JP7004796B2 - Laminated glass - Google Patents

Description

The present disclosure relates to laminated glass.

In recent years, as one of the energy saving measures for reducing carbon dioxide, a material for imparting heat ray shielding property to windows of automobiles and buildings has been developed.
In the past, such heat ray shielding materials were often installed inside windows (so-called lining), but in recent years, places where it is difficult to install scaffolding indoors or those that cannot be moved to the indoor side are placed. It is also required to install it in a place where it is squeezed, a place where the indoor environment is constantly dewed, and a place where the temperature is strict (so-called external attachment). Also, from the viewpoint of heat ray shielding, the outside of the window is used to suppress the re-radiation of the light absorbed inside the window and the re-reflection of the light reflected inside the window into the room by the window glass. Is required to absorb or reflect light. In addition, from the viewpoint of heat ray shielding property (solar heat acquisition rate), re-radiation was suppressed compared to the heat ray absorption type, which has re-radiation of absorbed light into the room (about 1/3 of the absorbed solar energy). The heat ray reflective type is desirable, and various proposals have been made.

Patent Document 1 has a heat ray reflecting layer containing silver tabular particles and a heat ray absorbing layer containing a plurality of types of metal oxide particles, and the content of the silver tabular particles in the heat ray reflecting layer is 15 to 45 mg. A heat ray shielding material characterized by being / m ² is described.

Patent Document 1: Japanese Unexamined Patent Publication No. 2014-194446

An object to be solved by the embodiment of the present invention is to provide a laminated glass in which the distortion of reflected light is suppressed in appearance.

Specific means for solving the above problems include the following aspects.
<1> A first glass plate, an adhesive layer, a transparent base material, a layer A having a refractive index of 1.4 or less, a metal particle-containing layer, and a second glass plate are provided in this order. The layer A satisfies the following condition 1, and the maximum heat shrinkage direction of the transparent base material and the maximum heat shrinkage direction of the adhesive layer are parallel to each other, or the maximum heat shrinkage direction of the transparent base material. Laminated glass having an angle of 10 ° or less with the maximum heat shrinkage direction of the adhesive layer.
(Λ / 4 + mλ / 2) <nA × dA <λ / 2 + mλ / 2 Condition 1
In condition 1, m represents an integer of 0 or more, λ represents a wavelength for which reflection is desired to be prevented, the unit of λ is nm, nA represents the refractive index of layer A at the wavelength λ, and dA represents layer A. The unit of dA representing the thickness is nm, and the wavelength λ for which reflection is desired to be prevented is 380 nm to 780 nm.
<2> The heat shrinkage rate of the transparent base material when held at 130 ° C. for 30 minutes is 0.0% to 1.0% in the maximum heat shrinkage direction, and the maximum heat shrinkage direction in the surface direction of the transparent base material. The laminated glass according to <1>, which is −1.0% to 0.5% in the direction perpendicular to the relative direction.
<3> The heat shrinkage rate of the adhesive layer held at 60 ° C. for 30 minutes is 1.0% to 3.0% in the maximum heat shrinkage direction, and is perpendicular to the maximum heat shrinkage direction in the surface direction of the adhesive layer. The laminated glass according to <1> or <2>, which is −2.0% to 0.0% in the direction.
<4> The laminated glass according to any one of <1> to <3>, wherein the laminated glass is a heat-shielding glass and the sunlight incident side is the first glass plate side.
<5> The laminated glass according to any one of <1> to <4>, wherein the metal particle-containing layer contains flat silver particles.
<6> The laminated glass according to any one of <1> to <5>, wherein the metal particle-containing layer contains flat silver particles whose at least a part is coated with gold.
<7> The laminated glass according to any one of <1> to <6>, wherein the layer A has a refractive index of 1.2 to 1.4.
<8> The laminated glass according to any one of <1> to <7>, wherein the layer A contains hollow particles.
<9> The laminated glass according to any one of <1> to <8>, which further has a second adhesive layer between the metal particle-containing layer and the second glass plate.
<10> The laminated glass according to any one of <1> to <9>, which is a laminated glass for an automobile windshield.

According to the embodiment of the present invention, it is possible to provide a laminated glass having less distortion of reflected light in appearance.

It is a schematic perspective view which shows an example of the silver nanoplatelet particles used in this disclosure. It is a schematic perspective view which shows another example of the silver nanoplatelet particle used in this disclosure. It is a schematic cross-sectional view in the example of the laminated glass which concerns on this disclosure. It is a schematic cross-sectional view in another example of the laminated glass which concerns on this disclosure. It is a figure which shows the transmission spectrum of the green glass used in an Example.

Hereinafter, the present disclosure will be described in detail.
In addition, in this specification, the description of "xx-yy" represents a numerical range including xx and yy.
In addition, the term "process" in the present specification is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term "process" will be used as long as the intended purpose of the process is achieved. included.
Unless otherwise specified, the hydrocarbon group such as an alkyl group, an aryl group, an alkylene group and an arylene group in the present disclosure may have a branch or a ring structure.
Further, in the present disclosure, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous.
Further, in the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.
Further, for the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present disclosure, unless otherwise specified, columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by Toso Co., Ltd.) are used. The molecular weight is detected by the solvent THF (tetrahydrofuran) and the differential refractometer by the gel permeation chromatography (GPC) analyzer and converted using polystyrene as a standard substance.

(Laminated glass)
The laminated glass according to the present disclosure includes a first glass plate, an adhesive layer, a transparent base material, a layer A having a refractive index of 1.4 or less, a metal particle-containing layer, and a second glass plate. In this order, the layer A satisfies the following condition 1, and the maximum heat shrinkage direction of the transparent base material and the maximum heat shrinkage direction of the adhesive layer are parallel or parallel to each other, or the transparent base material. The angle between the maximum heat shrinkage direction and the maximum heat shrinkage direction of the adhesive layer is 10 ° or less.
(Λ / 4 + mλ / 2) <nA × dA <λ / 2 + mλ / 2 Condition 1
In condition 1, m represents an integer of 0 or more, λ represents a wavelength for which reflection is desired to be prevented, the unit of λ is nm, nA represents the refractive index of layer A at the wavelength λ, and dA represents layer A. The unit of dA representing the thickness is nm, and the wavelength λ for which reflection is desired to be prevented is 380 nm to 780 nm.

Against the background of global reduction of CO ₂ emissions, it is required to improve fuel efficiency when using electric power and fossil fuels. For example, by suppressing heat inside an automobile or indoors, it is possible to reduce power consumption due to the use of an air conditioner and improve fuel efficiency. Therefore, it is desired to provide a heat shield function to the windshield and windows of an automobile.
As a method of imparting a heat-shielding function to the windshield or window of an automobile, a method of sandwiching a heat-shielding film in which flat silver nanoparticles are arranged in laminated glass is known.
However, when a transparent film member such as a heat-shielding film is sandwiched between laminated glass, distortion at intervals of several mm (looks like a twisted skin and is also called "orange peel") is visually recognized on the entire surface of the laminated glass. The present inventors have found that there is.
When heat is applied and bonded during the production of laminated glass, the film buckles at intervals of several mm due to the stress caused by the difference in heat shrinkage between the transparent base material of the film member and the adhesive layer, and the above strain occurs. The inventors are thinking. Further, if only the transparent base material and the adhesive layer are used, the difference in refractive index between the two is small, so that even if there is unevenness, it is not visible. However, when the metal particle-containing layer is present, reflection occurs at the interface having the difference in refractive index. The present inventors have also found that there is a problem that unevenness is visually recognized.
Further, in the invention described in Patent Document 1, a method of reducing glare by introducing an antireflection layer when sandwiching a heat shield film between glass is proposed. However, especially when the difference in heat shrinkage between the heat shield film and the adhesive layer is large, the introduction of the antireflection layer alone is not sufficient to reduce the deterioration of visibility due to the strain.

As a result of detailed studies by the present inventors, the layer A having a refractive index of 1.4 or less satisfies the above condition 1, and the maximum heat shrinkage direction of the transparent substrate and the maximum heat shrinkage direction of the adhesive layer. However, the distortion of the reflected light is suppressed in appearance by being parallel to each other or by having an angle formed by the maximum heat shrinkage direction of the transparent substrate and the maximum heat shrinkage direction of the adhesive layer of 10 ° or less. It was found that a laminated glass was obtained.
Although the detailed mechanism is unknown, the maximum heat shrinkage direction of the transparent substrate and the maximum heat shrinkage direction of the adhesive layer are parallel to each other, or the angle formed by these is 10 ° or less. By suppressing wrinkles and distortion in each layer inside the glass, and by satisfying condition 1 of the above layer A, the reflected light is suppressed and the distortion of the reflected light is made difficult to see, so that the distortion of the reflected light is apparently distorted. The present inventors presume that a suppressed laminated glass is obtained.

In the laminated glass according to the present disclosure, the maximum heat shrinkage direction of the transparent base material and the maximum heat shrinkage direction of the adhesive layer are parallel, or the maximum heat shrinkage direction of the transparent base material and the adhesive layer are The angle formed by the maximum heat shrinkage direction is 10 ° or less.
The maximum heat shrinkage direction of the transparent substrate and the maximum heat shrinkage direction of the adhesive layer shall be measured by the following methods.
The transparent base material is peeled off, the direction in the laminated glass is confirmed, and the transparent base material cut into 5 cm squares is placed on a hot plate heated to 130 ° C. and allowed to stand for 30 minutes. Measure the length, width, diagonal, etc. before and after heat application, and determine the direction with the largest shrinkage.
The adhesive layer is peeled off, the direction in the laminated glass is confirmed, and the adhesive layer cut into 5 cm squares is placed on a hot plate heated to 60 ° C. and allowed to stand for 30 minutes. Measure the length, width, diagonal, etc. before and after heat application, and determine the direction with the largest shrinkage.

In the laminated glass according to the present disclosure, from the viewpoint of reducing the visibility of strain, the maximum heat shrinkage direction of the transparent base material and the maximum heat shrinkage direction of the adhesive layer are parallel or parallel to each other, or the transparent base material. The angle between the maximum heat shrinkage direction of the above and the maximum heat shrinkage direction of the adhesive layer is preferably 8 ° or less, and the maximum heat shrinkage direction of the transparent substrate and the maximum heat shrinkage direction of the adhesive layer are It is more preferable that the angle between the maximum heat shrinkage direction of the transparent base material and the maximum heat shrinkage direction of the adhesive layer is 4 ° or less, and the maximum heat shrinkage direction of the transparent base material. And the maximum heat shrinkage direction of the adhesive layer are parallel to each other, or the angle between the maximum heat shrinkage direction of the transparent substrate and the maximum heat shrinkage direction of the adhesive layer is less than 2 °. Especially preferable.
Further, the maximum heat shrinkage direction of the transparent base material described later and the maximum heat shrinkage direction of the adhesive layer are parallel to each other, or the maximum heat shrinkage direction of the transparent base material described later and the maximum heat shrinkage direction of the adhesive layer described later. It is preferable that the angle between the two is in the above range.

In order to produce the laminated glass according to the present disclosure as described above, a method of using a transparent base material and an adhesive sheet forming an adhesive layer and laminating after confirming the maximum heat shrinkage direction in advance is preferably mentioned. Be done.

In the laminated glass according to the present disclosure, from the viewpoint of reducing the visibility of strain, the heat shrinkage rate of the transparent substrate when held at 130 ° C. for 30 minutes is 0.0% to 1.0% in the maximum heat shrinkage direction. In the plane direction of the transparent substrate, it is preferably −1.0% to 0.5% in the direction perpendicular to the maximum heat shrinkage direction.
Further, in the laminated glass according to the present disclosure, from the viewpoint of reducing the visibility of strain, the heat shrinkage rate of the adhesive layer held at 60 ° C. for 30 minutes is 1.0% to 3.0% in the maximum heat shrinkage direction. In the surface direction of the adhesive layer, it is preferably −2.0% to 0.0% in the direction perpendicular to the maximum heat shrinkage direction.
Further, when the heat shrinkage rates of the transparent substrate and the adhesive layer are in the above ranges, the visibility of the strain can be further reduced.

