WO2016171068A1 - 合わせガラス - Google Patents
合わせガラス Download PDFInfo
- Publication number
- WO2016171068A1 WO2016171068A1 PCT/JP2016/062020 JP2016062020W WO2016171068A1 WO 2016171068 A1 WO2016171068 A1 WO 2016171068A1 JP 2016062020 W JP2016062020 W JP 2016062020W WO 2016171068 A1 WO2016171068 A1 WO 2016171068A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- block copolymer
- laminated glass
- glass
- copolymer hydride
- resin
- Prior art date
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Classifications
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- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
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- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
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- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
- C08F297/046—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes polymerising vinyl aromatic monomers and isoprene, optionally with other conjugated dienes
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
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Definitions
- the present invention relates to a lightweight laminated glass, and more particularly, to a laminated glass having lightness while maintaining characteristics such as rigidity, impact resistance, and heat resistance.
- the weight reduction of automobiles is a useful technology for environmental protection by reducing fuel consumption.
- weight reduction is achieved by replacing a part of metal parts with plastic or using a window material using a transparent plastic such as polycarbonate instead of glass.
- a transparent plastic such as polycarbonate instead of glass.
- the thickness of the transparent plastic plate must be increased, so that the weight has not been reduced as expected.
- scratch resistance it is necessary to provide a hard coat layer, and there are problems such as high costs, and the spread has not progressed.
- Patent Document 1 As a countermeasure for this, in Patent Document 1, by using a resin interlayer made of a resin having a Young's modulus greater than a specific value, the thickness of the glass interlayer is reduced and the thickness of the resin interlayer is increased. Thus, it is disclosed that a laminated glass that is lighter than the glass plate can be obtained while maintaining the bending rigidity equivalent to that of the glass plate.
- a laminated glass using a resin interlayer made of polyethylene ionomer can be 34% lighter than a glass, and a laminated glass using a resin interlayer made of polycarbonate can be reduced by 27%. It is shown.
- polyethylene ionomer, polycarbonate, polyurethane, polyethylene terephthalate, acrylic resin, and the like are listed as specific materials constituting the resin intermediate film that can be made lighter than a glass plate alone. Further, this document also shows that a laminated glass that is lighter than a single glass plate while maintaining a certain bending rigidity cannot be obtained with a resin interlayer using polyvinyl butyral resin.
- the window material for automobiles using the lightweight laminated glass using the interlayer film made of the resin exemplified above maintains a certain bending rigidity, for example, it is defined in JIS R3211 which is a standard for automobile safety glass. Such properties as impact resistance (temperature conditions of 40 ° C. and ⁇ 20 ° C.), heat resistance, light resistance, moisture resistance and the like were not satisfied.
- Patent Document 2 discloses a surface density of 8.8 kg / m 2 using a resin intermediate film using ethylene-vinyl acetate copolymer (EVA) and / or polyvinyl butyral (PVB) and a thin glass.
- EVA ethylene-vinyl acetate copolymer
- PVB polyvinyl butyral
- a laminated glass having a sound insulation property and a heat insulation property is disclosed.
- this document only describes a laminated glass in which the thickness of the glass is reduced and the surface density is reduced by about 30% compared to the laminated glass of the comparative example. For example, bending rigidity is reduced. There is no mention of that.
- JP 11-001349 A (US Pat. No. 6,265,054 B1) JP 2002-326847 A (US2002 / 0,150,744A1, US2004 / 0,157,048 A1)
- the present invention has been made in view of the above-described circumstances, and reduces the weight per unit area while maintaining rigidity, and is excellent in heat resistance, impact resistance, moisture resistance, and the like.
- An object of the present invention is to provide a laminated glass useful as a window material for buildings.
- the present inventors have intensively studied to solve the above problems.
- impact resistance at low temperatures eg, -20 ° C.
- a resin interlayer containing a specific modified block copolymer hydride and appropriately selecting the thickness of glass and resin interlayer.
- the lightweight laminated glass useful as a window material for motor vehicles was maintained, maintaining rigidity at high temperature (for example, 90 degreeC), and came to complete this invention.
- a laminated glass formed by interposing a resin interlayer between glass plates and bonding and integrating the glass plates,
- the bending flexibility at a temperature of 90 ° C. is 7.3 N / mm 2 or more, and the weight per unit area is 7.5 kg / m 2 or less.
- the resin intermediate film has at least two polymer blocks [A] having a structural unit derived from an aromatic vinyl compound as a main component and at least one heavy component having a structural unit derived from a chain conjugated diene compound as a main component.
- Block copolymer of block copolymer [C] comprising a combined block [B], wherein 90% or more of carbon-carbon unsaturated bonds of main and side chains and carbon-carbon unsaturated bonds of aromatic rings are hydrogenated
- a modified block copolymer hydride [E] obtained by introducing an alkoxysilyl group into the hydride [D];
- Rigidity is generally the degree of difficulty of dimensional change (deformation) with respect to bending or twisting force. When the deformation is small with respect to the force, the rigidity is high (large) and the deformation is When it is large, the rigidity is low (small). “Rigidity” is expressed, for example, by the amount of deflection when a certain amount of bending stress is applied to the laminated glass.
- the weight per unit area is 11.3 kg / m 2.
- the weight per unit area can be reduced to 7.5 kg / m 2 or less (about 2/3 or less) while maintaining rigidity equal to or higher than that of the general-purpose laminated glass illustrated. it can.
- the laminated glass of the present invention is defined by the following (i) to (v).
- the resin intermediate film has at least two polymer blocks [A] having a structural unit derived from an aromatic vinyl compound as a main component and a structural unit derived from a chain conjugated diene compound as a main component, More than 90% of the main chain and side chain carbon-carbon unsaturated bonds and aromatic ring carbon-carbon unsaturated bonds of the block copolymer [C] composed of one polymer block [B] were hydrogenated.
- Modified block copolymer hydride [E] in which an alkoxysilyl group is introduced into the block copolymer hydride [D] hereinafter sometimes referred to as “modified block copolymer hydride [E]”). It contains.
- the storage elastic modulus of the resin interlayer in the dynamic viscoelastic property is 5 ⁇ 10 8 Pa or less at a temperature of ⁇ 20 ° C. and 2 ⁇ 10 7 Pa or more at a temperature of 90 ° C.
- Modified block copolymer hydride [E] The resin interlayer used for the laminated glass of the present invention contains a modified block copolymer hydride [E].
- the modified block copolymer hydride [E] which is a constituent component of the resin interlayer used in the present invention, has at least two polymer blocks [A] mainly comprising a structural unit derived from an aromatic vinyl compound, and Main chain and side chain carbon-carbon unsaturated bonds and fragrances of block copolymer [C] comprising at least one polymer block [B] mainly composed of a structural unit derived from a chain conjugated diene compound
- the polymer block [A] is mainly composed of a structural unit derived from an aromatic vinyl compound, and the content of the structural unit derived from the aromatic vinyl compound in the polymer block [A] is usually 95% by weight. Above, preferably 97% by weight or more, more preferably 99% by weight or more.
- the structural unit derived from the aromatic vinyl compound is in the above range, the laminated glass of the present invention is excellent in heat resistance and rigidity at high temperature.
- aromatic vinyl compound examples include styrene; ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, Styrenes having an alkyl group as a substituent such as 5-t-butyl-2-methylstyrene; Styrenes having an alkoxy group as a substituent such as 4-methoxystyrene and 3-methoxy-5-isopropoxystyrene; Examples thereof include styrenes having a halogen atom as a substituent such as monochlorostyrene, dichlorostyrene, 4-monofluorostyrene; styrenes having an aryl group as a substituent such as 4-phenylstyrene.
- those which do not contain a polar group in terms of hygroscopicity such as styrene, styrenes having an alkyl group as a substituent, styrenes having an aryl group as a substituent, etc. are preferable, and are easily available industrially.
- styrene is particularly preferred.
- the polymer block [A] can contain a structural unit derived from a chain conjugated diene and / or a structural unit derived from another vinyl compound as a component other than the structural unit derived from the aromatic vinyl compound. Its content is usually 5% by weight or less, preferably 3% by weight or less, more preferably 1% by weight or less. When there are too few structural units derived from the aromatic vinyl compound in the polymer block [A], the heat resistance of the laminated glass may be lowered.
- chain conjugated diene and other vinyl compounds examples include those similar to the chain conjugated diene and other vinyl compounds that are structural units of the polymer block [B] described later.
- the polymer block [B] has a structural unit derived from a chain conjugated diene compound as a main component, and the content of the structural unit derived from the chain conjugated diene compound in the polymer block [B] is usually 80. % By weight or more, preferably 90% by weight or more, more preferably 95% by weight or more.
- the structural unit derived from the chain conjugated diene compound is in the above range, the laminated glass of the present invention is excellent in thermal shock resistance and low temperature adhesiveness.
- chain conjugated diene compound a chain conjugated diene compound not containing a polar group is preferable from the viewpoint of hygroscopicity.
- Specific examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and the like. Of these, 1,3-butadiene and isoprene are particularly preferred from the viewpoint of industrial availability.
- the polymer block [B] can contain a structural unit derived from an aromatic vinyl compound and / or a structural unit derived from another vinyl compound as a component other than the structural unit derived from a chain conjugated diene compound.
