WO2018079732A1 - Laminated glass and film material for laminated-glass interlayer - Google Patents

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

Laminated glass and film material for interlayer film of laminated glass

The present invention relates to laminated glass and a film material for an interlayer film of laminated glass.

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.

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).

JP-A-62-100463 JP 2005-206445 A International Publication No. 2012/091117

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.

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.

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 to 1,000,000.

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.

Regarding laminated glass using a transparent plastic plate, it is possible to achieve both excellent optical properties and high splitting properties.

It is a schematic cross section which shows one Embodiment of a laminated glass. It is a schematic cross section which shows one Embodiment of the film material for interlayer films of a laminated glass.

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.

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.

<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.

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.

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).

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.

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. The upper limit of light transmittance is 100%.

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. The laminated glass exhibits an impact strength of 0.03 J / cm ² or more in at least an impact resistance test in which a hard sphere is dropped toward the laminated glass from the inorganic glass plate side. However, the laminated glass may exhibit an impact strength of 0.03 J / cm ² or more in an impact resistance test in which a hard sphere is dropped from either side of the two glass plates toward the laminated glass. 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.

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.

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.

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 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.

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. 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 pressurization 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.

<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.

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. 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 acrylic polymer may have a weight average molecular weight of 1,000,000 or less. If the weight average molecular weight of the acrylic polymer is 1,000,000 or less, a laminated glass showing a low haze and a high peel strength as well as an excellent impact strength is particularly easily obtained. Here, in this specification, 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-). 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.

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.

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.

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.

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.

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.

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.

<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.

The resin layer 5a may have at least one layer that satisfies the following viscoelasticity requirements (a) and (b). The viscoelasticity of the resin layer 5a itself may satisfy these requirements.
(A) The storage elastic modulus at a reference temperature of 25 ° C. and a frequency of 1000 Hz is 1 × 10 ⁵ to 1 × 10 ⁸ Pa. (B) The maximum value of the loss coefficient at a reference temperature of 25 ° C. and a frequency of 100 to 100,000 Hz is Over 0.4

The frequency range of 100 to 100,000 Hz corresponds to the strain rate generated in the laminated glass when a hard sphere that has fallen freely from a height of about several centimeters to a few tens of centimeters collides with the laminated glass. Therefore, for example, when the maximum value of the loss coefficient is larger than 0.4 in the range of the reference temperature of 25 ° C. and the frequency of 100 to 100,000 Hz, higher splitting properties are more easily exhibited than the glass single plate. The maximum value of the loss factor may be 0.5 or more, 1.1 or less, or 1.0 or less.

When the storage elastic modulus at a reference temperature of 25 ° C. and a frequency of 1000 Hz is 1 × 10 ⁵ or more, particularly excellent effects are obtained in terms of mechanical properties and reliability (heat resistance, weather resistance). When the storage elastic modulus at a reference temperature of 25 ° C. and a frequency of 1000 Hz is 1 × 10 ⁸ Pa or less, particularly excellent effects are obtained in terms of impact resistance. From the same viewpoint, the storage elastic modulus at a reference temperature of 25 ° C. and a frequency of 1000 Hz may be 1.5 × 10 ⁵ or more, or 5 × 10 ⁶ Pa or less.

Here, the values of the storage elastic modulus and the loss coefficient (tan δ) can be obtained from a composite curve (master curve) obtained from dynamic viscoelasticity measurement and a time-temperature conversion rule. The dynamic viscoelasticity measurement is, for example, a tensile measurement according to a method in accordance with JIS K 0129: 2005 under conditions of a temperature of −70 to 100 ° C., a frequency of 0.05 Hz, 0.5 Hz, 5 Hz or 50 Hz, and a strain amount of 1% Done in mode. From the measurement results of the viscoelasticity, a master curve is created by setting the reference temperature to 25 ° C. using the WLF method or the Arrhenius law. The maximum value of tan δ can be read.

In order to create a master curve, a time-temperature conversion factor α _T is calculated from the measurement result of the dynamic viscoelasticity measurement for each temperature value by the following WLF equation or Arrhenius equation.