<Metal particle-containing layer>
The laminated glass according to the present disclosure has at least a metal particle-containing layer between the layer A and the second glass plate.
Further, the laminated glass according to the present disclosure is preferably heat-shielding glass, and from the viewpoint of heat-shielding performance, it is more preferable that the sunlight incident side is the first glass plate side.

From the viewpoint of heat shielding performance, the maximum reflection wavelength of the metal particle-containing layer is preferably 500 nm or more and 2,100 nm or less, more preferably 700 nm or more and 2,000 nm or less, and 800 nm or more and 2,000 nm or less. Is even more preferable.
The method for measuring the maximum reflection wavelength of the metal particle-containing layer is a wavelength of 300 nm to 2,100 nm according to the method described in JIS R3106: 1998 "Test method for transmittance, reflectance, emissivity, and solar radiation acquisition rate of plate glass". The range is measured, and the maximum reflection value is obtained from the optical reflection spectrum obtained from the measurement result and used as the maximum reflection wavelength.
The metal particle-containing layer preferably contains at least metal particles and further contains a binder.

-Metal particles-
The metal particle-containing layer contains metal particles.
The ratio (aspect ratio) of the major axis length to the minor axis length of the metal particles is preferably 2 or more and 100 or less, and more preferably 3 or more and 60 or less, from the viewpoint of heat shielding performance. It is more preferably 4 or more and 30 or less.
The material of the metal particles is not particularly limited, and examples thereof include silver, aluminum, magnesium, tin, gold, and copper.
As the metal particles, flat silver particles are preferably used, and flat silver particles are more preferably used, from the viewpoints of light resistance, light transmission and heat shielding properties.
The flat particles in the present disclosure include flat particles (polygonal columnar particles, columnar particles, oval particles), ellipsoidal particles, spindle-shaped particles, and the like.
Examples of the flat metal particles include paragraphs 0019 to 0046 of JP2013-228649A, JP2013-083974, JP2013-080222, JP2013-080221, and JP2013-077007. The near-infrared shielding materials described in Japanese Patent Application Laid-Open No. 2013-066945 can be used, and the description of these publications is incorporated in the present specification.
Specifically, the metal particles have 60% or more of flat metal particles, and the main plane of the flat metal particles has an average of 0 ° to ± 30 ° with respect to one surface of the metal particle-containing layer. It is preferable that the surface is oriented in a range.

The content of the metal particles in the metal particle-containing layer is preferably 0.01 g / m ² to 0.2 g / m ² and 0.03 g / m ² to 0.1 g / m 2 from the viewpoint of heat shielding and light transmission. m ² is more preferable, and 0.04 g / m ² to 0.08 g / m ² is even more preferable.
The surface density of the silver particles in the metal particle-containing layer is preferably 10 area% to 80 area%, more preferably 15 area% to 70 area%, and 20 area% to 60 area%. Is more preferable, and 20 area% to 40 area% is particularly preferable.
The surface density of silver particles in the metal particle-containing layer in the present specification is the ratio of the total value B of the silver particles to the area A of the layer when viewed from the surface side of the metal particle-containing layer [(B /). A) × 100].
The surface density is measured, for example, by image processing an image obtained by observing a sulfur compound sensor from above by SEM (scanning electron microscope) observation or an image obtained by observing AFM (atomic force microscope). Can be done.

From the viewpoint of light resistance, heat shielding property and moisture heat resistance, the metal particle-containing layer preferably contains a metal nobler than silver, and more preferably contains flat particles partially coated with gold. preferable. Here, "a metal nobler than silver" means "a metal having a standard electrode potential higher than the standard electrode potential of silver".
The ratio of the metal nobler than silver to silver in the metal particle-containing layer is preferably 0.01 atomic% to 5 atomic%, more preferably 0.1 atomic% to 2 atomic%. It is more preferably 0.2 atom% to 0.5 atom%.
The content of a metal nobler than silver can be measured by, for example, high frequency inductively coupled plasma (ICP) emission spectroscopy after dissolving the sample with an acid or the like.

The position of the metal nobler than silver in the metal particle-containing layer is near the surface of the silver particles. By containing a metal nobler than silver in the vicinity of the surface of the silver particles, it is possible to prevent ionization (oxidation) of silver due to a moist heat environment and suppress deterioration of near-infrared transmittance.
Here, the vicinity of the surface of the silver particles includes the surface of the silver particles and the region from the surface to the 2nd to 4th atomic layers, and includes the case where a metal nobler than silver covers the surface of the silver particles. Is done.
Here, the presence of a metal nobler than silver in the vicinity of the surface of the silver nanoplatelet particles is, for example, Auger Electron Spectroscopy (AES), X-ray Photoelectron Spectroscopy. : XPS) and the like.

Examples of metals nobler than silver include gold, palladium, iridium, platinum, osmium, and the like. These may be used alone or in combination of two or more. Among these, palladium, gold, and platinum are particularly preferable from the viewpoint of easy availability of raw materials.

A metal nobler than silver can be contained near the surface of silver particles by photoreduction, addition of a reducing agent, or chemical reduction after the formation of silver particles, and a metal nobler than silver is produced by being reduced by silver. It is preferable to have.

As for the reduction, if it is added at the same time as the reducing agent, the noble metal is directly reduced and the effect is reduced. Therefore, a method of substituting with silver is preferable.
The reduction can also be achieved, for example, by heating the silver particles in a solvent containing a metal nobler than silver. By heating the solvent, silver reduces metals other than silver. Further, photoreduction, addition of a reducing agent, a chemical reduction method and the like may be combined as appropriate according to the purpose.
Further, it is preferable to coexist a complexing agent having a reduction potential of the complex formed with gold ions of 0.5 V or less at the time of reduction.
Examples of the complexing agent include cyanide (sodium cyanide, potassium cyanide, ammonium cyanide, etc.), thiosulfate, thiosulfate (sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate, etc.), and sulfite (sodium sulfite, etc.). Potassium sulfite, ammonium sulfite, etc.), thiourea, etc. may be mentioned. Among these, sodium sulfite or sodium thiosulfate is preferable from the viewpoint of complex stability and environmental load.

Among them, the metal particles are preferably flat silver particles containing gold from the viewpoint of light resistance, heat shielding property and light transmission, and are flat silver particles having at least a part of the surface coated with gold. It is more preferable, and it is particularly preferable that the surface is flat silver particles whose entire surface is coated with gold.

The average thickness of the coated gold in the metal particles is preferably 0.1 nm or more and 2 nm or less, more preferably 0.4 nm or more and 1.8 nm or less, and further preferably 0.7 nm or more and 1.5 nm or less.

For the average thickness of the coated gold, a HAADF-STEM (High-angle Annular Dark Field Scanning TEM) image in the particle cross-sectional direction is taken, and the thickness of the high-brightness gold coating layer in the captured image is determined by the main plane and the end face. For each of the above, 5 points in 1 particle were measured by an image analysis tool such as ImageJ (provided by the National Institutes of Health (NIH)), and the thickness of each of the 20 particles in total was obtained. Obtained by arithmetic averaging.

The ratio of the thickness of the coated gold on the main plane to the average thickness of the coated gold on the end face of the colloidal silver particles is preferably 0.02 or more, more preferably 0.1 or more, and 0.3 or more. Is more preferable. The upper limit of the thickness ratio is not particularly limited, but is preferably 10 or less. When the thickness ratio is 0.02 or more, excellent oxidation resistance is exhibited.

～ Silver nanoplatelets ～
Colloidal silver particles refer to tabular particles having a major axis length and a diameter of nano size.
As the metal particles, silver nanoparticles are particularly preferable from the viewpoint of heat shielding performance.
From the viewpoint of light transmission and heat shielding properties, the silver nanoplatelets are preferably in the shape of a flat plate having two opposing main planes as shown in FIGS. 1 and 2.

In the case of disc-shaped silver nanoplatelets (hereinafter, also referred to as "silver nanodisks" or "AgND") 35A and 35B shown in FIG. 1 or 2, the major axis length is the circle-equivalent diameter D of the main plane. The aspect ratio is the distance between the circle-equivalent diameter D and the facing main plane, that is, the ratio D / T with the thickness (plate thickness) T of the plate-shaped metal particles.

A silver nanodisk is a particle having two opposing principal planes as shown in FIG. 1 or FIG. Examples of the shape of the main plane include a hexagonal shape, a triangular shape, and a circular shape. Among these, it is preferable that the shape of the main plane is a hexagonal shape as shown in FIG. 1, a polygonal shape having a hexagonal shape or more, or a circular shape as shown in FIG. 2 in terms of high visible light transmittance.
Two or more kinds of these silver nanodisks having a plurality of shapes may be mixed and used.

The circular shape means a shape in which the number of sides having a length of 50% or more of the average circle-equivalent diameter of the silver nanodisk described later is 0 per silver nanodisk particle. The circular silver nanodisk is not particularly limited as long as it has no corners and has a round shape when the silver nanodisk is observed from above the main plane with a transmission electron microscope (TEM).

The hexagonal shape means a shape in which the number of sides having a length of 20% or more of the average circle-equivalent diameter of the silver nanodisk described later is 6 per silver nanodisk. The hexagonal silver nanodisk is not particularly limited as long as it is a hexagonal shape when the silver nanodisk is observed from above the main plane by TEM, and can be appropriately selected according to the purpose. For example, the hexagonal shape. The corners may be sharp or rounded, but the corners are preferably blunt in that absorption in the visible light region can be reduced. The degree of blunting of the angle is not particularly limited and can be appropriately selected depending on the purpose.

The equivalent circle diameter D, which is the major axis length of the flat metal particles, is represented by the diameter of a circle having an area equal to the projected area of the individual particles. The projected area of each particle can be obtained by a known method of measuring the area on an electron micrograph and correcting it with an imaging magnification. The average circle-equivalent diameter DAV is an arithmetic mean value obtained by calculation from the particle size distribution obtained by obtaining the particle size distribution (particle size distribution) from the statistics of the circle-equivalent diameter _D of 200 flat metal particles.

The size (major axis length) of the flat metal particles is not particularly limited and can be appropriately selected depending on the intended purpose. The average circle-equivalent diameter is preferably 10 nm to 500 nm, more preferably 20 nm to 300 nm. More preferably, it is 50 nm to 200 nm.

The thickness T of the flat metal particles is preferably 20 nm or less, more preferably 2 nm to 15 nm, and particularly preferably 4 nm to 12 nm.
The particle thickness T can be measured by an atomic force microscope (AFM) or a transmission electron microscope (TEM).

Examples of the method for measuring the average particle thickness by AFM include a method in which a particle dispersion liquid containing flat metal particles is dropped onto a glass substrate and dried to measure the thickness of one particle.
As a method for measuring the average particle thickness by TEM, for example, a particle dispersion containing flat metal particles is dropped on a silicon substrate, dried, and then coated with carbon vapor deposition or metal vapor deposition, and a focused ion beam is applied. (Focused Ion Beam: FIB) A method of preparing a cross-sectional section by processing and observing the cross-section with a TEM to measure the thickness of particles (hereinafter, also referred to as FIB-TEM) can be mentioned.

