WO2018078881A1 - Laminated glass and film material for laminated-glass interlayer - Google Patents

Laminated glass and film material for laminated-glass interlayer Download PDF

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Publication number
WO2018078881A1
WO2018078881A1 PCT/JP2016/082346 JP2016082346W WO2018078881A1 WO 2018078881 A1 WO2018078881 A1 WO 2018078881A1 JP 2016082346 W JP2016082346 W JP 2016082346W WO 2018078881 A1 WO2018078881 A1 WO 2018078881A1
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Prior art keywords
glass
laminated glass
laminated
acrylic polymer
plate
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PCT/JP2016/082346
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French (fr)
Japanese (ja)
Inventor
直己 高原
吉田　明弘
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日立化成株式会社
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Application filed by 日立化成株式会社 filed Critical 日立化成株式会社
Priority to PCT/JP2016/082346 priority Critical patent/WO2018078881A1/en
Priority to PCT/JP2017/038968 priority patent/WO2018079732A1/en
Priority to JP2018547796A priority patent/JPWO2018079732A1/en
Priority to TW106137338A priority patent/TW201823179A/en
Publication of WO2018078881A1 publication Critical patent/WO2018078881A1/en

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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

Definitions

  • the present invention relates to laminated glass and a film material for an interlayer film of laminated glass.
  • laminated glass is widely used as glass for vehicles such as automobiles, aircraft, buildings, etc., even if it is damaged by an external impact, it is safe because the glass fragments do not scatter. Yes.
  • Laminated glass is generally a laminate having at least one pair of glass plates and an intermediate film that is interposed between them and bonds the glass plates together.
  • An example of the interlayer film for laminated glass is a film formed from a polyvinyl acetal resin such as a polyvinyl butyral resin plasticized with a plasticizer (Patent Documents 1 to 3).
  • an object of the present invention is to achieve both sufficiently excellent optical properties and high splitting properties for laminated glass to which a transparent plastic plate is applied.
  • One aspect of the present invention provides a laminated glass including two opposing glass plates and an intermediate film sandwiched between the two glass plates.
  • One of the two glass plates is a transparent plastic plate, and the other is an inorganic glass plate.
  • the impact strength measured by an impact resistance test in which the intermediate film includes an acrylic polymer and a hard sphere is dropped toward the laminated glass may be 0.03 J / cm 2 or more.
  • the acrylic polymer may have a weight average molecular weight of 100,000 or more.
  • (meth) acrylate means at least one of “acrylate” or “methacrylate” corresponding thereto.
  • the content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition.
  • FIG. 1 is a schematic cross-sectional view showing an embodiment of a laminated glass.
  • a laminated glass 1 shown in FIG. 1 has two glass plates 11 and 12 facing each other and an intermediate film 5 sandwiched between the two glass plates 11 and 12.
  • the glass plate 11 also referred to as “first glass plate”
  • the intermediate film 5 and the glass plate 12 (also referred to as “second glass plate”) are laminated in this order.
  • One of the two glass plates 11 and 12 can be a transparent plastic plate and the other can be an inorganic glass plate.
  • the inorganic glass plate can be selected from those usually used as a glass plate constituting the laminated glass. By providing the inorganic glass plate, the surface of the laminated glass can have good scratch resistance.
  • the inorganic glass plate may be, for example, a float glass, a tempered glass (air-cooled tempered glass, chemically tempered glass, etc.), or a multilayer glass plate.
  • transparent plastic plate a plastic plate having optical properties such as transparency suitable for laminated glass is used.
  • transparent plastic plates include polycarbonate resin plates (PC plates), polymethyl methacrylate resin plates (PMMA plates), cyclopolyolefin resin plates (COP plates), polyethylene terephthalate resin plates (PET plates), polyethylene plates (PE plates) , Polypropylene plate (PP plate), polystyrene plate (PS plate), and triacetyl cellulose plate (TAC plate).
  • PC plates polycarbonate resin plates
  • PMMA plates polymethyl methacrylate resin plates
  • COP plates cyclopolyolefin resin plates
  • PET plates polyethylene terephthalate resin plates
  • PE plates polyethylene plates
  • PE plates Polypropylene plate
  • PS plate polystyrene plate
  • TAC plate triacetyl cellulose plate
  • the intermediate film 5 is a resin layer mainly containing an acrylic polymer.
  • the intermediate film 5 is in direct contact with most of the main surfaces of the adjacent glass plates 11 and 12 on the side of the intermediate film 5 (for example, 90% by area or more of the main surfaces), so that the two glass plates 11 and 12 are in contact with each other. Bonding together. Details of the resin composition for the intermediate film constituting the intermediate film 5 will be described later.
  • the thickness of the intermediate film 5 may be 10 to 5000 ⁇ m, or 25 to 1000 ⁇ m.
  • the light transmittance of each of the glass plates 11 and 12 and the intermediate film 5 in the visible light region may be 80% or more, 90% or more, or 95% or more.
  • the light transmittance of the entire laminated glass 1 with respect to light rays in the visible light region may be 80% or more, 90% or more, or 95% or more.
  • the impact strength measured by an impact resistance test in which a hard sphere is dropped toward the laminated glass 1 may be 0.03 J / cm 2 or more.
  • Laminated glass exhibiting high impact strength can have sufficient splitting resistance.
  • the upper limit of impact strength is not particularly limited, but is usually 10 J / cm 2 or less. Details of the method of measuring the impact strength will be described in Examples described later.
  • the impact strength of the laminated glass can be set to a predetermined value or more by appropriately setting the thicknesses of the glass plate and the interlayer film.
  • the thickness of the transparent plastic plate may be 0.1 to 100 mm, 0.5 to 10 mm, or 0.5 to 5 mm.
  • the thickness of the inorganic glass plate may be 0.1 to 50 mm, 0.5 to 30 mm, 1 to 20 mm, or 2 to 10 mm.
  • the total thickness of the laminated glass 1 is usually 0.5 to 1000 mm or 1 to 15 mm in many cases.
  • the laminated glass of the present embodiment having such a thickness is easy to show high impact strength while being sufficiently light compared to the laminated glass composed only of the inorganic glass plate and the intermediate film.
  • the thickness of the glass plate and the intermediate film is controlled within the above range, for example.
  • Impact strength can be easily increased.
  • the weight average molecular weight of the acrylic polymer being 100,000 or more can also contribute to the improvement of impact strength.
  • the peel strength between the intermediate film 5 and the glass plate 11 or the glass plate 12 may be 5 N / 10 mm or more, 8 N / 10 mm or more, 10 N / 10 mm or more, or 30 N / 10 mm or less.
  • the peel strength here was measured by a 180 ° peel test for 3 seconds at a peeling speed of 300 mm / min at 25 ° C. using a tensile tester (trade name “Tensilon RTC-1210” manufactured by Orientec Co., Ltd.). Value.
  • the laminated glass is not limited to the embodiment shown in FIG. 1 and can be appropriately changed.
  • the laminated glass may further include an inorganic glass plate and / or a transparent plastic plate as an additional glass plate (such as a third glass plate).
  • an additional intermediate film is usually provided also between the additional glass plate and the adjacent glass plate.
  • the additional intermediate film may also contain the same acrylic polymer as the intermediate film 5.
  • the laminated glass may further have various functional layers selected from an antireflection layer, an antifouling layer, a dye layer, a hard coat layer, and the like.
  • the antireflection layer is a layer having antireflection properties such that the visible light reflectance of the laminated glass is 5% or less.
  • the antireflection layer can be, for example, a transparent substrate such as a transparent plastic film treated by a known antireflection method.
  • the antifouling layer is provided in order to make the surface difficult to get dirty.
  • the dye layer is provided in order to reduce unnecessary wavelength light transmitted through the laminated glass.
  • the hard coat layer is provided to increase the surface hardness of the laminated glass.
  • the hard coat layer may be a laminated film having a base film such as a polyethylene film and a film made of an acrylic resin (urethane acrylate, epoxy acrylate, etc.) or an epoxy resin formed on the base film.
  • the laminated glass according to the present embodiment includes, for example, two glass plates 11 and 12 that are bonded together with a resin layer for forming the intermediate film 5 interposed therebetween, and includes the glass plates 11 and 12 and the resin layer. It can be manufactured by a method including a step of obtaining a body and a step of heating and pressurizing the laminate.
  • the glass plates 11 and 12 may be bonded together with a resin layer interposed, for example, by a method including providing a resin layer on the glass plate 11 and subsequently laminating the glass plate 12 on the resin layer. it can.
  • the resin layer can be provided on the glass plate 11 using, for example, a film material for an interlayer film of laminated glass described later.
  • the bubbles in the laminate can be efficiently removed by heating and pressurizing the laminate.
  • an autoclave is used for heating and pressurization.
  • the heating temperature may be 30 to 150 ° C, or 50 to 70 ° C.
  • the pressure may be 0.3 to 1.5 MPa, or 0.3 to 0.5 MPa.
  • the heating and heating time may be 5 to 60 minutes, or 10 to 30 minutes. If the heating and pressurizing conditions are within these ranges, bubbles in the laminate can be removed particularly effectively.
  • the intermediate film 5 is formed of a resin composition for an intermediate film of laminated glass containing an acrylic polymer.
  • This resin composition for an intermediate film can contribute to the development of high splitting properties of the laminated glass. Furthermore, an intermediate film formed from the resin composition for an intermediate film is less likely to cause whitening of the laminated glass even in a high humidity environment, and is excellent in terms of reliability.
  • the acrylic polymer is a polymer mainly composed of monomers having one (meth) acryloyl group in the molecule.
  • the acrylic polymer may be a homopolymer of one kind of monomer or a copolymer composed of two or more kinds of monomers.
  • the acrylic polymer may have a weight average molecular weight of 100,000 or more.
  • the weight average molecular weight of the acrylic polymer may be 110,000 or more, or 120,000 or more.
  • the upper limit of the weight average molecular weight of the acrylic polymer is not particularly limited, but may be 1,000,000 or less.
  • a weight average molecular weight means a standard polystyrene conversion value measured by gel permeation chromatography.
  • the glass transition temperature (Tg) of the acrylic polymer may be ⁇ 10 ° C. or lower. If the Tg of the acrylic polymer is low, the impact strength of the laminated glass tends to be high. From the same viewpoint, the Tg of the acrylic polymer may be ⁇ 15 ° C. or lower.
  • the lower limit of Tg of the acrylic polymer is not particularly limited. Usually, it is ⁇ 40 ° C. or higher.
  • the monomer having a (meth) acryloyl group constituting the acrylic polymer is typically a (meth) acryloyloxy group (CH 2 ⁇ CHC ( ⁇ O) O— or CH 2 ⁇ C (CH 3 ) C ( ⁇ O ) A monofunctional monomer having one O-).
  • (meth) acrylic acid methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl ( (Meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate (n-lauryl ( (Meth) acrylate), isomyristyl (meth) acrylate, stearyl (meth) acrylate and alkyl (meth) acrylate having an alkyl group such as isostearyl acrylate (the alkyl group
  • monomers constituting the acrylic polymer include (meth) acrylamide and derivatives thereof.
  • Acrylamide derivatives include (meth) acryloylmorpholine; N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-diethyl (meth) acrylamide And N-hydroxyethyl (meth) acrylamide.
  • the acrylic polymer may contain as a monomer unit a copolymerizable monomer copolymerizable with a monomer having a (meth) acryloyl group. However, usually 80% by mass or more, or 90% by mass or more of the whole acrylic polymer is composed of monomer units derived from a monomer having a (meth) acryloyl group.
  • the copolymerization monomer include styrene, 4-methylstyrene, vinylpyridine, vinylpyrrolidone, vinyl acetate, cyclohexylmaleimide, phenylmaleimide, and maleic anhydride.
  • the resin composition for an interlayer film according to this embodiment may further contain other components such as various additives.
  • various additives include polymerization inhibitors, antioxidants, light stabilizers, silane coupling agents, surfactants, leveling agents, inorganic fillers, and the like.
  • the polymerization inhibitor is added for the purpose of enhancing the storage stability of the resin composition, and an example thereof is paramethoxyphenol.
  • Antioxidants are added for the purpose of improving the heat resistant colorability of the interlayer film, and examples thereof include phosphorus-based; phenol-based; thiol-based antioxidants such as triphenyl phosphite.
  • the light stabilizer is added for the purpose of increasing the resistance to active energy rays such as ultraviolet rays, and an example thereof is HALS (Hindered Amine Light Stabilizer).
  • Silane coupling agents are added to improve adhesion to glass plates.
  • Examples include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and ⁇ -aminopropyltrimethoxysilane. , ⁇ -aminopropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, and ⁇ -glycidoxypropylmethyldiisopropenoxysilane.
  • the surfactant is added to control the peelability from the base material, and examples thereof include a polydimethylsiloxane compound and a fluorine compound.
  • the leveling agent is added to impart flatness to the resin composition, and examples thereof include compounds that lower the surface tension of silicon-based and fluorine-based compounds. These additives may be used alone, or a plurality of additives may be used in combination. The content of these additives is generally about 0.01 to 5% by mass with respect to the total amount of the resin composition.