- the content is usually 20% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less.
- Examples of other vinyl compounds include chain vinyl compounds (excluding chain conjugated diene compounds), cyclic vinyl compounds, unsaturated cyclic acid anhydrides, and unsaturated imide compounds. These compounds may have a substituent such as a nitrile group, an alkoxycarbonyl group, a hydroxycarbonyl group, or a halogen atom.
- the weight fraction of the entire block copolymer [C] in the entire polymer block [A] is wA
- the entire block copolymer [C] in the entire polymer block [B] is 40:60 to 60:40, preferably 45:55 to 55:45, where wB is the weight fraction in
- a modified block copolymer hydride [E] having flexibility and appropriate heat resistance can be obtained.
- the number of polymer blocks [A] in the block copolymer [C] is usually 3 or less, preferably 2 and the number of polymer blocks [B] is usually 2 or less, preferably 1 It is.
- the block form of the block copolymer [C] may be a chain type block or a radial type block, but a chain type block is preferred because of its excellent mechanical strength.
- the most preferred form of the block copolymer [C] is the [A]-[B]-[A] type triblock copolymer in which the polymer block [A] is bonded to both ends of the polymer block [B]. It is.
- the plurality of polymer blocks [A] may be the same as or different from each other. Moreover, when there are a plurality of polymer blocks [B], the polymer blocks [B] may be the same or different from each other.
- the molecular weight of the block copolymer [C] is a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, and is usually 40,000 to 200. , Preferably 45,000 to 150,000, more preferably 50,000 to 100,000. 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 1.5 or less. When Mw and Mw / Mn are within the above ranges, the modified block copolymer hydride [E] has good heat resistance and mechanical strength, and the heat resistance and mechanical strength of the laminated glass according to the present invention are excellent. There is no decline.
- the manufacturing method of a block copolymer (C) is not specifically limited, What is necessary is just to perform according to a well-known method. For example, it can be produced according to the method described in WO2003 / 018656 pamphlet, WO2011 / 096389 pamphlet, and the like.
- the block copolymer hydride [D] is obtained by hydrogenating the carbon-carbon unsaturated bond of the main chain and the side chain and the carbon-carbon unsaturated bond of the aromatic ring of the block copolymer [C]. Is a molecule.
- the hydrogenation rate is usually 90% or more, preferably 97% or more, more preferably 99% or more.
- the hydrogenation rate of the carbon-carbon unsaturated bonds in the main chain and side chain of the block copolymer (C) is preferably 97% or more, and more preferably 99% or more. Further, the hydrogenation rate of the carbon-carbon unsaturated bond of the aromatic ring of the block copolymer (C) is preferably 97% or more, and more preferably 99% or more.
- the hydrogenation rate of the block copolymer hydride (D) can be determined by measuring 1 H-NMR of the block copolymer hydride (D).
- the molecular weight of the block copolymer hydride [D] is a polystyrene-reduced weight average molecular weight (Mw) measured by GPC using THF as a solvent, and is usually 40,000 to 200,000, preferably 45,000 to 150. , 50,000, more preferably 50,000 to 100,000.
- the molecular weight distribution (Mw / Mn) of the block copolymer hydride [D] is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.5 or less. When Mw and Mw / Mn are within the above ranges, the modified block copolymer hydride [E] has good heat resistance and mechanical strength, and the heat resistance and mechanical strength of the laminated glass according to the present invention are excellent. It is preferable because it does not decrease.
- the modified block copolymer hydride [E] is obtained by introducing an alkoxysilyl group into the block copolymer hydride [D].
- an alkoxysilyl group into the block copolymer hydride [D]
- strong adhesion to glass can be imparted.
- alkoxysilyl group examples include a tri (C1-6 alkoxy) silyl group such as a trimethoxysilyl group and a triethoxysilyl group; a methyldimethoxysilyl group, a methyldiethoxysilyl group, an ethyldimethoxysilyl group, and an ethyldiethoxysilyl group.
- the alkoxysilyl group is bonded to the block copolymer hydride [D] via a divalent organic group such as an alkylene group having 1 to 20 carbon atoms or an alkyleneoxycarbonylalkylene group having 2 to 20 carbon atoms. You may do it.
- the amount of the alkoxysilyl group introduced into the block copolymer hydride [D] is usually 0.1 to 10 parts by weight, preferably 0.2 to 100 parts by weight with respect to 100 parts by weight of the block copolymer hydride [D]. 5 parts by weight, more preferably 0.5 to 3 parts by weight.
- the resulting modified block copolymer hydride [E] undergoes cross-linking between the alkoxysilyl groups decomposed with a small amount of moisture during storage, gelling, or melt molding
- the fluidity at the time is lowered, the temperature at which the resin interlayer can be melt-extruded and molded becomes high, or the surface of the molded resin interlayer is roughened.
- molded may fall.
- the modified block copolymer hydride [E] can be produced according to a known method. For example, the method described in WO2012 / 043708, WO2013 / 176258, etc. is mentioned.
- the modified block copolymer hydride [E] is obtained by reacting the block copolymer hydride [D] with an ethylenically unsaturated silane compound in the presence of an organic peroxide. Obtainable.
- the ethylenically unsaturated silane compound to be used is not particularly limited as long as it is graft-polymerized with the block copolymer hydride [D] and introduces an alkoxysilyl group into the block copolymer hydride [D].
- ethylenically unsaturated silane compounds may be used alone or in combination of two or more.
- the amount of the ethylenically unsaturated silane compound used is usually 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, more preferably 0, per 100 parts by weight of the block copolymer hydride [D]. .5-3 parts by weight.
- organic peroxide to be used those having a one-minute half-life temperature of 170 to 190 ° C. are preferably used.
- examples of the organic peroxide include t-butyl cumyl peroxide, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di- -T-butyl peroxide, di (2-t-butylperoxyisopropyl) benzene and the like are preferably used. These peroxides may be used alone or in combination of two or more.
- the amount of the organic peroxide used is usually 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight, based on 100 parts by weight of the block copolymer hydride [D].
- the molecular weight of the modified block copolymer hydride [E] is not substantially different from the molecular weight of the block copolymer hydride [D] used as a raw material because the amount of alkoxysilyl groups introduced is small.
- the cross-linking reaction and cleavage reaction of the polymer occur simultaneously, and the molecular weight distribution of the modified block copolymer hydride [E] is large. Become.
- the molecular weight of the modified block copolymer hydride [E] is a polystyrene-equivalent weight average molecular weight (Mw) measured by GPC using THF as a solvent, and is usually 40,000 to 200,000, preferably 45,000 to 150,000, more preferably 50,000 to 100,000.
- Mw / Mn 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. When Mw and Mw / Mn are within the above ranges, the heat resistance and mechanical strength of the modified block copolymer hydride [E] are maintained.
- the resin intermediate film used in the present invention contains the above-described modified block copolymer hydride [E].
- the content of the modified block copolymer hydride [E] in the resin interlayer is usually 40% by weight or more, preferably 50% by weight or more, more preferably 60% by weight or more.
- the storage elastic modulus in the dynamic viscoelastic properties of the resin interlayer used in the present invention is 5 ⁇ 10 8 Pa or less at ⁇ 20 ° C., preferably 3 ⁇ 10 8 Pa or less, and 2 ⁇ 10 7 at 90 ° C. Pa or higher, preferably 3 ⁇ 10 7 Pa or higher.
- the storage elastic modulus of the resin interlayer is in the above range at ⁇ 20 ° C., the adhesion and impact resistance at low temperatures of the laminated glass are imparted, and when it is in the above range at 90 ° C., the heat resistance of the laminated glass is It is ensured and is advantageous for developing rigidity at high temperatures.
- the storage elastic modulus in the dynamic viscoelastic property of the resin interlayer is obtained by using a test piece cut out from the resin interlayer and based on JIS K7244-2 method (torsion pendulum method), angular frequency: 1 rad / s, It is a value obtained by measuring a viscoelastic spectrum under the conditions of a measurement temperature range: ⁇ 100 to + 130 ° C. and a temperature rising rate: 5 ° C./min.
- the resin intermediate film is composed of a mixture of the modified block copolymer hydride [E] and another resin, even if the resin component is composed of the modified block copolymer hydride [E] alone. May be.
- the resin interlayer does not have the above storage elastic modulus, particularly when the storage elastic modulus at 90 ° C. is lower than the above value, in order to increase the storage elastic modulus of the resin intermediate film, , a.
- the block copolymer hydride [D] and / or the block copolymer hydride [D] which is a precursor of the modified block copolymer hydride [E] is added to the modified block copolymer hydride [E].
- a multilayer resin intermediate film in which layers composed of [D ′] are alternately laminated can be used.
- the block copolymer hydride [D ′] has a storage elastic modulus at 90 ° C. higher than that of the block copolymer hydride [D] which is a precursor of the modified block copolymer hydride [E]. It is preferable that it is high.
- the block copolymer hydride [D ′] is the main component of the block copolymer [C]. It is a polymer obtained by hydrogenating the carbon-carbon unsaturated bond of the chain and side chain and the carbon-carbon unsaturated bond of the aromatic ring.
- the hydrogenation rate is usually 90% or more, preferably 97% or more, more preferably 99% or more.