When the metal particles are silver nanodisks, the ratio D / T (aspect ratio) of the diameter (equivalent to a circle) D of the silver nanodisks to the thickness T is preferably 3 or more. It can be appropriately selected depending on the intended purpose, but from the viewpoint of absorbing visible light and reducing haze, 3 to 40 is preferable, and 5 to 40 is more preferable. If the aspect ratio is 3 or more, absorption of visible light can be suppressed, and if it is 40 or less, haze in the visible region can be suppressed.

The method for synthesizing silver nanodisks is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a liquid phase method such as a chemical reduction method, a photochemical reduction method, or an electrochemical reduction method may have a hexagonal shape or a circle. Examples include those capable of synthesizing silver nanodisks in shape. Among these, a liquid phase method such as a chemical reduction method or a photochemical reduction method is particularly preferable in terms of shape and size controllability. After synthesizing hexagonal to triangular silver nanodiscs, for example, by performing etching treatment with dissolved species that dissolve silver such as nitrate and sodium sulfite, aging treatment by heating, etc., hexagonal to triangular silver nanodiscs Hexagonal or circular silver nanodiscs may be obtained by blunting the corners of the.
As another method for synthesizing silver nanodisks, seed crystals may be fixed on the surface of a transparent substrate such as a film or glass in advance and then crystal-grown.

-binder-
The metal particle-containing layer preferably contains a binder from the viewpoint of durability.
The binder in the metal particle-containing layer preferably contains a polymer, and more preferably contains a transparent polymer. Examples of the polymer include natural products such as polyvinyl acetal resin, polyvinyl alcohol resin, polyvinyl butyral resin, polyacrylate resin, polymethylmethacrylate resin, polycarbonate resin, polyvinyl chloride resin, (saturated) polyester resin, polyurethane resin, gelatin or cellulose. Examples thereof include polymers such as polymers. Among them, the main polymer is preferably polyvinyl alcohol resin, polyvinyl butyral resin, polyvinyl chloride resin, (saturated) polyester resin, and polyurethane resin, and the polyester resin and polyurethane resin account for 80% or more of the metal particles. It is more preferable from the viewpoint that it can easily be present in the range from the surface of the particle-containing layer to half the thickness of the metal particle-containing layer. Two or more kinds of binders may be used in combination.

Among the polyester resins, the saturated polyester resin is more preferable from the viewpoint of imparting excellent weather resistance because it does not contain a double bond. Further, from the viewpoint of obtaining high hardness, durability and heat resistance by curing with a water-soluble or water-dispersible curing agent or the like, it is more preferable to have a hydroxyl group (hydroxy group) or a carboxy group at the molecular terminal.

As the polymer, a commercially available polymer can be preferably used. For example, a water-soluble polyester resin manufactured by Mutual Chemical Industry Co., Ltd., Pluscoat Z-687, and a polyester polyurethane copolymer manufactured by DIC Corporation are copolymerized. Hydran HW-350 and the like.

Further, in the present specification, the main polymer contained in the particle-containing layer refers to a polymer component that accounts for 50% by mass or more of the polymer contained in the particle-containing layer.

The content of the binder contained in the metal particle-containing layer is preferably 1 part by mass to 10,000 parts by mass, preferably 10 parts by mass to 1,000 parts by mass, based on 100 parts by mass of the metal particles. It is more preferably 20 parts by mass to 500 parts by mass.
The refractive index of the binder is preferably 1.4 to 1.7. Here, the refractive index is a numerical value at a wavelength of 550 nm at 25 ° C. Unless otherwise specified, the refractive index in the present specification is the refractive index at a wavelength of 550 nm at 25 ° C.

From the viewpoint of moisture and heat resistance, the metal particle-containing layer may contain a metal-adsorbing compound, but it is preferable that the metal particle-containing layer does not contain the metal-adsorbing compound.
Examples of the metal-adsorbing compound contained in the metal particle-containing layer include 1-phenyl-1H-tetrazole-5-thiol, 5-amino-1,3,4-thiadiazole-2-thiol and 5-phenyl-1,3. , 4-Oxiadiazole-2-thiol, and methylureidophenylmercaptoterazole and the like.
The content of the metal-adsorbing compound in the metal particle-containing layer is preferably 0 mg / m 2 to 2 mg / m ² from the viewpoint of light resistance, light transmission and heat shielding properties, and is preferably 0 mg / m ² to 0 mg / m ² . More preferably, it is 1.5 mg / m ² .

-Other additives-
The metal particle-containing layer may further contain a surfactant, a quick-drying accelerator, and the like.
Examples of the surfactant include Lapizol A-90 (manufactured by NOF CORPORATION, solid content concentration 1%), Naroacty CL-95 (manufactured by Sanyo Chemical Industries, Ltd., solid content concentration 1%), and the like. ..
Examples of the quick-drying accelerator include alcohol and the like, and ethanol is preferably used.

The thickness of the metal particle-containing layer is preferably 10 nm to 500 nm, more preferably 10 nm to 100 nm, and further preferably 10 nm to 50 nm from the viewpoint of light transmission and heat shielding properties.

<Layer A>
The laminated glass according to the present disclosure has a layer A having a refractive index of 1.4 or less between the transparent base material and the metal particle-containing layer, and the layer A satisfies the following condition 1.
(Λ / 4 + mλ / 2) <nA × dA <λ / 2 + mλ / 2 Condition 1
In condition 1, m represents an integer of 0 or more, λ represents a wavelength for which reflection is desired to be prevented, the unit of λ is nm, nA represents the refractive index of layer A at the wavelength λ, and dA represents layer A. The unit of dA representing the thickness is nm, and the wavelength λ for which reflection is desired to be prevented is 380 nm to 780 nm.

The λ in the above condition 1 may be one wavelength of 380 nm to 780 nm, but from the viewpoint of reducing the visibility of the strain, the layer A has the above condition in the entire range where the λ is 380 nm to 780 nm. It is preferable to satisfy 1.
The laminated glass according to the present disclosure may satisfy the above condition 1 at a value of 1 m.
From the viewpoint of reducing heat shielding performance and strain visibility, m is preferably an integer of 0 or more and 100 or less, more preferably an integer of 0 to 10, and preferably 0 or 1. It is more preferably 0, and particularly preferably 0.

The refractive index of the layer A at the wavelength λ is preferably 1.0 to 1.4, more preferably 1.2 to 1.4, and 1.3 to 1.4 from the viewpoint of reducing the visibility of strain. Is particularly preferable.
The refractive index can be measured, for example, at 25 ° C. by a spectroscopic ellipsometry method (VASE manufactured by Woolam Co., Ltd.).

The thickness of the layer A is preferably 5 nm to 5,000 nm, more preferably 20 nm to 1,000 nm, further preferably 100 nm to 500 nm, and 196 nm to 274 nm from the viewpoint of reducing the visibility of strain. Especially preferable.

From the viewpoint of visible light transmittance and heat shielding performance, the layer A preferably has a light transmittance in the wavelength range of 400 nm to 700 nm of 80% or more, and has a wavelength range of 380 nm to 2,500 nm. It is more preferable that the transmittance is 80% or more.

The layer A is preferably transparent in the visible light region.
The term "transparent" in the present disclosure means that the transmittance of light having a wavelength of 550 nm at 25 ° C. (visible light transmittance described later) is 40% or more. The light transmittance is the ratio of the transmitted light amount to the incident light amount.
Further, the layer A preferably has a transmittance of light having a wavelength of 550 nm at 25 ° C. of 80% or more, and more preferably 90% or more.
Examples of the material include inorganic compounds and organic compounds.
Examples of the inorganic compound include silica, quartz, glass, silicon nitride, titania, alumina, aluminum nitride, zinc oxide, germanium oxide, zirconium oxide, niobium oxide, molybdenum oxide, indium oxide, tin oxide, tantalum oxide, and tungsten oxide. , Lead oxide, diamond, boron nitride, carbon nitride, aluminum oxynitride, silicon oxynitride and the like.
Examples of the organic compound include polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate polymethylmethacrylate, polystyrene, methylstyrene resin, acrylonitrile butadiene styrene (ABS) resin, acrylonitrile styrene (AS) resin, polyethylene, polypropylene, and poly. Methylpentene, polyoxetane, nylon 6, nylon 66, polyvinyl chloride, polyether sulfone, polysulfone, cellulose triacetate, polyvinyl alcohol, polyacrylonitrile, cyclic polyolefin, acrylic resin, epoxy resin, cyclohexadiene polymer, amorphous polyester Examples thereof include resins, transparent polyimides, transparent polyurethanes, transparent fluororesins, thermoplastic elastomers, and polylactic acid.

Further, the layer A preferably has voids, more preferably contains hollow particles, and further preferably contains hollow metal oxide particles, from the viewpoint of adjusting the refractive index and reducing the visibility of strain. It is preferable to include hollow silica particles, and it is particularly preferable to contain hollow silica particles.
As the hollow particles, hollow metal oxide particles such as hollow silica particles, hollow titania particles, hollow silica titania composite particles, and hollow resin particles are preferable from the viewpoint of adjusting the refractive index and reducing the visibility of strain. Can be mentioned.
The arithmetic mean particle size of the hollow particles is preferably 30 nm or more and 100 nm or less, more preferably 35 nm or more and 80 nm or less, and further preferably 40 nm or more and 60 nm or less.

The layer A may contain one type of hollow particles alone, or may contain two or more types of hollow particles.
The content of the hollow particles in the layer A is preferably 10% by mass to 90% by mass, more preferably 30% by mass to 80% by mass, and 40% by mass with respect to the total mass of the layer A. It is particularly preferably about 70% by mass.

When the layer A contains hollow particles, the layer A preferably further contains a binder from the viewpoint of durability.
As the binder, the above-mentioned organic compound is preferably mentioned.
Further, the layer A may contain a fluorine-containing polymer which is a low refractive index binder and magnesium fluoride particles which are low refractive index particles.
The layer A may contain one kind of binder alone or two or more kinds of binders.
The content of the binder in the layer A is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 70% by mass, and more preferably 30% by mass or more, based on the total mass of the layer A. It is particularly preferably 60% by mass.

Further, the layer A may contain a surfactant.
As the surfactant, a known surfactant such as an anion-based or nonionic-based surfactant can be used as the surfactant used in the layer A.
The content of the surfactant in the layer A is preferably 0.1 mg / m ² to 10 mg / m ² , more preferably 0.5 mg / m ² to 3 mg / m ² .
Further, the layer A may contain other known additives.

The method for forming the layer A is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a composition containing a substance having a refractive index n, hollow particles, or the like is layered so that the thickness is d. A method of arranging and forming the particles can be mentioned. The film forming method is not particularly limited and may be appropriately selected depending on the intended purpose.

<Transparent substrate>
The laminated glass according to the present disclosure has a transparent base material between the adhesive layer and the layer A having a refractive index of 1.4 or less, and the maximum heat shrinkage direction of the transparent base material and the maximum heat of the adhesive layer. The shrinkage direction is parallel, or the angle between the maximum heat shrinkage direction of the transparent substrate and the maximum heat shrinkage direction of the adhesive layer is 10 ° or less.
The relationship between the maximum heat shrinkage direction of the transparent substrate and the maximum heat shrinkage direction of the adhesive layer is as described above.
The material of the transparent base material can be appropriately selected, but the material of the transparent base material is preferably a polymer and more preferably a thermoplastic resin. Examples of the polymer include polyolefins such as polyester, polycarbonate, polypropylene and polyethylene, and fluorine-based polymers such as polyvinyl fluoride. Among them, polyester is preferable from the viewpoint of cost, mechanical strength and light transmission.