  • the inorganic filler can be used as long as appropriate transparency of the laminated glass is maintained.
  • examples of the inorganic filler include crushed silica, fused silica, mica, clay mineral, short glass fiber, fine glass powder, hollow glass, calcium carbonate, quartz powder, and metal hydrate.
  • the content of the inorganic filler may be 0.01 to 100 parts by mass, 0.05 to 50 parts by mass, or 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin composition.
  • the resin composition for an interlayer film can be produced, for example, by mixing an acrylic polymer and an additive that is added as necessary and stirring them.
  • FIG. 2 is a schematic cross-sectional view showing an embodiment of a film material for an interlayer film of laminated glass.
  • the film material 2 for interlayer film of laminated glass shown in FIG. 2 has a base material 21, a resin layer 5a, and a base material 22, which are laminated in this order.
  • the resin layer 5a is a layer that becomes an intermediate film when sandwiched between glass plates, and can be a layer that includes the above-described resin composition for an intermediate film.
  • the resin layer 5a may have pressure-sensitive adhesiveness that allows easy bonding of glass plates. According to such a film material, the resin layer 5a can be easily stored and transported.
  • the base materials 21 and 22 may be, for example, polyethylene terephthalate, a polymer film selected from polypropylene and polyethylene, and in particular, may be a polyethylene terephthalate film (hereinafter also referred to as “PET film”). .
  • PET film polyethylene terephthalate film
  • the edge part of the base materials 21 and 22 may protrude outside the outer edge of the resin layer 5a.
  • One of the substrates 21 and 22 may be a substrate (heavy release separator) that exhibits a relatively large peel strength, and the other may be a substrate (light release separator) that exhibits a relatively small peel strength. .
  • the peel strength between the light release separator and the resin layer 5a is lower than the peel strength between the heavy release separator and the resin layer 5a.
  • the peelability of the substrate can be appropriately adjusted depending on the conditions of the surface treatment that imparts the peelability.
  • the base material as a light release separator is peeled off, and the exposed surface of the resin layer 5a is attached to the first glass plate.
  • the base material as the heavy release separator is released from the resin layer 5a.
  • the exposed surface of the resin layer 5a is attached to the second glass plate.
  • the thickness of the substrate as the heavy release separator may be 50 to 200 ⁇ m, 60 to 150 ⁇ m, or 70 to 130 ⁇ m from the viewpoint of workability.
  • the thickness of the substrate as the light release separator may be 25 to 150 ⁇ m, 30 to 100 ⁇ m, or 40 to 75 ⁇ m from the viewpoint of workability.
  • the film material 2 for an intermediate film can be obtained, for example, by forming a resin composition for an intermediate film on the substrate 21.
  • Film formation can be performed by a normal method. For example, by applying a coating liquid prepared by diluting the resin composition for an intermediate film with a solvent onto the substrate 21, and drying the solvent from the coating film to form the resin layer 5a.
  • An intermediate film material can be obtained.
  • the coating method include a flow coating method, a roll coating method, a gravure coating method, a wire bar coating method, and a lip die coating method.
  • the solid content concentration of the coating liquid may be 30% by mass or more, or 40% by mass or more, based on the mass of the coating liquid. It may be 70% by mass or less, or 60% by mass or less.
  • the viscosity of the coating solution may be 1 Pa ⁇ s or more, or 5 Pa ⁇ s or more, or 30 Pa ⁇ s or less, 5 Pa ⁇ s or less, or 15 Pa ⁇ s or less at the coating temperature.
  • Acrylic polymer synthetic acrylic polymer A 96.0 g of isostearyl acrylate (manufactured by Osaka Organic Chemical Co., Ltd., trade name “ISTA”) as an initial monomer was attached to a reaction vessel equipped with a cooling tube, a thermometer, a stirring device, a dropping funnel and a nitrogen introduction tube. 24.0 g of hydroxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name “HEA”) and 150.0 g of methyl ethyl ketone were added. The reaction solution was heated from 25 ° C. to 80 ° C. in 15 minutes while the inside of the reaction vessel was purged with nitrogen at a flow rate of 100 ml / min.
  • Acrylic polymer B 96.0 g and 2 of 2-ethylhexyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd., trade name “EHA”) as an initial monomer was attached to a reaction vessel equipped with a cooling tube, a thermometer, a stirring device, a dropping funnel and a nitrogen introducing tube.
  • EHA 2-ethylhexyl acrylate
  • -24.0 g of hydroxyethyl acrylate (trade name “HEA” manufactured by Osaka Organic Chemical Industry Co., Ltd.) and 150.0 g of methyl ethyl ketone were added.
  • the reaction solution was heated from 25 ° C. to 80 ° C. in 15 minutes while the inside of the reaction vessel was purged with nitrogen at a flow rate of 100 ml / min.
  • Acrylic polymer C In a reaction vessel equipped with a cooling tube, a thermometer, a stirrer, a dropping funnel and a nitrogen introduction tube, 120.0 g of lauryl acrylate as an initial monomer (manufactured by Kyoeisha Chemical Co., Ltd., trade name “Light Acrylate LA”), 150.0 g of methyl ethyl ketone was added. While the inside of the reaction vessel was purged with nitrogen at an air flow of 100 ml / min, it was heated from 25 ° C. to 80 ° C. for 15 minutes.
  • the weight average molecular weight and glass transition temperature of the synthesized acrylic polymer were measured by the following procedure. The measurement results are shown in Table 1.
  • Weight average molecular weight (Mw) The weight average molecular weight of the acrylic polymer was determined by converting from a chromatogram obtained by gel permeation chromatography (GPC) using a standard polystyrene calibration curve. As a standard polystyrene for preparing a calibration curve, 5 sample sets (PStQuick MP-H, PStQuick B [trade name, manufactured by Tosoh Corporation]) were used. GPC was measured with the following equipment and measurement conditions.
  • HLC-8320GPC High-speed GPC device HLC-8320GPC (detector: differential refractometer) (trade name, manufactured by Tosoh Corporation)
  • Solvent Tetrahydrofuran (THF) -Column: Column TSKGEL SuperMultipore HZ-H (trade name, manufactured by Tosoh Corporation)
  • Column size Column length is 15 cm and column inner diameter is 4.6 mm ⁇
  • Flow rate 0.35 mL / min ⁇
  • Sample concentration 10 mg / THF 5 mL
  • Injection volume 20 ⁇ L
  • Tg Glass transition temperature
  • the Tg of the acrylic polymer was determined by viscoelasticity measurement using a rheometer (manufactured by Anton Paar, MCR302). Measurement conditions and methods are shown below. Measurement conditions and rotor name: Parallel plate (PP12) ⁇ Frequency: 1 (s-1) ⁇ Strain amount: 1% Measuring method: The acrylic polymer formed to a thickness of 200 ⁇ m was attached to the metal stage of the rheometer. In this state, while heating the metal stage to 50 ° C., the acrylic polymer film was sandwiched between the metal stage and a parallel plate facing the metal stage. The distance between the metal stage and the parallel plate was set to 195 ⁇ m.
  • the metal plate was cooled to ⁇ 70 ° C., and then the viscoelasticity of the acrylic polymer was measured while increasing the temperature from ⁇ 70 ° C. to 50 ° C. at a temperature increase rate of 3 ° C./min.
  • the temperature at the maximum peak of tan ⁇ was recorded as the glass transition temperature (Tg).
  • Example 1 Preparation of laminated glass (Example 1) [Production of film material for interlayer film] Two types of polyethylene terephthalate films (thickness 75 ⁇ m, manufactured by Fujimori Kogyo Co., Ltd.) having different peelability were prepared as substrates. Using these, a film material for an intermediate film having a resin layer containing an acrylic polymer was produced by the following procedures (I) and (II).
  • the light release separator was peeled from the film material for the interlayer film.
  • the exposed resin layer is affixed to float glass (length 110 mm, width 110 mm, thickness 2.7 mm) as a first glass plate, and in that state, a roller is pressed from the side of the heavy release separator to put the resin layer on the float glass. Adhered. Thereafter, the heavy release separator was peeled from the resin layer.
  • the exposed resin layer was attached to a polycarbonate plate (PC plate, 110 mm long, 110 mm wide, 3.0 mm thick) as a second glass plate in a vacuum state using a vacuum laminator.
  • the obtained laminate was heated and pressurized in an autoclave under the conditions of a temperature of 50 ° C., a pressure of 0.5 MPa, and a 30-minute hold to obtain a laminated glass having a structure of float glass / interlayer film / PC.
  • Example 2 A film material for an intermediate film was obtained in the same manner as in Example 1 except that the acrylic polymer B was used instead of the acrylic polymer A. Using the obtained film material for interlayer film, a laminated glass having a structure of float glass / intermediate film / PC was obtained in the same manner as in Example 1.
  • Example 3 The same film material for an interlayer film as in Example 1 was used, except that a polymethyl methacrylate plate (PMMA plate, 110 mm long, 110 mm wide, 3.0 mm thick) was used instead of the PC plate. A laminated glass having a structure of float glass / intermediate film / PMMA was obtained.
  • PMMA plate polymethyl methacrylate plate
  • Example 4 The same tempered glass / intermediate as in Example 1, except that the same interlayer film material as in Example 1 was used and tempered glass (110 mm long, 110 mm wide, 0.55 mm thick) was used instead of float glass. A laminated glass having a film / PC configuration was obtained.
  • Example 5 The light release separator was peeled from the same film material for an interlayer film as in Example 1.
  • the exposed resin layer is affixed to tempered glass (length 110 mm, width 110 mm, thickness 0.55 mm) as the first glass plate, and in that state, a roller is pressed from the side of the heavy release separator to make the resin layer into tempered glass. Adhered. Thereafter, the heavy release separator was peeled from the resin layer.
  • the exposed resin layer was attached to a polycarbonate plate (PC plate, 110 mm long, 110 mm wide, 3.0 mm thick) as a second glass plate in a vacuum state using a vacuum laminator.
  • PC plate polycarbonate plate
  • the obtained laminate (tempered glass / resin layer / PC plate) was heated and pressurized in an autoclave under the conditions of a temperature of 50 ° C., a pressure of 0.5 MPa, and a 30-minute hold.
  • the light release separator was peeled from the same film material for an interlayer film as in Example 1.
  • the exposed resin layer is affixed to tempered glass (length 110 mm, width 110 mm, thickness 0.55 mm) as a third glass plate, and in that state, a roller is pressed from the side of the heavy release separator to make the resin layer into tempered glass. Adhered.
  • the heavy release separator was peeled off, and the laminate of the tempered glass / resin layer was laminated on the surface of the tempered glass / resin layer / PC plate laminate on the PC plate side so that the resin layer was inward. . Thereafter, the entire laminate is heated and pressurized in an autoclave under the conditions of a temperature of 50 ° C., a pressure of 0.5 MPa, and a holding time of 30 minutes to obtain a laminated glass / interlayer / PC / intermediate / tempered glass composition. Glass was obtained.
  • Example 1 A film material for an intermediate film was obtained in the same manner as in Example 1 except that the acrylic polymer C was used instead of the acrylic polymer A. Using the obtained film material for interlayer film, a laminated glass having a structure of float glass / intermediate film / PC was obtained in the same manner as in Example 1.
  • Comparative Example 2 100 parts by mass of polyvinyl butyral resin (PVB resin, degree of acetalization 68.0 mol%, vinyl acetate component ratio 0.6 mol%) and 38 parts by mass of triethylene glycol di-2-ethylhexanoate as a plasticizer Were mixed and sufficiently melt-kneaded with a mixing roll. The kneaded material was press-molded with a press molding machine at 150 ° C. for 30 minutes to form a resin layer having a thickness of 3.8 ⁇ 10 2 ⁇ m.
  • PVB resin polyvinyl butyral resin
  • degree of acetalization 68.0 mol%, vinyl acetate component ratio 0.6 mol% 38 parts by mass of triethylene glycol di-2-ethylhexanoate
  • the obtained resin layer was sandwiched between two float glasses (length 110 mm, width 110 mm, thickness 2.7 mm).
  • the obtained laminate was put in a rubber bag and deaerated at a vacuum degree of 2660 Pa for 20 minutes.
  • the rubber bag was put into an oven while being deaerated, and the laminate was pressurized with a vacuum pressure while being held at 90 ° C. for 30 minutes.
  • the laminate was pressed in an autoclave at 135 ° C. and a pressure of 118 N / cm 2 for 20 minutes to obtain a laminated glass having a resin layer containing a PVB resin as an intermediate film.
  • the laminated glasses prepared in the examples and comparative examples are fixed to a sample holder of an accelerated weather resistance tester (manufactured by Suga Test Instruments Co., Ltd., SX75), and an irradiation intensity of 180 W / m 2 and a wavelength of 300 are set using a xenon long life arc lamp as a light source.
  • the sample was subjected to an accelerated weathering test under the conditions of a temperature of 63 ° C., a humidity of 50% RH and a test time of 300 hours while irradiating light of ⁇ 400 nm.
  • the case where haze is 1.0 or less and the occurrence of bubbles is not visually confirmed is “Pass”, and the case where haze is 1.0 or more or the occurrence of bubbles is visually confirmed is “NG”. It was.