- the block copolymer hydride [D ′] represents the weight fraction of the entire block copolymer [C ′] of the entire polymer block [A ′] in the block copolymer [C ′] as the precursor.
- the block copolymer [C ′] having a ratio of 50:50 to 70:30, preferably 55:45 to 65:35, carbon-carbon unsaturated bonds in the main and side chains and carbon-carbon defects in the aromatic ring. Obtained by hydrogenating 90% or more of the saturated bonds.
- the mixture has excellent compatibility with the modified block copolymer hydride [E], and the mixture with the modified block copolymer hydride [E] is transparent.
- the storage modulus of the resin interlayer can be increased to a preferred range by mixing or laminating with the modified block copolymer hydride [E].
- the molecular weight of the block copolymer hydride [D ′] is a polystyrene-equivalent weight average molecular weight (Mw) measured by GPC using THF as a solvent, and is usually 40,000 to 200,000, preferably 45,000 to 150,000, more preferably 50,000 to 100,000.
- the molecular weight distribution (Mw / Mn) of the block copolymer hydride [D ′] is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.5 or less.
- the resin interlayer used in the present invention has good heat resistance and mechanical strength. It is advantageous to maintain the rigidity of the glass in the high temperature region.
- modified block copolymer hydride [E] pellets and block copolymer hydride [D ′] pellets are melt-kneaded by a continuous melt kneader such as a twin-screw extruder and extruded into pellets.
- the modified block copolymer hydride [E] uniformly blended by the method or the like can be produced.
- the blending amount of the block copolymer hydride [D ′] is the same as that of the modified block copolymer hydride [E].
- the amount is usually 60 parts by weight or less, preferably 50 parts by weight or less, more preferably 40 parts by weight or less with respect to 100 parts by weight.
- the resin interlayer includes an ultraviolet absorber, an antioxidant, a light stabilizer, an infrared ray
- Various compounding agents such as a screening agent can be added.
- Compounding agents such as an ultraviolet absorber, an antioxidant, a light stabilizer, and an infrared shielding agent can be used alone or in combination of two or more.
- the compounding amount of these additives is usually 5 parts by weight or less, preferably 3 parts by weight with respect to 100 parts by weight of the total amount of the modified block copolymer hydride [E] and the block copolymer hydride [D ′]. Part or less, more preferably 2 parts by weight or less.
- Examples of the ultraviolet absorber include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, and triazine compounds.
- Examples of the antioxidant include phosphorus antioxidants, phenol antioxidants, sulfur antioxidants and the like.
- Examples of the light resistant stabilizer include hindered amine light stabilizers.
- Examples of the infrared shielding agent include fine metal oxide particles such as indium-doped tin oxide, antimony-doped tin oxide, zinc oxide, and aluminum-doped zinc oxide.
- the method for molding the resin interlayer is not particularly limited, and a known melt extrusion molding method, coextrusion molding method, extrusion laminating method, thermal laminating method, inflation molding method, calendar molding method, and the like can be applied.
- the resin temperature is usually in the range of 200 to 270 ° C., preferably 210 to 260 ° C., more preferably 220 to 250 ° C. If the resin temperature is too low, the fluidity is deteriorated, and the resulting resin interlayer is liable to cause defects such as skin and die lines, and the extrusion speed of the resin interlayer is not increased, which is industrially disadvantageous. There is a fear.
- the thickness of the resin interlayer is not particularly limited, but is usually in the range of 0.2 to 3.5 mm, preferably 0.5 to 2.5 mm, more preferably 0.7 to 1.5 mm.
- the total thickness of the resin intermediate film of the laminated glass in the present invention is appropriately selected depending on the combination with the glass plate to be used in consideration of the rigidity and weight reduction of the laminated glass.
- the thickness of the layer containing the modified block copolymer hydride [E] is usually 0.01 mm or more, preferably 0.02 mm or more, more preferably 0.03 mm or more. . If the thickness of the layer containing the modified block copolymer hydride [E] is less than 0.01 mm, sufficient adhesion to the glass plate may not be obtained.
- the laminated glass of the present invention is intended to reduce the weight, and it is preferable to use a thin glass plate.
- the thickness of the glass plate to be used is usually 0.5 to 1.5 mm, preferably 0.6 to 1.3 mm.
- glass plates having different thicknesses can be used, such as a glass plate having a thickness of 0.7 mm / a resin intermediate film / a glass plate having a thickness of 1.3 mm. Since the modified block copolymer hydride [E] maintains flexibility in a wide temperature range from a low temperature range of about ⁇ 50 ° C. to a high temperature range of about + 120 ° C., two or more glass plates having different thermal expansion coefficients are used. Can be bonded together, and glass breakage can be reduced by a sudden temperature change.
- the material of the glass plate to be used is not particularly limited.
- heat ray reflective glass, infrared reflective glass, colored glass, or the like having an extremely thin metal film or metal oxide film formed on the surface can also be used.
- General-purpose float glass, heat tempered glass, chemically tempered glass, and the like can be used depending on the production method.
- the laminated glass of the present invention comprises at least two or more glass plates and the above-described resin intermediate film interposed between the bonding surfaces of these glass plates.
- t is 3.5 mm or more
- the ratio of t R to t (t R / t) is usually 20 It is ⁇ 80%, preferably 30 to 70%, more preferably 40 to 60%.
- the ratio of the thickness of the resin interlayer (t R / t) is less than 20% and more than 80%, maintaining the rigidity of the laminated glass may reduce the effect of reducing the weight per unit area. There is.
- the laminated glass of the present invention can maintain a rigidity equal to or higher than that of a general-purpose laminated glass and can reduce the weight per unit area to about 2/3 or less.
- the laminated glass of the present invention has a small weight per unit area.
- the weight per unit area of the laminated glass of the present invention is usually 7.5 kg / m 2 or less, preferably 7.0 kg / m 2 or less, more preferably 6.5 kg / m 2 or less.
- the weight per unit area of the laminated glass can be determined by the method described in the examples.
- the rigidity of laminated glass is a bending measured at a temperature of 90 ° C. based on JIS R1602 method (4-point bending test method) using a laminated glass test piece having a length of 100 mm, a width of 20 mm, and a thickness of 2 to 5 mm. It is a value indicated by flexibility.
- the bending flexibility of the laminated glass can be obtained by equation (1).
- the laminated glass of the present invention is excellent in impact resistance.
- the laminated glass of the present invention is excellent in impact resistance.
- the resin intermediate film is sandwiched between two blue plate glasses having a thickness of 0.5 to 1.5 mm, a width of 300 mm, and a length of 300 mm, and bonded and integrated.
- JIS R3212 method automotive safety glass test method
- the laminated glass of the present invention is excellent in heat resistance.
- the laminated glass of the present invention is excellent in heat resistance.
- a resin intermediate film is sandwiched between two blue plate glasses having a thickness of 0.5 to 1.5 mm, a width of 300 mm, and a length of 300 mm, and bonded and integrated.
- a glass test piece in accordance with JIS R3212 method, immersed in a vertical state at 100 ° C. in boiling water, held for 2 hours, and observed for appearance. As a result of observation of the appearance, bubbles exceeding 15 mm from the edge of the test piece, etc. This can be confirmed by the absence of defects.
- the laminated glass of the present invention is excellent in moisture resistance.
- the laminated glass of the present invention is excellent in moisture resistance.
- a resin interlayer is sandwiched between two blue plate glasses having a thickness of 0.5 to 1.5 mm, a width of 300 mm, and a length of 300 mm, and bonded and integrated.
- a glass test piece in accordance with JIS R3212 method, after maintaining for 2 weeks under a temperature and humidity condition of 50 ° C. and relative humidity of 95% RH in a constant temperature and humidity chamber, a visual evaluation of the appearance change was performed. This can be confirmed by no change (discoloration, foam, peeling, turbidity, etc.) exceeding 10 mm from the edge of the test piece.
- Examples of the layer structure of the laminated glass of the present invention include a three-layer structure of glass plate / resin intermediate film / glass plate, glass plate / resin intermediate film / transparent resin film / resin intermediate film / glass plate, and glass plate / resin intermediate.
- Glass / glass plate / resin interlayer / glass plate, etc. 5 layers, glass plate / resin interlayer / glass plate / resin interlayer / glass plate / resin interlayer / glass plate, etc.
- the plate is preferably the outermost layer. When the glass layer is the outermost layer, the wear resistance required for the laminated glass for automobiles can be maintained.
- Examples of the transparent resin film include films made of polyester, polyamide, polyolefin, polycarbonate, acrylic resin, fluororesin and the like.
- the laminated glass has a plurality of resin interlayers, the plurality of resin interlayers may be the same or different.
- a glass plate and a resin intermediate film alternately laminated are placed in a heat laminating bag that can be depressurized by using a vacuum laminator or by adhering them under reduced pressure by heating. After deaeration, a method of using an autoclave and bonding under heat and pressure can be applied.
- the resin interlayer used in the present invention and the glass plate can be firmly bonded by pressing at a temperature of usually 120 to 180 ° C., preferably 130 to 160 ° C., more preferably 135 to 150 ° C.