Examples of the polyester include linear saturated polyester synthesized from an aromatic dibasic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof. Specific examples of the linear saturated polyester include polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate, poly (1,4-cyclohexylene methylene terephthalate), polyethylene-2,6-naphthalate and the like. Of these, polyethylene terephthalate, polyethylene-2,6-naphthalate, and poly (1,4-cyclohexylene methylene terephthalate) are particularly preferable in terms of the balance between mechanical properties and cost.
The polyester may be a homopolymer or a copolymer. Further, a polyester may be blended with another kind of resin, for example, polyimide in a small amount.
The type of polyester is not limited to the above, and known polyesters may be used. As the known polyester, a dicarboxylic acid component and a diol component may be used for synthesis, or a commercially available polyester may be used.

When synthesizing a polyester, for example, (a) a dicarboxylic acid component and (b) a diol component can be obtained by subjecting them to at least one of an esterification reaction and a transesterification reaction by a well-known method.

(A) Examples of the dicarboxylic acid component include malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecandionic acid, dimer acid, eicosandionic acid, pimelic acid, azelaic acid, and methylmalonic acid. , Alicyclic dicarboxylic acids such as ethylmalonic acid; alicyclic dicarboxylic acids such as adamantandicarboxylic acid, norbornenedicarboxylic acid, cyclohexanedicarboxylic acid, decalindicarboxylic acid; terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid. , 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 5-sodium sulfoisophthalic acid, Examples thereof include dicarboxylic acids such as phenylindandicarboxylic acid, anthracendicarboxylic acid, phenanthrangecarboxylic acid, aromatic dicarboxylic acid such as 9,9'-bis (4-carboxyphenyl) fluorenic acid; or an ester derivative thereof.
(B) Examples of the diol component include fats such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, and 1,3-butanediol. Group diols; alicyclic diols such as cyclohexanedimethanol, spiroglycol, isosorbide; bisphenol A, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 9,9'-bis (4-hydroxyphenyl) ) Aromatic diols such as fluorene; diol compounds such as.

The polyester film in which the raw material resin is polyester may contain at least one of a carbodiimide compound and a ketenimine compound. The carbodiimide compound and the ketenimine compound may be used alone, or both may be used in combination. This makes it possible to suppress the deterioration of polyester in a moist heat environment.

The carbodiimide compound or ketenimine compound is preferably contained in an amount of 0.1% by mass to 10% by mass, more preferably 0.1% by mass to 4% by mass, and 0.1% by mass, based on the polyester. It is more preferably contained in an amount of% to 2% by mass. By setting the content of the carbodiimide compound or the ketenimine compound within the above range, the adhesion between the base material and the adjacent layer can be further enhanced. In addition, the heat resistance of the base material can be improved.
When the carbodiimide compound and the ketenimine compound are used in combination, it is preferable that the total content of the two types of compounds is within the above range.

Examples of the polycarbonate include diol polycarbonate. The diol polycarbonate is also produced through a reaction such as a demethanol condensation reaction between a dialcohol and a dimethyl carbonate, a dephenol condensation reaction between a dialcohol and a diphenyl carbonate, or a deethylene glycol condensation reaction between a dialcohol and an ethylene carbonate. Examples of the polyhydric alcohol used in these reactions include 1,6-hexanediol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, and pentane. Various saturated or unsaturated glycols such as diol, 3-methyl-1,5-pentanediol, octanediol, 1,4-butanediol, dipropylene glycol, tripropylene glycol, polytetramethylene ether glycol, 1,4 -Alicyclic glycols such as cyclohexanediglycol and 1,4-cyclohexanedimethanol can be mentioned.

The thickness of the transparent substrate is preferably 20 μm to 150 μm, more preferably 30 μm to 120 μm, further preferably 40 μm to 100 μm, and even more preferably 50 μm to 50 μm from the viewpoint of light transmission and handleability. It is particularly preferably 80 μm.

<Adhesive layer and second adhesive layer>
The laminated glass according to the present disclosure has an adhesive layer between the first glass plate and the transparent base material.
Further, the laminated glass according to the present disclosure preferably has a second adhesive layer between the metal particle-containing layer and the second glass plate.
The preferred embodiment of the adhesive layer and the preferred embodiment of the second adhesive layer are the same except for the position where they are formed.
The material that can be used for forming the adhesive layer is not particularly limited as long as it does not impair the transparency, and can be appropriately selected depending on the intended purpose. For example, polyvinyl butyral (PVB), acrylic resin, etc. Examples thereof include styrene / acrylic resin, urethane resin, polyester resin, and silicone resin.
Among them, polyvinyl butyral is particularly preferable as the material of the adhesive layer from the viewpoint of light transmission and handleability.
These may be used alone or in combination of two or more.
The adhesive layer made of these materials may be formed by laminating or by coating. When it is formed by laminating, it is preferable to use an adhesive sheet from the viewpoint that the thickness can be reduced. That is, the adhesive layer is preferably a layer formed of an adhesive sheet.
Further, an antistatic agent, a lubricant, an antiblocking agent and the like may be added to the adhesive layer.

The thickness of the adhesive layer is preferably 5 μm to 1,000 μm, more preferably 50 μm to 700 μm, and particularly preferably 200 μm to 500 μm.

<First glass plate and second glass plate>
The laminated glass according to the present disclosure has a first glass plate and a second glass plate.
The term "glass plate" shall be used to describe both the first glass plate and the second glass plate.
The glass plate used for the laminated glass according to the present disclosure is not particularly limited, and a known glass plate can be used.
Further, from the viewpoint of heat shielding performance, the laminated glass according to the present disclosure uses clear glass as the glass on the side that is on the side of the incident light of solar radiation, and the inside (the side opposite to the incident light of solar radiation, the side that is incident on non-solar radiation). It is preferable to use green glass as the glass on the side of the glass.
Here, the glass in the present specification includes a glass substitute resin. That is, a glass substitute resin forming body or a combination of a glass substitute resin forming body and glass can be used. Examples of the glass substitute resin include polycarbonate resin, acrylic resin, and methacrylic resin. A hard coat layer coated on such a glass substitute resin can also be used. Examples of the hard coat layer include acrylic hard coat materials, silicone hard coat materials, melamine hard coat materials, and inorganic particles such as silica, titania, alumina, and zirconia dispersed in these hard coat materials. Things can be mentioned.
The thickness of the glass plate is not particularly limited and may be appropriately set according to the intended use.

<Hard coat layer>
The laminated glass according to the present disclosure may have a hard coat layer, and preferably has a hard coat layer on a surface opposite to the surface on which the metal particle-containing layer of the transparent substrate is formed. It is more preferable to have a hardcoat layer between the adhesive layer and the transparent substrate. The laminated glass according to the present disclosure has improved scratch resistance and strength by having a hard coat layer.

-Filler-
The hardcoat layer preferably contains a filler from the viewpoint of scratch resistance and strength.
The filler is not particularly limited as long as it can maintain the transparency of the hard coat layer. Examples of the filler include inorganic particles such as silica particles.
Of these, silica particles are preferable.

~ Silica particles ~
Examples of the silica particles include fumed silica and colloidal silica.
Humed silica can be obtained by reacting a compound containing a silicon atom with oxygen and hydrogen in the gas phase. Examples of the silicon compound as a raw material include silicon halide (for example, silicon chloride and the like).
Colloidal silica can be synthesized by a sol-gel method in which a raw material compound is hydrolyzed and condensed. Examples of the raw material compound of colloidal silica include alkoxysilicon (for example, tetraethoxysilane and the like), halogenated silane compound (for example, diphenyldichlorosilane and the like) and the like.

The shape of the silica particles is not particularly limited, and examples thereof include a spherical shape, a plate shape, a needle shape, a bead shape, or a shape in which two or more of these are combined. The spherical shape referred to here includes not only a true spherical shape but also a spheroid, an oval shape, or the like.

The volume average particle diameter of the silica particles is preferably 1 nm to 100 nm, more preferably 1 nm to 50 nm, still more preferably 1 nm to 30 nm, from the viewpoint of transparency of the hard coat layer.
The volume average particle size can be measured by a particle size distribution meter (MT-3300, manufactured by Nikkiso Co., Ltd.) using a dynamic light scattering method, a static light scattering method, or the like.

As the silica particles, commercially available products on the market may be used. For example, Snowtex (registered trademark) series manufactured by Nissan Chemical Industry Co., Ltd. and Cataloid (registered trademark) -S manufactured by JGC Catalysts and Chemicals Co., Ltd. Examples include the series and the Bayer Levacil series.
Specifically, for example, Snowtex (registered trademark) ST-20, ST-30, ST-40, ST-C, ST-N, ST-20L, ST-O, ST manufactured by Nissan Chemical Industry Co., Ltd. -OL, ST-S, ST-XS, ST-XL, ST-YL, ST-ZL, ST-OZL, ST-AK, Snowtex (registered trademark) AK series, Snowtex (registered trademark) PS series, Snow Examples include the TEX (registered trademark) UP series.

The content of the filler in the hardcoat layer is preferably 0.01% by mass to 5% by mass, preferably 0.05% by mass to 2% by mass, based on the solid content of the hardcoat layer from the viewpoint of scratch resistance and transparency. Is more preferable, and 0.1% by mass to 1% by mass is further preferable.

-binder-
The hardcourt layer preferably contains a binder.
Examples of the binder include the same as those exemplified for the binder in the above-mentioned ultraviolet absorbing layer.

-Glidant-
The hardcourt layer preferably contains at least one of the lubricants.
By including the lubricant, the decrease in slipperiness (that is, the increase in the coefficient of dynamic friction) that tends to occur when fluororesin is used is suppressed, so the scratch resistance against external forces such as scratching or scratching and collision with pebbles is dramatically improved. do. Further, it is possible to improve the surface-like repelling of the coating liquid which is likely to occur when the fluororesin is used, and it is possible to form a hard coat layer containing the fluororesin having a good surface condition.

The lubricant is preferably contained in the hardcourt layer in the range of 0.2 mg / m ² to 200 mg / m ² . When the content ratio of the lubricant is 0.2 mg / m ² or more, the effect of reducing the coefficient of dynamic friction is large. Further, when the content ratio of the lubricant is 200 mg / m ² or less, uneven coating or agglomerates are less likely to occur when the hard coat layer is applied and formed, and it becomes easy to suppress the occurrence of cissing.
Within the above range, the range of 1.0 mg / m ² to 1150 mg / m ² is preferable, and the range of 5.0 mg / m ² to 100 mg / m ² is more preferable, from the viewpoint of the effect of reducing the dynamic friction coefficient and the suitability for application.

Examples of the lubricant include synthetic wax compounds, natural wax compounds, surfactant compounds, inorganic compounds, organic resin compounds and the like. Among them, a compound selected from synthetic wax compounds, natural wax compounds, and surfactant compounds is preferable in terms of the surface strength of the hard coat layer.

Examples of the synthetic wax compound include olefin waxes such as polyethylene wax and polypropylene wax, esters such as stearic acid, oleic acid, erucic acid, lauric acid, bechenic acid, palmitic acid and adipic acid, amides, bisamides and ketones. Examples thereof include metal salts and derivatives thereof, synthetic hydrocarbon waxes such as Fisher Tropsch wax, phosphoric acid esters, hardened castor oil, and hydrides of cured castor oil derivatives.

Examples of natural wax compounds include vegetable waxes such as carnauba wax, candelilla wax and wood wax, petroleum waxes such as paraffin wax and microcrystalline wax, mineral waxes such as montan wax, beeswax and animal waxes such as lanolin. Wax and the like can be mentioned.

Examples of the surfactant-based compound include a cationic surfactant such as an alkylamine salt, an anionic surfactant such as an alkyl sulfate ester salt, a nonionic surfactant such as polyoxyethylene alkyl ether, and an alkyl betaine. Examples include amphoteric surfactants and fluorosurfactants.