From the time-temperature conversion factor α _T and the value of the angular frequency ω at an arbitrary temperature T, the angular frequency ω ′ with respect to the reference temperature T ₀ can be calculated by the following equation (A). By drawing the relationship between the angular frequency ω ′ and the measured dynamic viscoelastic property, a master curve with the horizontal axis changed to frequency can be obtained.
α _T = ω ′ / ω (A)
The series of calculations can be performed using, for example, TRIOS Software (product name of TA Instruments Co., Ltd.) attached to the dynamic viscoelasticity measuring device “RSA-G2”.

The base materials 21 and 22 may be, for example, a polymer film selected from polyethylene terephthalate, polypropylene, and polyethylene, and in particular, may be a polyethylene terephthalate film (hereinafter sometimes 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.

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.

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.

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.

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. The 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.

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.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

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.

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, by distilling off methyl ethyl ketone, acrylic polymer B (weight average molecular weight 128000, Tg: −20 ° C.), which is a copolymer of 2-ethyhexyl acrylate and 2-hydroxyethyl acrylate, was obtained.

Acrylic polymer C
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. Heating was performed from 25 ° C. to 80 ° C. for 15 minutes while purging nitrogen with an air flow of 100 ml / min. 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 30000, Tg: -18 ° C.), which was a copolymer of isostearyl acrylate and 2-hydroxyethyl acrylate.

Acrylic polymer D
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 acrylic polymer C (weight average molecular weight 30000, Tg: −3 ° C.), which is a copolymer of isostearyl acrylate and 2-hydroxyethyl acrylate.

Acrylic polymer E
In a reaction vessel equipped with a cooling tube, a thermometer, a stirrer, a dropping funnel and a nitrogen introducing tube, 78.4 g of n-butyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.) as an initial monomer and 2-ethylhexyl acrylate 19. 6.0 g, 2.0 g of acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) and 100.0 g of ultrapure water (manufactured by Wako Pure Chemical Industries, Ltd.) and 3.0 g of polyvinyl alcohol as a stabilizer were added. The reaction vessel was heated from 25 ° C. to 65 ° C. over 15 minutes while purging with nitrogen at a flow rate of 100 ml / min. Thereafter, 0.1 g of t-butylperoxy-2-ethylhexanoate was added while maintaining the temperature at 65 ° C., and the reaction was allowed to proceed for 6 hours. By distilling off water, acrylic polymer E (weight average molecular weight 2270000, Tg: −18 ° C.) which is a copolymer of n-butyl acrylate, 2-ethylhexyl acrylate and acrylic acid was obtained.

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.
・ 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

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).

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): 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.

The viscoelasticity of the resin layer of the obtained film material for interlayer film was measured using a dynamic viscoelasticity measuring device (TA Instruments Co., Ltd., product name “RSA-G2”) in the temperature range of −70 to 100 ° C. The measurement was performed in the tensile measurement mode under the conditions of a frequency of 0.05 Hz, 0.5 Hz, 5 Hz or 50 Hz, and a strain amount of 1%. From the measurement results, a master curve was created using TRIOS Software (TA Instruments Co., Ltd., product name) using the Arrhenius equation with a reference temperature of 25 ° C. From the obtained master curve, the storage elastic modulus at a frequency of 1000 Hz and the maximum value of the loss coefficient (tan δ) within a frequency range of 100 to 100,000 Hz were read. The viscoelasticity of the intermediate films produced in other examples or comparative examples described later was also measured.

[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.

(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.

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)
[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 the acrylic polymer A was prepared by the following procedures (I) and (II).

(I): 60 parts by mass of an acrylic polymer, 40.0 parts by mass of 2-butanone, and 0.12 parts by mass of a polyisocyanate compound (Tosoh Corporation, product name “Coronate HL”) as a thermal crosslinking agent were mixed by stirring. Thus, a coating liquid is obtained.
(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 obtain a thickness. A 100 μm 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.

[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 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 laminated body was 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 having a configuration of tempered glass / interlayer film / PC.

(Example 6)
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.

(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.

(Comparative Example 2)
A film material for an intermediate film was obtained in the same manner as in Example 1 except that the acrylic polymer D was used in place 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 3)
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.