  • the light release separator was peeled from the film material for the interlayer film.
  • the exposed resin layer is affixed to float glass (length 110 mm, width 110 mm, thickness 2.7 mm) as a first glass plate, and in that state, a roller is pressed from the side of the heavy release separator to put the resin layer on the float glass. Adhered. Thereafter, the heavy release separator was peeled from the resin layer.
  • a polyester film having a length of 200 mm, a width of 100 mm, and a thickness of 125 ⁇ m was bonded to the exposed resin layer to obtain a test sample.
  • a cut having a length of 200 mm and a width of 10 mm was cut into the sample with a cutter from above the polyester film.
  • a tensile tester (Orientec Co., Ltd., trade name: RTC-1210)
  • the polyester film at the incised part was grasped, the peeling angle was 180 °, the peeling speed was 300 mm / min, and the measurement time was 3 seconds.
  • a peel test was performed under the condition of a temperature of 25 ° C. From the load at this time, peel strength (N / 10 mm) was determined.
  • the laminated glass of each example showed excellent impact strength with sufficiently low haze.
  • SYMBOLS 1 Laminated glass, 2 ... Film material for intermediate films of laminated glass, 5 ... Intermediate film, 5a ... Resin layer, 11, 12 ... Glass plate, 21, 22 ... Base material.

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Abstract

Disclosed is a laminated glass provided with: two glass plates that are disposed so as to face each other; and an interlayer that is sandwiched between the two glass plates. Of the two glass plates, one is a transparent plastic plate, and the other is an inorganic glass plate. The interlayer contains an acrylic polymer. This laminated glass has an impact strength of at least 0.03 J/cm2 as measured by an impact resistance test in which a rigid sphere is dropped on the laminated glass.

Description

合わせガラス、及び合わせガラスの中間膜用フィルム材Laminated glass and film material for interlayer film of laminated glass
　本発明は、合わせガラス、及び合わせガラスの中間膜用フィルム材に関する。 The present invention relates to laminated glass and a film material for an interlayer film of laminated glass.
　現在、自動車のような車輌、航空機、建築物等用のガラスとしては、外部衝撃を受けて破損しても、ガラスの破片が飛散することが少なく安全であるため、合わせガラスが広く用いられている。 Currently, laminated glass is widely used as glass for vehicles such as automobiles, aircraft, buildings, etc., even if it is damaged by an external impact, it is safe because the glass fragments do not scatter. Yes.
　合わせガラスは、一般に、少なくとも１対のガラス板と、それらの間に介在してガラス板同士を接着する中間膜とを有する積層体である。合わせガラス用中間膜の一例として、可塑剤により可塑化されたポリビニルブチラール樹脂等のポリビニルアセタール樹脂から形成された膜が挙げられる（特許文献１～３）。 Laminated glass is generally a laminate having at least one pair of glass plates and an intermediate film that is interposed between them and bonds the glass plates together. An example of the interlayer film for laminated glass is a film formed from a polyvinyl acetal resin such as a polyvinyl butyral resin plasticized with a plasticizer (Patent Documents 1 to 3).
特開昭６２－１００４６３号公報JP-A-62-100463 特開２００５－２０６４４５号公報JP 2005-206445 A 国際公開第２０１２／０９１１１７号International Publication No. 2012/091117
　合わせガラスの軽量化のために、無機ガラス板と透明プラスチック板との組み合わせが検討されている。ところが、その場合、従来の中間膜を適用するとヘーズが大きくなる傾向がある。そのため、透明プラスチック板を適用した合わせガラスに関して、外部からの衝撃に耐えるための高い防割性とともに、十分に優れた光学特性を得ることが困難であった。 In order to reduce the weight of laminated glass, combinations of inorganic glass plates and transparent plastic plates are being studied. However, in that case, when a conventional intermediate film is applied, the haze tends to increase. For this reason, it has been difficult to obtain sufficiently excellent optical characteristics as well as high splitting ability to withstand external impacts for laminated glass to which a transparent plastic plate is applied.
　そこで本発明の目的は、透明プラスチック板を適用した合わせガラスに関して、十分に優れた光学特性及び高い防割性を両立させることにある。 Therefore, an object of the present invention is to achieve both sufficiently excellent optical properties and high splitting properties for laminated glass to which a transparent plastic plate is applied.
　本発明の一側面は、対向する２枚のガラス板と、２枚のガラス板の間に挟まれた中間膜と、を備える合わせガラスを提供する。２枚のガラス板のうち一方が透明プラスチック板で、他方が無機ガラス板である。中間膜がアクリル重合体を含み、当該合わせガラスに向けて剛球を落下させる耐衝撃試験によって測定される衝撃強度が、０．０３Ｊ／ｃｍ２以上であってもよい。あるいは、アクリル重合体が１０万以上の重量平均分子量を有していてもよい。 One aspect of the present invention provides a laminated glass including two opposing glass plates and an intermediate film sandwiched between the two glass plates. One of the two glass plates is a transparent plastic plate, and the other is an inorganic glass plate. The impact strength measured by an impact resistance test in which the intermediate film includes an acrylic polymer and a hard sphere is dropped toward the laminated glass may be 0.03 J / cm 2 or more. Alternatively, the acrylic polymer may have a weight average molecular weight of 100,000 or more.
　本発明者らの知見によれば、透明プラスチック板と無機ガラス板との組み合わせを含む合わせガラスに関して、アクリル重合体を含む中間膜を適用することにより、十分に優れた光学特性及び高い防割性を両立させることができる。 According to the knowledge of the present inventors, for laminated glass including a combination of a transparent plastic plate and an inorganic glass plate, by applying an interlayer film containing an acrylic polymer, sufficiently excellent optical properties and high splitting property Can be made compatible.
　透明プラスチック板を用いた合わせガラスに関して、十分に優れた光学特性及び高い防割性を両立させることができる。 Regarding laminated glass using a transparent plastic plate, it is possible to achieve both excellent optical properties and high splitting properties.
合わせガラスの一実施形態を示す模式断面図である。It is a schematic cross section which shows one Embodiment of a laminated glass. 合わせガラスの中間膜用フィルム材の一実施形態を示す模式断面図である。It is a schematic cross section which shows one Embodiment of the film material for interlayer films of a laminated glass.
　以下、場合により図面を参照しつつ本発明の実施形態について説明をする。ただし、本発明は以下の実施形態に何ら限定されるものではない。 Hereinafter, embodiments of the present invention will be described with reference to the drawings depending on cases. However, the present invention is not limited to the following embodiments.
　本明細書において「（メタ）アクリレート」とは、「アクリレート」又はそれに対応する「メタクリレート」のうち少なくとも一方を意味する。（メタ）アクリロイル等の他の類似表現についても同様である。組成物中の各成分の含有量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。 In this specification, “(meth) acrylate” means at least one of “acrylate” or “methacrylate” corresponding thereto. The same applies to other similar expressions such as (meth) acryloyl. The content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition.
＜合わせガラス＞
　図１は、合わせガラスの一実施形態を示す模式断面図である。図１に示す合わせガラス１は、対向する２枚のガラス板１１，１２と、２枚のガラス板１１，１２の間に挟まれた中間膜５とを有する。言い換えると、ガラス板１１（「第１のガラス板」ともいう。）、中間膜５、及びガラス板１２（「第２のガラス板」ともいう）がこの順で積層されている。２枚のガラス板１１，１２のうち、一方が透明プラスチック板で、他方が無機ガラス板であることができる。 <Laminated glass>
FIG. 1 is a schematic cross-sectional view showing an embodiment of a laminated glass. A laminated glass 1 shown in FIG. 1 has two glass plates 11 and 12 facing each other and an intermediate film 5 sandwiched between the two glass plates 11 and 12. In other words, the glass plate 11 (also referred to as “first glass plate”), the intermediate film 5, and the glass plate 12 (also referred to as “second glass plate”) are laminated in this order. One of the two glass plates 11 and 12 can be a transparent plastic plate and the other can be an inorganic glass plate.
　無機ガラス板は、合わせガラスを構成するガラス板として通常用いられているものから選択することができる。無機ガラス板が設けられることにより、合わせガラスの表面が良好な耐傷性を有することができる。無機ガラス板は、例えば、フロートガラス、強化ガラス（風冷強化ガラス、化学強化ガラス等）、又は複層ガラスの板であってもよい。 The inorganic glass plate can be selected from those usually used as a glass plate constituting the laminated glass. By providing the inorganic glass plate, the surface of the laminated glass can have good scratch resistance. The inorganic glass plate may be, for example, a float glass, a tempered glass (air-cooled tempered glass, chemically tempered glass, etc.), or a multilayer glass plate.
　透明プラスチック板としては、合わせガラスに適した透明性等の光学特性を有するプラスチック板が用いられる。透明プラスチック板の例としては、ポリカーボネート樹脂板（ＰＣ板）、ポリメチルメタクリレート樹脂板（ＰＭＭＡ板）、シクロポリオレフィン樹脂板（ＣＯＰ板）、ポリエチレンテレフタレート樹脂板（ＰＥＴ板）、ポリエチレン板（ＰＥ板）、ポリプロピレン板（ＰＰ板）、ポリスチレン板（ＰＳ板）、及びトリアセチルセルロース板（ＴＡＣ板）が挙げられる。 As the transparent plastic plate, a plastic plate having optical properties such as transparency suitable for laminated glass is used. Examples of transparent plastic plates include polycarbonate resin plates (PC plates), polymethyl methacrylate resin plates (PMMA plates), cyclopolyolefin resin plates (COP plates), polyethylene terephthalate resin plates (PET plates), polyethylene plates (PE plates) , Polypropylene plate (PP plate), polystyrene plate (PS plate), and triacetyl cellulose plate (TAC plate).
　中間膜５は、主としてアクリル重合体を含む樹脂層である。中間膜５は、隣接するガラス板１１，１２それぞれの中間膜５側の主面の大部分（例えば、主面のうち９０面積％以上）に直接接することで、２枚のガラス板１１，１２同士を接着している。中間膜５を構成する中間膜用樹脂組成物の詳細については後述される。中間膜５の厚みは、１０～５０００μｍ、又は、２５～１０００μｍであってもよい。 The intermediate film 5 is a resin layer mainly containing an acrylic polymer. The intermediate film 5 is in direct contact with most of the main surfaces of the adjacent glass plates 11 and 12 on the side of the intermediate film 5 (for example, 90% by area or more of the main surfaces), so that the two glass plates 11 and 12 are in contact with each other. Bonding together. Details of the resin composition for the intermediate film constituting the intermediate film 5 will be described later. The thickness of the intermediate film 5 may be 10 to 5000 μm, or 25 to 1000 μm.
　ガラス板１１，１２、及び中間膜５それぞれの可視光領域（波長：３８０ｎｍ～７８０ｎｍ）の光線に対する光透過率が、８０％以上、９０％以上、又は９５％以上であってもよい。合わせガラス１全体の可視光領域の光線に対する光透過率が、８０％以上、９０％以上、又は９５％以上であってもよい。 The light transmittance of each of the glass plates 11 and 12 and the intermediate film 5 in the visible light region (wavelength: 380 nm to 780 nm) may be 80% or more, 90% or more, or 95% or more. The light transmittance of the entire laminated glass 1 with respect to light rays in the visible light region may be 80% or more, 90% or more, or 95% or more.
　合わせガラス１に向けて剛球を落下させる耐衝撃試験によって測定される衝撃強度が、０．０３Ｊ／ｃｍ２以上であってもよい。高い衝撃強度を示す合わせガラスは、十分な防割性を有することができる。同様の理由から、合わせガラス１の衝撃強度は、０．０５Ｊ／ｃｍ２以上、又は０．０６Ｊ／ｃｍ２以上であってもよい。衝撃強度の上限は、特に限定されないが、通常、１０Ｊ／ｃｍ２以下である。衝撃強度の測定方法の詳細は、後述の実施例で説明される。 The impact strength measured by an impact resistance test in which a hard sphere is dropped toward the laminated glass 1 may be 0.03 J / cm 2 or more. Laminated glass exhibiting high impact strength can have sufficient splitting resistance. For the same reason, the impact strength of the laminated glass 1, 0.05 J / cm 2 or more, or may be 0.06 J / cm 2 or more. The upper limit of impact strength is not particularly limited, but is usually 10 J / cm 2 or less. Details of the method of measuring the impact strength will be described in Examples described later.