As the lubricant, a commercially available product on the market may be used.
Specifically, as synthetic wax-based lubricants, for example, the Chemipearl (registered trademark) series manufactured by Mitsui Chemicals, Inc. (for example, Chemipearl (registered trademark) W700, W900, W950, etc.), Chukyo Yushi Co., Ltd. Polylon P-502, Hymicron L-271, Hydrin L-536, etc.
Examples of the natural wax-based lubricant include Hydrin L-703-35, Celozol 524, and Cellozol R-586 manufactured by Chukyo Yushi Co., Ltd.
As surfactant-based lubricants, for example, the NIKKOL® series manufactured by Nikko Chemicals Co., Ltd. (for example, NIKKOL® SCS, etc.) and the Emar® series manufactured by Kao Corporation (eg, registered trademark). Emar (registered trademark) 40, etc.).

Among the above, the hard coat layer in the present disclosure is a binder polymer manufactured by Obrigato (registered trademark) series manufactured by AGC Cortec Co., Ltd., Ceranate (registered trademark) series manufactured by DIC Corporation, or JSR Co., Ltd. It is preferable to use an inorganic / acrylic composite emulsion and use the Chemipearl (registered trademark) series manufactured by Mitsui Chemicals, Inc. as the lubricant.

-Other additives-
For the hard coat layer, if necessary, an organic solvent, a silane coupling agent (for example, TSL8340 (manufactured by Momentive Performance Materials Japan GK, solid content concentration 2%)), a cross-linking agent, a surfactant, etc. May be added.

The hard coat layer becomes a layer having a better surface shape by adding a silane coupling agent.
As the silane coupling agent, an alkoxysilane compound is preferable, and examples thereof include tetraalkoxysilane and trialkoxysilane. Of these, trialkoxysilanes are preferable, and alkoxysilane compounds having an amino group are particularly preferable.

The content of the silane coupling agent is preferably 0.3% by mass to 1.0% by mass, more preferably 0.5% by mass to 0.8% by mass, based on the solid content of the hard coat layer.
When the content is 0.3% by mass or more, the surface improvement effect is excellent, and when the content is 1.0% by mass or less, when a layer is formed using the coating liquid, aggregation of the coating liquid can be suppressed. ..

It is preferable to add a cross-linking agent to the hard coat layer to form a cross-linked structure from the viewpoint of improving weather resistance. Examples of the cross-linking agent used for the hard coat layer include those listed as the cross-linking agent used for the ultraviolet absorbing layer.

As the surfactant used for the hard coat layer, a known surfactant such as an anion type or nonion type can be used. When a surfactant is added, the amount of the surfactant added is preferably 0 mg / m ² to 15 mg / m ² , more preferably 0.5 mg / m ² to 5 mg / m ² . When the amount of the surfactant added is 0.1 mg / m ² or more, the generation of repellent is suppressed and a good layer is obtained, and when it is 15 mg / m ² or less, good adhesion can be performed.

The method of forming the hard coat layer is not particularly limited. Examples of the method for forming the hard coat layer include a method in which a coating liquid containing a filler, a binder and the like is applied onto a base material or an undercoat layer provided on the base material and dried.
The coating method or the solvent of the coating liquid to be used is not particularly limited. Examples of the coating method include coating using a gravure coater or a bar coater. The solvent used for the coating liquid may be water or an organic solvent such as toluene or methyl ethyl ketone. From the viewpoint of environmental load, it is preferable to prepare an aqueous coating liquid using water as a solvent.
One type of coating solvent may be used alone, or two or more types may be mixed and used.
When an aqueous coating liquid in which a filler is dispersed in water is formed and the coating liquid is applied to form a hard coat layer, the proportion of water in the solvent is preferably 60% by mass or more, more preferably 80% by mass or more.

Examples of the coating liquid forming the hard coat layer include, for example, a silane coupling agent (for example, KBE-403 and KBE-04 (both manufactured by Shin-Etsu Chemical Industries, Ltd.)), silica particles (for example, Snowtex (registered)). Trademarks) OZL35 (manufactured by Nissan Chemical Industries, Ltd.)), surfactants (for example, Lapizol A-90 (manufactured by NOF Corporation), Naroacty CL-95 (manufactured by Sanyo Chemical Industries, Ltd.)), etc. Those containing are preferably mentioned.

The thickness of the hard coat layer is preferably 0.1 μm to 5.0 μm, more preferably 0.3 μm to 3.0 μm, and even more preferably 0.4 μm to 2.0 μm from the viewpoint of scratch resistance and transparency. ..

<Overcoat layer>
The laminated glass according to the present disclosure may have an overcoat layer, preferably having an overcoat layer on the metal particle-containing layer, and between the metal particle-containing layer and the second glass plate, It is more preferable to have an overcoat layer, it is more preferable to have an overcoat layer between the metal particle-containing layer and the second adhesive layer, and the laminated glass according to the present disclosure has an overcoat layer. , The decrease in transparency due to the construction liquid at the time of construction is suppressed.
The overcoat layer preferably contains at least one kind of organic particles having an arithmetic mean particle size of 0.1 μm to 15 μm and a glass transition temperature of 100 ° C. or higher.
In the heat-shielding material of the present invention, since the overcoat layer contains specific organic particles, the decrease in transparency derived from the construction liquid at the time of construction is suppressed.

The arithmetic mean particle size of the organic particles is preferably 0.1 μm to 15 μm, more preferably 0.35 μm to 5.0 μm, from the viewpoint of suppressing the decrease in transparency derived from the construction liquid at the time of construction. 0.8 μm to 1.8 μm is particularly preferable.

For the arithmetic average particle size (μm) of the organic particles, a scanning electron microscope photograph (SEM image) of 100 organic particles was taken with a scanning electron microscope (for example, S-3700N, manufactured by Hitachi High-Technologies Co., Ltd.). It can be obtained by measuring the particle size of the particle using an image processing measuring device (Luzex AP; manufactured by Nireco Co., Ltd.) and obtaining an arithmetic average value. That is, the arithmetic mean particle size is expressed by the diameter when the projected shape of the organic particle is circular, and is expressed by the diameter when it is made into a circle having the same area as the projected area when it is an amorphous shape other than a sphere. ..

The glass transition temperature (Tg) of the organic particles is preferably 100 ° C. or higher, more preferably 130 ° C. or higher, from the viewpoint of productivity and suppression of deterioration of transparency derived from the construction liquid at the time of construction. , 150 ° C. or higher is more preferable, and 200 ° C. or higher is particularly preferable.
The glass transition temperature (Tg) of the organic particles is a value measured under the following conditions using a differential scanning calorimeter "X-DSC7000" (manufactured by SII Nanotechnology Co., Ltd.). The measurement is performed twice for the same sample, and the result of the second measurement is adopted.
-conditions-
・ Atmosphere in the measurement room: Nitrogen (50 mL / min)
・ Temperature rise rate: 5 ° C / min
-Measurement start temperature: -100 ° C
・ Measurement end temperature: 200 ° C
・ Sample pan: Aluminum pan ・ Mass of measurement sample: 5 mg
-Calculation of Tg: Tg was calculated by rounding off the decimal point of the intermediate temperature between the descending start point and the descending end point of the DSC chart.

The content of the organic particles in the overcoat layer is the total mass of the overcoat layer from the viewpoint of suppressing the decrease in transparency derived from the construction liquid and the surface friction coefficient (productivity) of the overcoat layer. On the other hand, 0.3% by mass to 6.0% by mass is preferable, 0.5% by mass to 5.5% by mass is more preferable, and 1.5% by mass to 3.5% by mass is particularly preferable.

The thickness of the overcoat layer is preferably 0.1 μm or more, preferably 0.1 μm to 1.8 μm, from the viewpoint of suppressing the decrease in transparency derived from the construction liquid and the surface friction coefficient of the overcoat layer. More preferably, 0.2 μm to 1.5 μm is further preferable, and 0.4 μm to 1.3 μm is particularly preferable.
The thickness of the overcoat layer can be measured by observing the cross section of the overcoat layer using a scanning electron microscope (for example, S-3700N, manufactured by Hitachi High-Technologies Corporation).
As for the thickness of the overcoat layer, when organic particles are buried in the overcoat layer and the surface of the layer is smooth, the thickness of any 10 points in the cross section of the layer is measured, and the arithmetic mean value of 10 points is adopted. do. On the other hand, if the surface of the overcoat layer has irregularities, the thickness of any 100 points on the cross section of the layer is measured, and the arithmetic mean value of 10 points from the thinnest of the measured 100 points is used as the overcoat layer. Adopted as a thickness.

The ratio of the arithmetic mean particle size of the organic particles to the thickness of the overcoat layer is the arithmetic mean of the organic particles from the viewpoint of suppressing the decrease in transparency derived from the construction liquid and the surface friction coefficient of the overcoat layer. Particle size / thickness of the overcoat layer = 1.00 or more is preferable, 1.10 or more and 8.50 or less is more preferable, and 1.15 to 3.75 is particularly preferable.

The organic particles are not particularly limited as long as they are organic compounds having the shape of particles. The shape of the particles may be spherical, flat, or hollow.
The type of the organic particles is not particularly limited, but the particles of the hydrophobic resin are preferable from the viewpoint of suppressing the decrease in transparency derived from the construction liquid.
The particles of the hydrophobic resin include poly (meth) acrylic acid ester, polystyrene, polyolefin, poly (meth) acrylonitrile, polycarbonate, polytetrafluoroethylene, polyurethane, polyamide, polyacrylamide, polyvinyl acetate, polyvinyl chloride, and polyvinyl acetal. , Polyvinyl butyral, (meth) acrylic-styrene copolymer, (meth) acrylonitrile-styrene copolymer, and styrene-divinylbenzene copolymer.
Among them, particles of poly (meth) acrylic acid ester, polystyrene, and polyolefin are preferable, particles of poly (meth) acrylic acid ester are more preferable from the viewpoint of refractive index, and particles of methyl poly (meth) acrylate are further preferable. Particles of polymethyl methacrylate (PMMA) are particularly preferred.

Examples of the monomer that can form a poly (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. , Lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-propyl (meth) acrylate, chloro-2-hydroxyethyl (meth) acrylate, diethylene glycol Examples thereof include mono (meth) acrylate, methoxyethyl (meth) acrylate, glycidyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate and isobornyl (meth) acrylate.

Examples of the monomer capable of forming polystyrene include alkyl styrenes such as styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene and octyl styrene. Halogenized styrene such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, iodostyrene and chloromethylstyrene; and nitrostyrene, acetylstyrene and methoxystyrene.

Examples of the monomer capable of forming a polyolefin include alkene such as ethylene, butylene and propylene; and monomers other than alkene such as unsaturated carboxylic acid such as (meth) acrylic acid, itaconic acid, maleic acid and maleic acid anhydride. ; And so on.

Organic particles can be obtained by polymerizing one or more of the above-mentioned monomers by a known method.
Organic particles may be used in the form of so-called latex, an aqueous dispersion.
As a method for producing an aqueous dispersion, there are a method by emulsification and a method by emulsification dispersion, and the former is preferable. For a specific method, for example, the method described in Japanese Patent No. 369935 can be referred to.

As the organic particles, those already commercially available as a dispersion may be used. When commercially available organic particles are used as the dispersion, they can be once powdered and used by a known method such as freeze-drying.