- the laminated glass of the present invention is lightweight while maintaining rigidity, and is excellent in heat resistance, light resistance, moisture resistance, and the like. Therefore, in addition to window materials for automobiles and roof materials, window materials for buildings, roof materials, and floor materials. , Electric vehicle window materials, sound insulation window materials, heat insulation window materials, ship and aircraft window materials, observation deck materials, surface protection materials such as liquid crystal displays and organic EL displays, railroad home door window materials, road sound insulation walls, It is useful as a surface protective cover for solar cells, a protective cover for lighting fixtures, and the like.
- Evaluation in this example is performed by the following method.
- Mw Weight average molecular weight
- Mw / Mn molecular weight distribution
- the molecular weights of the block copolymer and the hydride of the block copolymer were measured at 38 ° C. as standard polystyrene equivalent values by GPC using THF as an eluent.
- THF as an eluent.
- HLC8020GPC manufactured by Tosoh Corporation was used.
- Hydrogenation rate The hydrogenation rate of the main chain, side chain, and aromatic ring of the block copolymer hydride [D] was calculated by measuring a 1 H-NMR spectrum.
- P X is the applied load at displacement x of the load point (unit: N)
- y X is displacement of the load point (unit: mm)
- w is the width of the test piece (unit: mm)
- l is the distance between the support rolls (unit: mm)
- t is the thickness of the test piece (unit: mm)
- E is the elastic modulus (unit: MPa) by 4-point bending.
- Weight per unit area of laminated glass A resin intermediate film is sandwiched between two blue plate glasses having a thickness of 0.5 to 1.5 mm, a width of 300 mm, and a length of 300 mm, and the laminated glass bonded and integrated is a test piece. It was. The weight of the test piece was measured using an electronic balance, and the weight per unit area (unit: kg / m 2 ) was calculated.
- Heat resistance of laminated glass A laminated glass obtained by sandwiching a resin intermediate film between two blue plate glasses having a thickness of 0.5 to 1.5 mm, a width of 300 mm, and a length of 300 mm and bonding them together was used as a test piece. Using this test piece, in accordance with JIS R3212 method, it was immersed in a vertical state in boiling water at 100 ° C. and held for 2 hours. Evaluation is “ ⁇ ” (good) when there is no bubble and other defects beyond 15 mm from the edge of the test piece, and “X” when there are bubbles and other defects beyond 15 mm from the edge of the test piece. (Defect).
- Moisture resistance of laminated glass A laminated glass obtained by sandwiching a resin intermediate film between two blue plate glasses having a thickness of 0.5 to 1.5 mm, a width of 300 mm, and a length of 300 mm and bonding them together was used as a test piece. Using this test piece, in accordance with JIS R3212 method, it was kept in a constant temperature and humidity chamber at 50 ° C. and a relative humidity of 95% RH for 2 weeks, and then the visual change of the appearance was evaluated.
- Evaluation is “ ⁇ ” (good) when there is no change (discoloration, foam, peeling, turbidity, etc.) beyond 10 mm from the edge of the test piece, and “ ⁇ ” when there is a change beyond 10 mm from the edge of the test piece. "(Bad).
- the above polymer solution is transferred to a pressure-resistant reactor equipped with a stirrer, and a diatomaceous earth supported nickel catalyst (product name “E22U”, nickel supported amount 60%, manufactured by JGC Catalysts & Chemicals) as a hydrogenation catalyst 8 0.0 part and 100 parts dehydrated cyclohexane were added and mixed.
- the inside of the reactor was replaced with hydrogen gas, and hydrogen was supplied while stirring the solution.
- a hydrogenation reaction was performed at a temperature of 190 ° C. and a pressure of 4.5 MPa for 6 hours.
- the weight average molecular weight (Mw) of the block copolymer hydride [D-1] contained in the reaction solution obtained by the hydrogenation reaction was 51,200, and the molecular weight distribution (Mw / Mn) was 1.06.
- the reaction solution was filtered to remove the hydrogenation catalyst, and then the phenolic antioxidant pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) ) Propionate] (product name “Songnox 1010”, manufactured by Matsubara Sangyo Co., Ltd.) 2.0 parts of xylene solution in which 0.1 part was dissolved was added and dissolved.
- the above solution was filtered with a metal fiber filter (pore size 0.4 ⁇ m, manufactured by Nichidai) to remove minute solids, and then a cylindrical concentration dryer (product name “Contro”, manufactured by Hitachi, Ltd.) ), The solvent 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 polymer was extruded into a strand form from a die, cooled, and then 95 parts of pellets of the block copolymer hydride [D-1] were produced by a pelletizer.
- the resulting block-like block copolymer hydride [D-1] had a weight average molecular weight (Mw) of 50,700, a molecular weight distribution (Mw / Mn) of 1.10, and a hydrogenation rate of almost 100%. It was.
- the polymer solution was subjected to a hydrogenation reaction in the same manner as in Production Example 1.
- the weight average molecular weight (Mw) of the block copolymer hydride [D-2] after the hydrogenation reaction was 54,200, and the molecular weight distribution (Mw / Mn) was 1.06.
- the resulting block-like block copolymer hydride [D-2] had a weight average molecular weight (Mw) of 53,700, a molecular weight distribution (Mw / Mn) of 1.11 and a hydrogenation rate of almost 100%. It was.
- the polymer solution was subjected to a hydrogenation reaction in the same manner as in Production Example 1.
- the weight average molecular weight (Mw) of the block copolymer hydride [D′-3] after the hydrogenation reaction was 58,900, and the molecular weight distribution (Mw / Mn) was 1.06.
- the pelletized block copolymer hydride [D'-3] had a weight average molecular weight (Mw) of 58,300, a molecular weight distribution (Mw / Mn) of 1.10, and a hydrogenation rate of almost 100%. there were.
- the polymer solution was subjected to a hydrogenation reaction in the same manner as in Production Example 1.
- the weight average molecular weight (Mw) of the block copolymer hydride [D′-4] after the hydrogenation reaction was 75,700, and the molecular weight distribution (Mw / Mn) was 1.06.
- the resulting block-like block copolymer hydride [D′-4] had a weight average molecular weight (Mw) of 74,900, a molecular weight distribution (Mw / Mn) of 1.10, and a hydrogenation rate of almost 100%. there were.
- the sheet [F (E-1) ] made of the modified block copolymer hydride [E-1] has a width of 330 mm and a thickness of [F (E-1) 760 ] 760 ⁇ m and [F (E-1) ) 380 ] 380 ⁇ m, [F (E-1) 200 ] 200 ⁇ m, [F (E-1) 100 ] 100 ⁇ m, and [F (E-1) 50 ] 50 ⁇ m were molded.
- the sheet [F (E-1) ] was transferred with an embossed pattern by pressing one side of the extruded sheet against the embossing roll with a nip roll.
- the obtained sheet [F (E-1) ] was wound around a roll and collected.
- a laminated glass manufactured by Osaka Glass Industrial Co., Ltd.
- Example 1 One sheet [F (E-1) 760 ] produced in Production Example 5 between two blue plate glasses having a length of 300 mm, a width of 300 mm, and a thickness of 1.3 mm and 0.7 mm, [F (E -1) 380 ], [F (E-1) 760 ] and 1 [F (E-1) 200 ] were stacked in this order.
- This laminate is put into a 75 ⁇ m-thick resin bag having a layer structure of nylon / adhesive layer / polypropylene, and the inside of the bag is deaerated using a sealed pack device (BH-951, manufactured by Panasonic Corporation). The opening was heat sealed while the laminate was hermetically packaged.
- BH-951 manufactured by Panasonic Corporation
- the laminated package was 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 laminated glass test piece having a glass plate / resin interlayer / glass plate layer structure [G-1 300 ].
- the appearance of the laminated glass test piece [G-1 300 ] was good with no defects such as bubbles observed.
- Laminated sheets made of polytetrafluoroethylene were laminated and laminated glass was produced under the same conditions as described above. The glass plate and the polytetrafluoroethylene release sheet were peeled from the produced laminated glass to separate the resin interlayer.
- the thickness of the obtained resin intermediate film was 2.1 mm.
- the storage elastic modulus (G ′) was 1.2 ⁇ 10 8 Pa at ⁇ 20 ° C. and 2.8 ⁇ 10 7 Pa at 90 ° C. It was.
- Example 2 Two sheets of blue glass having a thickness of 1.3 mm were used, one sheet [F (E-1) 760 ] prepared in Production Example 5, one sheet [F (E-1) 50 ], and [F (E-1) 200 ] Laminated glass test piece having a layer configuration of glass plate / resin intermediate film / glass plate in the same manner as in Example 1 except that one piece is stacked in this order [G-2 300 ] A laminated glass test piece “G-2 100 ” and a resin interlayer (thickness: 1.0 mm) were prepared.
- Example 3 Two sheets of blue glass having a thickness of 0.7 mm were used, and the sheet [F (E-1) ] produced in Production Example 5 and the sheet [F (D-1) ] produced in Production Example 7 were used.
- [F (E-1) 200] 1 sheet, [F (D-1) 760] 1 sheet Like, [F (E-1) 200] 1 sheet, [F (D-1) 760] 1 sheet, except that the arranged to overlap one [F (E-1) 200 ], in this order, example Laminated glass test piece [G-3 300 ], laminated glass test piece “G-3 100 ” having a layer structure of glass plate / resin intermediate film / glass plate in the same manner as in 1, and resin intermediate film (thickness 3 0.1 mm).
