, and 150,000. It is particularly preferred that: Further, 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.
  • a resin composition (X) having a block copolymer hydride (D) obtained by hydrogenating the block copolymer (C) as a main component is sufficient. Melt moldability and heat resistance can be imparted.
  • the method for producing the block copolymer (C) is not particularly limited, and a known method can be employed. For example, a method described in WO 2003/018656, WO 2011/096389, or the like can be used. No.
  • the hydrogenated block copolymer (D) is obtained by hydrogenating at least 95% or more of carbon-carbon unsaturated bonds in the main chain and side chains derived from the chain conjugated diene compound in the block copolymer (C). Is a molecule.
  • the block copolymer hydride (D) is a polymer obtained by selectively hydrogenating only carbon-carbon unsaturated bonds in the main chain and side chains derived from the chain conjugated diene compound in the block copolymer (C).
  • the chain in the block copolymer hydride (D) is used.
  • 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 preferably 99% or more.
  • 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 more preferably 5% or less. Is more preferable, and particularly preferably 3% or less.
  • 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 In addition, light resistance and heat deterioration resistance are improved as compared with the block copolymer (C).
  • the block copolymer hydride (D ) can be improved in light resistance and heat deterioration resistance of the resin composition (X).
  • the hydrogenation rate of the carbon-carbon unsaturated bond of the aromatic ring derived from the aromatic vinyl compound in the block copolymer (C) is set to the above upper limit or less so that the hydrogenated block copolymer (D) can be obtained. It is easy to maintain the heat resistance of the resin composition (X) as a main component.
  • the hydrogenation rate of carbon-carbon unsaturated bonds in the hydrogenated block copolymer (D) is preferably at least 90% of the total amount of carbon-carbon unsaturated bonds. , 95% or more, more preferably 99% or more.
  • the hydrogenation rate of carbon-carbon unsaturated bonds in the block copolymer hydride (D) can be determined, for example, by the 1 H-NMR of the block copolymer (C) as a precursor and the block copolymer hydride (D). By measuring the hydrogenation rate of the carbon-carbon unsaturated bond of the main chain and the side chain derived from the chain conjugated diene compound, and the carbon-carbon unsaturated bond of the aromatic ring derived from the aromatic vinyl compound, The hydrogenation rate can be determined respectively.
  • the method of hydrogenating the unsaturated bond in the block copolymer (C), the reaction form, and the like are not particularly limited, and may be performed according to a known method.
  • a method for selectively hydrogenating carbon-carbon unsaturated bonds in the main chain and side chains derived from the chain conjugated diene compound in the block copolymer (C) is described in, for example, JP-A-2015-78090.
  • Publicly known hydrogenation method In the block copolymer (C), the carbon-carbon unsaturated bond of the main chain and the side chain derived from the chain conjugated diene compound and the carbon-carbon unsaturated bond of the aromatic ring derived from the aromatic vinyl compound are defined.
  • the hydrogenation method for example, the methods described in WO 2011/096389, WO 2012/043708 and the like can be mentioned.
  • the molecular weight of the block copolymer hydride (D) is a weight average molecular weight (Mw) in terms of polystyrene measured by GPC using THF as a solvent, and is preferably 30,000 or more, and 40,000 or more. Is more preferably, 50,000 or more, particularly preferably 200,000 or less, more preferably 170,000 or less, and particularly preferably 150,000 or less. Further, the molecular weight distribution (Mw / Mn) of the hydride (D) of the block copolymer 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, it is possible to impart sufficient melt moldability and mechanical strength to the resin composition (X) containing the block copolymer hydride (D) as a main component. it can.
  • Mw weight average molecular weight
  • the resin composition (X) containing the resin (x) as a main component may contain various additives in addition to the resin (x) as a main component.
  • Preferred additives include an ultraviolet absorber for shielding ultraviolet rays, an infrared absorber for shielding infrared rays, an antioxidant and an antiblocking agent for improving workability, and a light stabilizer for improving durability. , And the like.
  • UV absorber examples include oxybenzophenone-based compounds, benzotriazole-based compounds, salicylate-based compounds, benzophenone-based compounds, and triazine-based compounds.
  • the infrared absorber examples 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, immonium compounds, diimonium compounds, polymethine compounds, diphenylmethane compounds, anthraquinone compounds, pentadiene compounds; And the like; Zomechin compounds, particulate near infrared absorbing dye, such as lanthanum hexaboride.
  • antioxidant examples include a phosphorus-based antioxidant, a phenol-based antioxidant, and a sulfur-based antioxidant.
  • Light stabilizer examples include a hindered amine light stabilizer.
  • Additives such as an ultraviolet absorber, an infrared absorber, an antioxidant, and a light stabilizer, which are blended in the resin (x), may be used alone or in combination of two or more at an arbitrary ratio. it can.
  • the total amount of additives such as an ultraviolet absorber, an infrared absorber, an antioxidant, and a light stabilizer is preferably 5 parts by mass or less, more preferably 3 parts by mass or less based on 100 parts by mass of the resin (x). It is preferably at most 2 parts by mass.
  • a known method generally used can be applied.
  • a resin (x) pellet and a compounding agent are uniformly mixed using a mixer such as a tumbler, a ribbon blender, a Henschel type mixer, and the like, and then mixed with a continuous melt kneader such as a twin screw extruder.
  • a resin composition containing a resin (x) in which a compounding agent is uniformly dispersed can be produced by a method of forming a pellet, or the like.
  • an intermediate film including a resin layer (X) having a temperature range in which tan ⁇ in the dynamic viscoelastic property shows a maximum value at ⁇ 20 ° C. or more and 20 ° C. or less reduces the coincidence effect of the glass plate and makes the laminated glass The sound insulation performance is improved.
  • the thickness of the resin layer (X) is preferably at least 0.02 mm, more preferably at least 0.03 mm, still more preferably at least 0.04 mm, particularly preferably at least 0.08 mm, and preferably at most 0.6 mm, 0.5 mm or less is more preferable, and 0.4 mm or less is particularly preferable.
  • the thickness of the resin layer (X) is preferably at least 0.02 mm, more preferably at least 0.03 mm, still more preferably at least 0.04 mm, particularly preferably at least 0.08 mm, and preferably at most 0.6 mm, 0.5 mm or less is more preferable, and 0.4 mm or less is particularly preferable.
  • a plurality of resin layers (X) can be used to enhance the sound insulation of the laminated glass.
  • a reduction in rigidity of the laminated glass is achieved by stacking a plurality of resin layers (X) between the plurality of resin layers (X) via a resin layer having a high elastic modulus. Can be suppressed.
  • 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. Is a layer that is 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 insulation of the laminated glass.
  • the resin composition (Y) contains the resin (y) as a main component and, if necessary, other components.
  • the storage elastic modulus in the dynamic viscoelastic properties of the laminate (Z) is from 1.0 ⁇ 10 7 Pa to 5.0 ⁇ 10 8 Pa in a temperature range of ⁇ 20 ° C. to 40 ° C.
  • the resin is not particularly limited as long as it is a resin having the following value.
  • a specific block copolymer hydride (H) composed of an aromatic vinyl compound, a chain conjugated diene compound, or the like.
  • the resin layer (Y) is a layer composed of the resin composition (Y) containing the modified block copolymer hydride (J) as a main component
  • the resin layer (Y) and the glass plate form an adhesive layer. It can be firmly bonded without any intervention.
  • the resin (y) include, for example, polyester (co) polymer, polyamide (co) polymer, polyolefin (co) polymer, polystyrene (co) polymer, acrylonitrile / butadiene / styrene copolymer.
  • Polymer polystyrene / diene-based block copolymer, polyolefin-based block copolymer, polyurethane-based block copolymer, polyester-based block copolymer, polyamide-based block copolymer, acrylic-based block copolymer, polyvinyl acetal-based 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. And modified polymers into which groups have been introduced. These may be used alone or in combination of two or more at an arbitrary ratio.
  • hydrogenated polystyrene (co) polymer hydrogenated polypropylene (co) polymer, hydrogenated polyurethane (co) polymer, acrylic (co) poly
  • the combined hydride is preferable, and from the viewpoint of transparency when the interlayer is used for laminated glass, a hydride of a polystyrene-based block copolymer composed of an aromatic vinyl compound and a chain conjugated diene compound, etc., methyl methacrylate And a hydride of an acrylic block copolymer composed of a long-chain alkyl methacrylate or the like, and / or a modified polymer having an adhesive reactive group introduced therein.
  • 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, more preferably 0.17 W / (m ⁇ K) or less.
  • the thermal conductivity is a value obtained by measuring based on the ASTM E1530 method (disc heat flow meter method).
  • the block copolymer hydride (H) is composed of an aromatic vinyl compound, a chain conjugated diene compound and the like, and has at least two predetermined polymer blocks (E) and at least one or more predetermined polymer blocks (F).
  • polymer block (E) contains a structural unit [e] derived from an aromatic vinyl compound as a main component.
  • the structural unit [e] is a structural unit derived from an aromatic vinyl compound, and is the same as that described above as the structural unit [a], and preferred examples thereof are also the same as those described above.
  • the polymer block (E) may include other structural units other than the structural unit [e].
  • Other structural units that can be included in the polymer block (E) are the same as those described above as other structural units that can be included in the polymer block (A), and preferred examples thereof are also the same as those described above. It is.