(Comparative Example 4)
100 parts by mass of acrylic polymer E, 0.5 parts by mass of acetylacetone zinc salt (manufactured by Tokyo Chemical Industry) and 0.7 parts by mass of acetylacetone aluminum salt (manufactured by Wako Pure Chemical Industries, Ltd.) were melt-kneaded. The obtained melt-kneaded material was deposited on a polyethylene terephthalate film as a heavy release separator to form a resin layer having a thickness of 3.8 × 10 ² μm. A polyethylene terephthalate film as a light release separator was laminated on the formed resin layer to obtain an interlayer film material.
Float glass / intermediate film / in the same manner as in Example 1 except that the obtained film material for interlayer film 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 structure of float glass was obtained.

(Comparative Example 5)
A laminate having the structure of float glass / intermediate film / PC in the same manner as in Comparative Example 4 except that one of the two float glasses was replaced with a PC plate (110 mm long, 110 mm wide, 3.0 mm thick). Glass was obtained.

(Comparative Example 6)
Acrylic polymer E was dissolved in ethyl acetate to prepare an acrylic polymer solution having a concentration of 40% by mass. Tolylene diisocyanate (Nikka Trading, trade name “TDI”) as a crosslinking agent was dissolved in ethyl acetate to prepare a crosslinking agent solution having a concentration of 25% by mass. 100 parts by mass of the acrylic polymer solution and 2.0 parts by mass of the crosslinking agent solution were mixed and stirred. The obtained mixed solution was formed on a polyethylene terephthalate film as a heavy release separator, and the coating film was dried to form a resin layer having a thickness of 3.8 × 10 ² μm. A polyethylene terephthalate film as a light release separator was laminated on the formed resin layer to obtain an interlayer film material.
Float glass / intermediate film / in the same manner as in Example 1 except that the obtained film material for interlayer film 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 structure of float glass was obtained.

(Comparative Example 7)
Structure of float glass / intermediate film / PC as in Comparative Example 6 except that a PC plate (110 mm long, 110 mm wide, 3.0 mm thick) was used instead of the float glass plate as the second glass plate A laminated glass having

(Comparative Example 8)
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.

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.

(Comparative Example 9)
Laminated glass having the structure of float glass / PVB / PC in the same manner as in Comparative Example 8 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.

(Comparative Example 10)
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.

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 ]
The impact strength of the laminated glass was measured for each of a test in which a hard sphere collides with the laminated glass from the first glass plate side and a test in which the rigid sphere collides with the laminated glass from the second glass plate or the third glass plate side. .

[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.

[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.

[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.

[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.

As shown in Table 2, the laminated glass of each example showed excellent impact strength with sufficiently low haze. The laminated glass of each comparative example shown in Table 3 or Table 4 was not sufficient in terms of impact resistance and / or showed high haze, such as peeling in an impact resistance test.

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 (12)

1. 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. The laminated glass according to claim 1, wherein the acrylic polymer has a weight average molecular weight of 100,000 to 1,000,000.
3. 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 includes an acrylic polymer having a weight average molecular weight of 100,000 to 1,000,000.
   Laminated glass.
4. 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. The laminated glass according to any one of claims 1 to 4, wherein the intermediate film has at least one layer containing the acrylic polymer and satisfying the following viscoelastic requirements (a) and (b).
   (A) The storage elastic modulus at a reference temperature of 25 ° C. and a frequency of 1000 Hz is 1 × 10 ⁵ to 1 × 10 ⁸ Pa. (B) The maximum value of the loss coefficient at a reference temperature of 25 ° C. and a frequency of 100 to 100,000 Hz is Over 0.4
6. The laminated glass according to any one of claims 1 to 5, wherein the laminated glass has a thickness of 0.5 to 1000 mm.
7. The laminated glass according to any one of claims 1 to 6, wherein the transparent plastic plate is a polycarbonate resin plate or a polymethyl methacrylate resin plate.
8. Including an acrylic polymer having a weight average molecular weight of 100,000 to 1,000,000,
   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.
9. The resin composition for interlayer films of laminated glass according to claim 8, wherein the acrylic polymer has a glass transition temperature of -10 ° C or lower.
10. 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 8 or 9.
11. A method for producing the laminated glass according to any one of claims 1 to 7,
    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:
12. The method according to claim 11, further comprising heating and pressurizing the laminate.

Images