　一般に、合わせガラスの厚みが大きくなると、衝撃強度が大きくなる傾向がある。そのため、ガラス板及び中間膜の厚みを適切に設定することにより、合わせガラスの衝撃強度を所定の値以上とすることができる。十分な衝撃強度等の観点から、透明プラスチック板の厚みは、０．１～１００ｍｍ、又は、０．５～１０ｍｍ、又は０．５～５ｍｍであってもよい。無機ガラス板の厚みは、０．１～５０ｍｍ、０．５～３０ｍｍ、１～２０ｍｍ、又は２～１０ｍｍであってもよい。合わせガラス１全体の厚みは、通常、０．５～１０００ｍｍ、又は１～１５ｍｍである場合が多い。この程度の厚みを有する本実施形態の合わせガラスは、無機ガラス板と中間膜のみから構成された合わせガラスと比較して十分に軽量でありながら、高い衝撃強度を示し易い。 Generally, as the thickness of laminated glass increases, the impact strength tends to increase. Therefore, the impact strength of the laminated glass can be set to a predetermined value or more by appropriately setting the thicknesses of the glass plate and the interlayer film. From the viewpoint of sufficient impact strength and the like, the thickness of the transparent plastic plate may be 0.1 to 100 mm, 0.5 to 10 mm, or 0.5 to 5 mm. The thickness of the inorganic glass plate may be 0.1 to 50 mm, 0.5 to 30 mm, 1 to 20 mm, or 2 to 10 mm. The total thickness of the laminated glass 1 is usually 0.5 to 1000 mm or 1 to 15 mm in many cases. The laminated glass of the present embodiment having such a thickness is easy to show high impact strength while being sufficiently light compared to the laminated glass composed only of the inorganic glass plate and the intermediate film.
　中間膜としてアクリル重合体を含む樹脂層を適用することにより、合わせガラスの十分な光学特性を維持しながら、ガラス板及び中間膜の厚みを例えば上記の範囲内で制御することで、合わせガラスの衝撃強度を容易に高めることができる。アクリル重合体の重量平均分子量が１０万以上であることも、衝撃強度の向上に寄与することができる。 By applying a resin layer containing an acrylic polymer as an intermediate film, while maintaining sufficient optical properties of the laminated glass, the thickness of the glass plate and the intermediate film is controlled within the above range, for example. Impact strength can be easily increased. The weight average molecular weight of the acrylic polymer being 100,000 or more can also contribute to the improvement of impact strength.
　中間膜５とガラス板１１又はガラス板１２との間の剥離強度は、５Ｎ／１０ｍｍ以上、８Ｎ／１０ｍｍ以上、１０Ｎ／１０ｍｍ以上、又は３０Ｎ／１０ｍｍ以下であってもよい。ここでの剥離強度は、引張試験機（株式会社オリエンテック製、商品名「テンシロン　ＲＴＣ－１２１０」）を用いた、２５℃において引き剥がし速度３００ｍｍ／分で３秒間の１８０度ピール試験により測定される値を意味する。 The peel strength between the intermediate film 5 and the glass plate 11 or the glass plate 12 may be 5 N / 10 mm or more, 8 N / 10 mm or more, 10 N / 10 mm or more, or 30 N / 10 mm or less. The peel strength here was measured by a 180 ° peel test for 3 seconds at a peeling speed of 300 mm / min at 25 ° C. using a tensile tester (trade name “Tensilon RTC-1210” manufactured by Orientec Co., Ltd.). Value.
　合わせガラスの構成は図１の態様に限定されず、適宜変更が可能である。例えば、合わせガラスが、追加のガラス板（第３のガラス板等）として、無機ガラス板及び／又は透明プラスチック板を更に有していてもよい。その場合、通常、追加のガラス板とそれに隣り合うガラス板との間にも追加の中間膜が設けられる。追加の中間膜も、中間膜５と同様のアクリル重合体を含んでいてもよい。 The configuration of the laminated glass is not limited to the embodiment shown in FIG. 1 and can be appropriately changed. For example, the laminated glass may further include an inorganic glass plate and / or a transparent plastic plate as an additional glass plate (such as a third glass plate). In that case, an additional intermediate film is usually provided also between the additional glass plate and the adjacent glass plate. The additional intermediate film may also contain the same acrylic polymer as the intermediate film 5.
　合わせガラスは、反射防止層、防汚層、色素層、及びハードコート層等から選ばれる各種の機能層を更に有していてもよい。 The laminated glass may further have various functional layers selected from an antireflection layer, an antifouling layer, a dye layer, a hard coat layer, and the like.
　反射防止層は、合わせガラスの可視光反射率を５％以下とするような反射防止性を有している層である。反射防止層は、例えば、既知の反射防止方法で処理された透明プラスチックフィルム等の透明基材であることができる。防汚層は、表面に汚れがつきにくくするために設けられる。色素層は、合わせガラスで透過する不要な波長の光を低減するために設けられる。ハードコート層は、合わせガラスの表面硬度を高めるために設けられる。ハードコート層は、ポリエチレンフィルム等の基材フィルムと、基材フィルム上に形成された、アクリル樹脂（ウレタンアクリレート、エポキシアクリレート等）、エポキシ樹脂等の膜とを有する積層フィルムであってもよい。 The antireflection layer is a layer having antireflection properties such that the visible light reflectance of the laminated glass is 5% or less. The antireflection layer can be, for example, a transparent substrate such as a transparent plastic film treated by a known antireflection method. The antifouling layer is provided in order to make the surface difficult to get dirty. The dye layer is provided in order to reduce unnecessary wavelength light transmitted through the laminated glass. The hard coat layer is provided to increase the surface hardness of the laminated glass. The hard coat layer may be a laminated film having a base film such as a polyethylene film and a film made of an acrylic resin (urethane acrylate, epoxy acrylate, etc.) or an epoxy resin formed on the base film.
　本実施形態に係る合わせガラスは、例えば、２枚のガラス板１１，１２を、中間膜５を形成するための樹脂層を介在させながら貼り合せて、ガラス板１１，１２及び樹脂層を有する積層体を得る工程と、積層体を加熱及び加圧する工程とを含む方法により、製造することができる。 The laminated glass according to the present embodiment includes, for example, two glass plates 11 and 12 that are bonded together with a resin layer for forming the intermediate film 5 interposed therebetween, and includes the glass plates 11 and 12 and the resin layer. It can be manufactured by a method including a step of obtaining a body and a step of heating and pressurizing the laminate.
　ガラス板１１，１２は、例えば、ガラス板１１上に樹脂層を設けることと、続いて樹脂層上にガラス板１２を積層することとを含む方法により、樹脂層を介在させながら貼り合せることができる。樹脂層は、例えば後述の合わせガラスの中間膜用フィルム材を用いて、ガラス板１１上に設けることができる。 The glass plates 11 and 12 may be bonded together with a resin layer interposed, for example, by a method including providing a resin layer on the glass plate 11 and subsequently laminating the glass plate 12 on the resin layer. it can. The resin layer can be provided on the glass plate 11 using, for example, a film material for an interlayer film of laminated glass described later.
　積層体の加熱及び加圧によって、積層体内の気泡を効率的に除去することができる。加熱及び加圧のために、例えば、オートクレーブが用いられる。加熱温度は、３０～１５０℃、又は５０～７０℃であってもよい。圧力は０．３～１．５ＭＰａ、又は０．３～０．５ＭＰａであってもよい。加熱及び加熱の時間は、５～６０分、又は１０～３０分であってもよい。加熱及び加圧の条件がこれらの範囲内であれば、積層体内の気泡を特に効果的に除去できる。 The bubbles in the laminate can be efficiently removed by heating and pressurizing the laminate. For example, an autoclave is used for heating and pressurization. The heating temperature may be 30 to 150 ° C, or 50 to 70 ° C. The pressure may be 0.3 to 1.5 MPa, or 0.3 to 0.5 MPa. The heating and heating time may be 5 to 60 minutes, or 10 to 30 minutes. If the heating and pressurizing conditions are within these ranges, bubbles in the laminate can be removed particularly effectively.
＜合わせガラスの中間膜用樹脂組成物＞
　中間膜５は、アクリル重合体を含む、合わせガラスの中間膜用樹脂組成物から形成されている。この中間膜用樹脂組成物は、合わせガラスの高い防割性の発現に寄与することができる。さらに、この中間膜用樹脂組成物から形成された中間膜は、高湿度環境下でも合わせガラスの白化を生じさせ難く、信頼性の点でも優れている。 <Resin composition for interlayer film of laminated glass>
The intermediate film 5 is formed of a resin composition for an intermediate film of laminated glass containing an acrylic polymer. This resin composition for an intermediate film can contribute to the development of high splitting properties of the laminated glass. Furthermore, an intermediate film formed from the resin composition for an intermediate film is less likely to cause whitening of the laminated glass even in a high humidity environment, and is excellent in terms of reliability.
　アクリル重合体は、（メタ）アクリロイル基を分子内に１つ有するモノマーから主として構成される重合体である。アクリル重合体は、１種のモノマーの単独重合体であってもよいし、２種以上のモノマーから構成された共重合体であってもよい。 The acrylic polymer is a polymer mainly composed of monomers having one (meth) acryloyl group in the molecule. The acrylic polymer may be a homopolymer of one kind of monomer or a copolymer composed of two or more kinds of monomers.
　アクリル重合体が、１０万以上の重量平均分子量を有していてもよい。アクリル重合体の重量平均分子量が大きいと、アクリレート重合体の分子鎖同士の絡み合いが複雑化することで中間膜が強靭化して、合わせガラスの衝撃強度が高くなる傾向がある。同様の観点から、アクリル重合体の重量平均分子量は、１１万以上、又は１２万以上であってもよい。アクリル重合体の重量平均分子量の上限は、特に制限されないが、１００万以下であってもよい。ここで、本明細書において、重量平均分子量は、ゲルパーミエーションクロマトグラフィーによって測定される、標準ポリスチレン換算値を意味する。 The acrylic polymer may have a weight average molecular weight of 100,000 or more. When the weight average molecular weight of the acrylic polymer is large, the entanglement of the molecular chains of the acrylate polymer is complicated, so that the interlayer film is toughened and the impact strength of the laminated glass tends to be high. From the same viewpoint, the weight average molecular weight of the acrylic polymer may be 110,000 or more, or 120,000 or more. The upper limit of the weight average molecular weight of the acrylic polymer is not particularly limited, but may be 1,000,000 or less. Here, in this specification, a weight average molecular weight means a standard polystyrene conversion value measured by gel permeation chromatography.
　アクリル重合体のガラス転移温度（Ｔｇ）が、－１０℃以下であってもよい。アクリル重合体のＴｇが低いと、合わせガラスの衝撃強度が高くなる傾向がある。同様の観点から、アクリル重合体のＴｇは、－１５℃以下であってもよい。アクリル重合体のＴｇの下限は、特に制限されないが。通常、－４０℃以上である。 The glass transition temperature (Tg) of the acrylic polymer may be −10 ° C. or lower. If the Tg of the acrylic polymer is low, the impact strength of the laminated glass tends to be high. From the same viewpoint, the Tg of the acrylic polymer may be −15 ° C. or lower. The lower limit of Tg of the acrylic polymer is not particularly limited. Usually, it is −40 ° C. or higher.
　アクリル重合体を構成する（メタ）アクリロイル基を有するモノマーは、典型的には（メタ）アクリロイルオキシ基（ＣＨ２＝ＣＨＣ（＝Ｏ）Ｏ－又はＣＨ２＝Ｃ（ＣＨ３）Ｃ（＝Ｏ）Ｏ－）を１つ有する単官能モノマーである。その具体例としては、（メタ）アクリル酸；メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、ｎ－ペンチル（メタ）アクリレート、ｎ－ヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ドデシル（メタ）アクリレート（ｎ－ラウリル（メタ）アクリレート）、イソミリスチル（メタ）アクリレート、ステアリル（メタ）アクリレート及びイソステアリルアクリレート等のアルキル基を有するアルキル（メタ）アクリレート（アルキル基の炭素数が１～１８であってもよい）；グリシジル（メタ）アクリレート；３－ブテニル（メタ）アクリレート等のアルケニル基を有するアルケニル（メタ）アクリレート（アルキル基の炭素数が２～１８であってもよい）；ベンジル（メタ）アクリレート及びフェノキシエチル（メタ）アクリレート等の芳香環を有する（メタ）アクリレート；メトキシテトラエチレングリコール（メタ）アクリレート、メトキシヘキサエチレングリコール（メタ）アクリレート、メトキシオクタエチレングリコール（メタ）アクリレート、メトキシノナエチレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、メトキシヘプタプロピレングリコール（メタ）アクリレート、エトキシテトラエチレングリコール（メタ）アクリレート、ブトキシエチレングリコール（メタ）アクリレート及びブトキシジエチレングリコール（メタ）アクリレート等のアルコキシポリアルキレングリコール（メタ）アクリレート；シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート及びジシクロペンタニル（メタ）アクリレート等の脂環式基を有する（メタ）アクリレート；２－ヒドロキシエチル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート及び４－ヒドロキシブチル（メタ）アクリレート等の水酸基を有する（メタ）アクリレート；テトラヒドロフルフリル（メタ）アクリレート；Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、２－（２－メタクリロイルオキシエチルオキシ）エチルイソシアネート及び２－（メタ）アクリロイルオキシエチルイソシアネート等のイソシアネート基を有する（メタ）アクリレート；テトラエチレングリコールモノ（メタ）アクリレート、ヘキサエチレングリコールモノ（メタ）アクリレート、オクタプロピレングリコールモノ（メタ）アクリレート、ジプロピレングリコールモノ（メタ）アクリレート、トリプロピレングリコールモノ（メタ）アクリレート及びオクタプロピレングリコールモノ（メタ）アクリレート等のポリアルキレングリコールモノ（メタ）アクリレート；シロキサン骨格を有する（メタ）アクリレートが挙げられる。これらの化合物は、１種単独で又は２種以上を組み合わせて用いることができる。 The monomer having a (meth) acryloyl group constituting the acrylic polymer is typically a (meth) acryloyloxy group (CH 2 ═CHC (═O) O— or CH 2 ═C (CH 3 ) C (═O ) A monofunctional monomer having one O-). Specific examples thereof include (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl ( (Meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate (n-lauryl ( (Meth) acrylate), isomyristyl (meth) acrylate, stearyl (meth) acrylate and alkyl (meth) acrylate having an alkyl group such as isostearyl acrylate (the alkyl group may have 1 to 18 carbon atoms); Lysidyl (meth) acrylate; alkenyl (meth) acrylate having an alkenyl group such as 3-butenyl (meth) acrylate (the alkyl group may have 2 to 18 carbon atoms); benzyl (meth) acrylate and phenoxyethyl ( (Meth) acrylate having an aromatic ring such as (meth) acrylate; methoxytetraethylene glycol (meth) acrylate, methoxyhexaethylene glycol (meth) acrylate, methoxyoctaethylene glycol (meth) acrylate, methoxynonaethylene glycol (meth) acrylate, Methoxypolyethylene glycol (meth) acrylate, methoxyheptapropylene glycol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, butoxyethylene Alkali polyalkylene glycol (meth) acrylates such as recall (meth) acrylate and butoxydiethylene glycol (meth) acrylate; alicyclic groups such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate (Meth) acrylate having; (meth) acrylate having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; tetrahydrofurfuryl (meth) acrylate; N, N-dimethylaminoethyl (meth) acrylate, 2- (2-methacryloyloxyethyloxy) ethyl isocyanate and 2- (meth) acryloyloxyethyl isocyanate (Meth) acrylates having isocyanate groups such as nates; tetraethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, octapropylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene Examples include polyalkylene glycol mono (meth) acrylates such as glycol mono (meth) acrylate and octapropylene glycol mono (meth) acrylate; and (meth) acrylates having a siloxane skeleton. These compounds can be used individually by 1 type or in combination of 2 or more types.