  • the content ratio of the structural unit [e] in the polymer block (E) is preferably 90% by mass or more when all the repeating units in the polymer block (E) are 100% by mass. It is more preferably at least 95% by mass, particularly preferably at least 98% by mass. When the content ratio 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 secured.
  • the content ratio of other 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. % Is particularly preferable.
  • the heat resistance of the resin composition (Y) containing the hydride (H) of the block copolymer as a main component is reduced. It can be prevented from lowering.
  • the polymer block (F) contains a structural unit [f] derived from a chain conjugated diene compound as a main component.
  • the structural unit [f] is a structural unit derived from a chain conjugated diene compound, and is the same as that described above as the structural unit [b], and preferred examples thereof are also the same as those described above.
  • the polymer block (F) may include other structural units other than the structural unit [f].
  • Other structural units that can be included in the polymer block (F) are the same as those described above as other structural units that can be included in the polymer block (B), and preferred examples thereof are also the same as those described above. It is.
  • the content ratio of the structural unit [f] in the polymer block (F) is preferably 90% by mass or more when all the repeating units in the polymer block (F) are 100% by mass. It is more preferably at least 95% by mass, particularly preferably at least 98% by mass.
  • flexibility can be imparted to the block copolymer hydride (H), and the block copolymer hydride can be provided.
  • (H) is the main component of the resin composition (Y)
  • the resin layer (Y) can maintain flexibility, and imparts impact resistance to the laminated glass used for the interlayer (Z) as the intermediate film. be able to.
  • the content ratio of other 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 more preferably 2% by mass. It is particularly preferred that: By setting the content ratio of other structural units in the polymer block (F) to the upper limit or less, the flexibility of the block copolymer hydride (H) can be maintained, and the block copolymer hydride (H 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 used for the intermediate film. Can be.
  • the structural unit [f] in the polymer block (F) is mainly composed of a structural unit derived from 1,4-addition polymerization, and the remainder is derived from 1,2-addition polymerization and / or 3,4-addition polymerization. Including structural units.
  • the ratio of the structural unit derived from the 1,4-addition polymerization of the chain conjugated diene compound is preferably 70% by mass or more based on the entire structural unit [f] in the polymer block (F). It is more preferably at least 90 mass%, particularly preferably at least 90 mass%.
  • the softness of the block copolymer hydride (H) can be improved.
  • the glass transition temperature derived from the segment can be controlled within a range from -60 ° C to -30 ° C.
  • aromatic vinyl compound which is a component of the polymer block (E) and / or the polymer block (F)
  • the same aromatic vinyl compound as that used for the polymer block (A) and / or the polymer block (B) is used.
  • An aromatic vinyl compound can be used.
  • chain conjugated diene compound which is a component of the polymer block (E) and / or the polymer block (F)
  • the same as that used for the polymer block (A) and / or the polymer block (B) is used.
  • Chain conjugated diene compounds can be used.
  • vinyl compound which may be contained as a component of the polymer block (E) and / or the polymer block (F), the same as those used for the polymer block (A) and / or the polymer block (B) described above.
  • a chain vinyl compound or a cyclic vinyl compound can be used.
  • Block copolymer (G) which is a 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 the polymer blocks (E) in the block copolymer (G) is not particularly limited as long as it is two or more, but is usually three or less, preferably two, and the block copolymer (G)
  • the number of polymer blocks (F) in the polymer is not particularly limited as long as it is one or more, but is usually two or less, preferably one.
  • the composition of the structural units in the polymer block (E) may be the same or different.
  • the block copolymer (G) has a plurality of polymer blocks (F)
  • the composition of the structural units in the polymer block (F) may be the same or different.
  • the ratio between wE and wF is preferably 40/60 or more and 60/40 or less, more preferably 42/58 or more, even more preferably 45/55 or more, The ratio is particularly preferably at least 48/52, more preferably at most 58/42, further preferably at most 55/45, particularly preferably at most 52/48.
  • the ratio of wE and wF (wE / wF) is made equal to or more than the lower limit, it is possible to prevent a decrease in the elastic modulus of the resin layer (Y).
  • wF is equal to or less than the upper limit, the flexibility of the resin layer (Y) is prevented from lowering, and the impact resistance of the laminated glass using the laminate (Z) as the interlayer is prevented from lowering. can do.
  • the form of the block of the block copolymer (G) is not particularly limited, and may be a chain block or a radial block, but a chain block is preferable in terms of excellent mechanical strength.
  • the most preferred form of the block copolymer (G) is a triblock copolymer (EFE) in which the polymer block (E) is bonded to both ends of the polymer block (F).
  • the molecular weight of the block copolymer (G) is 30,000 or more as a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent. Is preferably 40,000 or more, more preferably 50,000 or more, particularly preferably 100,000 or less, more preferably 90,000 or less, and 80,000. It is still more preferably not more than 70,000, still more preferably not more than 70,000, and particularly preferably not more than 60,000. Further, 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.
  • a resin composition (Y) containing a block copolymer hydride (H) obtained by hydrogenating the block copolymer (G) as a main component is sufficient. Melt formability and mechanical strength can be imparted.
  • the method for producing the block copolymer (G) is not particularly limited, and a known method can be employed. For example, a method described in WO2003 / 018656, WO2011 / 096389, or the like can be used. No.
  • the block copolymer hydride (H) is a polymer obtained by hydrogenating at least 95% or more of carbon-carbon unsaturated bonds in the main chain and side chains derived from the chain conjugated diene compound in the block copolymer (G). It is.
  • the block copolymer hydride (H) is a polymer in which only the main chain and side chain carbon-carbon unsaturated bonds derived from the chain conjugated diene compound in the block copolymer (G) are selectively hydrogenated.
  • the main chain and side chain carbon-carbon unsaturated bonds derived from the chain conjugated diene compound in the block copolymer (G), and the aromatic vinyl compounds derived from the aromatic vinyl compound in the block copolymer (G) It may be a polymer in which the carbon-carbon unsaturated bond of the aromatic ring is hydrogenated, or a mixture thereof.
  • the chain in the block copolymer hydride (H) is used.
  • the hydrogenation rate of the carbon-carbon unsaturated bond in the main chain and side chain derived from the conjugated diene compound is preferably 95% or more, more preferably 97% or more, and preferably 99% or more.
  • the hydrogenation rate of the carbon-carbon unsaturated bond of the aromatic ring derived from the aromatic vinyl compound in the hydrogenated block copolymer (H) is preferably 10% or less, and more preferably 5% or less. Is more preferable, and particularly preferably 3% or less.
  • 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 As compared with the block copolymer (G), light resistance and heat deterioration resistance are improved.
  • the hydrogenation rate of the carbon-carbon unsaturated bond of the main chain and the side chain derived from the chain conjugated diene compound in the block copolymer (G) equal to or more than the lower limit, the hydride of the block copolymer (H ) Can be improved in light resistance and heat resistance deterioration of the resin composition (Y).
  • the hydrogenated block copolymer (H) can be obtained. It becomes easy to maintain the heat deterioration resistance of the resin composition (Y) as a main component.
  • the hydrogenation rate of carbon-carbon unsaturated bonds in the hydrogenated block copolymer (H) is preferably at least 90% of the total amount of carbon-carbon unsaturated bonds. , 95% or more, more preferably 99% or more.
  • the hydrogenation rate of the carbon-carbon unsaturated bond in the block copolymer hydride (H) can be determined, for example, by the 1 H-NMR of the block copolymer (G) as a precursor and the block copolymer hydride (H). By measuring the hydrogenation rate of the carbon-carbon unsaturated bond of the main chain and the side chain derived from the chain conjugated diene compound, and the carbon-carbon unsaturated bond of the aromatic ring derived from the aromatic vinyl compound, The hydrogenation rate can be determined respectively.
  • the method for hydrogenating the unsaturated bond in the block copolymer (G), the reaction mode, and the like are not particularly limited, and are the same as the hydrogenation method, the reaction mode, and the like for the unsaturated bond in the block copolymer (C) described above. It can be carried out.
  • the molecular weight of the block copolymer hydride (H) is a weight average molecular weight (Mw) in terms of polystyrene measured by GPC using THF as a solvent, and is preferably 30,000 or more, and 40,000 or more. Is more preferably, 50,000 or more, particularly preferably 100,000 or less, more preferably 90,000 or less, and still more preferably 80,000 or less, It is still more preferably 70,000 or less, particularly preferably 60,000 or less. Further, the molecular weight distribution (Mw / Mn) of the hydride (H) of the block copolymer 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, it is possible to impart sufficient melt moldability and mechanical strength to the resin composition (Y) containing the hydride (H) of the block copolymer as a main component. it can.
  • Mw weight average molecular weight
  • the modified block copolymer hydride (J) is introduced with an alkoxysilyl group by reacting the above-mentioned block copolymer hydride (H) with an ethylenically unsaturated silane compound in the presence of an organic peroxide. It was done.
  • the resin composition (Y) containing the hydride (J) of the modified block copolymer as a main component maintains the elastic modulus and transparency. Thus, strong adhesion to glass or metal is provided.
  • the outermost layer of the laminate (Z) of the present invention is composed of the modified block copolymer hydride (J)
  • no adhesive is required between the laminate (Z) and the glass plate.
  • a laminated glass using the laminate (Z) as an intermediate film can be produced.