- Example 4 Two sheets of blue glass having a thickness of 1.1 mm were used, and the sheet configuration [F (E-2) (D′-3) ] prepared in Production Example 8 was used to change the sheet configuration to [F (E-2 ) (D′-3) 760 ]
- a laminated glass test piece “G-4 100 ” and a resin intermediate film (thickness: 1.5 mm) were prepared.
- Example 1 Glass was obtained in the same manner as in Example 1 except that two sheets of blue glass having a thickness of 0.7 mm were used and three sheets [F (E-1) 760 ] prepared in Production Example 5 were stacked.
- the laminated glass of the present invention maintains rigidity, reduces the weight per unit area compared to general-purpose laminated glass, is excellent in heat resistance, impact resistance, light resistance, moisture resistance, etc. It is useful as a window material for buildings, roofing materials, flooring materials, window materials for ships and aircraft.
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Abstract
Description
しかしながら、ガラスと同等の剛性を維持するためには、透明プラスチック板の厚さを厚くしなければならないため、期待するほどの軽量化に至っていない。また、耐スクラッチ性を付与するためには、ハードコート層を設ける必要があり、費用が高くなる等の課題があり、普及は進んでいない。
また、この文献には、ガラス板単体よりも軽量化ができる樹脂中間膜を構成する具体的な材料として、ポリエチレンアイオノマー、ポリカーボネート、ポリウレタン、ポリエチレンテレフタレート、アクリル樹脂等が挙げられている。更にこの文献には、ポリビニルブチラール樹脂を使用した樹脂中間膜では、一定の曲げ剛性を維持してガラス板単体よりも軽量化した合わせガラスが得られないことも示されている。
しかしながら、上記の例示された樹脂からなる中間膜を使用した軽量合わせガラスを使用した自動車用窓材は、一定の曲げ剛性を維持するものの、例えば、自動車用安全ガラスの規格であるJIS R3211に定められたような耐衝撃性(温度40℃及び-20℃の条件)、耐熱性、耐光性、耐湿性等の特性も満足するものではなかった。
しかしながら、この文献には、ガラスの厚みを薄くして、面密度を比較例の合わせガラスに比べて約30%低下させた合わせガラスが記載されているのみであり、例えば、曲げ剛性が低下することに関しては記載されていない。
温度90℃における曲げたわみ性が7.3N/mm2以上であり、かつ、単位面積当たりの重量が7.5kg/m2以下であり、
前記樹脂中間膜が、芳香族ビニル化合物由来の構造単位を主成分とする、少なくとも2つの重合体ブロック[A]と、鎖状共役ジエン化合物由来の構造単位を主成分とする、少なくとも1つの重合体ブロック[B]とからなるブロック共重合体[C]の、主鎖及び側鎖の炭素-炭素不飽和結合及び芳香環の炭素-炭素不飽和結合の90%以上を水素化したブロック共重合体水素化物[D]に、アルコキシシリル基が導入されてなる変性ブロック共重合体水素化物[E]を含有するものであり、
前記樹脂中間膜の動的粘弾性特性における貯蔵弾性率が、温度-20℃で5×108Pa以下、及び、温度90℃で2×107Pa以上であることを特徴とする合わせガラスが提供される。
剛性とは、一般的には、曲げやねじりの力に対する、寸法変化(変形)のしづらさの度合いのことであり、力に対して変形が小さいときは剛性が高い(大きい)、変形が大きいときは剛性が低い(小さい)という。「剛性」は、例えば、合わせガラスに一定の大きさの曲げ応力を与えた際のたわみの大きさで表される。
汎用の合わせガラスとして、例えば、厚さ2.1mmのガラス板を、厚さ0.76mmのポリビニルブチラール樹脂製中間膜で積層した合わせガラスの場合、単位面積当たりの重量は11.3kg/m2であるが、本発明によれば、例示の汎用合わせガラスと同等以上の剛性を維持して、単位面積当たりの重量を7.5kg/m2以下(約2/3以下)に低減することができる。
本発明の合わせガラスは、下記(i)~(v)で規定されるものである。
(i)樹脂中間膜をガラス板間に介在させ、当該ガラス板を接着させて一体化してなる合わせガラスである。
(ii)温度90℃における曲げたわみ性が7.3N/mm2以上である合わせガラスである。
(iii)単位面積当たりの重量が7.5kg/m2以下の合わせガラスである。
(iv)前記樹脂中間膜が、芳香族ビニル化合物由来の構造単位を主成分とする、少なくとも2つの重合体ブロック[A]と、鎖状共役ジエン化合物由来の構造単位を主成分とする、少なくとも1つの重合体ブロック[B]とからなるブロック共重合体[C]の、主鎖及び側鎖の炭素-炭素不飽和結合及び芳香環の炭素-炭素不飽和結合の90%以上を水素化したブロック共重合体水素化物[D]に、アルコキシシリル基が導入されてなる変性ブロック共重合体水素化物[E](以下、「変性ブロック共重合体水素化物[E]」ということがある。)を含有するものである。
(v)前記樹脂中間膜の動的粘弾性特性における貯蔵弾性率が、温度-20℃で5×108Pa以下、及び、温度90℃で2×107Pa以上である。
本発明の合わせガラスに用いる樹脂中間膜は、変性ブロック共重合体水素化物[E]を含有するものである。
芳香族ビニル化合物由来の構造単位が上記範囲にあると、本発明の合わせガラスの耐熱性、高温での剛性に優れる。
重合体ブロック[A]中の芳香族ビニル化合物由来の構造単位が少な過ぎると、合わせガラスの耐熱性が低下するおそれがある。
鎖状共役ジエン化合物由来の構造単位が上記範囲にあると、本発明の合わせガラスの耐熱衝撃性、低温での接着性に優れる。
これらの化合物は、ニトリル基、アルコキシカルボニル基、ヒドロキシカルボニル基、ハロゲン原子等の置換基を有していてもよい。
これらの中でも、吸湿性の観点から、エチレン、プロピレン、1-ブテン、1-ペンテン、1-ヘキセン、1-ヘプテン、1-オクテン、1-ノネン、1-デセン、1-ドデセン、1-エイコセン、4-メチル-1-ペンテン、4,6-ジメチル-1-ヘプテン等の炭素数2~20の鎖状オレフィン;ビニルシクロヘキサン、ノルボルネン等の炭素数5~20の環状オレフィン;1,3-シクロヘキサジエン、ノルボルナジエン等の環状ジエン化合物;等の極性基を含有しないものが好ましい。
ブロック共重合体[C]のブロックの形態は、鎖状型ブロックでもラジアル型ブロックでも良いが、鎖状型ブロックであるものが、機械的強度に優れ好ましい。ブロック共重合体[C]の最も好ましい形態は、重合体ブロック[B]の両端に重合体ブロック[A]が結合した、[A]-[B]-[A]型のトリブロック共重合体である。
複数の重合体ブロック[A]同士は、互いに同一であっても、相異なっていても良い。また、重合体ブロック[B]が複数有る場合には、重合体ブロック[B]は、互いに同一であっても、相異なっていても良い。
また、ブロック共重合体[C]の分子量分布(Mw/Mn)は、好ましくは3以下、より好ましくは2以下、特に好ましくは1.5以下である。
Mw及びMw/Mnが上記範囲となるようにすると、変性ブロック共重合体水素化物[E]は、耐熱性や機械的強度が良好となり、本発明に係る合わせガラスの耐熱性や機械的強度が低下することがない。
また、ブロック共重合体(C)の主鎖及び側鎖の炭素-炭素不飽和結合の水素化率は、97%以上であることが好ましく、99%以上であることがより好ましい。また、ブロック共重合体(C)の芳香環の炭素-炭素不飽和結合の水素化率は、97%以上であることが好ましく、99%以上であることがより好ましい。
水素化率が高いほど、本発明で使用するブロック共重合体水素化物(D)の耐光性や耐熱劣化性が良好となる。
ブロック共重合体水素化物(D)の水素化率は、ブロック共重合体水素化物(D)の1H-NMRを測定することにより求めることができる。
また、ブロック共重合体水素化物[D]の分子量分布(Mw/Mn)は、好ましくは3以下、より好ましくは2以下、特に好ましくは1.5以下にする。
Mw及びMw/Mnが上記範囲となるようにすると、変性ブロック共重合体水素化物[E]は、耐熱性や機械的強度が良好となり、本発明に係る合わせガラスの耐熱性や機械的強度が低下することがなく好ましい。