　アクリル重合体を構成するモノマーの他の例として、（メタ）アクリルアミド及びその誘導体がある。アクリルアミド誘導体としては、（メタ）アクリロイルモルホリン；Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ－イソプロピル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチル（メタ）アクリルアミド及びＮ－ヒドロキシエチル（メタ）アクリルアミドが挙げられる。 Other examples of monomers constituting the acrylic polymer include (meth) acrylamide and derivatives thereof. Acrylamide derivatives include (meth) acryloylmorpholine; N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-diethyl (meth) acrylamide And N-hydroxyethyl (meth) acrylamide.
　アクリル重合体は、（メタ）アクリロイル基を有するモノマーと共重合可能な共重合モノマーをモノマー単位として含んでいてもよい。ただし、通常、アクリル重合体全体のうち８０質量％以上、又は９０質量％以上は、（メタ）アクリロイル基を有するモノマーに由来するモノマー単位から構成される。共重合モノマーとしては、例えば、スチレン、４－メチルスチレン、ビニルピリジン、ビニルピロリドン、酢酸ビニル、シクロヘキシルマレイミド、フェニルマレイミド及び無水マレイン酸が挙げられる。 The acrylic polymer may contain as a monomer unit a copolymerizable monomer copolymerizable with a monomer having a (meth) acryloyl group. However, usually 80% by mass or more, or 90% by mass or more of the whole acrylic polymer is composed of monomer units derived from a monomer having a (meth) acryloyl group. Examples of the copolymerization monomer include styrene, 4-methylstyrene, vinylpyridine, vinylpyrrolidone, vinyl acetate, cyclohexylmaleimide, phenylmaleimide, and maleic anhydride.
　中間膜用樹脂組成物、又は、これから形成される樹脂層及び中間膜におけるアクリル重合体の含有量は、中間膜用樹脂組成物、樹脂層又は中間膜の全体量に対して、８０質量％以上、９０質量％以上、又は９５質量％以上であってもよい。 The content of the acrylic polymer in the resin composition for an intermediate film, or the resin layer and the intermediate film formed therefrom is 80% by mass or more based on the total amount of the resin composition for the intermediate film, the resin layer or the intermediate film. 90 mass% or more, or 95 mass% or more.
　本実施形態の中間膜用樹脂組成物は、各種添加剤等の他の成分を更に含有していてもよい。各種添加剤としては、重合禁止剤、酸化防止剤、光安定化剤、シランカップリング剤、界面活性剤、レベリング剤、無機充填剤等が挙げられる。 The resin composition for an interlayer film according to this embodiment may further contain other components such as various additives. Examples of the various additives include polymerization inhibitors, antioxidants, light stabilizers, silane coupling agents, surfactants, leveling agents, inorganic fillers, and the like.
　重合禁止剤は、樹脂組成物の保存安定性を高める目的で添加され、その例としてはパラメトキシフェノールが挙げられる。酸化防止剤は、中間膜の耐熱着色性を高める目的で添加され、その例としてはトリフェニルホスファイト等のリン系；フェノール系；チオール系の酸化防止剤が挙げられる。光安定化剤は、紫外線等の活性エネルギー線に対する耐性を高める目的で添加され、その例としてはＨＡＬＳ（Ｈｉｎｄｅｒｅｄ　Ａｍｉｎｅ　Ｌｉｇｈｔ　Ｓｔａｂｉｌｉｚｅｒ）が挙げられる。シランカップリング剤は、ガラス板との密着性を高めるために添加され、その例としてはメチルトリメトキシシラン、メチルトリエトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、γ－アミノプロピルトリメトキシシラン、γ－アミノプロピルトリエトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γ－グリシドキシプロピルメチルジエトキシシラン、及びγ－グリシドキシプロピルメチルジイソプロペノキシシランが挙げられる。界面活性剤は、基材との剥離性を制御するために添加され、その例としてはポリジメチルシロキサン系化合物、及びフッ素系化合物が挙げられる。レベリング剤は、樹脂組成物の平坦性を付与するために添加され、その例としてはシリコン系、フッ素系の表面張力を下げる化合物が挙げられる。これらの添加剤は、単独で用いてもよく、また、複数の添加剤を組み合わせて用いてもよい。これらの添加剤の含有量は、一般に樹脂組成物の全量に対して０．０１～５質量％程度である。 The polymerization inhibitor is added for the purpose of enhancing the storage stability of the resin composition, and an example thereof is paramethoxyphenol. Antioxidants are added for the purpose of improving the heat resistant colorability of the interlayer film, and examples thereof include phosphorus-based; phenol-based; thiol-based antioxidants such as triphenyl phosphite. The light stabilizer is added for the purpose of increasing the resistance to active energy rays such as ultraviolet rays, and an example thereof is HALS (Hindered Amine Light Stabilizer). Silane coupling agents are added to improve adhesion to glass plates. Examples include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and γ-aminopropyltrimethoxysilane. , Γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and γ-glycidoxypropylmethyldiisopropenoxysilane. The surfactant is added to control the peelability from the base material, and examples thereof include a polydimethylsiloxane compound and a fluorine compound. The leveling agent is added to impart flatness to the resin composition, and examples thereof include compounds that lower the surface tension of silicon-based and fluorine-based compounds. These additives may be used alone, or a plurality of additives may be used in combination. The content of these additives is generally about 0.01 to 5% by mass with respect to the total amount of the resin composition.
　無機充填剤は、合わせガラスの適切な透明性が維持される範囲で、用いられ得る。無機充填剤としては、例えば、破砕シリカ、溶融シリカ、マイカ、粘土鉱物、ガラス短繊維、ガラス微粉末、中空ガラス、炭酸カルシウム、石英粉末、及び金属水和物が挙げられる。無機充填剤の含有量は、樹脂組成物１００質量部に対し、０．０１～１００質量部、０．０５～５０質量部、又は０．１～３０質量部であってもよい。 The inorganic filler can be used as long as appropriate transparency of the laminated glass is maintained. Examples of the inorganic filler include crushed silica, fused silica, mica, clay mineral, short glass fiber, fine glass powder, hollow glass, calcium carbonate, quartz powder, and metal hydrate. The content of the inorganic filler may be 0.01 to 100 parts by mass, 0.05 to 50 parts by mass, or 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin composition.
　中間膜用樹脂組成物は、例えば、アクリル重合体及び必要により加えられる添加剤を混合し、これらを撹拌することにより製造することができる。 The resin composition for an interlayer film can be produced, for example, by mixing an acrylic polymer and an additive that is added as necessary and stirring them.
＜合わせガラスの中間膜用フィルム材＞
　図２は、合わせガラスの中間膜用フィルム材の一実施形態を示す模式断面図である。図２に示す合わせガラスの中間膜用フィルム材２は、基材２１、樹脂層５ａ、及び基材２２を有し、これらがこの順で積層されている。樹脂層５ａは、ガラス板に挟まれたときに中間膜となる層であり、上述の中間膜用樹脂組成物を含む層であることができる。樹脂層５ａは、ガラス板同士の容易な貼り合せを可能にする感圧接着性を有していていてもよい。このようなフィルム材によれば、樹脂層５ａを、容易に保管及び運搬することができる。 <Film material for interlayer film of laminated glass>
FIG. 2 is a schematic cross-sectional view showing an embodiment of a film material for an interlayer film of laminated glass. The film material 2 for interlayer film of laminated glass shown in FIG. 2 has a base material 21, a resin layer 5a, and a base material 22, which are laminated in this order. The resin layer 5a is a layer that becomes an intermediate film when sandwiched between glass plates, and can be a layer that includes the above-described resin composition for an intermediate film. The resin layer 5a may have pressure-sensitive adhesiveness that allows easy bonding of glass plates. According to such a film material, the resin layer 5a can be easily stored and transported.
　基材２１，２２は、例えば、ポリエチレンテレフタレート、及びポリプロピレン、ポリエチレンから選ばれる重合体のフィルムであってもよく、特にポリエチレンテレフタレートフィルム（以下、「ＰＥＴフィルム」という場合もある）であってもよい。基材２１，２２の端部が、樹脂層５ａの外縁よりも外側に張り出していてもよい。 The base materials 21 and 22 may be, for example, polyethylene terephthalate, a polymer film selected from polypropylene and polyethylene, and in particular, may be a polyethylene terephthalate film (hereinafter also referred to as “PET film”). . The edge part of the base materials 21 and 22 may protrude outside the outer edge of the resin layer 5a.
　基材２１，２２のうち一方が相対的に大きい剥離強度を発現する基材（重剥離セパレータ）で、他方が相対的に小さい剥離強度を発現する基材（軽剥離セパレータ）であってもよい。軽剥離セパレータと樹脂層５ａとの間の剥離強度は、重剥離セパレータと樹脂層５ａとの間の剥離強度よりも低い。基材の剥離性は、剥離性を付与する表面処理の条件によって適宜調整することができる。 One of the substrates 21 and 22 may be a substrate (heavy release separator) that exhibits a relatively large peel strength, and the other may be a substrate (light release separator) that exhibits a relatively small peel strength. . The peel strength between the light release separator and the resin layer 5a is lower than the peel strength between the heavy release separator and the resin layer 5a. The peelability of the substrate can be appropriately adjusted depending on the conditions of the surface treatment that imparts the peelability.
　中間膜用フィルム材２を合わせガラス１を製造するために用いる場合、まず、軽剥離セパレータとしての基材を剥離し、露出した樹脂層５ａの表面を第１のガラス板に貼り付ける。重剥離セパレータとしての基材側からローラー等で押し付けてもよい。続いて、重剥離セパレータとしての基材を樹脂層５ａから剥離する。露出した樹脂層５ａの表面を、第２のガラス板に貼り付ける。この方法により、樹脂層５ａを介在させながら、２枚のガラス板を容易に貼り合せることができる。 When using the film material 2 for interlayer films for manufacturing the laminated glass 1, first, the base material as a light release separator is peeled off, and the exposed surface of the resin layer 5a is attached to the first glass plate. You may press with a roller etc. from the base-material side as a heavy peeling separator. Subsequently, the base material as the heavy release separator is released from the resin layer 5a. The exposed surface of the resin layer 5a is attached to the second glass plate. By this method, two glass plates can be easily bonded together with the resin layer 5a interposed.
　重剥離セパレータとしての基材の厚みは、作業性の観点から、５０～２００μｍで、６０～１５０μｍ、又は７０～１３０μｍであってもよい。軽剥離セパレータとしての基材の厚みは、作業性の観点から、２５～１５０μｍ、３０～１００μｍ、又は４０～７５μｍであってもよい。 The thickness of the substrate as the heavy release separator may be 50 to 200 μm, 60 to 150 μm, or 70 to 130 μm from the viewpoint of workability. The thickness of the substrate as the light release separator may be 25 to 150 μm, 30 to 100 μm, or 40 to 75 μm from the viewpoint of workability.