  • alkoxysilyl group to be introduced examples include, for example, tri (silicon alkoxy) silyl groups such as trimethoxysilyl group and triethoxysilyl group; methyldimethoxysilyl group, methyldiethoxysilyl group, ethyldimethoxysilyl group (Alkyl having 1 to 20 carbon atoms) di (alkoxy having 1 to 6 carbon atoms) silyl group such as ethyl, diethoxysilyl group, propyldimethoxysilyl group, propyldiethoxysilyl group; phenyldimethoxysilyl group, phenyldiethoxy group (Aryl) di (alkoxy having 1 to 6 carbon atoms) silyl group such as silyl group; 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. You may.
  • the amount of the alkoxysilyl group introduced into the block copolymer hydride (H) is preferably at least 0.1 part by mass, and more preferably 0.2 part by mass, based on 100 parts by mass of the block copolymer hydride (H). Parts by mass or more, more preferably 0.3 parts by mass or more, particularly preferably 1.0 parts by mass or more, particularly preferably 5 parts by mass or less, and more preferably 4 parts by mass or less. More preferably, it is more preferably 3 parts by mass or less, particularly preferably 2 parts by mass or less.
  • the alkoxysilyl group introduced When the amount of the alkoxysilyl group introduced is equal to or less than the upper limit, the alkoxysilane decomposed with a trace amount of water or the like before melt-forming the obtained alkoxysilyl group-containing block copolymer hydride (J) into a desired shape. Crosslinking between silyl groups progresses, and it is possible to prevent problems such as generation of an unmelted product and deterioration of flowability at the time of melting and deterioration of moldability.
  • the amount of the alkoxysilyl group introduced is at least the lower limit, the resin layer (Y) composed of the resin composition (Y) containing the hydride (H) of the block copolymer having the alkoxysilyl group as a main component is formed. When bonding with a glass plate, it can be prevented that a sufficient adhesive force cannot be obtained.
  • the introduction of the alkoxysilyl group can be confirmed by an IR spectrum. Further, the amount introduced can be calculated
  • a compound which undergoes a graft reaction with a block copolymer hydride (H) to introduce an alkoxysilyl group into the block copolymer hydride (H) is used.
  • the amount of the ethylenically unsaturated silane compound to be used is preferably at least 0.1 part by mass, more preferably at least 0.2 part by mass, per 100 parts by mass of the block copolymer hydride (H). Preferably, it is more preferably at least 0.3 part by mass, particularly preferably at least 1.0 part by mass, further preferably at most 5 parts by mass, more preferably at most 4 parts by mass. Is more preferably 3 parts by mass or less, particularly preferably 2.5 parts by mass or less.
  • the peroxide used for the introduction reaction of the alkoxysilyl group is preferably a half-life temperature of 170 ° C. for 1 minute in order to react the ethylenically unsaturated silane compound in the molten state of the block copolymer hydride (H). Those having a temperature of 190 ° C. or lower are preferably used.
  • t-butylcumyl peroxide, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxide) 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 in combination of two or more.
  • the amount of the peroxide to be used is preferably at least 0.05 part by mass, more preferably at least 0.1 part by mass, based on 100 parts by mass of the block copolymer hydride (H). It is particularly preferably at least 2 parts by mass, more preferably at most 2 parts by mass, more preferably at most 1 part by mass, particularly preferably at most 0.5 part by mass.
  • the method of reacting the above-mentioned hydrogenated modified block copolymer (J) with an ethylenically unsaturated silane compound in the presence of a peroxide is not particularly limited, and is described in, for example, WO2012 / 043708. The known methods described may 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 raw material because the amount of the introduced alkoxysilyl group is small.
  • a cleavage reaction and a crosslinking reaction of the polymer occur simultaneously, and the value of the molecular weight distribution of the hydrogenated modified block copolymer (J) is large. Become.
  • the molecular weight of the modified block copolymer hydride (J) is preferably 30,000 or more, more preferably 40,000 or more, as a weight average molecular weight (Mw) in terms of polystyrene measured by GPC using THF as a solvent. More preferably, it is particularly preferably 50,000 or more, more preferably 100,000 or less, more preferably 90,000 or less, and particularly preferably 80,000 or less. Further, 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, it is possible to impart sufficient melt moldability and mechanical strength to the resin composition (Y) containing the hydrogenated modified block copolymer (J) as a main component. it can.
  • the resin composition (Y) containing the resin (y) as a main component may contain various additives in addition to the resin (y) as a main component.
  • Preferable additives include a plasticizer and a softener for adjusting the storage elastic modulus in the dynamic viscoelastic properties of the laminate (Z) including the resin layer (X) and the resin layer (Y) to a desired value; Examples thereof include an ultraviolet absorber for shielding ultraviolet rays, an infrared absorber for shielding infrared rays, an antioxidant and an antiblocking agent for improving workability, and a light stabilizer for improving durability.
  • the plasticizer is not particularly limited as long as it can be blended with the resin (y) containing a large amount of polar groups to make the storage elastic modulus in the dynamic viscoelastic properties of the laminate (Z) a desired value.
  • organic plasticizers such as monobasic organic acid esters and polybasic organic acid esters; and phosphoric acid plasticizers such as organic phosphoric acid compounds and organic phosphorous acid compounds.
  • plasticizer examples include, for example, diethylene glycol-di-2-ethylbutyrate, diethylene glycol-di-n-heptanoate, diethylene glycol-di-2-ethylhexanoate, triethylene glycol-di-2-ethylbutyrate , Triethylene glycol di-n-heptanoate, triethylene glycol di-2-ethylhexanoate, tetraethylene glycol di-2-ethyl butyrate, tetraethylene glycol di-n-heptanoate, tetraethylene glycol Di-2-ethylhexanoate, and the like.
  • the blending amount of the plasticizer can be appropriately selected depending on the resin (y), the thickness configuration of the resin layer (X) and the resin layer (Y), and the like, so that the storage modulus of the laminate (Z) becomes a desired value.
  • the amount is preferably 30 parts by mass or less based on 100 parts by mass of the resin (y).
  • the softener is a hydrocarbon-based resin containing no polar group, or a softener that can be added to the resin (y) so that the storage elastic modulus in the dynamic viscoelastic properties of the laminate (Z) can be set to a desired value.
  • low molecular weight olefins such as polyisobutylene, polybutene, poly-4-methylpentene, poly-1-octene, ethylene / ⁇ -olefin copolymer and the like and hydrogenated products thereof; polyisoprene; Low molecular weight conjugated diene such as polyisoprene-butadiene copolymer and hydride thereof; low molecular weight paraffin such as liquid paraffin;
  • the above-mentioned low molecular weight body having a number average molecular weight of 300 or more and 5,000 or less is preferable, and further excellent. From the viewpoint that transparency and light resistance are maintained and the effect of adjusting the storage elastic modulus is excellent, a low molecular weight polyisobutylene hydride and a low molecular weight polyisoprene hydride are more preferable
  • the amount of the softener is appropriately selected such that the storage modulus of the laminate (Z) becomes a desired value depending on the resin (y), the thickness configuration of the resin layer (X) and the resin layer (Y), and the like. Although it is possible, it is preferably 30 parts by mass or less for 100 parts by mass of the resin (y).
  • additives other than the plasticizer and the softener for example, an ultraviolet absorber, an infrared absorber, an antioxidant, a light stabilizer, and the like
  • the same additives as those added to the resin composition (X) described above are used.
  • the compounding amount of the 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 more preferably 2 parts by mass or less with respect to 100 parts by mass of the resin (y). Parts or less is particularly preferred.
  • 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 insulation to the laminated glass when the laminate (Z) is used as an interlayer of 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.
  • the thickness of the resin layer (Y) By setting the thickness of the resin layer (Y) to be equal to or more than the lower limit value, it is possible to prevent the elasticity of the laminate (Z) from becoming insufficient and to insulate the laminated glass using the laminate (Z) as an intermediate film. Insufficiency can be prevented. Further, by setting the thickness of the resin layer (Y) to be equal to or less than the upper limit value, it is possible to prevent the laminate (Z) from being difficult to be wound into a roll and to store it, and to perform an operation at the time of manufacturing a laminated glass. It is possible to prevent the property from lowering.
  • (C) Laminate (Z) In the laminate (Z) of the present invention, at least one resin layer (X) having the above characteristics is laminated between at least two resin layers (Y).
  • the storage elastic modulus in the dynamic viscoelastic properties of the laminate (Z) needs to be 1.0 ⁇ 10 7 Pa or more in the temperature range of ⁇ 20 ° C. to 40 ° C., and 1.5 ⁇ 10 7 Pa It is preferably at least 1.7 ⁇ 10 7 Pa, more preferably at least 2.0 ⁇ 10 7 Pa, particularly preferably at least 2.4 ⁇ 10 7 Pa.
  • the laminate (Z) has the above-mentioned laminated structure and the above-mentioned dynamic viscoelastic properties, so that when used as an interlayer film of a laminated glass, the rigidity of the laminated glass is maintained, and the sound insulating property is maintained. In addition, a laminated glass having excellent heat insulating properties can be provided.
  • 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. Preferably, it is 1.5 mm or less, more preferably, 1.0 mm or less.
  • FIG. 1 is a diagram showing an example of an embodiment of the laminate (Z) of the present invention.
  • the laminate (Z) 3a of FIG. 1 one resin layer (X) 1a is sandwiched between two resin layers (Y) 2a and 2b, and the resin layer (Y) / the resin layer (X) / the resin layer (Y) has a three-layer structure.