Specific examples of commercially available organic particles include MP-300 (manufactured by Soken Kagaku Co., Ltd., PMMA particles, average particle size 0.1 μm, Tg 128 ° C.), MP-1451 (manufactured by Soken Kagaku Co., Ltd., PMMA particles, etc.). Average particle size 0.15 μm, Tg128 ° C), MP-2200 (Soken Kagaku Co., Ltd., PMMA particles, average particle size 0.35 μm, Tg128 ° C), MP-1000 (Soken Kagaku Co., Ltd., PMMA particles, Average particle size 0.4 μm, Tg 128 ° C), MX-80H3wT (Soken Kagaku Co., Ltd., PMMA particles, average particle size 0.8 μm, Tg 200 ° C or higher), MX-150 (Soken Kagaku Co., Ltd., PMMA particles) , Average particle size 1.5 μm, Tg 200 ° C or higher), MX-180TA (manufactured by Soken Kagaku Co., Ltd., PMMA particles, average particle size 1.8 μm, Tg 200 ° C or higher), MX-300 (manufactured by Soken Kagaku Co., Ltd., PMMA particles, average particle size 3.0 μm, Tg 200 ° C or higher), MX-500 (manufactured by Soken Kagaku Co., Ltd., PMMA particles, average particle size 5.0 μm, Tg 200 ° C or higher), MX-1000 (Soken Kagaku Co., Ltd.) , PMMA particles, average particle size 10 μm, Tg 200 ° C or higher), MX-1500H (Soken Kagaku Co., Ltd., PMMA particles, average particle size 15 μm, Tg 200 ° C or higher), SX-130H (Soken Kagaku Co., Ltd., Examples thereof include polystyrene particles, average particle size of 1.3 μm, Tg of 200 ° C. or higher), Chemipearl (registered trademark) W900 (manufactured by Mitsui Kagaku Co., Ltd., polyolefin particles, average particle size of 0.8 μm, Tg of 132 ° C.).

The overcoat layer preferably contains a binder.
The binder is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a thermosetting resin such as a urethane resin, a (meth) acrylic resin, a silicone resin, a melamine resin, an alkyd resin, or a fluororesin, or light Examples include curable resin.
Of these, (meth) acrylic resin or urethane resin is preferable.
Only one kind of binder may be used, or two or more kinds of binders may be combined.

The (meth) acrylic resin is a weight obtained by homopolymerizing a (meth) acrylic monomer such as the above-mentioned monomer capable of forming a poly (meth) acrylic acid ester or copolymerizing it with another monomer. It can be mentioned that it is a coalescence. Examples of other monomers copolymerized with the (meth) acrylic monomer include polymers having a carbon-carbon double bond. Polymers include, for example, block copolymers, graft copolymers, and the like. The (meth) acrylic resin may have at least one group selected from a hydroxy group and an amino group as the other monomer from the viewpoint of improving the adhesion with the adjacent layer.

Urethane resin is a general term for polymers having a urethane bond in the main chain, and examples thereof include resins obtained by the reaction of diisocyanate and polyol. Examples of the diisocyanate include TDI (toluene diisocyanate), MDI (diphenylmethane diisocyanate), NDI (naphthalenediisocyanate), TODI (trizine diisocyanate), HDI (hexamethylene diisocyanate), IPDI (isophorone diisocyanate) and the like.
Examples of the polyol include ethylene glycol, propylene glycol, glycerin, and hexanetriol. Further, as the isocyanate, a resin obtained by subjecting a urethane resin obtained by the reaction of diisocyanate and a polyol to a chain extension treatment to increase the molecular weight can also be used. The above-mentioned diisocyanate, polyol, and chain extension treatment are described in, for example, "Polyurethane Handbook" (edited by Keiji Iwata, Nikkan Kogyo Shimbun, Ltd., published in 1987).

As the binder, a commercially available product may be used.
For example, as urethane resin, Superflex (registered trademark) 150HS, 110, 420 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), Hydran (registered trademark) HW350 (manufactured by DIC Corporation), Takelac (registered trademark) WS400, WS5100 (manufactured by Mitsui Chemicals, Inc.) can be mentioned.
Examples of the (meth) acrylic resin include Aquabrid (registered trademark) AS-563A (manufactured by Daicel FineChem Co., Ltd.), Julima (registered trademark) ET-410 (manufactured by Toagosei Co., Ltd.), and Bonron (registered trademark) PS002 (registered trademark). Mitsui Chemicals Co., Ltd.).

The content of the binder contained in the overcoat layer is preferably 50% by mass to 99% by mass, more preferably 70% by mass to 95% by mass, based on the total mass of the overcoat layer.

The overcoat layer may contain a surfactant.
Examples of the surfactant include known anionic surfactants, nonionic surfactants, cationic surfactants, fluorine-based surfactants, silicone-based surfactants and the like. Surfactants are described, for example, in "Surfactant Handbook" (edited by Nishiichiro, Imai Yochiichiro, Kasai Masazo, Sangyo Tosho Co., Ltd., published in 1960). As the surfactant, an anionic surfactant or a nonionic surfactant is particularly preferable.
Only one type of surfactant may be used, or two or more types may be combined.

As the surfactant, a commercially available product on the market may be used.
Commercially available anionic surfactants include Lapizol (registered trademark) A-90, A-80, BW-30, B-90, C-70 (all manufactured by NOF CORPORATION), NIKKOL (registered trademark). OTP-100 (above, manufactured by Nikko Chemical Co., Ltd.), Kohakul (registered trademark) ON, L-40, Phosphanol (registered trademark) 702 (above, manufactured by Toho Chemical Industries, Ltd.), Viewlite (registered trademark) ) A-5000, SSS (all manufactured by Sanyo Chemical Industries, Ltd.) and the like.

Commercially available nonionic surfactants include Naroacty (registered trademark) CL-95, HN-100 (trade name: manufactured by Sanyo Chemical Industries, Ltd.), and Resolex BW400 (trade name: manufactured by Higher Alcohol Industry Co., Ltd.). , EMALEX (registered trademark) ET-2020 (above, manufactured by Nippon Emulsion Co., Ltd.), Unilube (registered trademark) 50MB-26, Nonion (registered trademark) IS-4 (above, manufactured by Nichiyu Co., Ltd.), etc. Will be.

Examples of commercially available cationic surfactants include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and (meth) acrylic acid type. (Co) Polymer, Polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like can be mentioned.

Examples of commercially available fluorine-based surfactants include Megafuck (registered trademark) F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, and F780. F781 (above, manufactured by DIC Co., Ltd.), Florard FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Ltd.), Surfron (registered trademark) S-382, SC-101, SC-103, SC-104, SC -105, SC1068, SC-381, SC-383, S393, KH-40 (manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA) and the like.

Examples of commercially available silicone-based surfactants include Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (all manufactured by Toray Dow Corning Co., Ltd.), TSF-4440, TSF-4300, etc. TSF-4445, TSF-4460, TSF-4452 (above, Momentive Performance Materials), KP341, KF6001, KF6002 (above, Shin-Etsu Chemical Co., Ltd.), BYK307, BYK323, BYK330 (above, Big Chemie) (Manufactured by the company) and the like.

When a surfactant is added to the overcoat layer, the amount of the surfactant added is preferably 0 mg / m ² to 15 mg / m ² , more preferably 0.5 mg / m ² to 5 mg / m ² .

The overcoat layer may contain other components such as a cross-linking agent, a matting agent, and an ultraviolet absorber, if necessary.
The cross-linking agent is not particularly limited, and examples thereof include cross-linking agents such as epoxy-based cross-linking agents, isocyanate-based cross-linking agents, melamine-based cross-linking agents, carbodiimide-based cross-linking agents, and oxazoline-based cross-linking agents. Of these, carbodiimide-based cross-linking agents and oxazoline-based cross-linking agents are preferable. Specific examples of the carbodiimide-based cross-linking agent include carbodilite (registered trademark) V-02-L2 (manufactured by Nisshinbo Chemical Co., Ltd.).

The method for forming the overcoat layer is not particularly limited, and a known method can be used, but from the viewpoint of cost reduction, a method of forming by coating is preferable. The coating method at this time is not particularly limited, and a known method can be used. For example, a coating liquid of the composition forming the overcoat layer is prepared, and a dip coater, a die coater, a slit coater, etc. Examples thereof include a method of applying with a bar coater, a gravure coater, and the like.

The laminated glass according to the present disclosure may have other known layers in addition to the above-mentioned layers.
Examples of other layers include an undercoat layer, an ultraviolet absorbing layer, a far infrared reflecting layer, and a backcoat layer.
Further, as the other layer, for example, Japanese Patent Application Laid-Open No. 2014-194446 can be referred to.

The method for producing the laminated glass according to the present disclosure is not particularly limited, and a known method can be used.

The method for producing laminated glass according to the present disclosure is a laminated member sandwiched between two glass plates (at least an adhesive layer, a transparent base material, a layer A having a refractive index of 1.4 or less, and a metal particle-containing layer). It is preferable to include a step of crimping while heating (a laminated member having the above in this order).
The laminated member and the two glass plates are bonded together, for example, under reduced pressure in a vacuum bag or the like, after pre-crimping at a temperature of 80 ° C. to 120 ° C. and a time of 30 minutes to 60 minutes, and then 1.0 MPa in an autoclave. A method of laminating at a temperature of 120 ° C. to 150 ° C. under a pressure of about 1.5 MPa to form a laminated glass in which a laminated member is sandwiched between two glass plates can be preferably mentioned. Further, they may be bonded using an adhesive, an adhesive, an adhesive sheet or the like.
At this time, the heat crimping time at a temperature of 120 ° C. to 150 ° C. under a pressure of 1.0 MPa to 1.5 MPa is preferably 20 minutes to 90 minutes.
After the completion of the heat crimping, there is no particular limitation on the method of allowing to cool, and the laminated glass may be obtained by allowing to cool while releasing the pressure as appropriate. In the present disclosure, it is preferable to lower the temperature while maintaining the pressure after the completion of the heat crimping from the viewpoint of further improving the wrinkles and cracks of the obtained laminated glass body. Here, when the temperature is lowered while maintaining the pressure, the internal pressure of the device at 40 ° C. is 75% to 100% of the internal pressure at the time of heat crimping (preferably 130 ° C.). It means to lower the temperature. The method of lowering the temperature while maintaining the pressure is not particularly limited as long as the pressure when the temperature is lowered to 40 ° C. is within the above range, but the internal pressure of the pressure device naturally decreases as the temperature decreases. It is preferable to lower the temperature without leaking pressure from the inside of the device, or to lower the temperature while further pressurizing from the outside so that the pressure inside the device does not decrease as the temperature decreases. When the temperature is lowered while maintaining the pressure, it is preferable that the temperature is pressure-bonded at 120 ° C. to 150 ° C. and then allowed to cool to 40 ° C. over 1 hour to 5 hours.
In the present disclosure, it is preferable to include a step of lowering the temperature while holding the pressure and then releasing the pressure. Specifically, it is preferable to lower the temperature while maintaining the pressure, and then release the pressure to lower the temperature after the temperature in the autoclave becomes 40 ° C. or lower.
Based on the above, the method for producing laminated glass according to the present disclosure is a step of sandwiching the heat ray shielding material according to the present disclosure between at least two pieces of glass, and then under a pressure of 1.0 MPa to 1.5 MPa, 120 ° C. to 150 ° C. It is preferable to include a step of heat-pressing at a temperature of ° C., a step of lowering the temperature while maintaining the pressure, and a step of releasing the pressure.

The range of thermocompression bonding between the glass and the laminated member may be a range covering the entire area of one surface of the glass, but may be only the peripheral portion of the glass, and the thermocompression bonding of the peripheral portion further suppresses the occurrence of wrinkles. You can also.

<Use of laminated glass>
The laminated glass according to the present disclosure can be suitably used as a heat shield glass.
The use of the laminated glass according to the present disclosure is not particularly limited, and examples thereof include laminated glass for vehicles and laminated glass for building materials.
Among these, laminated glass for vehicles is preferable, laminated glass for automobiles is more preferable, and laminated glass for automobile front glass is particularly preferable, in terms of energy saving effect.