　中間膜用フィルム材２は、例えば、中間膜用樹脂組成物を基材２１上に製膜することにより得ることができる。製膜は、通常の方法により行うことができる。例えば、中間膜用樹脂組成物を溶剤で希釈して調製した塗工液を基材２１上に塗布することと、塗膜から溶剤を乾燥して樹脂層５ａを形成することとを含む方法により、中間膜用フィルム材を得ることができる。塗工法としては、例えばフローコート法、ロールコート法、グラビアコート法、ワイヤバーコート法、及びリップダイコート法が挙げられる。 The film material 2 for an intermediate film can be obtained, for example, by forming a resin composition for an intermediate film on the substrate 21. Film formation can be performed by a normal method. For example, by applying a coating liquid prepared by diluting the resin composition for an intermediate film with a solvent onto the substrate 21, and drying the solvent from the coating film to form the resin layer 5a. An intermediate film material can be obtained. Examples of the coating method include a flow coating method, a roll coating method, a gravure coating method, a wire bar coating method, and a lip die coating method.
　上記塗工液を調製するための溶剤としては、例えば２－ブタノン、シクロヘキサノン等のケトン溶媒を用いることができる。塗工性の観点からは、塗工液の固形分濃度（溶剤以外の成分の濃度）は、塗工液の質量を基準として、３０質量％以上、又は４０質量％以上であってもよく、７０質量％以下、又は６０質量％以下であってもよい。塗工液の粘度は、塗工温度で１Ｐａ・ｓ以上、又は５Ｐａ・ｓ以上であってもよく、３０Ｐａ・ｓ以下、５Ｐａ・ｓ以下、又は１５Ｐａ・ｓ以下であってもよい。 As a solvent for preparing the coating liquid, for example, a ketone solvent such as 2-butanone or cyclohexanone can be used. From the viewpoint of coating properties, the solid content concentration of the coating liquid (concentration of components other than the solvent) may be 30% by mass or more, or 40% by mass or more, based on the mass of the coating liquid. It may be 70% by mass or less, or 60% by mass or less. The viscosity of the coating solution may be 1 Pa · s or more, or 5 Pa · s or more, or 30 Pa · s or less, 5 Pa · s or less, or 15 Pa · s or less at the coating temperature.
　以下、実施例を挙げて本発明をより具体的に説明する。ただし、本発明はこれらの実施例に制限されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
１．アクリル重合体の合成
アクリル重合体Ａ
　冷却管、温度計、撹拌装置、滴下漏斗及び窒素導入管を取り付けた反応容器に、初期モノマーとしてのイソステアリルアクリレート（大阪有機化学工業株式会社製、商品名「ＩＳＴＡ」）９６．０ｇ及び２－ヒドロキシエチルアクリレート（大阪有機化学工業株式会社製、商品名「ＨＥＡ」）２４．０ｇと、メチルエチルケトン１５０．０ｇとを入れた。反応容器内を１００ｍｌ／分の風量で窒素置換しながら、反応液を１５分間で２５℃から８０℃まで加熱した。その後、反応液の温度を８０℃に維持しながら、追加モノマーとしてのイソステアリルアクリレート２４．０ｇ及び２－ヒドロキシエチルアクリレート６．０ｇと、ｔ－ブチルパーオキシ－２－エチルヘキサノエート１．０ｇとを含む溶液を１２０分間かけて滴下した。滴下終了後、更に２時間反応を進行させた。続いて、メチルエチルケトンを留去することによりイソステアリルアクリレートと２－ヒドロキシエチルアクリレートとの共重合体であるアクリル重合体Ａ（重量平均分子量：１２００００、Ｔｇ：－１８℃）を得た。 1. Acrylic polymer synthetic acrylic polymer A
96.0 g of isostearyl acrylate (manufactured by Osaka Organic Chemical Co., Ltd., trade name “ISTA”) as an initial monomer was attached to a reaction vessel equipped with a cooling tube, a thermometer, a stirring device, a dropping funnel and a nitrogen introduction tube. 24.0 g of hydroxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name “HEA”) and 150.0 g of methyl ethyl ketone were added. The reaction solution was heated from 25 ° C. to 80 ° C. in 15 minutes while the inside of the reaction vessel was purged with nitrogen at a flow rate of 100 ml / min. Thereafter, while maintaining the temperature of the reaction solution at 80 ° C., 24.0 g of isostearyl acrylate and 6.0 g of 2-hydroxyethyl acrylate as additional monomers and 1.0 g of t-butylperoxy-2-ethylhexanoate were added. The solution containing was added dropwise over 120 minutes. After completion of the dropwise addition, the reaction was further allowed to proceed for 2 hours. Subsequently, methyl ethyl ketone was distilled off to obtain an acrylic polymer A (weight average molecular weight: 120,000, Tg: -18 ° C.), which is a copolymer of isostearyl acrylate and 2-hydroxyethyl acrylate.
アクリル重合体Ｂ
　冷却管、温度計、撹拌装置、滴下漏斗及び窒素導入管を取り付けた反応容器に、初期モノマーとしての２－エチルヘキシルアクリレート（和光純薬工業株式会社製、商品名「ＥＨＡ」）９６．０ｇ及び２－ヒドロキシエチルアクリレート（大阪有機化学工業株式会社製、商品名「ＨＥＡ」）２４．０ｇと、メチルエチルケトン１５０．０ｇとを入れた。反応容器内を１００ｍｌ／分の風量で窒素置換しながら、反応液を１５分間で２５℃から８０℃まで加熱した。その後、温度を８０℃に維持しながら、追加モノマーとしての２－エチルヘキシルアクリレート２４．０ｇ及び２－ヒドロキシエチルアクリレート６．０ｇと、ｔ－ブチルパーオキシ－２－エチルヘキサノエート１．０ｇとを含む溶液を１２０分間かけて滴下した。滴下終了後、更に２時間反応を進行させた。続いて、メチルエチルケトンを留去することにより２－エチシルヘキシルアクリレートと２－ヒドロキシエチルアクリレートとの共重合であるアクリル重合体Ｂ（重量平均分子量１２８０００、Ｔｇ：－２０℃）を得た。 Acrylic polymer B
96.0 g and 2 of 2-ethylhexyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd., trade name “EHA”) as an initial monomer was attached to a reaction vessel equipped with a cooling tube, a thermometer, a stirring device, a dropping funnel and a nitrogen introducing tube. -24.0 g of hydroxyethyl acrylate (trade name “HEA” manufactured by Osaka Organic Chemical Industry Co., Ltd.) and 150.0 g of methyl ethyl ketone were added. The reaction solution was heated from 25 ° C. to 80 ° C. in 15 minutes while the inside of the reaction vessel was purged with nitrogen at a flow rate of 100 ml / min. Thereafter, while maintaining the temperature at 80 ° C., 24.0 g of 2-ethylhexyl acrylate and 6.0 g of 2-hydroxyethyl acrylate as additional monomers and 1.0 g of t-butylperoxy-2-ethylhexanoate were added. The containing solution was added dropwise over 120 minutes. After completion of the dropwise addition, the reaction was further allowed to proceed for 2 hours. Subsequently, methyl ethyl ketone was distilled off to obtain acrylic polymer B (weight average molecular weight 128000, Tg: −20 ° C.), which was a copolymer of 2-ethyhexyl acrylate and 2-hydroxyethyl acrylate.
アクリル重合体Ｃ
　冷却管、温度計、撹拌装置、滴下漏斗及び窒素導入管を取り付けた反応容器に、初期モノマーとしてのラウリルアクリレート（共栄社化学株式会社製、商品名「ライトアクリレートＬ-Ａ」）１２０．０ｇと、メチルエチルケトン１５０．０ｇとを入れた。反応容器内を１００ｍｌ／分の風量で窒素置換しながら、１５分間で２５℃から８０℃まで加熱した。その後、温度を８０℃に維持しながら、追加モノマーとしてのイソステアリルアクリレート２４．０ｇ及び２－ヒドロキシエチルアクリレート６．０ｇと、ｔ－ブチルパーオキシ－２－エチルヘキサノエート５．０ｇとを含む溶液を１２０分間かけて滴下した。滴下終了後、更に２時間反応を進行させた。続いて、メチルエチルケトンを留去することによりイソステアリルアクリレートと２－ヒドロキシエチルアクリレートとの共重合体であるアクリル重合体Ｃ（重量平均分子量３０，０００、Ｔｇ：－３℃）を得た。 Acrylic polymer C
In a reaction vessel equipped with a cooling tube, a thermometer, a stirrer, a dropping funnel and a nitrogen introduction tube, 120.0 g of lauryl acrylate as an initial monomer (manufactured by Kyoeisha Chemical Co., Ltd., trade name “Light Acrylate LA”), 150.0 g of methyl ethyl ketone was added. While the inside of the reaction vessel was purged with nitrogen at an air flow of 100 ml / min, it was heated from 25 ° C. to 80 ° C. for 15 minutes. Thereafter, while maintaining the temperature at 80 ° C., 24.0 g of isostearyl acrylate and 6.0 g of 2-hydroxyethyl acrylate as additional monomers and 5.0 g of t-butylperoxy-2-ethylhexanoate are contained. The solution was added dropwise over 120 minutes. After completion of the dropwise addition, the reaction was further allowed to proceed for 2 hours. Subsequently, methyl ethyl ketone was distilled off to obtain an acrylic polymer C (weight average molecular weight 30,000, Tg: −3 ° C.), which is a copolymer of isostearyl acrylate and 2-hydroxyethyl acrylate.
　合成したアクリル重合体の重量平均分子量及びガラス転移温度を以下の手順で測定した。測定結果を表１に示す。 The weight average molecular weight and glass transition temperature of the synthesized acrylic polymer were measured by the following procedure. The measurement results are shown in Table 1.
重量平均分子量（Ｍｗ）
　アクリル重合体の重量平均分子量を、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）によって得られたクロマトグラムから、標準ポリスチレンの検量線を使用して換算することによって決定した。検量線の作成のための標準ポリスチレンとして、５サンプルセット（ＰＳｔＱｕｉｃｋ　ＭＰ－Ｈ，ＰＳｔＱｕｉｃｋ　Ｂ［東ソー株式会社製、商品名］）を用いた。ＧＰＣは下記の装置及び測定条件で測定した、
・装置：高速ＧＰＣ装置　ＨＬＣ－８３２０ＧＰＣ（検出器：示差屈折計）（東ソー株式会社製、商品名）
・溶媒：テトラヒドロフラン（ＴＨＦ）
・カラム：カラムＴＳＫＧＥＬ　ＳｕｐｅｒＭｕｌｔｉｐｏｒｅ　ＨＺ－Ｈ（東ソー株式会社製、商品名）
・カラムサイズ：カラム長が１５ｃｍ、カラム内径が４．６ｍｍ
・測定温度：４０℃
・流量：０．３５ｍＬ／分
・試料濃度：１０ｍｇ／ＴＨＦ５ｍＬ
・注入量：２０μＬ Weight average molecular weight (Mw)
The weight average molecular weight of the acrylic polymer was determined by converting from a chromatogram obtained by gel permeation chromatography (GPC) using a standard polystyrene calibration curve. As a standard polystyrene for preparing a calibration curve, 5 sample sets (PStQuick MP-H, PStQuick B [trade name, manufactured by Tosoh Corporation]) were used. GPC was measured with the following equipment and measurement conditions.
・ Device: High-speed GPC device HLC-8320GPC (detector: differential refractometer) (trade name, manufactured by Tosoh Corporation)
・ Solvent: Tetrahydrofuran (THF)
-Column: Column TSKGEL SuperMultipore HZ-H (trade name, manufactured by Tosoh Corporation)
Column size: Column length is 15 cm and column inner diameter is 4.6 mm
・ Measurement temperature: 40 ℃
・ Flow rate: 0.35 mL / min ・ Sample concentration: 10 mg / THF 5 mL
・ Injection volume: 20μL
ガラス転移温度（Ｔｇ）
　アクリル重合体のＴｇを、レオメータ（Ａｎｔｏｎ　Ｐａａｒ製、ＭＣＲ３０２)を用いた粘弾性測定によって求めた。測定条件及び方法を以下に示す。
測定条件
・ローター名称：パラレルプレート（ＰＰ１２）
・周波数：１(s-1)
・ひずみ量：１％
測定方法：
厚み２００μｍに製膜されたアクリル重合体を、レオメータの金属ステージに貼り付けた。この状態で金属ステージを５０℃に加温しながら、金属ステージ及びこれと対向するパラレルプレートでアクリル重合体の膜を挟んだ。金属ステージとパラレルプレートの間隔を１９５μｍに設定した。その後、金属プレートを－７０℃まで冷却してから、－７０℃から５０℃まで、昇温速度３℃／分で昇温させながらアクリル重合体の粘弾性を測定した。ｔａｎδの最大ピークにおける温度をガラス転移温度（Ｔｇ）として記録した。 Glass transition temperature (Tg)
The Tg of the acrylic polymer was determined by viscoelasticity measurement using a rheometer (manufactured by Anton Paar, MCR302). Measurement conditions and methods are shown below.