  • FIG. 3 is a diagram showing another example of the embodiment of the laminate of the present invention.
  • one resin layer (X) 1a is sandwiched between two resin layers (Y) 2a and 2b, and between the two resin layers (Y) 2b and 2c.
  • the resin layer (Y) 2a, 2b and 2c may have the same or different compositions and thicknesses.
  • the laminate configuration in the laminate (Z) can be appropriately selected depending on the purpose, and includes, for example, the configurations illustrated in FIGS. 1 and 3 and the following laminate configurations (i) to (x).
  • 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 on the laminated glass, and (iii) a laminated glass. It may have a laminated structure in which another resin film layer for imparting a desired function, such as a highly elastic resin film for increasing rigidity, is laminated. When the resin layer (Y) does not have adhesiveness to glass, an adhesive layer may be provided outside the resin layer (Y).
  • the laminate (Z) is, for example, (I): adhesive layer / resin layer (Y) / resin layer (X) / resin layer (Y) / adhesive layer, (Ii): A laminated structure of an adhesive layer / resin layer (Y) / resin layer (X) / resin layer (Y) / resin layer (Y) / adhesive layer may be used.
  • the production method for producing the laminate (Z) of the present invention is not particularly limited.
  • the resin layer (X) and / or the resin composition (Y) are formed by a known production method such as an extrusion molding method, a calendar molding method, a press molding method, a casting molding method, an inflation molding method, and the like.
  • a known production method such as an extrusion molding method, a calendar molding method, a press molding method, a casting molding method, an inflation molding method, and the like.
  • Each layer of the resin layer (Y) is manufactured in advance, and the resin layer (X), the resin layer (Y), and other functional resin layers as necessary are laminated, and then heat-pressed to form a laminate (Z). Can be manufactured.
  • the resin composition (X) is melt-extruded onto a film by extrusion lamination or the like on one side of the resin layer (Y) previously molded by the above molding method or the like, and the resin layer (X) is laminated and laminated.
  • the body (Z) can also be manufactured.
  • the resin composition (X), the resin composition (Y), and, if necessary, another functional resin may be co-extruded to produce a laminate (Z) having a desired layer configuration. .
  • a plurality of the same or different resin layers (Y) may be used.
  • a plurality of resin layers (Y) for example, (i) the penetration resistance of a laminated glass such as a polyethylene terephthalate film, a polycarbonate film, an ionomer resin film, etc., between the plurality of resin layers (Y).
  • a functional film such as a resin film for enhancing, (ii) a polyethylene terephthalate film on which an infrared reflective layer is vapor-deposited, and the like can be provided.
  • the laminate (Z) of the present invention may have an embossed surface.
  • Specific examples of the emboss shape include JP-A-6-198809, WO 1995/19885, JP-A-9-40444, JP-A-9-241045, JP-A-9-295839, and JP-A-9-295839.
  • an adhesive layer can be arranged on the side of the resin layer (Y) facing the glass plate.
  • the adhesive include a polyurethane-based adhesive, a silicone resin-based adhesive, a modified polyolefin-based adhesive, and a modified block copolymer-based adhesive.
  • a modified polyolefin adhesive having an alkoxysilyl group and a modified block copolymer-based hydride adhesive having an alkoxysilyl group from the viewpoint of excellent adhesion to both the resin layer (Y) and the glass plate. preferable.
  • 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 more preferably 0.7 mm or more. It is particularly preferable that it is not more than 3 mm, more preferably not more than 2.5 mm, and particularly preferably not more than 2 mm.
  • 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 material, wall material, partition material, floor material, etc. for automobiles and buildings). In the laminated glass of the present invention, usually, two glass plates, and if necessary, three or more glass plates are used. The thicknesses of the plurality of glass plates used may be the same or different.
  • the material of the glass plate is not particularly limited.
  • the material of the glass plate include, for example, aluminosilicate glass, borosilicate glass, aluminoborosilicate glass, barium borosilicate glass, silicate glass, crystallized glass, germanium glass, quartz glass, soda lime glass, white plate glass, and lead glass , Uranium glass, potash glass, non-alkali glass and the like.
  • the thermal conductivity in the thickness direction of the glass plate used in the present invention is generally about 0.9 W / (m ⁇ K) or more and about 1.3 W / (m ⁇ K) or less.
  • the thermal conductivity in the thickness direction of the glass plate is a value obtained by measuring based on the ASTM E1530 method (disk heat flow meter method).
  • a heat ray reflection film, an infrared reflection film, or the like may be formed on the glass plate.
  • a glass plate having a heat ray reflection film, an infrared reflection film, or the like made of an extremely thin metal film or metal oxide film on the surface is also provided with heat shielding properties. Therefore, a laminated glass provided with the glass plate is preferable because the flow of heat through the glass plate can be reduced.
  • a general-purpose float glass, a heat-strengthened glass, a chemically strengthened glass, or the like having different production methods can be used.
  • the laminated glass of the present invention includes two glass plates and an interlayer formed of a laminate (Z) disposed between the two glass plates. Are bonded and integrated via an intermediate film.
  • the thermal conductivity of the laminated glass in the thickness direction (lamination direction) needs to be 0.5 W / (m ⁇ K) or less, and preferably 0.4 W / (m ⁇ K) or less. , 0.3 W / (m ⁇ K) or less, particularly preferably 0.25 W / (m ⁇ K) or less.
  • the heat conductivity of the laminated glass of the present invention is about ⁇ or less, and the heat conductivity is excellent, as compared with the heat conductivity of the glass plate which is usually about 1 W / (m ⁇ K).
  • the thermal conductivity of the laminated glass in the thickness direction (laminating direction) is obtained by measuring in a temperature atmosphere of 60 ° C. using a thermal conductivity measuring device in accordance with ASTM E1530 method (disc heat flow meter method). Value.
  • the laminated glass of the present invention has a flexural modulus at 25 ° C. of preferably 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 a laminated glass composed of two sheets of glass having a thickness of 2 mm, which is generally used as a laminated glass for automobiles, and an intermediate film mainly composed of polyvinyl butyral having a thickness of 0.76 mm is about 11 GPa.
  • the laminated glass of the present invention has a bending elastic modulus equal to or higher than that of the present invention, and provides a laminated glass having excellent rigidity.
  • the laminated glass of the present invention has a storage elastic modulus in dynamic viscoelasticity of 1.0 ⁇ 10 7 Pa to 5.0 ⁇ 10 8 Pa in a temperature range of ⁇ 20 ° C. to 40 ° C. ) Is used as an intermediate film, whereby the above-described 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 preferably 3 mm or more. Preferably, it is 15 mm or less, more preferably 10 mm or less, and particularly preferably 7 mm or less. When 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 a building material, a display, or the like, or may be a curved surface shape such as a laminated glass for an automobile or a laminated glass for a railway vehicle.
  • FIG. 2 is a diagram showing an example of an embodiment of the laminated glass of the present invention.
  • one resin layer (X) 1a is sandwiched between two resin layers (Y) 2a and 2b, and the resin layer (Y) / the resin layer (X) / the resin layer (Y)
  • the laminated body (Z) 3a having a three-layer structure consisting of an intermediate film is used as an intermediate film, and the laminated body (Z) 3a as the intermediate film is disposed between the two glass plates 5a and 5b.
  • FIG. 4 is a diagram showing another example of the embodiment of the laminated glass of the present invention. In the laminated glass 6b shown in FIG.
  • one resin layer (X) 1a is sandwiched between two resin layers (Y) 2a and 2b, and infrared rays are reflected between the two resin layers (Y) 2b and 2c.
  • a laminate (Z) 3b having a five-layer structure of resin layer (Y) / resin layer (X) / resin layer (Y) / infrared reflective film / resin layer (Y) sandwiching film 4 is intermediate.
  • a laminate (Z) 3b as an intermediate film is disposed between the two glass plates 5a and 5b.
  • the composition and thickness of the resin layers (Y) 2a, 2b, 2c may be the same or different.
  • the glass plates 5a and 5b may have the same material or the same thickness, or may have different thicknesses.
  • the laminated structure of the laminated glass of the present invention can be appropriately selected depending on the purpose, and examples thereof include the structures illustrated in FIGS. 2 and 4 and the following laminated structures (i) to (xiii).
  • the method for producing the laminated glass of the present invention is not particularly limited.
  • a general method of laminated glass having a curved surface shape such as laminated glass for automobiles, for example, a laminated body in which a glass plate / laminate (Z) / glass plate is laminated in this order, and the laminated body is degassed. After degassing the inside by putting it in a possible flexible resin bag, put it in an autoclave, and press-bond under the conditions of temperature: 100 ° C to 150 ° C, pressure: 0.5MPa to 1.5MPa. Can be.
  • an adhesive is interposed between the laminate (Z) and the glass plate, for example, a glass plate / adhesive / laminate ( Z) / adhesive / glass plate is laminated in this order to produce a laminated glass in the same manner as described above.
  • a method of bonding and integrating the above-mentioned laminate by heating using a vacuum laminator, a hot press or the like is also applicable.
  • the laminate (Z) used as the intermediate film has a specific resin layer (X) having a maximum value in a temperature range where tan ⁇ in dynamic viscoelastic properties is ⁇ 20 ° C. or more and 20 ° C. or less. Since it has, in addition to the heat insulation property, the coincidence effect of the glass is reduced and the sound insulation performance is improved, so that it is particularly useful as a laminated glass for automobiles.