An example of the laminated glass according to the present disclosure is shown in FIGS. 3 and 4, but it goes without saying that the present invention is not limited to these.
FIG. 3 is a schematic cross-sectional view of an example of the laminated glass according to the present disclosure.
In the laminated glass 10 shown in FIG. 3, a first glass plate 12, an adhesive layer 14, a transparent base material 16, a layer A18, a metal particle-containing layer 20, and a second glass plate 22 are provided in this order.
FIG. 4 is a schematic cross-sectional view of another example of the laminated glass according to the present disclosure.
The laminated glass 10 shown in FIG. 4 includes a first glass plate 12, an adhesive layer 14, a hard coat layer 24, a transparent base material 16, layer A18, a metal particle-containing layer 20, an overcoat layer 26, and a second adhesive layer 28. , The second glass plate 22 is provided in this order.

Hereinafter, the present disclosure will be specifically described with reference to Examples, but the present disclosure is not limited to the following Examples as long as the gist thereof is not exceeded. Unless otherwise specified, "parts" and "%" are based on mass.

(Examples 1 to 8 and Comparative Examples 1 to 3)
<Formation of layer A>
The following layer A forming coating liquid A-1 or A-2 was applied onto the polyethylene terephthalate (PET) film shown in Table 3. Then, it was heated at 130 ° C. for 2 minutes, dried and solidified to form layer A.

-Preparation of coating liquid A-1 for forming layer A-
Aqueous polyurethane solution (Hydran HW-350, manufactured by DIC Co., Ltd., solid content concentration 30% by mass): 1.83 parts by mass Silica particles isopropyl alcohol (IPA) dispersion liquid (Thruria 4110, manufactured by JGC Catalysts and Chemicals Co., Ltd., solid content) Concentration 20.5% by mass): 14.21 parts by mass Surface active agent B (Naroacty CL-95, manufactured by Sanyo Kasei Kogyo Co., Ltd., solid content 1% by mass): 1.18 parts by mass Water: 54.48% by mass Part IPA: 28.3 parts by mass

-Preparation of coating liquid A-2 for forming layer A-
Aqueous polyurethane solution (Hydran HW-350, manufactured by DIC Co., Ltd., solid content concentration 30% by mass): 1.83 parts by mass Silica particle IPA dispersion (Thruria 4110, manufactured by JGC Catalysts and Chemicals Co., Ltd., solid content concentration 20.5) Mass%): 4.06 mass parts Surface active agent B (Naroacty CL-95, manufactured by Sanyo Kasei Kogyo Co., Ltd., solid content 1 mass%): 1.18 mass parts Water: 64.63 mass parts IPA: 28 .3 parts by mass

<Formation of metal particle-containing layer>
An amount of the Ag-1 coating solution or the Ag-2 coating solution prepared according to the following formulation on the layer A obtained above, and the average thickness after drying using a wire bar becomes the thickness shown in Table 3. Was applied with. Then, it was heated at 130 ° C. for 1 minute, dried and solidified to form a metal particle-containing layer.

-Preparation of silver nanodisc dispersion b2-
1. 1. Preparation of silver nanodisc dispersion liquid b1 First, the silver nanodisk dispersion liquid b1 is prepared.
Weigh 13 L (liter) of ion-exchanged water in a reaction vessel made of NTKR-4 (stainless steel, manufactured by Nissin Steel Industry Co., Ltd.), and put a propeller 4 made of NTKR-4 on a shaft made of stainless steel (SUS316L). 10 g / L trisodium citrate (anhydrous) while stirring at a stirring speed of 400 rpm (revolutions per min: rotation / min) using a chamber equipped with a sheet and an agitator equipped with four NTKR-4 paddles. 1.0 L of an aqueous solution was added and the temperature was kept at 35 ° C. 0.68 L of a polystyrene sulfonic acid aqueous solution having a concentration of 8.0 g / L was added, and 0.041 L of a sodium borohydride aqueous solution prepared to 23 g / L using a 0.04 mol / L sodium hydroxide aqueous solution was added. .. 13 L of 0.10 g / L silver nitrate aqueous solution was added at 5.0 L / min.

Next, 1.0 L of a 10 g / L trisodium citrate (anhydrous) aqueous solution and 11 L of ion-exchanged water were added, and further, 0.68 L of an 80 g / L potassium hydroquinone sulfonate aqueous solution was added. The stirring speed was increased to 800 rpm, 8.1 L of a 0.10 g / L silver nitrate aqueous solution was added at 0.95 L / min, and then the temperature was lowered to 30 ° C.
Then, 8.0 L of a 44 g / L aqueous solution of methyl hydroquinone was added, and then the entire amount of a gelatin aqueous solution at 40 ° C. described later was added. The stirring speed was increased to 1,200 rpm, and the entire amount of the silver sulfite white precipitate mixture described later was added.
When the pH change of the prepared solution stopped, 5.0 L of 1 mol / L NaOH aqueous solution was added at 0.33 L / min. Then, it was adjusted within the range of pH = 7.0 ± 1.0 using a 2.0 g / L 1- (m-sulfophenyl) -5-mercaptotetrazole sodium aqueous solution (NaOH and citric acid (anhydrous)). 0.18 L of the aqueous solution dissolved in the above was added, and 0.078 L of a 70 g / L 1,2-benzisothiazolin-3-one aqueous solution (an aqueous solution adjusted to be alkaline using an aqueous solution of NaOH) was further added. .. In this way, the silver nanodisk dispersion liquid b1 was prepared.

2. 2. Preparation of Gelatin Aqueous Solution 16.7 L of ion-exchanged water was weighed in a SUS316 L dissolution tank. 1.4 kg of deionized alkaline-treated beef bone gelatin (GPC weight average molecular weight 200,000) was added while stirring at low speed with an agitator made of SUS316L.
Further, 0.91 kg of alkali-treated beef bone gelatin (GPC weight average molecular weight 21,000) subjected to deionization treatment, proteolytic enzyme treatment, and oxidation treatment with hydrogen peroxide was added. After that, the temperature was raised to 40 ° C., and the gelatin was swollen and dissolved at the same time to completely dissolve it, thereby obtaining a gelatin aqueous solution used for preparing the silver nanodisk dispersion liquid b1 described above.

3. 3. Preparation of Silver Sulfite White Precipitate Mixture 8.2 L of ion-exchanged water was weighed in a SUS316 L dissolution tank, and 8.2 L of 100 g / L silver nitrate aqueous solution was added. While performing high-speed stirring with an agitator made of SUS316L, 2.7 L of a 140 g / L sodium sulfite aqueous solution was added in a short time, and a mixed solution containing a white precipitate of silver sulfite, that is, the silver nanodisk dispersion described above. A silver sulfite white precipitate mixed solution used for preparing b1 was prepared. This silver sulfite white precipitate mixture was prepared immediately before use.

4. Preparation of Silver Nanodisc Dispersion Liquid b2 800 g of the silver nanodisk dispersion liquid b1 obtained above was collected in a centrifuge tube, and 1 mol / L NaOH and 0.5 mol / L sulfuric acid were used to prepare the silver nanodisk dispersion liquid b1. The pH of the liquid at 25 ° C. was adjusted to the range of 9.2 ± 0.2.
Using a centrifuge (Hitachi Koki Co., Ltd., himacCR22GIII, angle rotor R9A), set the liquid temperature to 35 ° C, perform a centrifuge operation at 9,000 rpm for 60 minutes, and then perform the supernatant liquid. Was separated and removed by 784 g. A 0.2 mmol / L NaOH aqueous solution was added to the precipitated silver nanodisks to make a total of 400 g, and the mixture was manually stirred with a stirring rod to prepare a crude dispersion.
By the same operation as this, 24 crude dispersions were prepared to make a total of 9,600 g, added to a tank made of SUS316L, and mixed.
Further, 10 ml (milliliter) of a 10 g / L solution of Pluronic31R1 (manufactured by BASF) (diluted with a mixed solution of methanol: ion-exchanged water = 1: 1 (volume ratio)) was added.

Using an automixer 20 type (stirring part is homomixer MARKII) manufactured by Primix Corporation, a batch-type dispersion at 9,000 rpm for 120 minutes in a mixture of a crude dispersion in a tank and the above-mentioned solution of Pluronic31R1. Processed. The liquid temperature during dispersion was maintained at 50 ° C. After the dispersion, the temperature was lowered to 25 ° C., and then single-pass filtration was performed using a profile II filter (manufactured by Nippon Pole Co., Ltd., product model MCY1001Y030H13) to obtain a silver nanodisk dispersion liquid b2.
That is, the prepared silver nanodisc dispersion liquid b1 was subjected to desalting treatment and redispersion treatment according to the procedure described above to prepare a silver nanodisk dispersion liquid b2.

-Preparation of Ag-2 coating solution-
Further, an Ag-2 coating liquid (coating liquid for forming a metal particle-containing layer) was prepared so as to have the composition shown in Table 1.

Further, additional explanations of each component in Table 1 are described below.
・ Hydran HW-350: Polyester polyurethane resin ・ Rapisol A-90: Anionic surfactant ・ Naroacty CL-95: Nonionic surfactant (polyoxyalkylene ether)

-Preparation of gold-coated silver nanodisc dispersion b2A-
144 g of silver tabular particle dispersion (silver concentration: 0.5% by mass = about 46 mmol / L) to which 13.6 g of hexadecyltrimethylammonium chloride (CTAC) was added to 130.4 g of silver nanodisk dispersion b2. , The gold-coated silver nanodisk dispersion b2A was obtained by adding to the gold-coated treatment liquid F1 in the following reaction vessel and stirring at 60 ° C. for 4 hours.

-Preparation of gold coating treatment liquid F1-
266.3 g of water, 177 g of 0.5 mol / L ascorbic acid (reducing agent), and 608 g of the following gold reducing solution G1 were sequentially added to the reaction vessel, stirred for 5 minutes, and then a 1 mol / L sodium hydroxide aqueous solution was added. The pH was adjusted to 10 or more by using the product to obtain a gold coating treatment liquid F1.

-Preparation of gold reducing solution G1-
In a container, 18.2 g of water, 1.88 mmol / L gold chloride tetrahydrate (water-soluble gold compound) 353.6 g, 0.2 mol / L sodium hydroxide (pH regulator) 15.6 g and 0. .1 mol / L sodium sulfate (complexing agent) (220.6 g) was sequentially added with light stirring to obtain a gold reduction liquid G1.

-Preparation of Ag-1 coating solution-
An Ag-1 coating liquid was prepared by the same method as the Ag-2 coating liquid except that the gold-coated silver nanodisk dispersion liquid b2A was used instead of the silver nanodisc dispersion liquid b2.

<Formation of overcoat layer>
As shown in Table 3, the following coating liquid for forming an overcoat layer is applied onto the metal particle-containing layer obtained in accordance with the above, if necessary, and the average thickness after drying using a wire bar is shown in Table 3. It was applied in an amount having the thickness described in 1. Then, it was heated at 135 ° C. for 2 minutes, dried and solidified to form a dielectric layer.