ブロック共重合体水素化物[D]にアルコキシシリル基を導入することにより、ガラスに対する強固な接着性を付与することができる。
また、アルコキシシリル基は、ブロック共重合体水素化物[D]に、炭素数1~20のアルキレン基や、炭素数2~20のアルキレンオキシカルボニルアルキレン基等の2価の有機基を介して結合していても良い。
アルコキシシリル基の導入量が多過ぎると、得られる変性ブロック共重合体水素化物[E]を保存中に微量の水分等で分解されたアルコキシシリル基同士の架橋が進み、ゲル化したり、溶融成形時の流動性が低下して、樹脂中間膜を溶融押出し成形できる温度が高くなったり、成形される樹脂中間膜の表面が荒れたりするおそれがある。また、アルコキシシリル基の導入量が少な過ぎると、成形される樹脂中間膜のガラスに対する接着性が低下するおそれがある。
エチレン性不飽和シラン化合物の使用量は、ブロック共重合体水素化物[D]100重量部に対して、通常0.1~10重量部、好ましくは0.2~5重量部、より好ましくは0.5~3重量部である。
有機過酸化物としては、例えば、t-ブチルクミルパーオキシド、ジクミルパーオキサイド、ジ-t-ヘキシルパーオキシド、2,5-ジメチル-2,5-ジ(t-ブチルパーオキシ)ヘキサン、ジ-t-ブチルパーオキシド、ジ(2-t-ブチルパーオキシイソプロピル)ベンゼン等が好適に用いられる。
これらの過酸化物は、それぞれ単独で用いてもよいし、2種以上を組み合わせて使用してもよい。
有機過酸化物の使用量は、ブロック共重合体水素化物[D]100重量部に対して、通常0.01~1重量部、好ましくは0.05~0.5重量部である。
Mw及びMw/Mnが上記範囲となるようにすると、変性ブロック共重合体水素化物[E]の耐熱性や機械的強度が維持される。
本発明に用いる樹脂中間膜は、上記の変性ブロック共重合体水素化物[E]を含有するものである。樹脂中間膜における変性ブロック共重合体水素化物[E]の含有量は、通常40重量%以上、好ましくは50重量%以上、より好ましくは60重量%以上である。
例えば、樹脂中間膜が上記の貯蔵弾性率を有さない場合、特に90℃での貯蔵弾性率が上記の値を下まわる場合、樹脂中間膜の貯蔵弾性率を高めるために、樹脂中間膜は、
a.変性ブロック共重合体水素化物[E]に、変性ブロック共重合体水素化物[E]の前駆体であるブロック共重合体水素化物[D]、及び/又は、ブロック共重合体水素化物[D]よりも貯蔵弾性率の高いブロック共重合体水素化物[D’]を混合して得られる樹脂組成物からなる樹脂中間膜、あるいは、
b.変性ブロック共重合体水素化物[E]からなる層と、変性ブロック共重合体水素化物[E]の前駆体であるブロック共重合体水素化物[D]、及び/又は、ブロック共重合体水素化物[D’]からなる層を交互に積層した多層の樹脂中間膜、等とすることができる。
これらの場合、ブロック共重合体水素化物[D’]は、変性ブロック共重合体水素化物[E]の前駆体であるブロック共重合体水素化物[D]よりも、90℃における貯蔵弾性率が高いものであることが好ましい。
比(wA’:wB’)がこの範囲にあれば、上記変性ブロック共重合体水素化物[E]に対する優れた相溶性を有し、変性ブロック共重合体水素化物[E]との混合物は透明性が良好であり、変性ブロック共重合体水素化物[E]と混合あるいは積層することにより樹脂中間膜の貯蔵弾性率を好ましい範囲に高めることができる。
これらの添加剤の配合量は、変性ブロック共重合体水素化物[E]及びブロック共重合体水素化物[D’]の合計量100重量部に対して、通常5重量部以下、好ましくは3重量部以下、より好ましくは2重量部以下である。
酸化防止剤としては、リン系酸化防止剤、フェノ-ル系酸化防止剤、硫黄系酸化防止剤等が挙げられる。
耐光安定剤としては、ヒンダードアミン系光安定剤などが挙げられる。
また、赤外線遮蔽剤としては、インジウムドープ酸化錫、アンチモンドープ酸化錫、酸化亜鉛、アルミニウムドープ酸化亜鉛等の金属酸化物微粒子等が挙げられる。
例えば、溶融押出し成形法により、樹脂中間膜を成形する場合は、樹脂温度を、通常200~270℃、好ましくは210~260℃、より好ましくは220~250℃の範囲にすればよい。
樹脂温度が低過ぎる場合は、流動性が悪化し、得られる樹脂中間膜にゆず肌やダイライン等の不良を生じ易く、また、樹脂中間膜の押出し速度が上げられず、工業的に不利となるおそれがある。樹脂温度が高過ぎる場合は、樹脂中間膜のガラスヘの接着性が不良となったり、樹脂中間膜の貯蔵安定性が低下して、樹脂中間膜を常温(20~25℃程度)常湿(相対湿度40~79%程度)環境下で長期間貯蔵した後のガラスに対する接着性が低下したりするおそれがある。
薄いガラス板を使用した軽量合わせガラスで剛性を維持するには、樹脂中間膜の厚さを大きくする必要があるが、樹脂中間膜の1枚当たりの厚さを厚くするよりも、1枚当たりの厚さが薄い樹脂中間膜を重ねて使用する方が、自動車用の曲面形状をした薄いガラス板と積層する際に、柔軟性が良く、作業性が優れる場合がある。
本発明における合わせガラスの樹脂中間膜の総厚は、合わせガラスの剛性と軽量化を勘案し、使用するガラス板との組み合わせにより適宜選択される。
変性ブロック共重合体水素化物[E]を含む層の厚さが0.01mmよりも薄いと、ガラス板との接着性が十分に得られなくなるおそれがある。
本発明の合わせガラスは軽量化を目的としており、薄い厚さのガラス板を使用することが好ましい。使用するガラス板の厚さは、通常0.5~1.5mm、好ましくは0.6~1.3mmである。また、例えば、厚さ0.7mmのガラス板/樹脂中間膜/厚さ1.3mmのガラス板のように、異なる厚さのガラス板を使用することもできる。
変性ブロック共重合体水素化物[E]は、-50℃程度の低温領域から、+120℃程度の高温領域まで幅広い温度帯域で柔軟性を維持するため、熱膨張係数の異なる2種以上のガラス板を貼り合わせることもでき、急激な温度変化によってもガラスの割れを低減することができる。
また、表面に極薄の金属膜や金属酸化物膜を形成した熱線反射ガラスや赤外線反射ガラス、着色したガラス等も使用できる。製法の違いによる、汎用的なフロートガラス、熱強化ガラス、化学強化ガラス等も使用できる。
本発明の合わせガラスは、少なくとも2枚以上のガラス板と、これらのガラス板相互の接合面に介在する前述した樹脂中間膜とからなるものである。
本発明の合わせガラスの総厚をt、樹脂中間膜の厚さをtRとした場合、tは3.5mm以上であって、tに対するtRの比(tR/t)は、通常20~80%、好ましくは30~70%、より好ましくは40~60%である。
樹脂中間膜の厚さの比(tR/t)が、20%を下回る場合及び80%を超える場合は、合わせガラスの剛性を維持すると、単位面積当たりの重量を低減する効果が小さくなるおそれがある。
合わせガラスの単位面積当たりの重量は、実施例に記載された方法で求めることができる。
式(1)から、曲げ試験の支持ロール間距離を一定にすると、合わせガラスの曲げたわみ性は、試験片の厚さと曲げ弾性率に依存することが分かる。
前記透明樹脂フィルムとしては、ポリエステル、ポリアミド、ポリオレフィン、ポリカーボネート、アクリル系樹脂、フッ素樹脂等よりなるフィルムが挙げられる。
また、合わせガラスが複数の樹脂中間膜を有する場合、複数の樹脂中間膜同士は同一でも相異なっていてもよい。
本発明で使用する樹脂中間膜とガラス板は、通常120~180℃、好ましくは130~160℃、より好ましくは135~150℃の温度で圧着することにより、強固に接着させることができる。
(1)重量平均分子量(Mw)及び分子量分布(Mw/Mn)
ブロック共重合体及びブロック共重合体水素化物の分子量は、THFを溶離液とするGPCによる標準ポリスチレン換算値として38℃において測定した。測定装置としては、東ソー社製HLC8020GPCを用いた。
(2)水素化率
ブロック共重合体水素化物[D]の主鎖、側鎖及び芳香環の水素化率は、1H-NMRスペクトルを測定して算出した。
樹脂中間膜から採取した長さ70mm、幅10mmのシートを試験片とした。
粘弾性スペクトルは、粘弾性測定装置(ティー・エイ・インスツルメント・ジャパン社製、ARES)を使用し、JIS K7244-2法(ねじり振子法)に基づき、角周波数:1rad/s、測定温度範囲:-100~+130℃、昇温速度:5℃/minの条件で測定した。得られた粘弾性スペクトルから、-20℃及び+90℃における樹脂中間膜のG’の値を求めた。
2枚のガラス板(長さ100mm、幅20mm、厚さ0.5~1.5mm)を中間膜で貼り合わせた合わせガラス(総厚3.0~6.0mm)を試験片とした。
加熱オーブンを備えたオートグラフ(インストロン社製、INSTRON5582)を使用し、JIS R1602法(4点曲げ試験法)に基づいて、回転形4点曲げ試験治具を使用して、支点間距離:上部=27mm、下部=81mm、支持棒直径6mm、温度25℃及び90℃の2条件で曲げ試験を行い、下記式(1)により曲げたわみ性の値を算出した。
樹脂中間膜を、厚さ0.5~1.5mm、幅300mm、長さ300mmの2枚の青板ガラスに挟み、接着一体化した合わせガラスを試験片とした。
電子天秤を使用して試験片の重量を測定し、単位面積当たりの重量(単位:kg/m2)を算出した。