  • the rigidity is maintained even when the thickness of the interlayer is increased and the thickness of the glass plate is reduced without increasing the thickness of the entire laminated glass.
  • the heat insulating property can be enhanced, it contributes to the weight reduction of the laminated glass. For this reason, especially for automobile use, it can be expected that the use as a side glass, a rear glass, a roof glass, a windshield, etc. will also show an effect of improving fuel efficiency.
  • Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) The molecular weights of the block copolymer (C), the block copolymer hydride (D), the block copolymer (G), and the block copolymer hydride (H) were determined at 38 ° C. using tetrahydrofuran (THF) as an eluent. , And a standard polystyrene equivalent value was calculated.
  • GPC gel permeation chromatography
  • Tan ⁇ of resin layer (X) A required number of the produced resin layers (X) were laminated and press-molded to produce 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 prepared from this sheet.
  • a viscoelasticity measuring apparatus (ARES, manufactured by TA Instruments Japan Co., Ltd.) is used, and the JIS K7244-2 method (plastic-a test method for dynamic mechanical properties-part 2: Based on the torsional pendulum method), the dynamic viscoelastic properties were measured under the conditions of an angular frequency: 1 rad / s, a measurement temperature range: -100 ° C or more and 100 ° C or less, and a heating rate: 5 ° C / min. The temperature showing the maximum value was measured.
  • Heat insulation of laminated glass At least one or more laminates (Z) and, if necessary, between two circular blue plate glasses (diameter 50 mm, thickness 0.5 mm or more and 1.5 mm or less) Other resin layers, adhesive layers, etc. were arranged and bonded and integrated to produce a laminated glass, which was used as a test piece.
  • a thermal conductivity measuring device product name: Unithermo 2021, manufactured by Antar
  • the test piece was subjected to a thermal conductivity measurement at a temperature of 25 ° C. in accordance with the ASTM E1530 method (disc heat flow meter method). Was done.
  • the case where the thermal conductivity of the laminated glass was 0.5 W / (m ⁇ K) or less was evaluated as good, and the case where the thermal conductivity exceeded 0.5 W (m ⁇ K) was evaluated as poor.
  • Rigidity of laminated glass At least one or more laminates (Z) and, if necessary, between two soda lime glasses (length 100 mm, width 20 mm, thickness 0.5 mm or more and 1.5 mm or less) Other resin layers, adhesive layers, etc. were arranged and bonded and integrated to produce a laminated glass, which was used as a test piece.
  • the test piece was used in accordance with JIS R1602 method (four-point bending test method) and a rotary four-point bending test jig.
  • the distance between the fulcrums the upper part was 27 mm, the lower part was 81 mm, the support rod diameter was 6 mm, and the bending test was performed under the conditions of a temperature of 25 ° C., and the bending elastic modulus was measured.
  • the rigidity of the laminated glass the case where the bending elastic modulus of the laminated glass was 11 GPa (11 ⁇ 10 9 Pa) or more was evaluated as good, and the case where it was less than 11 GPa (11 ⁇ 10 9 Pa) was evaluated as poor.
  • Sound insulation property At least one or more laminates (Z) and, if necessary, other two glass sheets (length 300 mm, width 25 mm, thickness 0.5 mm or more and 1.5 mm or less) between two sheets of blue sheet glass.
  • a resin layer, an adhesive layer, and the like were arranged and bonded and integrated to produce a laminated glass, which was used as a test piece.
  • a loss coefficient corresponding to the frequency was measured by a central vibration method using a vibration attenuation test apparatus (manufactured by Rion) in accordance with JIS-K7391. The sound transmission loss corresponding to the frequency was obtained from the ratio between the loss coefficient obtained here and the resonance frequency of the laminated glass test piece.
  • the sound insulation was evaluated as good when there was no region where the value of the sound transmission loss was less than 35 dB in a frequency range of 2000 Hz or more and 4000 Hz or less, and the case where there was a region below 35 dB was evaluated as poor.
  • a block copolymer hydride (D1) was prepared by the following procedure. Into a reactor equipped with a stirrer and fully purged with nitrogen, 300 parts of dehydrated cyclohexane, 5 parts of dehydrated styrene, and 0.53 part of ethylene glycol dibutyl ether were charged. While stirring the whole volume at 60 ° C., 0.47 parts of n-butyllithium (15% cyclohexane solution) was added to initiate polymerization.
  • the block copolymer (C1) contained in the polymer solution is a triblock copolymer of the polymer block (A) -polymer block (B) -polymer block (A) type, and has a weight average molecular weight (Mw).
  • Mw weight average molecular weight
  • the ratio of structural units derived from 3,4-addition polymerization was 58%.
  • the above “wA: wB” is defined as wA where 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 chain conjugated diene is The ratio (wA: wB) of wA and wB when the mass fraction of the structural unit [b] derived from the compound (isoprene in Production Example 1) occupies the block copolymer (C1) with respect to wB is shown. The same applies to Production Examples 2 and 3.
  • 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 in 1.0 part of toluene were used as a hydrogenation catalyst.
  • a solution obtained by mixing 0.122 parts of aluminum chloride was added and mixed.
  • the inside of the reactor was replaced with hydrogen gas, and hydrogen was supplied while stirring the solution, and a hydrogenation reaction was performed at a temperature of 90 ° C. and a pressure of 1.0 MPa for 5 hours.
  • the weight average molecular weight (Mw) of the block copolymer hydride (D1) contained in the reaction solution obtained by the hydrogenation reaction was 88,700, and the molecular weight distribution (Mw / Mn) was 1.04.
  • a phenolic antioxidant, pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (product name "Songnox1010", manufactured by SONGWON) is added to the filtered solution. 1.0 part of a xylene solution in which 1 part was dissolved was added and dissolved.
  • the solution is filtered through a metal fiber filter (pore size: 0.4 ⁇ m, manufactured by Nichidai Co., Ltd.) to remove minute solids. ), Cyclohexane, xylene and other volatile components were removed from the solution at a temperature of 260 ° C and a pressure of 0.001 MPa or less.
  • the molten resin was extruded from a die directly connected to a concentration dryer, and after cooling with water, 91 parts of pellets of a block copolymer hydride (D1) were produced with an underwater cutter. About 100 ppm of fine powder of ethylene bisstearic acid amide was added to the pellets as an antiblocking agent.
  • the obtained pelletized block copolymer hydride (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 the double bond derived from the chain conjugated diene (main chain and side chain) was 99%, and the hydrogenation rate of the double bond derived from the aromatic ring was less than 3%.
  • Table 1 shows the physical property values of the produced block copolymer (C1) and hydrogenated block copolymer (D1).
  • Block copolymer hydride (D2) was prepared by the following procedure. The same reactor as in Production Example 1 was charged with 300 parts of dehydrated cyclohexane, 5 parts of dehydrated styrene, and 0.53 part of ethylene glycol dibutyl ether. 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 whole volume at 60 ° C., 4 parts of dehydrated styrene was continuously added to the reactor over a period of 15 minutes to proceed with the polymerization reaction. Was stirred.
  • the polymerization conversion rate at this time was 99.5%.
  • 82 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.
  • the reaction solution was analyzed by GC, and as a result, the polymerization conversion was 99.5%.
  • 9 parts of dehydrated styrene were continuously added to the reaction solution over a period of 60 minutes, and the mixture was stirred for 30 minutes after completion of the addition.
  • the reaction solution was analyzed by GC, and as a result, the polymerization conversion was almost 100%.
  • 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).
  • Mw weight average molecular weight
  • Is 78,600 the molecular weight distribution (Mw / Mn) is 1.03
  • wA: wB 18: 82
  • 1,2-addition polymerization of all isoprene-derived structural units in the block copolymer (C2) is performed.
  • the proportion of structural units derived from 3,4-addition polymerization was 58%.
  • the above polymer solution was transferred to the same pressure-resistant reactor as in Production Example 1, and as a hydrogenation catalyst, a diatomaceous earth-supported nickel catalyst (product name “Product name“ E22U ”, nickel supported amount 60%, Nikki And 7.0 parts of dehydrated cyclohexane were added and mixed.
  • the inside of the reactor was replaced with hydrogen gas, hydrogen was supplied while stirring the solution, and a hydrogenation reaction was performed at a temperature of 150 ° C. and a pressure of 3.0 MPa for 1 hour, and subsequently at a temperature of 190 ° C. and a pressure of 4.5 MPa. And the hydrogenation reaction was carried out for 6 hours.
  • the weight average molecular weight (Mw) of the block copolymer hydride (D2) contained in the reaction solution obtained by the hydrogenation reaction was 83,100, and the molecular weight distribution (Mw / Mn) was 1.04.
  • the reaction solution was filtered to remove the hydrogenation catalyst, and the same phenolic antioxidant as in Production Example 1, pentaerythrityl tetrakis [3- (3,5-di-t-butyl). -4-Hydroxyphenyl) propionate] was dissolved by adding 2.0 parts of a xylene solution in which 0.1 parts of xylene was dissolved. Next, the above solution was treated in the same manner as in Production Example 1 to produce 93 parts of pellets of a hydrogenated block copolymer (D2).