Measurement conditions and rotor name: Parallel plate (PP12)
・ Frequency: 1 (s-1)
・ Strain amount: 1%
Measuring method:
The acrylic polymer formed to a thickness of 200 μm was attached to the metal stage of the rheometer. In this state, while heating the metal stage to 50 ° C., the acrylic polymer film was sandwiched between the metal stage and a parallel plate facing the metal stage. The distance between the metal stage and the parallel plate was set to 195 μm. Thereafter, the metal plate was cooled to −70 ° C., and then the viscoelasticity of the acrylic polymer was measured while increasing the temperature from −70 ° C. to 50 ° C. at a temperature increase rate of 3 ° C./min. The temperature at the maximum peak of tan δ was recorded as the glass transition temperature (Tg).
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
２．合わせガラスの作製
（実施例１）
［中間膜用フィルム材の作製］
　基材として、剥離性の異なる２種類のポリエチレンテレフタレートフィルム（厚さ７５μｍ、藤森工業株式会社製）を準備した。これらを用いて、以下の（Ｉ）、（ＩＩ）の手順で、アクリル重合体を含有する樹脂層を有する中間膜用フィルム材を作製した。 2. Preparation of laminated glass (Example 1)
[Production of film material for interlayer film]
Two types of polyethylene terephthalate films (thickness 75 μm, manufactured by Fujimori Kogyo Co., Ltd.) having different peelability were prepared as substrates. Using these, a film material for an intermediate film having a resin layer containing an acrylic polymer was produced by the following procedures (I) and (II).
（Ｉ）：アクリル重合体６０質量部及び２－ブタノンを４０．０質量部を、撹拌によって混合して、塗工液を得る。
（ＩＩ）：（Ｉ）で得られた塗工液を重剥離セパレータとしてのポリエチレンテレフタレートフィルム上にバーコーターを用いて塗布し、塗膜を１００℃で５分間の加熱により乾燥して、厚み１００μｍの樹脂層を形成させる。樹脂層上に軽剥離セパレータとしてのポリエチレンテレフタレートフィルムを積層して、中間膜用フィルム材を得る。 (I): 60 parts by mass of an acrylic polymer and 40.0 parts by mass of 2-butanone are mixed by stirring to obtain a coating solution.
(II): The coating liquid obtained in (I) was applied onto a polyethylene terephthalate film as a heavy release separator using a bar coater, and the coating film was dried by heating at 100 ° C. for 5 minutes to a thickness of 100 μm. The resin layer is formed. A polyethylene terephthalate film as a light release separator is laminated on the resin layer to obtain an intermediate film material.
［合わせガラスの作製］
　中間膜用フィルム材から、軽剥離セパレータを剥離した。露出した樹脂層を、第１のガラス板としてのフロートガラス（縦１１０ｍｍ、横１１０ｍｍ、厚み２．７ｍｍ）に貼り付け、その状態で重剥離セパレータ側からローラーを押し付けて、樹脂層をフロートガラスに密着させた。その後、重剥離セパレータを樹脂層から剥離した。露出した樹脂層を、真空積層機を用いて真空状態で第２のガラス板としてのポリカーボネート板（ＰＣ板、縦１１０ｍｍ、横１１０ｍｍ、厚み３．０ｍｍ）に貼り付けた。得られた積層体を温度５０℃、圧力０．５ＭＰａ、３０分保持の条件でオートクレーブ内で加熱及び加圧して、フロートガラス／中間膜／ＰＣの構成を有する合わせガラスを得た。 [Production of laminated glass]
The light release separator was peeled from the film material for the interlayer film. The exposed resin layer is affixed to float glass (length 110 mm, width 110 mm, thickness 2.7 mm) as a first glass plate, and in that state, a roller is pressed from the side of the heavy release separator to put the resin layer on the float glass. Adhered. Thereafter, the heavy release separator was peeled from the resin layer. The exposed resin layer was attached to a polycarbonate plate (PC plate, 110 mm long, 110 mm wide, 3.0 mm thick) as a second glass plate in a vacuum state using a vacuum laminator. The obtained laminate was heated and pressurized in an autoclave under the conditions of a temperature of 50 ° C., a pressure of 0.5 MPa, and a 30-minute hold to obtain a laminated glass having a structure of float glass / interlayer film / PC.
（実施例２）
　アクリル重合体Ａに代えてアクリル重合体Ｂを用いたこと以外は実施例１と同様にして、中間膜用フィルム材を得た。得られた中間膜用フィルム材を用いて、実施例１と同様にしてフロートガラス／中間膜／ＰＣの構成を有する合わせガラスを得た。 (Example 2)
A film material for an intermediate film was obtained in the same manner as in Example 1 except that the acrylic polymer B was used instead of the acrylic polymer A. Using the obtained film material for interlayer film, a laminated glass having a structure of float glass / intermediate film / PC was obtained in the same manner as in Example 1.
（実施例３）
　実施例１と同じ中間膜用フィルム材を用い、ＰＣ板に代えてポリメチルメタクリレート板（ＰＭＭＡ板、縦１１０ｍｍ、横１１０ｍｍ、厚み３．０ｍｍ）を用いたこと以外は実施例１と同様にして、フロートガラス／中間膜／ＰＭＭＡの構成を有する合わせガラスを得た。 (Example 3)
The same film material for an interlayer film as in Example 1 was used, except that a polymethyl methacrylate plate (PMMA plate, 110 mm long, 110 mm wide, 3.0 mm thick) was used instead of the PC plate. A laminated glass having a structure of float glass / intermediate film / PMMA was obtained.
（実施例４）
　実施例１と同じ中間膜用フィルム材を用い、フロートガラスに代えて強化ガラス（縦１１０ｍｍ、横１１０ｍｍ、厚み０．５５ｍｍ）を用いたこと以外は実施例１と同様にして、強化ガラス／中間膜／ＰＣの構成を有する合わせガラスを得た。 Example 4
The same tempered glass / intermediate as in Example 1, except that the same interlayer film material as in Example 1 was used and tempered glass (110 mm long, 110 mm wide, 0.55 mm thick) was used instead of float glass. A laminated glass having a film / PC configuration was obtained.
（実施例５）
　実施例１と同じ中間膜用フィルム材から、軽剥離セパレータを剥離した。露出した樹脂層を、第１のガラス板としての強化ガラス（縦１１０ｍｍ、横１１０ｍｍ、厚み０．５５ｍｍ）に貼り付け、その状態で重剥離セパレータ側からローラーを押し付けて、樹脂層を強化ガラスに密着させた。その後、重剥離セパレータを樹脂層から剥離した。露出した樹脂層を、真空積層機を用いて真空状態で第２のガラス板としてのポリカーボネート板（ＰＣ板、縦１１０ｍｍ、横１１０ｍｍ、厚み３．０ｍｍ）に貼り付けた。得られた積層体（強化ガラス／樹脂層／ＰＣ板）を温度５０℃、圧力０．５ＭＰａ、３０分保持の条件でオートクレーブ内で加熱及び加圧した。
　実施例１と同じ中間膜用フィルム材から、軽剥離セパレータを剥離した。露出した樹脂層を、第３のガラス板としての強化ガラス（縦１１０ｍｍ、横１１０ｍｍ、厚み０．５５ｍｍ）に貼り付け、その状態で重剥離セパレータ側からローラーを押し付けて、樹脂層を強化ガラスに密着させた。続いて重剥離セパレータを剥離し、強化ガラス／樹脂層の積層体を、上記の強化ガラス／樹脂層／ＰＣ板の積層体のＰＣ板側の表面に、樹脂層が内側になる向きで積層した。その後、全体の積層体を、オートクレーブ内で温度５０℃、圧力０．５ＭＰａ、３０分保持の条件で加熱及び加圧して、強化ガラス／中間膜／ＰＣ／中間膜／強化ガラスの構成を有する合わせガラスを得た。 (Example 5)
The light release separator was peeled from the same film material for an interlayer film as in Example 1. The exposed resin layer is affixed to tempered glass (length 110 mm, width 110 mm, thickness 0.55 mm) as the first glass plate, and in that state, a roller is pressed from the side of the heavy release separator to make the resin layer into tempered glass. Adhered. Thereafter, the heavy release separator was peeled from the resin layer. The exposed resin layer was attached to a polycarbonate plate (PC plate, 110 mm long, 110 mm wide, 3.0 mm thick) as a second glass plate in a vacuum state using a vacuum laminator. The obtained laminate (tempered glass / resin layer / PC plate) was heated and pressurized in an autoclave under the conditions of a temperature of 50 ° C., a pressure of 0.5 MPa, and a 30-minute hold.
The light release separator was peeled from the same film material for an interlayer film as in Example 1. The exposed resin layer is affixed to tempered glass (length 110 mm, width 110 mm, thickness 0.55 mm) as a third glass plate, and in that state, a roller is pressed from the side of the heavy release separator to make the resin layer into tempered glass. Adhered. Subsequently, the heavy release separator was peeled off, and the laminate of the tempered glass / resin layer was laminated on the surface of the tempered glass / resin layer / PC plate laminate on the PC plate side so that the resin layer was inward. . Thereafter, the entire laminate is heated and pressurized in an autoclave under the conditions of a temperature of 50 ° C., a pressure of 0.5 MPa, and a holding time of 30 minutes to obtain a laminated glass / interlayer / PC / intermediate / tempered glass composition. Glass was obtained.
（比較例１）
　アクリル重合体Ａに代えてアクリル重合体Ｃを用いたこと以外は実施例１と同様にして、中間膜用フィルム材を得た。得られた中間膜用フィルム材を用いて、実施例１と同様にしてフロートガラス／中間膜／ＰＣの構成を有する合わせガラスを得た。 (Comparative Example 1)
A film material for an intermediate film was obtained in the same manner as in Example 1 except that the acrylic polymer C was used instead of the acrylic polymer A. Using the obtained film material for interlayer film, a laminated glass having a structure of float glass / intermediate film / PC was obtained in the same manner as in Example 1.
（比較例２）
　ポリビニルブチラール樹脂（ＰＶＢ樹脂、アセタール化度６８．０モル％、ビニルアセテート成分の割合０．６モル％ ）１００質量部と、可塑剤としてのトリエチレングリコールジ－２－エチルヘキサノエート３８質量部とを混合し、これをミキシングロールで充分に溶融混練した。混錬物をプレス成形機で１５０℃、３０分間プレス成形して、厚み３．８×１０２μｍの樹脂層を形成させた。 (Comparative Example 2)
100 parts by mass of polyvinyl butyral resin (PVB resin, degree of acetalization 68.0 mol%, vinyl acetate component ratio 0.6 mol%) and 38 parts by mass of triethylene glycol di-2-ethylhexanoate as a plasticizer Were mixed and sufficiently melt-kneaded with a mixing roll. The kneaded material was press-molded with a press molding machine at 150 ° C. for 30 minutes to form a resin layer having a thickness of 3.8 × 10 2 μm.
　得られた樹脂層を２枚のフロートガラス（縦１１０ｍｍ、横１１０ｍｍ、厚み２．７ｍｍ）で挟み込んだ。得られた積層体をゴムバック内に入れ、２６６０Ｐａの真空度で２０分間脱気した。脱気した状態のままゴムバックをオーブンに入れ、９０℃で３０分間保持しながら、積層体を真空圧で加圧した。さらに、積層体をオートクレーブ中で１３５℃、圧力１１８Ｎ／ｃｍ２の条件で２０分間圧着して、ＰＶＢ樹脂を含有する樹脂層を中間膜として有する合わせガラスを得た。 The obtained resin layer was sandwiched between two float glasses (length 110 mm, width 110 mm, thickness 2.7 mm). The obtained laminate was put in a rubber bag and deaerated at a vacuum degree of 2660 Pa for 20 minutes. The rubber bag was put into an oven while being deaerated, and the laminate was pressurized with a vacuum pressure while being held at 90 ° C. for 30 minutes. Furthermore, the laminate was pressed in an autoclave at 135 ° C. and a pressure of 118 N / cm 2 for 20 minutes to obtain a laminated glass having a resin layer containing a PVB resin as an intermediate film.
（比較例３）
　２枚のフロートガラスのうち１枚をＰＣ板（縦１１０ｍｍ、横１１０ｍｍ、厚み３．０ｍｍ）に代えたこと以外は比較例２と同様にして、フロートガラス／ＰＶＢ／ＰＣの構成を有する合わせガラスを得た。 (Comparative Example 3)
Laminated glass having the structure of float glass / PVB / PC in the same manner as in Comparative Example 2 except that one of the two float glasses is replaced with a PC plate (110 mm long, 110 mm wide, 3.0 mm thick). Got.
（比較例４）
　縦１１０ｍｍ、横１１０ｍｍ、厚み６ｍｍのポリカーボネート板を、比較用のガラス板として準備した。 (Comparative Example 4)
A polycarbonate plate having a length of 110 mm, a width of 110 mm, and a thickness of 6 mm was prepared as a comparative glass plate.
（参考例）
　実施例１と同じ中間膜用フィルム材を用い、ＰＣ板に代えてフロートガラス（縦１１０ｍｍ、横１１０ｍｍ、厚み２．７ｍｍ）を用いたこと以外は実施例１と同様にして、フロートガラス／中間膜／フロートガラスの構成を有する合わせガラスを得た。 (Reference example)
Float glass / intermediate in the same manner as in Example 1 except that the same film material for an interlayer film as in Example 1 was used, and float glass (110 mm long, 110 mm wide, 2.7 mm thick) was used instead of the PC plate. A laminated glass having a membrane / float glass configuration was obtained.