樹脂中間膜を、厚さ0.5~1.5mm、幅300mm、長さ300mmの2枚の青板ガラスに挟み、接着一体化した合わせガラスを試験片とした。
この試験片を使用し、JIS R3212法(自動車安全ガラス試験方法)に従って、質量227gの鋼球を所定の高さから試験片に落下させ、貫通の有無、衝撃面の反対側からのガラスの剥離破片の総重量を測定した。あらかじめ-20℃の温度に4時間保持した試験片は、鋼球の落下高さ8.5m、40℃の温度に4時間保持した試験片は、落下高さ9mとした。
評価は、鋼球の貫通が無く、ガラス破片の総重量が12g以下の場合を「○」(良好)、貫通が有る場合、又は、貫通が無いが、ガラス破片の総重量が12gを超える場合を「×」(不良)とした。
樹脂中間膜を、厚さ0.5~1.5mm、幅300mm、長さ300mmの2枚の青板ガラスに挟み、接着一体化した合わせガラスを試験片とした。
この試験片を使用し、JIS R3212法に従って、100℃の沸騰水中で、鉛直の状態に浸漬し、2時間保持した後、外観変化の目視評価を行った。
評価は、試験片の縁から15mmを超えて泡、その他の欠陥が無い場合を「○」(良好)、試験片の縁から15mmを超えて、泡、その他の欠陥が有る場合を「×」(不良)とした。
樹脂中間膜を、厚さ0.5~1.5mm、幅300mm、長さ300mmの2枚の青板ガラスに挟み、接着一体化した合わせガラスを試験片とした。
この試験片を使用し、JIS R3212法に従って、恒温恒湿槽内で、50℃、相対湿度95%RHの温度湿度条件下に2週間保持した後、外観変化の目視評価を行った。
評価は、試験片の縁から10mmを超えて変化(変色、泡、剥離、濁り等)が無い場合を「○」(良好)、試験片の縁から10mmを超えて変化が有る場合を「×」(不良)とした。
内部が十分に窒素置換された、攪拌装置を備えた反応器に、脱水シクロヘキサン320部、脱水スチレン25.0部、及び、ジ-n-ブチルエーテル0.475部を入れた。全容を60℃で攪拌しながら、n-ブチルリチウムの15%シクロヘキサン溶液0.85部を加えて重合を開始させ、攪拌しながら60℃で60分反応させた。この時点で、反応液をガスクロマトグラフィー(GC)により分析した結果、重合転化率は99.5%であった。
重合体溶液に含まれるブロック共重合体[C-1]の重量平均分子量(Mw)は48,400、分子量分布(Mw/Mn)は1.04、wA:wB=50:50であった。
次いで、上記溶液を、金属ファイバー製フィルター(孔径0.4μm、ニチダイ社製)にてろ過して微小な固形分を除去した後、円筒型濃縮乾燥器(製品名「コントロ」、日立製作所社製)を用いて、温度260℃、圧力0.001MPa以下で、溶液から、溶媒であるシクロヘキサン、キシレン及びその他の揮発成分を除去した。溶融ポリマーをダイからストランド状に押出し、冷却後、ペレタイザーによりブロック共重合体水素化物[D-1]のペレット95部を作製した。
得られたペレット状のブロック共重合体水素化物[D-1]の重量平均分子量(Mw)は50,700、分子量分布(Mw/Mn)は1.10、水素化率はほぼ100%であった。
変性ブロック共重合体水素化物[E-1]のFT-IRスペクトルを測定したところ、1090cm-1にSi-OCH3基、825cm-1と739cm-1にSi-CH2基に由来する新たな吸収帯が、ビニルトリメトキシシランのSi-OCH3基、Si-CH2基に由来する吸収帯(1075cm-1、808cm-1及び766cm-1)と異なる位置に観察された。
また、変性ブロック共重合体水素化物[E-1]の1H-NMRスペクトル(重クロロホルム中)を測定したところ、3.6ppmにメトキシ基のプロトンに基づくピークが観察され、ピーク面積比からブロック共重合体水素化物[D-1]の100部に対してビニルトリメトキシシラン1.8部が結合したことが確認された。
製造例1において、スチレン20.0部、イソプレン60.0部、スチレン20.0部をそれぞれ3回に分けて、この順に加え、n-ブチルリチウム(15%シクロヘキサン溶液)を0.80部に変える以外は、製造例1と同様に重合反応及び反応停止操作を行った。
得られたブロック共重合体[C-2]の重量平均分子量(Mw)は51,200、分子量分布(Mw/Mn)は1.04、wA:wB=40:60であった。
得られた変性ブロック共重合体水素化物[E-2]は、製造例1と同様にして分析し、ブロック共重合体水素化物[D-2]の100部に対してビニルトリメトキシシラン1.8部が結合したことが確認された。
製造例1において、スチレン30.0部、イソプレン40.0部、スチレン30.0部をそれぞれ3回に分けて、この順に加え、n-ブチルリチウム(15%シクロヘキサン溶液)を0.75部に変える以外は、製造例1と同様に重合反応及び反応停止操作を行った。
得られたブロック共重合体[C’-3]の重量平均分子量(Mw)は55,600、分子量分布(Mw/Mn)は1.04、wA:wB=60:40であった。
製造例1において、スチレン40.0部、イソプレン20.0部、スチレン40.0部をそれぞれ3回に分けて、この順に加え、n-ブチルリチウム(15%シクロヘキサン溶液)を0.65部に変える以外は、製造例1と同様に重合反応及び反応停止操作を行った。
得られたブロック共重合体[C’-4]の重量平均分子量(Mw)は71,400、分子量分布(Mw/Mn)は1.04、wA:wB=80:20であった。
製造例1で得た変性ブロック共重合体水素化物[E-1]のペレットを、37mmφのスクリューを備えた二軸混練機を有するTダイ式フィルム溶融押出し成形機(Tダイ幅400mm)、キャストロール(エンボスパターン付き)、及び、ゴム製ニップロール及びシート引き取り装置を備えた押出しシート成形機を使用して、シートを押出し成形した。成形条件は、溶融樹脂温度200℃、Tダイ温度200℃、キャストロール温度80℃とした。変性ブロック共重合体水素化物[E-1]からなるシート[F(E-1)]は、幅330mmで、厚さは、[F(E-1)760]760μm、[F(E-1)380]380μm、[F(E-1)200]200μm、[F(E-1)100]100μm、[F(E-1)50]50μmの5種を成形した。シート[F(E-1)]は、押出しシートの片面をニップロールでエンボスロールに押し当てることにより、エンボスパターンを転写した。得られたシート[F(E-1)]はロールに巻き取り回収した。
製造例2で得た変性ブロック共重合体水素化物[E-2]のペレットを、製造例5と同様にしてシート成形し、変性ブロック共重合体水素化物[E-2]からなる厚さ50~760μmのシート[F(E-2)760]、[F(E-2)380]、[F(E-2)200]、[F(E-2)100]、[F(E-2)50]を作製した。
製造例1で製造したブロック共重合体水素化物[D-1]のペレットを、製造例5と同様にしてシート成形し、ブロック共重合体水素化物[D-1]からなる厚さ380~760μmのシート[F(D-1)760]、[F(D-1)380]を作製した。
製造例2で得た変性ブロック共重合体水素化物[E-2]のペレット65部と製造例3で製造したブロック共重合体水素化物[D’-3]のペレット35部を混合した。混合したペレットを使用し、製造例5と同様にしてシート成形し、変性ブロック共重合体水素化物[E-2]及びブロック共重合体水素化物[D’-3]を含有してなる厚さ760~50μmのシート[F(E-2)(D’-3)760]、[F(E-2)(D’-3)380]、[F(E-2)(D’-3)200]、[F(E-2)(D’-3)100]、[F(E-2)(D’-3)50]を作製した。
製造例1で得た変性ブロック共重合体水素化物[E-1]のペレット50部と製造例4で製造したブロック共重合体水素化物[D’-4]のペレット50部を混合した。混合したペレットを使用し、製造例5と同様にしてシート成形し、変性ブロック共重合体水素化物[E-1]及びブロック共重合体水素化物[D’-4]を含有してなる厚さ760~50μmのシート[F(E-1)(D’-4)760]、[F(E-1)(D’-4)380]、[F(E-1)(D’-4)200]、[F(E-1)(D’-4)100]、[F(E-1)(D’-4)50]を作製した。
縦300mm、横300mm、厚さ2.1mmの青板ガラス2枚が、厚さが0.76mmのポリビニルブチラール製中間膜で貼り合わされた合わせガラス、及び、縦100mm、横20mmで、厚さが2.1mmの青板ガラス2枚が、厚さが0.76mmのポリビニルブチラール製中間膜で貼り合わされた合わせガラス(大阪硝子工業社製)を試験サンプルとした。
この合わせガラス試験サンプルの重量測定から、単位面積当たりの重量は11.3kg/m2と算出された。
この合わせガラス試験サンプルの曲げたわみ性は、25℃で7.9N/mm2、90℃で7.3N/mm2であった。
縦300mm、横300mmで、厚さが1.3mm及び0.7mmの2枚の青板ガラスの間に、製造例5で作製したシート[F(E-1)760]1枚、[F(E-1)380]1枚、[F(E-1)760]1枚及び、[F(E-1)200]1枚をこの順に重ねて配置した。この積層物を、ナイロン/接着層/ポリプロピレンの層構成を有する厚さ75μmの樹脂製の袋に入れ、密封パック器(BH-951、パナソニック社製)を使用して、袋内を脱気しながら開口部をヒートシールして積層物を密封包装した。