  • D2 hydrogenated block copolymer
  • the produced pelletized 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). And the hydrogenation rate of the double bond derived from the aromatic ring were almost 100%.
  • Table 1 shows the physical property values of the produced block copolymer (C2) and hydrogenated block copolymer (D2).
  • Block copolymer hydride (D3) was prepared by the following procedure.
  • the amount of ethylene glycol dibutyl ether was 0.55 parts
  • the amount of n-butyllithium (15% cyclohexane solution) was 0.55 parts
  • the monomers to be polymerized 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 a block copolymer (C3).
  • Mw weight average molecular weight
  • Mw / Mn molecular weight distribution
  • all isoprene in the block copolymer (C3) The proportion of structural units derived from 1,2-addition polymerization and 3,4-addition polymerization among the structural units derived from the polymer was 50%.
  • the obtained block copolymer hydride (D3) has a weight average molecular weight (Mw) of 76,900, a molecular weight distribution (Mw / Mn) of 1.07, and originates from a chain conjugated diene (main chain and side chain). And the hydrogenation rate of the double bond derived from the aromatic ring were almost 100%.
  • Table 1 shows the physical property values of the produced block copolymer (C3) and hydrogenated block copolymer (D3).
  • a modified block copolymer hydride (J1) was prepared by the following procedure. The same reactor as in Production Example 1 was charged with 400 parts of dehydrated cyclohexane, 10 parts of dehydrated styrene, and 0.475 part of dibutyl ether. While stirring the whole volume at 60 ° C., 0.90 parts of n-butyllithium (15% cyclohexane solution) was added to initiate polymerization. Subsequently, while stirring the whole volume at 60 ° C., 15 parts of dehydrated styrene was continuously added into the reactor over a period of 40 minutes to proceed with the polymerization reaction. Was stirred.
  • the polymerization conversion rate at this time was 99.5%.
  • 50 parts of dehydrated isoprene was continuously added to the reaction solution over a period of 130 minutes, and after the addition was completed, stirring was continued for 30 minutes. At this time, the reaction solution was analyzed by GC, and as a result, the polymerization conversion was 99.5%.
  • 25 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 time, the reaction solution was analyzed by gas chromatography (GC), and as a result, the polymerization conversion was almost 100%.
  • wE: wF is defined as wE where 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 chain conjugated diene is The ratio (wE: wF) of wE to wF when the mass fraction of the structural unit [f] derived from the compound (Isoprene in Production Example 1) occupies the block copolymer (G1) is represented by wF.
  • wE 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
  • the chain conjugated diene is The ratio (wE: wF) of wE to wF when the mass fraction of the structural unit [f] derived from the compound (Isoprene in Production Example 1) occupies the block copolymer (G1) is represented by wF.
  • the weight average molecular weight (Mw) of the block copolymer hydride (H1) contained in the reaction solution obtained by the hydrogenation reaction was 47,900, and the molecular weight distribution (Mw / Mn) was 1.06.
  • the obtained pelletized block copolymer hydride (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 almost 100%.
  • the FT-IR spectrum of the modified block copolymer hydride (J1) shows a new absorption band derived from the Si—OCH 3 group at 1090 cm ⁇ 1 and the Si—CH 2 group at 825 cm ⁇ 1 and 739 cm ⁇ 1 .
  • Si-OCH 3 groups of vinyltrimethoxysilane and absorption bands (1075 cm ⁇ 1 , 808 cm ⁇ 1 and 766 cm ⁇ 1 ) derived from the Si—CH groups were observed at different positions. Further, when the 1 H-NMR spectrum (in deuterated chloroform) of the hydrogenated modified block copolymer (J1) was measured, a peak based on a proton of a methoxy group was observed at 3.6 ppm. From the peak area ratio, it was confirmed that 1.8 parts of vinyltrimethoxysilane was bonded to 100 parts of the hydride (H1) of the block copolymer.
  • Table 1 shows the physical property values of the produced block copolymer (G1), block copolymer hydride (H1), and modified block copolymer hydride (J1).
  • Block copolymer hydride (H2) was prepared by the following procedure. The same reactor as in Production Example 1 was charged with 400 parts of dehydrated cyclohexane, 10 parts of dehydrated styrene, and 0.475 part of dibutyl ether. While stirring the whole volume at 60 ° C., 0.80 parts of n-butyllithium (15% cyclohexane solution) was added to initiate polymerization. Subsequently, while stirring the whole volume at 60 ° C., 20 parts of dehydrated styrene was continuously added into the reactor over a period of 40 minutes to proceed with the polymerization reaction. Was stirred.
  • the polymerization conversion rate at this time was 99.5%.
  • 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.
  • the reaction solution was analyzed by GC, and as a result, the polymerization conversion was 99.5%.
  • 30 parts of dehydrated styrene were continuously added to the reaction solution over 70 minutes, and after the addition was completed, the mixture was stirred for 60 minutes.
  • the reaction solution was analyzed by gas chromatography (GC), and as a result, the polymerization conversion was almost 100%.
  • the weight average molecular weight (Mw) of the block copolymer hydride (H2) contained in the reaction solution obtained by the hydrogenation reaction was 55,200, and the molecular weight distribution (Mw / Mn) was 1.06.
  • the obtained pelletized block copolymer hydride (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 almost 100%.
  • Table 1 shows the physical property values of the produced block copolymer (G2) and hydrogenated block copolymer (H2).
  • 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, and a block copolymer ( A polymer solution containing G3) was obtained.
  • the proportion of structural units derived from 1,4-addition polymerization among the structural units derived from the polymer was 91%.
  • 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.
  • the reaction solution was treated in the same manner as in Production Example 1 to remove the hydrogenation catalyst.
  • -Di-t-butyl-4-hydroxyphenyl) propionate was added and dissolved in 2.0 parts of a xylene solution in which 0.1 part of xylene was dissolved.
  • the above solution was treated in the same manner as in Production Example 1 to produce 96 parts of pellets of a block copolymer hydride (H3).
  • the prepared pelletized block copolymer hydride (H3) had a weight average molecular weight (Mw) of 54,400 and a molecular weight distribution (Mw / Mn) of 1.08.
  • Mw weight average molecular weight
  • Mw / Mn molecular weight distribution
  • the hydrogenation rate of the double bond derived from the chain conjugated diene (main chain and side chain) was 99%, and the hydrogenation rate of the double bond derived from the aromatic ring was less than 3%.
  • ⁇ Multilayer sheet (W1)> Two types 3 consisting of two single-screw extruders equipped with a screw having a diameter of 20 mm, a feed block, a T-die (width 400 mm), and a sheet take-off machine provided with a cast roll (width 400 mm) having a matte embossed pattern on the surface.
  • the resin composition (X1) is an inner layer (resin layer (X))
  • the resin composition (Y1) is an outer layer ( A multilayer sheet (W1) to be a resin layer (Y)) was manufactured.
  • the extrusion conditions were as follows: extruder temperature of resin composition (X1) 200 ° C., extruder temperature of resin composition (Y1) 210 ° C., cast roll temperature 50 ° C. End of sheet was cut off, width 320 mm 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). It has a structure, 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> The resin composition (Y1) was not supplied to the extruder, but only the resin composition (X1) was supplied to one extruder using the above-mentioned two-type and three-layer co-extrusion film forming machine.
  • a single-layer sheet (0.50 mm in width and 320 mm in width) of the resin composition (X1) composed of the resin composition (X1) was prepared under the conditions of 0 ° C. and a cast roll temperature of 50 ° C. or lower.
  • the sheet of the resin composition (X1) was layered on a releasable PET film (manufactured by Toray Industries, Inc., product name "Lumirror (registered trademark) S10", thickness: 50 ⁇ m), thickness: 0.050 mm). .
  • ⁇ Single-layer resin composition (Y1) sheet> The resin composition (X1) was not supplied to the extruder, but the resin composition (Y1) was supplied to one extruder using the above-mentioned two-type three-layer coextrusion film forming machine, and the extruder temperature was 210 ° C.
  • a single-layer sheet (0.10 mm in width and 320 mm in width) of the resin composition (Y1) composed of the resin composition (Y1) was prepared under the conditions of a cast roll temperature of 50 ° C.
  • LG1> Between two circular blue glass sheets (diameter 50 mm, thickness 1.1 mm), one multilayer sheet (W1) (0.80 mm thickness) and a sheet of the resin composition (Y1) (0.10 mm thickness) 1) One sheet was stacked and sandwiched, and arranged in the order of glass plate / multilayer sheet (W1) / sheet of resin composition (Y1) / glass plate.
  • This laminate is put in a 75 ⁇ m-thick resin bag having a layer structure of nylon / adhesive layer / polypropylene, and the inside of the bag is evacuated using a sealed packer (BH-951, manufactured by Panasonic Corporation). The laminate was hermetically packaged by heat-sealing the opening.
  • a laminated glass (LG1-1) having the above configuration was produced.
  • the thickness of the laminated glass (LG1-1) was 3.1 mm.
  • the composition of the thickness of the laminated glass (LG1-1) is as follows: 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 bubbles observed.
  • the glass sheet / multilayer sheet (W1) / sheet of resin composition (Y1) / glass sheet A laminated glass (LG1-2) having a layer configuration was produced.
  • the composition of the thickness of the laminated glass (LG1-2) is the same as described 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 bubbles observed.
  • the glass plate / multilayer sheet (W1) / sheet of resin composition (Y1) / glass plate A laminated glass (LG1-3) having a layer configuration was produced.