-Preparation of coating liquid for forming overcoat layer-
A coating liquid for forming an overcoat layer was prepared so as to have the composition shown below.
Water: 52.7 parts Cross-linking agent: 6.0 parts (Carbodilite (registered trademark) V-02-L2, manufactured by Nisshinbo Chemical Co., Ltd., solid content 20% by mass)
Acrylic binder: 1.7 parts (AS-563A, manufactured by Daicel FineChem Co., Ltd., solid content 27.5% by mass)
Surfactant: 8.2 parts (Rapisol® A-90, manufactured by NOF CORPORATION, solid content 1.0% by mass, anionic surfactant)
Surfactant: 11.4 parts (Naroacty (registered trademark) CL-95, manufactured by Sanyo Chemical Industries, Ltd., solid content 1.0% by mass, nonionic surfactant)
Urethane binder: 18.6 parts (Takelac (registered trademark) WS5100, manufactured by Mitsui Chemicals, Inc., solid content 30% by mass)
Organic particles: 1.3 parts (MP-300, average particle diameter 0.1 μm, manufactured by Soken Chemical Co., Ltd., polymethylmethacrylate particles)

<Formation of hard coat layer>
As shown in Table 3, a coating liquid for forming a hard coat layer prepared below is applied to the surface of the transparent substrate opposite to the side on which the metal particle-containing layer is formed, if necessary. A hard coat layer (HC layer) having a thickness of 1.0 μm was formed to prepare a laminated member.

-Preparation of coating liquid for forming hard coat layer-
The components shown in Table 2 below were mixed to prepare a coating liquid for forming a hard coat layer.
Specifically, 3-glycidoxypropyltrimethoxysilane (KBM-403) was added dropwise into the acetic acid aqueous solution over 3 minutes while vigorously stirring the acetic acid aqueous solution. Next, tetraethoxysilane (KBE-04) was added to the acetic acid aqueous solution over 3 minutes with vigorous stirring. Subsequently, stirring was continued for 2 hours. Next, colloidal silica (Snowtex OZL35), a chelating agent (aluminum chelate D), and a surfactant (Labizol A-90 and Naracty CL-95) are sequentially added to prepare a coating liquid for forming a hard coat layer. Prepared.

<Making laminated glass>
-Preparation of laminated body-
Next, the manufactured laminated member, a polyvinyl butyral film for laminated glass with an embossed surface (thickness 0.38 mm, softening point 130 ° C., manufactured by Sekisui Chemical Industry Co., Ltd.), and a glass plate with a thickness of 2 mm (thickness: 0.38 mm, softening point: 130 ° C., manufactured by Sekisui Chemical Industry Co., Ltd.) (Clear glass manufactured by Corning Co., Ltd.), the polyvinyl butyral film for laminated glass from the glass plate side, and the manufactured laminated member in this order, the maximum heat shrinkage direction of the transparent substrate and the maximum heat of the adhesive layer shown in Table 4. The laminated members were superposed so as to form an angle with the shrinkage direction, and the laminated member, the polyvinyl butyral film, and the glass plate were heat-bonded using a laminator (manufactured by Taisei Laminator Co., Ltd.) to prepare a laminated body. At this time, the temperature of the laminator roll was 120 ° C., the nip pressure was 0.2 MPa, and the transport speed was 0.15 m / min.

The direction in which the heat shrinkage rate became maximum was measured as follows.
Transparent substrate: A transparent substrate cut into 5 cm squares was placed on a hot plate heated to 130 ° C. and allowed to stand for 30 minutes. The length, width, and diagonal length before and after heat application were measured, and the direction with the largest shrinkage was determined.
Adhesive sheet (adhesive layer): An adhesive sheet cut into 5 cm squares was placed on a hot plate heated to 60 ° C. and allowed to stand for 30 minutes. The length, width, and diagonal length before and after heat application were measured, and the direction with the largest shrinkage was determined.
The directions in which the heat shrinkage of the transparent base material and the adhesive sheet obtained as described above are maximized are superposed in the above so as to be the corners shown in Table 4.

-Laminated glass-
~ Preliminary crimping ~
A polyvinyl butyral film for laminated glass and a glass plate were placed on the laminated member of the produced laminated body, placed in a rubber bag, and depressurized by a vacuum pump. Then, the temperature was raised to 90 ° C. under reduced pressure, held for 30 minutes, and then returned to normal temperature and pressure to complete the preliminary crimping step.

~ Main crimping ~
Each laminated glass after pre-crimping is held in an autoclave under the conditions of pressure 1.3 MPa and temperature 130 ° C for 30 minutes, then returned to normal temperature and pressure (25 ° C 1 atm), the main crimping process is completed, and the laminated glass is completed. Was produced.

<Evaluation of metal particles>
-Average circle-equivalent diameter of metal particles-
For the average circle-equivalent diameter of the metal particles, image analysis was performed on 200 particles arbitrarily extracted from the observed SEM image, the circle-equivalent diameter of each particle was calculated, and the average value was taken as the mean circle-equivalent diameter.

-Average thickness-
The obtained dispersion containing silver particles was dropped onto a glass substrate and dried, and the thickness of one silver tabular particle was measured using an atomic force microscope (AFM) (Nanocute II, manufactured by Seiko Instruments). It was measured. The measurement conditions using the AFM were a self-detection sensor, a DFM mode, a measurement range of 5 μm, a scanning speed of 180 seconds / frame, and a data score of 256 × 256.

-aspect ratio-
The aspect ratio was calculated by dividing the average circle-equivalent diameter by the average thickness from the average circle-equivalent diameter and the average thickness of the obtained silver particles.

The metal particles (gold-coated silver nanodisks) of the Ag-1 coating liquid had an average circle equivalent diameter of 110 nm, an average thickness of 7.5 nm, and an aspect ratio of 14.7.
The metal particles (silver nanodisks) of the Ag-2 coating liquid had an average circle equivalent diameter of 110 nm, an average thickness of 7.5 nm, and an aspect ratio of 14.7.

-Area density-
A surface SEM image (magnification of 20,000 times) of the metal particles of the metal particle-containing image in the laminated glass is observed using an S4300 scanning electron microscope manufactured by Hitachi, Ltd., and the projected area of the metal particles in one field image thereof. Was calculated as the surface density.

<Evaluation>
-Measurement of visual reflectance-
The visual reflectance was calculated by multiplying r3 (λ) obtained by the following formula by the weighting factor of JIS R3106: 1998 Appendix Table 1. The smaller the value of the visual reflectance, the more the visual recognition of the strain can be suppressed.
R (λ) = r1 (λ) + r2 (λ) + r3 (λ)
R (λ): Average spectral reflectance of 380 nm to 780 nm in the entire laminated glass measured by JIS R3106: 1998 r1 (λ): Surface average spectral reflectance of 380 nm to 780 nm in the glass plate on the front side r2 (λ) : Surface average spectral reflectance of 380 nm to 780 nm on the glass plate on the back surface side r3 (λ): Spectral reflectance of the metal particle-containing layer λ: Wavelength 380 nm to 780 nm
In addition, r1 (λ) and r2 (λ) were measured by a surface reflectance measuring device (FE3000 manufactured by Otsuka Electronics Co., Ltd.).

<Strain visibility evaluation (appearance evaluation)>
The obtained laminated glass was visually inspected from an inclination angle of 45 degrees under a fluorescent lamp, and the appearance was judged in three stages as follows.
A: Wrinkles and orange peel are not visible on the entire surface B: Wrinkles and orange peel are not visible except at the edges C: Wrinkles or orange peel are visible on the entire surface

<Durability evaluation>
Visible light of the obtained laminated glass before and after super xenon (180 W / m ² , 89 ° C., 50% RH, 2,500 hours, no water shower) from the side shown by the arrangement of the transparent substrate in Table 4. The degree of change in the light transmittance was calculated and evaluated in the following three stages.
A: More than -1% and less than + 1% B: More than + 1% and less than + 2%, or more than -2% and less than -1% C: More than + 2% or less than -2%

The evaluation results are summarized in Table 4.

The thickness of each layer shown in Table 3 is an average thickness.
Further, the "outside of the vehicle" in Table 4 means that the incident side of sunlight in the durability evaluation is the side on which the transparent base material is provided with the metal particle-containing layer as a reference, and the "inside of the vehicle" means. It indicates that the incident side of sunlight in the durability evaluation is the side opposite to the side where the transparent base material is provided with reference to the metal particle-containing layer.

As shown in Tables 3 and 4, the laminated glass according to the present disclosure has less distortion of reflected light in appearance than the laminated glass of the comparative example.

(Example 9)
Laminated in the same manner as in Example 1 except that the glass plate inside the vehicle was changed to a glass plate made of green glass (glass having a transmission spectrum shown in FIG. 5 (glass that absorbs near infrared rays)) having a thickness of 2 mm. Glass was made.
As a result of the same evaluation as in Example 1, the same evaluation results as in Example 1 were obtained in the evaluation of appearance, durability and visual reflectance.

The disclosure of Japanese Patent Application No. 2018-035197, filed February 28, 2018, is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards described herein are to the same extent as if the individual documents, patent applications, and technical standards were specifically and individually stated to be incorporated by reference. Is incorporated herein by reference.

10: Laminated glass, 12: First glass plate, 14: Adhesive layer, 16: Transparent substrate, 18: Layer A, 20: Metal particle-containing layer, 22: Second glass plate, 24: Hard coat layer, 26: Overcoat layer, 28: Second adhesive layer, 35A, 35B: Silver nanodisk, T: Thickness, D: Circle equivalent diameter

Claims (10)

It has a first glass plate, an adhesive layer, a transparent base material, a layer A having a refractive index of 1.4 or less, a metal particle-containing layer, and a second glass plate in this order.
When m is 0 , the layer A satisfies the following condition 1 and satisfies the following condition 1.
The adhesive layer contains polyvinyl butyral.
The transparent substrate contains polyester and
The thickness of the adhesive layer is 200 μm to 1,000 μm.
The thickness of the transparent substrate is 40 μm to 100 μm.
The thickness of the layer A is 100 nm to 274 nm.
The thickness of the metal particle-containing layer is 10 nm to 50 nm, and the thickness is 10 nm to 50 nm.
The maximum heat shrinkage direction of the transparent base material and the maximum heat shrinkage direction of the adhesive layer are parallel, or the angle formed by the maximum heat shrinkage direction of the transparent base material and the maximum heat shrinkage direction of the adhesive layer. Is 10 ° or less, laminated glass.
(Λ / 4 + mλ / 2) <nA × dA <λ / 2 + mλ / 2 Condition 1
In condition 1, m represents 0 , λ represents the wavelength at which reflection is desired to be prevented, the unit of λ is nm, nA represents the refractive index of layer A at the wavelength λ, and dA represents the thickness of layer A. The unit of dA is nm, and the wavelength λ for which reflection is desired to be prevented is at least one wavelength of 380 nm to 780 nm. The heat shrinkage rate of the transparent base material when held at 130 ° C. for 30 minutes is 0.0% to 1.0% in the maximum heat shrinkage direction, and is perpendicular to the maximum heat shrinkage direction in the surface direction of the transparent base material. The laminated glass according to claim 1, which is −1.0% to 0.5% in any direction. The heat shrinkage rate of the adhesive layer held at 60 ° C. for 30 minutes is 1.0% to 3.0% in the maximum heat shrinkage direction, and in the surface direction of the adhesive layer, in the direction perpendicular to the maximum heat shrinkage direction. The laminated glass according to claim 1 or 2, which is 2.0% to 0.0%. The laminated glass is a heat shield glass,
The laminated glass according to any one of claims 1 to 3, wherein the sunlight incident side is the first glass plate side. The laminated glass according to any one of claims 1 to 4, wherein the metal particle-containing layer contains flat silver particles. The laminated glass according to any one of claims 1 to 5, wherein the metal particle-containing layer contains flat silver particles whose at least a part is coated with gold. The laminated glass according to any one of claims 1 to 6, wherein the layer A has a refractive index of 1.2 to 1.4. The laminated glass according to any one of claims 1 to 7, wherein the layer A contains hollow particles. The laminated glass according to any one of claims 1 to 8, further comprising a second adhesive layer between the metal particle-containing layer and the second glass plate. The laminated glass according to any one of claims 1 to 9, which is a laminated glass for an automobile windshield.

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