その後、密封包装した積層物をオートクレーブに入れて、温度140℃、圧力0.8MPaで30分間処理して、ガラス板/樹脂中間膜/ガラス板の層構成をした合わせガラス試験片[G-1300]を作製した。合わせガラス試験片[G-1300]の外観は気泡等の欠陥は観察されず、良好であった。
合わせガラス試験片[G-1300□]の重量測定から、単位面積当たりの重量は6.9kg/m2と算出された。この重量は、参考例の合わせガラスに比較し39%軽量であった。
縦300mm、横300mmで、厚さが1.3mmの2枚の青板ガラスの間に、厚さ0.2mmのポリテトラフルオロエチレン製離形シート、製造例5で作製したシート[F(E-1)760]1枚、[F(E-1)380]1枚、[F(E-1)760]1枚、[F(E-1)200]1枚、及び厚さ0.1mmのポリテトラフルオロエチレン製離形シートを重ねて配置し、上記と同様の条件にて、合わせガラスを作製した。作製した合わせガラスからガラス板と、ポリテトラフルオロエチレン製離形シートを剥がして、樹脂中間膜を分離した。得られた樹脂中間膜の厚さは2.1mmであった。
この樹脂中間膜を使用して、粘弾性スペクトルを測定した結果、貯蔵弾性率(G’)は、-20℃で1.2×108Pa、90℃で2.8×107Paであった。
縦100mm、横20mmで、厚さが1.3mm及び0.7mmの2枚の青板ガラスの間に、製造例5で作製したシート[F(E-1)760]1枚、[F(E-1)380]1枚、[F(E-1)760]1枚及び、[F(E-1)200]1枚をこの順に重ねて、上記と同様の条件にて、曲げ試験用の合わせガラス試験片[G-1100]を作製した。
合わせガラス試験片[G-1100]の1.3mm厚ガラス側から荷重をかけた場合の曲げたわみ性は、25℃で12.9N/mm2、90℃で7.4N/mm2であった。このたわみ性は、参考例の合わせガラスの曲げたわみ性と比較し、25℃では高く、90℃ではほぼ同等であった。
合わせガラス試験片[G-1300]を使用し、1.3mm厚ガラス側から落球衝撃を与え耐衝撃性の評価を行った。その結果、-20℃で保持した試験片も、40℃で保持した試験片も、いずれも鋼球は貫通せず、ガラス破片の量は、それぞれ、0~0.31g、及び、0~0.48gであった。
耐衝撃性の評価は、-20℃で保持した試験片も40℃で保持した試験片も、いずれも「○(良好)」であった。
合わせガラス試験片[G-1300]を使用し、耐熱性の評価を行った。その結果、試験片の外観には全く変化が認められず、評価は「○(良好)」であった。
合わせガラス試験片[G-1300]を使用し、耐湿性の評価を行った。その結果、試験片の外観には全く変化が認められず、評価は「○(良好)」であった。
これらの評価結果を表1に示した。
厚さが1.3mmの青板ガラス2枚を使用し、製造例5で作製したシート[F(E-1)760]1枚、[F(E-1)50]1枚、及び、[F(E-1)200]1枚をこの順に重ねて配置する以外は、実施例1と同様にしてガラス板/樹脂中間膜/ガラス板の層構成をした合わせガラス試験片[G-2300]、合わせガラス試験片「G-2100」、及び、樹脂中間膜(厚さ1.0mm)を作製した。
厚さが0.7mmの青板ガラス2枚を使用し、製造例5で作製したシート[F(E-1)]及び製造例7で作製したシート[F(D-1)]を使用して、シート構成を[F(E-1)200]1枚、[F(D-1)760]1枚、[F(E-1)200]1枚、[F(D-1)760]1枚、[F(E-1)200]1枚、[F(D-1)760]1枚、[F(E-1)200]1枚、をこの順に重ねて配置する以外は、実施例1と同様にしてガラス板/樹脂中間膜/ガラス板の層構成をした合わせガラス試験片[G-3300]、合わせガラス試験片「G-3100」、及び、樹脂中間膜(厚さ3.1mm)を作製した。
厚さが1.1mmの青板ガラス2枚を使用し、製造例8で作製したシート[F(E-2)(D’-3)]を使用して、シート構成を[F(E-2)(D’-3)760]2枚を重ねて配置する以外は、実施例1と同様にしてガラス板/樹脂中間膜/ガラス板の層構成をした合わせガラス試験片[G-4300]、合わせガラス試験片「G-4100」、及び、樹脂中間膜(厚さ1.5mm)を作製した。
厚さが0.7mmの青板ガラス2枚を使用し、製造例5で作製したシート[F(E-1)760]3枚、を重ねて配置する以外は、実施例1と同様にしてガラス板/樹脂中間膜/ガラス板の層構成をした合わせガラス試験片[G-5300]、合わせガラス試験片「G-5100」、及び、樹脂中間膜(厚さ2.3mm)を作製した。
厚さが1.3mm及び0.7mmの2枚の青板ガラスを使用し、製造例6で作製したシート[F(E-2)760]1枚、[F(E-2)380]1枚、[F(E-2)760]1枚、[F(E-2)200]1枚、を重ねて配置する以外は、実施例1と同様にしてガラス板/樹脂中間膜/ガラス板の層構成をした合わせガラス試験片[G-6300]、合わせガラス試験片「G-6100」、及び、樹脂中間膜(厚さ2.1mm)を作製した。
厚さが1.3mm及び0.7mmの2枚の青板ガラスを使用し、製造例9で作製したシート[F(E-1)(D’-4)760]1枚、[F(E-1)(D’-4)380]1枚、[F(E-1)(D’-4)760]1枚、[F(E-1)(D’-4)200]1枚、を重ねて配置する以外は、実施例1と同様にしてガラス板/樹脂中間膜/ガラス板の層構成をした合わせガラス試験片[G-7300]、合わせガラス試験片「G-7100」、及び、樹脂中間膜(厚さ2.1mm)を作製した。
変性ブロック共重合体水素化物[E]を含有する樹脂中間膜の貯蔵弾性率が、本発明の範囲にある場合、ガラス板の厚さと樹脂中間膜の厚さを選定することにより、90℃の高温での剛性を維持し、PVBを中間膜とした汎用合わせガラスに比べて単位面積当たりの重量を約2/3以下に低減した合わせガラスが得られる。また、自動車用安全ガラスに要求される耐衝撃性、耐熱性、耐湿性も有している(実施例1~4)。
変性ブロック共重合体水素化物[E]を含有する樹脂中間膜の貯蔵弾性率が、本発明の範囲にある場合も、ガラス板の厚さと樹脂中間膜の厚さを共に小さくして合わせガラスを薄く軽量にし過ぎた場合は、高温での剛性が十分に維持できなくなる(比較例1)。
高温での貯蔵弾性率が低い樹脂中間膜を使用した軽量合わせガラスでは、厚いガラス板を使用した汎用の合わせガラスに比べて高温(90℃)での剛性を維持できない(比較例2)。
高温での貯蔵弾性率が高いが、低温(-20℃)での貯蔵弾性率も高くなりすぎた樹脂中間膜を使用した軽量合わせガラスでは、高温での剛性は維持できるが、耐衝撃性が劣る(比較例3)。
Claims (1)
- 樹脂中間膜をガラス板間に介在させ、当該ガラス板を接着させて一体化してなる合わせガラスであって、
温度90℃における曲げたわみ性が7.3N/mm2以上であり、かつ、単位面積当たりの重量が7.5kg/m2以下であり、
前記樹脂中間膜が、芳香族ビニル化合物由来の構造単位を主成分とする、少なくとも2つの重合体ブロック[A]と、鎖状共役ジエン化合物由来の構造単位を主成分とする、少なくとも1つの重合体ブロック[B]とからなるブロック共重合体[C]の、主鎖及び側鎖の炭素-炭素不飽和結合及び芳香環の炭素-炭素不飽和結合の90%以上を水素化したブロック共重合体水素化物[D]に、アルコキシシリル基が導入されてなる変性ブロック共重合体水素化物[E]を含有するものであり、
前記樹脂中間膜の動的粘弾性特性における貯蔵弾性率が、温度-20℃で5×108Pa以下、及び、温度90℃で2×107Pa以上であることを特徴とする合わせガラス。
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EP16783089.2A EP3287426A4 (en) | 2015-04-22 | 2016-04-14 | COMPOSITE GLASS |
JP2017514090A JP6658743B2 (ja) | 2015-04-22 | 2016-04-14 | 合わせガラス |
US15/567,079 US10889091B2 (en) | 2015-04-22 | 2016-04-14 | Laminated glass |
KR1020177031345A KR102491476B1 (ko) | 2015-04-22 | 2016-04-14 | 합판 유리 |
CN201680022100.1A CN107531565B (zh) | 2015-04-22 | 2016-04-14 | 夹层玻璃 |
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US10889091B2 (en) | 2021-01-12 |
KR102491476B1 (ko) | 2023-01-20 |
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US20180099486A1 (en) | 2018-04-12 |
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