  • the composition of the thickness 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 bubbles observed.
  • ⁇ Laminate (Z1)> One multilayer sheet (W1) and one sheet of the resin composition (Y1) between two PET films (product name “Lumirror (registered trademark) R75” manufactured by Toray Industries, Inc., thickness 75 ⁇ m) as release films. The sheets were stacked and sandwiched, and the PET film / multilayer sheet (W1) / sheet of the resin composition (Y1) / PET film were stacked in this order. 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 obtain a PET film / multilayer sheet (W1) / resin composition (Y1). A laminate having a sheet / PET film layer configuration was prepared.
  • the PET film was peeled off from the laminate to produce a laminate (Z1).
  • the thickness configuration 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).
  • the appearance of the obtained laminate (Z1) was good, with no defects such as air bubbles observed.
  • ⁇ Temperature at which tan ⁇ of the resin layer (X1) shows the maximum value> Three sheets (thickness 0.50 mm) of the resin composition (X1) produced above were stacked and press-molded to produce a 1.5 mm thick sheet. The dynamic viscoelastic properties were measured using a test piece having a length of 70 mm and a width of 10 mm produced from this sheet. As a result, the temperature at which tan ⁇ had 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. The 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 a temperature range of ⁇ 20 ° C. or more and 40 ° C. or less. 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 evaluation of the heat insulating property was good.
  • ⁇ rigidity The flexural modulus of the laminated glass (LG1-2) was 12 GPa (12 ⁇ 10 9 Pa) at 25 ° C., and the evaluation of the rigidity of the laminated glass was good.
  • ⁇ Sound insulation >> The value of the sound transmission loss of the laminated glass (LG1-3) was not less than 35 dB in the frequency range of 2,000 Hz to 4,000 Hz, and the sound insulation of the laminated glass was good. Table 2 shows the results.
  • Example 2 ⁇ Resin composition (X2)>
  • 2- (5-chloro-2H-benzotriazol-2-yl) as an ultraviolet absorber was added to 100 parts of pellets of the hydride (D2) of the block copolymer produced in Production Example 2.
  • 0.2 parts of -6-tert-butyl-p-cresol was added to produce 95 parts of a pellet of the resin composition (X2).
  • ⁇ Multilayer sheet (W2)> In the same manner as in Example 1 except that the resin composition (X2) is used instead of the resin composition (X1), the resin composition (X2) contains the inner layer (the resin layer (X2)) and the resin composition (Y1). ) Produced 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 as follows: resin layer (Y1): 0.35 mm / resin layer (X2): 0.10 mm / resin layer ( Y1): 0.35 mm
  • ⁇ Single-layer resin composition (X2) sheet> In the same manner as in Example 1 except that the resin composition (X2) is used instead of the resin composition (X1), a sheet of the single-layer resin composition (X2) composed of the resin composition (X2) ( 0.50 mm in thickness and 320 mm in width).
  • ⁇ Single-layer resin composition (Y2) sheet> In the same manner as in Example 1 except that the resin composition (Y2) is used instead of the resin composition (Y1), a sheet of the single-layer resin composition (Y2) composed of the resin composition (Y2) ( 0.80 mm in thickness and 320 mm in width).
  • Laminated glass (LG2)> instead of one multi-layer sheet (W1) and one sheet of the resin composition (Y1), one multi-layer sheet (W2) (0.80 mm thick) and one sheet of the resin composition (Y2) (thickness of 0.1 mm) are used. 80 mm) and one sheet of the resin composition (Y1) (thickness 0.10 mm) prepared in Example 1 and used as a glass plate / multilayer sheet (W2) / sheet of the resin composition (Y2).
  • Laminated glass (LG2-1, LG2-2, LG2-3) was produced in the same manner as in Example 1, except that the resin composition (Y1) sheet and the glass plate were laminated in this order.
  • the thickness of the laminated glass (LG2-1, LG2-2, LG2-3) was 3.9 mm.
  • the composition of the thickness of the laminated glass (LG2-1, LG2-2, LG2-3) is 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).
  • the appearance of the obtained laminated glass (LG2-1, LG2-2, LG2-3) was good, with no defects such as bubbles observed.
  • ⁇ Laminate (Z2)> Instead of the multilayer sheet (W1) and the sheet of the resin composition (Y1), a multilayer sheet (W2), a sheet of the resin composition (Y2), and a sheet of the resin composition (Y1) are used.
  • a laminate (Z2) was produced in the same manner as in Example 1 except that the sheet (W2) / the sheet of the resin composition (Y2) / the sheet of the resin composition (Y1) / the PET film were stacked in this order.
  • the thickness configuration 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).
  • the appearance of the obtained laminate (Z2) was good without defects such as bubbles being observed.
  • ⁇ Storage elastic 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).
  • the storage elastic modulus (G ′) is 0.017 GPa (1.7 ⁇ 10 7 Pa) or more and 0.31 GPa (3.1 ⁇ 10 8 Pa) or less in a temperature range of ⁇ 20 ° C. or more and 40 ° C. or less. 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 evaluation of the heat insulating property was good.
  • ⁇ rigidity The flexural modulus of the laminated glass (LG2-2) was 11 GPa (11 ⁇ 10 9 Pa) at 25 ° C., and the evaluation of the rigidity of the laminated glass was good.
  • ⁇ Sound insulation >> The value of the sound transmission loss of the laminated glass (LG2-3) was not less than 35 dB in the frequency range of 2,000 Hz to 4,000 Hz, and the sound insulation of the laminated glass was good. Table 2 shows the results.
  • ⁇ Single-layer resin composition (Y3) sheet> In the same manner as in Example 1 except that the resin composition (Y3) is used instead of the resin composition (Y1), a single-layer sheet (0.80 mm in thickness and 320 mm in width) of the resin composition (Y3) was prepared. Produced.
  • the thickness of the laminated glass (LG3-1, LG3-2, LG3-3) was 4.7 mm.
  • the composition of the thickness of the laminated glass (LG3-1, LG3-2, LG3-3) is 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).
  • the appearance of the obtained laminated glass (LG3-1, LG3-2, LG3-3) was good, with no defects such as bubbles observed.
  • ⁇ Laminate (Z3)> Instead of the multilayer sheet (W1) and the sheet of the resin composition (Y1), a multilayer sheet (W2), a sheet of the resin composition (Y3), and a sheet of the resin composition (Y1) are used. 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 were arranged in this order. A laminate (Z3) was produced.
  • the thickness configuration of the laminate (Z3) is as follows: 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).
  • the appearance of the obtained laminate (Z3) was good, with no defects such as 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).
  • the storage elastic modulus (G ′) is not less than 0.024 GPa (2.4 ⁇ 10 7 Pa) and not more than 0.45 GPa (4.5 ⁇ 10 8 Pa) in a temperature range from ⁇ 20 ° C. to 40 ° C. 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 evaluation of heat insulation was good.
  • ⁇ rigidity The flexural modulus of the laminated glass (LG3-2) was 12 GPa (12 ⁇ 10 9 Pa) at 25 ° C., and the evaluation of the rigidity of the laminated glass was good.
  • ⁇ Sound insulation >> The value of the sound transmission loss of the laminated glass (LG3-3) was not less than 35 dB in the frequency range of 2,000 Hz to 4,000 Hz, and the sound insulation of the laminated glass was good. Table 2 shows the results.
  • Example 4 ⁇ Resin composition (Y4)> 100 parts of pellets of the hydrogenated modified block copolymer (J3) produced in Production Example 6 were added with 2- (5-chloro-2H-benzotriazol-2-yl) -6-tert-butyl- as an ultraviolet absorber. 0.2 parts of p-cresol was added. This mixture was kneaded at a resin temperature of 220 ° C. using a twin-screw extruder, extruded into strands, and cut with a pelletizer to produce 95 parts of resin composition (Y4) pellets.
  • Example 1 In Example 1, except that the resin composition (Y4) was used instead of the resin composition (Y1), the resin composition (X1) was replaced with an inner layer (resin layer (X1)) in the same manner as in Example 1.
  • the obtained 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 multilayer sheet (W4) has a total thickness of 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.
  • LG4> ⁇ Laminated glass (LG4)> Instead of one multi-layer sheet (W1) and one sheet of the resin composition (Y1), one multi-layer sheet (W4) (0.80 mm in thickness) and a sheet of the resin composition (Y4) (thickness of 0.1 mm) were used. 10 mm), and laminated glass (LG4-1, LG4) in the same manner as in Example 1 except that one glass plate / multilayer sheet (W4) / sheet of resin composition (Y4) / glass plate is laminated in this order. -2, LG4-3). The thickness of the laminated glass (LG4-1, LG4-2, LG4-3) was 3.1 mm.
  • the composition of the thickness of the laminated glass (LG4-1, LG4-2, LG4-3) is 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).
  • the appearance of the obtained laminated glass (LG4-1, LG4-2, LG4-3) was good, with no defects such as bubbles observed.
  • ⁇ Laminate (Z4)> instead of the sheet of the multilayer sheet (W1) and the resin composition (Y1), a sheet of the multilayer sheet (W4) and the sheet of the resin composition (Y4) are used, and the PET film / the multilayer sheet (W4) / the resin composition (Y4)
  • the laminate (Z4) was manufactured in the same manner as in Example 1 except that the sheet / PET film was superposed in this order.