３．評価
　得られた合わせガラスを、以下の方法により評価した。結果を表２に示した。
［耐衝撃試験］
　１００ｍｍ×１００ｍｍの正方形の開口を有する支持枠を準備した。この支持枠の開口全体が合わせガラスで塞がれるように、合わせガラスを支持枠で水平に保持した。支持枠の開口内の合わせガラスの中心点から半径２５ｍｍ以内の位置に向けて、合わせガラス上方の所定の高さから質量約１０４０ｇ、直径６３．５ｍｍの鋼球を垂直に自由落下させた。剛球を落下させる高さを、５ｃｍから１００ｃｍまで、５ｃｍ刻みで順次増加させながら試験を繰返し、合わせガラスが割れたときの、剛球を落下させる高さ（割れ高さＨ）を記録した。それぞれの合わせガラス６枚について試験し、割れ高さの平均値を算出した。この値が大きいほど合わせガラスの防割性の高いといえる。割れ高さＨ、剛球の質量ｍ、及び合わせガラスの面積（１００ｃｍ２）から、下記式により衝撃強度Ｅを求めた。
　Ｅ＝ｍｇＨ／Ａ
Ｅ：衝撃強度［Ｊ／ｃｍ２］、ｍ：剛球の質量［ｋｇ］、ｇ：重力加速度、Ｈ：割れ高さ［ｍ］、Ａ：合わせガラスの面積［ｃｍ２］ 3. Evaluation The obtained laminated glass was evaluated by the following methods. The results are shown in Table 2.
[Shock resistance test]
A support frame having a square opening of 100 mm × 100 mm was prepared. The laminated glass was held horizontally by the support frame so that the entire opening of the support frame was closed with the laminated glass. A steel ball having a mass of approximately 1040 g and a diameter of 63.5 mm was freely dropped vertically from a predetermined height above the laminated glass toward a position within a radius of 25 mm from the center point of the laminated glass in the opening of the support frame. The test was repeated while gradually increasing the height at which the hard sphere was dropped from 5 cm to 100 cm in increments of 5 cm, and the height at which the hard sphere was dropped when the laminated glass broke (crack height H) was recorded. Each of the 6 laminated glasses was tested, and the average value of the crack heights was calculated. It can be said that the larger the value, the higher the splitting property of the laminated glass. From the crack height H, the mass m of the hard sphere, and the area (100 cm 2 ) of the laminated glass, the impact strength E was determined by the following formula.
E = mgH / A
E: Impact strength [J / cm 2 ], m: Mass of hard sphere [kg], g: Gravitational acceleration, H: Crack height [m], A: Laminated glass area [cm 2 ]
［ヘーズ］
　ＪＩＳ　Ｋ　７１３６に準拠した測定により、合わせガラスの中心点のヘーズを測定した。測定装置として日本電色工業株式会社製、商品名：Ｓｐｅｃｔｒａｌ　ｈａｚｅ　ｍｅｔｅｒ　ＳＨ７０００を用い、光源をＣ、基準を空気をとした。 [Haze]
The haze at the center point of the laminated glass was measured by measurement based on JIS K 7136. A product name: Spectral haze meter SH7000 manufactured by Nippon Denshoku Industries Co., Ltd. was used as the measuring device, the light source was C, and the standard was air.
［表面硬度］
　表面硬度の評価は、Ｎｏ．５５３－Ｍ電動鉛筆引っかき硬度試験機（株式会社 安田精機製作所製）を用いて、ＪＩＳ　Ｋ５６００－５－４に準じて行った。各種硬度の鉛筆を４５゜の角度で試料の表面にあて、荷重をかけて引っ掻き試験を行い、傷がつかない最も硬い鉛筆の硬さを鉛筆硬度とした。 [surface hardness]
Evaluation of surface hardness is No. Using a 553-M electric pencil scratch hardness tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd.), the test was conducted according to JIS K5600-5-4. A pencil having various hardnesses was applied to the surface of the sample at an angle of 45 °, and a scratch test was performed by applying a load. The hardness of the hardest pencil that was not damaged was defined as pencil hardness.
［耐光性試験］
　実施例及び比較例で作製した合わせガラスを、促進耐候性試験機（スガ試験機社製、ＳＸ７５）のサンプルホルダーに固定し、キセノンロングライフアークランプを光源として照射強度１８０Ｗ／ｍ２、波長３００～４００ｎｍの光を照射しながら、温度６３℃、湿度５０％ＲＨ、試験時間３００時間の条件で促進耐候性試験に供した。試験後のサンプルにおいて、ヘーズが１．０以下で目視によって気泡の発生が確認されない場合を「Ｐａｓｓ」、ヘーズが１．０以上である又は目視によって気泡の発生が認められた場合を「ＮＧ」とした。 [Light resistance test]
The laminated glasses prepared in the examples and comparative examples are fixed to a sample holder of an accelerated weather resistance tester (manufactured by Suga Test Instruments Co., Ltd., SX75), and an irradiation intensity of 180 W / m 2 and a wavelength of 300 are set using a xenon long life arc lamp as a light source. The sample was subjected to an accelerated weathering test under the conditions of a temperature of 63 ° C., a humidity of 50% RH and a test time of 300 hours while irradiating light of ˜400 nm. In the sample after the test, the case where haze is 1.0 or less and the occurrence of bubbles is not visually confirmed is “Pass”, and the case where haze is 1.0 or more or the occurrence of bubbles is visually confirmed is “NG”. It was.
［剥離強度］
　中間膜用フィルム材から、軽剥離セパレータを剥離した。露出した樹脂層を、第１のガラス板としてのフロートガラス（縦１１０ｍｍ、横１１０ｍｍ、厚み２．７ｍｍ）に貼り付け、その状態で重剥離セパレータ側からローラーを押し付けて、樹脂層をフロートガラスに密着させた。その後、重剥離セパレータを樹脂層から剥離した。露出した樹脂層に、長さ２００ｍｍ、幅１００ｍｍ、厚み１２５μｍのポリエステルフィルム（東洋紡株式会社製、商品名：コスモシャインＡ４３００）を貼り合わせ試験用サンプルを得た。サンプルに、ポリエステルフィルムの上からカッターで長さ２００ｍｍ、幅１０ｍｍの長さの切り込みを入れた。引張試験機(オリエンテック社製、商品名：ＲＴＣ－１２１０)を用いて、切込みを入れた部分のポリエステルフィルムを掴み、引き剥がし角度１８０°、引き剥がし速度３００ｍｍ／分で、測定時間３秒間、温度２５℃の条件で剥離試験を行った。このときの荷重から、剥離強度（Ｎ／１０ｍｍ）を求めた。 [Peel strength]
The light release separator was peeled from the film material for the interlayer film. The exposed resin layer is affixed to float glass (length 110 mm, width 110 mm, thickness 2.7 mm) as a first glass plate, and in that state, a roller is pressed from the side of the heavy release separator to put the resin layer on the float glass. Adhered. Thereafter, the heavy release separator was peeled from the resin layer. A polyester film having a length of 200 mm, a width of 100 mm, and a thickness of 125 μm (Toyobo Co., Ltd., trade name: Cosmo Shine A4300) was bonded to the exposed resin layer to obtain a test sample. A cut having a length of 200 mm and a width of 10 mm was cut into the sample with a cutter from above the polyester film. Using a tensile tester (Orientec Co., Ltd., trade name: RTC-1210), the polyester film at the incised part was grasped, the peeling angle was 180 °, the peeling speed was 300 mm / min, and the measurement time was 3 seconds. A peel test was performed under the condition of a temperature of 25 ° C. From the load at this time, peel strength (N / 10 mm) was determined.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２に示されるように、各実施例の合わせガラスは、十分に低いヘーズとともに、優れた衝撃強度を示した。 As shown in Table 2, the laminated glass of each example showed excellent impact strength with sufficiently low haze.
　１…合わせガラス、２…合わせガラスの中間膜用フィルム材、５…中間膜、５ａ…樹脂層、１１，１２…ガラス板、２１，２２…基材。 DESCRIPTION OF SYMBOLS 1 ... Laminated glass, 2 ... Film material for intermediate films of laminated glass, 5 ... Intermediate film, 5a ... Resin layer, 11, 12 ... Glass plate, 21, 22 ... Base material.

Claims (11)

  1. 　対向する２枚のガラス板と、前記２枚のガラス板の間に挟まれた中間膜と、を備える合わせガラスであって、
    　前記２枚のガラス板のうち一方が透明プラスチック板で、他方が無機ガラス板であり、
    　前記中間膜がアクリル重合体を含み、
    　当該合わせガラスに向けて剛球を落下させる耐衝撃試験によって測定される衝撃強度が、０．０３Ｊ／ｃｍ２以上である、
    合わせガラス。     A laminated glass comprising two opposing glass plates and an intermediate film sandwiched between the two glass plates,
    One of the two glass plates is a transparent plastic plate, the other is an inorganic glass plate,
    The intermediate film includes an acrylic polymer;
    The impact strength measured by an impact resistance test in which a hard sphere is dropped toward the laminated glass is 0.03 J / cm 2 or more.
    Laminated glass.
  2. 　前記アクリル重合体が、１０万以上の重量平均分子量を有する、請求項１に記載の合わせガラス。 The laminated glass according to claim 1, wherein the acrylic polymer has a weight average molecular weight of 100,000 or more.
  3. 　対向する２枚のガラス板と、前記２枚のガラス板の間に挟まれた中間膜と、を備える合わせガラスであって、
    　前記２枚のガラス板のうち一方が透明プラスチック板で、他方が無機ガラス板であり、
    　前記中間膜が、１０万以上の重量平均分子量を有するアクリル重合体を含む、
    合わせガラス。     A laminated glass comprising two opposing glass plates and an intermediate film sandwiched between the two glass plates,
    One of the two glass plates is a transparent plastic plate, the other is an inorganic glass plate,
    The interlayer film comprises an acrylic polymer having a weight average molecular weight of 100,000 or more,
    Laminated glass.
  4. 　前記アクリル重合体が－１０℃以下のガラス転移温度を有する、請求項１～３のいずれか一項に記載の合わせガラス。 The laminated glass according to any one of claims 1 to 3, wherein the acrylic polymer has a glass transition temperature of -10 ° C or lower.
  5. 　当該合わせガラスの厚みが０．５～１０００ｍｍである、請求項１～４のいずれか一項に記載の合わせガラス。 The laminated glass according to any one of claims 1 to 4, wherein the thickness of the laminated glass is 0.5 to 1000 mm.
  6. 　前記透明プラスチック板が、ポリカーボネート樹脂板、又はポリメチルメタクリレート樹脂板である、請求項１～５のいずれか一項に記載の合わせガラス。 The laminated glass according to any one of claims 1 to 5, wherein the transparent plastic plate is a polycarbonate resin plate or a polymethyl methacrylate resin plate.
  7. 　１０万以上の重量平均分子量を有するアクリル重合体を含み、
    　対向する２枚のガラス板と前記２枚のガラス板の間に挟まれた中間膜とを備える合わせガラスの前記中間膜を形成するために用いられ、
    　前記２枚のガラス板のうち一方が透明プラスチック板で、他方が無機ガラス板である、
    合わせガラスの中間膜用樹脂組成物。     Including an acrylic polymer having a weight average molecular weight of 100,000 or more,
    Used to form the intermediate film of laminated glass comprising two glass plates facing each other and an intermediate film sandwiched between the two glass plates;
    One of the two glass plates is a transparent plastic plate and the other is an inorganic glass plate.
    A resin composition for an interlayer film of laminated glass.
  8. 　前記アクリル重合体が－１０℃以下のガラス転移温度を有する、請求項７に記載の合わせガラスの中間膜用樹脂組成物。 The resin composition for interlayer films of laminated glass according to claim 7, wherein the acrylic polymer has a glass transition temperature of -10 ° C or lower.
  9. 　基材と、前記基材上に設けられた樹脂層と、を有し、
    　前記樹脂層が、請求項７又は８に記載の合わせガラスの中間膜用樹脂組成物を含む層である、合わせガラスの中間膜用フィルム材。     A base material, and a resin layer provided on the base material,
    The film material for intermediate films of a laminated glass whose said resin layer is a layer containing the resin composition for interlayer films of the laminated glass of Claim 7 or 8.
  10. 　請求項１～６のいずれか一項に記載の合わせガラスを製造する方法であって、
    　当該方法が、２枚の前記ガラス板を、前記アクリル重合体を含み前記中間膜を形成するための樹脂層を介在させながら貼り合せて、２枚の前記ガラス板及び前記樹脂層を有する積層体を得る工程を含む、方法。     A method for producing the laminated glass according to any one of claims 1 to 6,
    In this method, the two glass plates are bonded to each other with the resin layer for forming the intermediate film including the acrylic polymer interposed therebetween, and the laminate having the two glass plates and the resin layer. A method comprising the steps of:
  11. 　前記積層体を加熱及び加圧する工程を更に含む、請求項１０に記載の方法。 The method according to claim 10, further comprising heating and pressurizing the laminate.
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