  • the configuration of 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).
  • the appearance of the obtained laminate (Z4) was good, with no defects such as 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).
  • 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 a temperature range of ⁇ 20 ° C. to 40 ° C. Was in the range.
  • ⁇ 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 evaluation of heat insulation was good.
  • ⁇ rigidity The flexural modulus of the laminated glass (LG4-2) was 12 GPa (12 ⁇ 10 9 ) Pa at 25 ° C., and the evaluation of the rigidity of the laminated glass was good.
  • ⁇ Sound insulation >> The value of the sound transmission loss of the laminated glass (LG4-3) was not less than 35 dB in the frequency range of 2,000 Hz to 4,000 Hz, and the sound insulation of the laminated glass was good. Table 2 shows the results.
  • the thickness of the laminated glass (LG5-1, LG5-2, LG5-3) is as follows: 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). Further, the appearance of the obtained laminated glass (LG5-1, LG5-2, LG5-3) was good without any defects such as bubbles being observed.
  • the laminate (Z5) used for bonding the two glasses 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).
  • the storage elastic modulus (G ′) was in the range of 0.85 ⁇ 10 7 Pa to 1.4 ⁇ 10 8 Pa in the temperature range of ⁇ 20 ° C. to 40 ° C.
  • ⁇ 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 evaluation of heat insulation was good.
  • ⁇ rigidity The flexural modulus of the laminated glass (LG5-2) was 10 GPa (10 ⁇ 10 9 Pa) at 25 ° C., and the rigidity of the laminated glass was poorly evaluated.
  • ⁇ Sound insulation >> The value of the sound transmission loss of the laminated glass (LG5-3) was not less than 35 dB in the frequency range of 2,000 Hz to 4,000 Hz, and the sound insulation of the laminated glass was good. Table 2 shows the results.
  • the thickness of the laminated glass (LG6-1, LG6-2, LG6-3) was 3.86 mm.
  • the composition of the thickness of the laminated glass (LG6-1, LG6-2, LG6-3) is 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).
  • the appearance of the obtained laminated glass (LG6-1, LG6-2, LG6-3) was good, with no defects such as bubbles observed.
  • ⁇ Laminate (Z6)> a multilayer sheet (W2), a PVB sheet (Y5) and a resin composition (Y1) sheet are used, and the PET film / multilayer sheet (W2) is used.
  • the thickness configuration of the laminate (Z6) is as follows: resin layer (Y1) (0.35 mm) / resin layer (X2) (0.10 mm) / resin layer (Y1) (0.35 mm) / sheet made of PVB (Y5) ) (0.76 mm) / resin layer (Y1) (0.10 mm). Further, the appearance of the obtained laminate (Z6) was good, with no defects such as bubbles observed.
  • ⁇ Storage elastic 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 not less than 0.0028 GPa (0.28 ⁇ 10 7 Pa) and not more than 0.3 GPa (3.0 ⁇ 10 8 Pa) in a temperature range of ⁇ 20 ° C. to 40 ° C. Range.
  • Example 3 A sheet (0.80 mm thick) of the resin composition (Y1) was used in place of the multilayer sheet (W1), and one sheet (0.80 mm thick) of the resin composition (Y1) was used. Using two sheets (0.80 mm thick) of the resin composition (Y3) prepared in the above and one sheet (0.10 mm thick) of the resin composition (Y1) prepared in Example 1.
  • the thickness of the laminated glass (LG7-1, LG7-2, LG7-3) is as follows: 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) had no resin layer (X).
  • the appearance of the obtained laminated glass (LG7-1, LG7-2, LG7-3) was good, with no defects such as bubbles observed.
  • ⁇ Laminate (Z7)> A sheet (thickness 0.80 mm) of the resin composition (Y1) is used instead of the multilayer sheet (W2), and a PET film / sheet (thickness 0.80 mm) of the resin composition (Y1) / 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
  • a laminate (Z7) was produced in the same manner as in Example 3 except that the laminated body (Z7) was disposed.
  • the thickness configuration 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 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).
  • 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. 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 evaluation of the heat insulating property was good.
  • ⁇ rigidity The flexural modulus of the laminated glass (LG7-2) at 25 ° C. was 20 GPa (20 ⁇ 10 9 Pa), and the evaluation of the rigidity of the laminated glass was good.
  • ⁇ Sound insulation >> The value of the sound transmission loss of the laminated glass (LG7-3) was less than 35 dB in the frequency range of 2000 Hz to 4000 Hz, and the sound insulation of the laminated glass was poor. Table 2 shows the results.
  • Example 1 was repeated except that the resin composition (X3) was used in place of the resin composition (X1) and the extrusion ratio of the same two-type three-layer co-extrusion film forming machine used in Example 1 was changed.
  • a multilayer sheet (W8) in which the resin composition (X3) becomes the inner layer (resin layer (X3)) and the resin composition (Y1) becomes the outer layer (resin layer (Y1)).
  • 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 multilayer sheet (W8) has a total thickness of 0.76 mm, and the thickness of each layer is as follows: resin layer (Y1): 0.08 mm / resin layer (X3): 0.60 mm / resin layer ( Y1): 0.08 mm.
  • ⁇ Single-layer resin composition (X3) sheet> In the same manner as in Example 1 except that the resin composition (X3) is used instead of the resin composition (X1), a sheet of the single-layer resin composition (X3) composed of the resin composition (X3) ( 0.60 mm in thickness and 320 mm in width).
  • ⁇ Laminated glass (LG8)> instead of one multi-layer sheet (W1) and one sheet of the resin composition (Y1), only one multi-layer sheet (W8) (0.76 mm in thickness) was used to form a 1.1 mm thick glass plate. Instead, a laminated glass (LG8-1, LG8-2, LG8-2, LG8-3) was prepared. The thickness of the laminated glass (LG8-1, LG8-2, LG8-3) was 3.16 mm. The thickness of the laminated glass (LG8-1, LG8-2, LG8-3) is 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 glass (LG8-1, LG8-2, LG8-3) was good, with no defects such as bubbles observed.
  • ⁇ Storage elastic modulus of laminate (Z8)> the laminate (Z8) used for bonding the two glasses was 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).
  • 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 a temperature range of ⁇ 20 ° C. or more and 40 ° C. or less. 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 evaluation of heat insulation was good.
  • ⁇ rigidity The flexural modulus of the laminated glass (LG8-2) was 10 GPa (10 ⁇ 10 9 Pa) at 25 ° C., and the rigidity of the laminated glass was poorly evaluated.
  • ⁇ Sound insulation >> The value of the sound transmission loss of the laminated glass (LG8-3) was not less than 35 dB in the frequency range of 2,000 Hz to 4,000 Hz, and the sound insulation of the laminated glass was good. Table 2 shows the results.
  • the laminate (Z) does not have the resin layer (X) having the maximum value in the range where the tan ⁇ in the dynamic viscoelastic properties is ⁇ 20 ° C. or more and 20 ° C. or less, the laminate (Z) is used as an intermediate film. The sound insulation of the laminated glass cannot be maintained (Comparative Example 3).
  • the laminate (Z) of the present invention By using the laminate (Z) of the present invention as an interlayer film for laminated glass, the heat insulating property of the laminated glass is improved, the cooling / heating effect is enhanced, and the sound insulation is provided.
  • the laminated glass of the present invention is used as a window material for automobiles, railway vehicles, ships, buildings, and the like, it is useful because it can enhance the cooling and heating effects and also enhance the sound insulation.
  • the laminated glass of the present invention is useful as a window material for automobiles, a window material for buildings, a roof material, a window material for ships and aircraft, etc. from the viewpoint of energy saving.

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  • Laminated Bodies (AREA)
  • Joining Of Glass To Other Materials (AREA)

Abstract

Le but de la présente invention est de fournir : un stratifié apte à former un verre feuilleté dans lequel un équilibre entre la rigidité, une isolation phonique et une isolation thermique est obtenu à un niveau élevé ; et un verre feuilleté pourvu d'un film intermédiaire comprenant ledit stratifié. Le stratifié (Z) comporte au moins une couche de résine (X) composée d'une composition de résine (x), et deux couches de résine (Y) ou plus composées d'une composition de résine (Y), et est caractérisé en ce que : (a) la couche de résine (X) est stratifiée entre au moins deux des couches de résine (Y) ; (b) la couche de résine (X) affiche une propriété viscoélastique dynamique dans laquelle tan δ comporte une valeur maximale locale dans une plage de température de -20 °C à 20 °C ; et (c) le stratifié (Z) affiche une propriété viscoélastique dynamique comportant un module d'élasticité de stockage de 1,0×107-5,0×108 Pa dans une plage de température de -20 °C à 40 °C.
PCT/JP2019/026121 2018-07-05 2019-07-01 Stratifié et verre feuilleté Ceased WO2020009064A1 (fr)

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WO2019044267A1 (fr) * 2017-08-28 2019-03-07 日本ゼオン株式会社 Verre feuilleté

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EP3168202B1 (fr) * 2014-07-09 2024-06-05 Zeon Corporation Verre feuilleté
EP3239181A4 (fr) * 2014-12-25 2018-08-22 Zeon Corporation Hydrure de copolymère séquencé et verre feuilleté
WO2016163409A1 (fr) * 2015-04-09 2016-10-13 日本ゼオン株式会社 Composition de résine et son utilisation
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