CN113518711A

CN113518711A - Laminated glass

Info

Publication number: CN113518711A
Application number: CN202080017393.0A
Authority: CN
Inventors: 青木时彦; 仪间裕平; 宫坂诚一
Original assignee: Asahi Glass Co Ltd
Current assignee: AGC Inc
Priority date: 2019-03-04
Filing date: 2020-02-18
Publication date: 2021-10-19
Also published as: DE112020001086T5; JPWO2020179433A1; WO2020179433A1

Abstract

A laminated glass comprising: 1 pair of glass plates opposite to each other, 1 pair of middle adhesive layers which are positioned between 1 pair of glass plates and are respectively connected with 1 pair of glass plates, and a light adjusting film which is positioned between 1 pair of middle adhesive layers and can switch visible light transmissivity, wherein the laminated glass is approximate polygon in a plan view, the periphery of the light adjusting film is positioned at a distance w [ mm ] from the periphery of the laminated glass in the plan view on at least 1 side of the periphery, the thickness of the light adjusting film is ts [ mm ], the total thickness of the thicknesses of 1 pair of middle adhesive layers is ti [ mm ], w, ti and ts satisfy the formula 1: 0 < w/ti < 7/ts, and 1 pair of intermediate adhesive layers are in contact with each other in a region from the outer periphery of the laminated glass to the outer periphery of the light adjusting film.

Description

Laminated glass

Technical Field

The present invention relates to a laminated glass, and to a laminated glass provided with a light adjusting film.

Background

As a window glass suitable for a vehicle, there is known a smart glass in which a light adjusting film is sealed inside a laminated glass and the transmittance can be electrically switched by turning on/off a power switch.

In order to protect the end portions of the light adjusting film from the external environment, the light adjusting film is often cut to a size smaller than that of the glass plate or the intermediate adhesive layer, and is enclosed in the laminated glass so that the end portions are covered with the intermediate adhesive layer. Specifically, a general configuration is such that a frame-shaped intermediate adhesive layer is disposed on the peripheral portion of the light adjusting film, and the light adjusting film is sandwiched between 2 intermediate adhesive layers and then sandwiched between 1 pair of glass plates (see, for example, patent document 1).

However, when the frame-shaped intermediate adhesive layer is used, there is a problem that the workability of the laminating step is deteriorated, and the amount of the intermediate adhesive layer used is increased, thereby increasing the cost.

In the conventional technique, when a functional film (for example, an infrared-reflective film) having a small thickness is sealed in a laminated glass, the sealing is generally performed without using a frame-shaped intermediate adhesive layer (for example, see patent document 2). However, the structure of the light control film is generally formed by sandwiching the light control material between 2 plastic films, and the thickness is likely to be thicker than other functional films, and appearance defects such as air remaining and foaming may occur if a frame-shaped intermediate adhesive layer is not used. The present inventors have conducted extensive studies and found that the above problems can be solved by controlling the thickness of the light adjusting film and the positional relationship thereof in the laminated glass.

Documents of the prior art

Patent document

Patent document 1: japanese patent No. 5666128

Patent document 2: japanese patent laid-open publication No. 2017-186179

Disclosure of Invention

Technical problem to be solved by the invention

The present invention aims to provide a laminated glass provided with a light-adjusting film, which can protect the end of the light-adjusting film without damaging the appearance and can improve the productivity.

Technical scheme for solving technical problem

The laminated glass of the present invention comprises:

1 pair of glass plates facing each other,

1 pair of intermediate bonding layers positioned between and respectively connected with the 1 pair of glass plates,

A light adjusting film which is located between the 1 pair of intermediate adhesive layers and can switch the visible light transmittance,

the laminated glass is substantially polygonal in plan view, and at least 1 side of the outer peripheral portion of the laminated glass satisfies the following requirements (i-1) to (i-3).

(i-1) the periphery of the light adjusting film is located inward from the periphery of the laminated glass by a distance of w [ mm ] in a plan view.

(i-2) when the thickness of the light adjusting film is ts [ mm ] and the total thickness of the pair of intermediate adhesive layers 1 is ti [ mm ], w, ti, and ts satisfy the following formula 1.

W/ti < 7/ts 0, 1

(i-3) the 1 pair of intermediate adhesive layers are in contact with each other in a region from the outer periphery of the laminated glass to the outer periphery of the light adjusting film.

Effects of the invention

The present invention can provide a laminated glass having a light-adjusting film, in which the end portion of the light-adjusting film is protected, and which is free from damage to the appearance of the laminated glass and has high productivity.

Drawings

Fig. 1 is a front view showing an example of the embodiment of the laminated glass of the present invention.

Fig. 2 is a cross-sectional view of the laminated glass shown in fig. 1 taken along line X-X.

FIG. 3 is a table showing the evaluation results of examples and comparative examples.

Detailed Description

Embodiments of the present invention will be described below. The present invention is not limited to these embodiments, and these embodiments may be modified or changed without departing from the spirit and scope of the present invention.

The laminated glass of the present invention comprises 1 pair of glass plates facing each other, 1 pair of intermediate adhesive layers located between the 1 pair of glass plates and in contact with the 1 pair of glass plates, respectively, and a light control film located between the 1 pair of intermediate adhesive layers and capable of switching visible light transmittance, and is characterized in that the laminated glass is substantially polygonal in plan view, and at least 1 side of the outer peripheral portion of the laminated glass satisfies the following requirements (i-1) to (i-3).

W/ti < 7/ts 0, 1

In the present specification, the end portion refers to a ridge formed by joining a surface to a surface, and the peripheral portion refers to a region having a constant width from the end portion of the surface to the central portion of the surface. In the laminated glass, the end portion refers to the outer periphery of the main surface of the laminated glass. The thickness of the laminated glass measured at the end portion is a distance from the end portion of one main surface of the laminated glass to the end portion of the other main surface at the measurement position. The thickness of the laminated glass measured at the end is also referred to as the end thickness of the laminated glass.

In addition, the outer periphery of the main surface of the laminated glass of the present invention coincides with the outer periphery of the main surface of the glass plate constituting the laminated glass. In the present specification, the outer peripheral side of the principal surfaces of the laminated glass and the glass plate as viewed from the central portion is referred to as the outer side, and the central portion as viewed from the outer periphery is referred to as the inner side.

In the present specification, "substantially the same shape and substantially the same size" means that they have the same shape and the same size in human sight, and for example, 2 "substantially the same shape and the same size" also includes a case where one has an outer peripheral shape having no irregularities such as a notch and the other has an outer peripheral shape having a partially fine notch or the like. In other cases, "substantially" also means the same meaning as described above. In the present specification, "to" indicating a numerical range includes upper and lower numerical values.

Hereinafter, embodiments of the laminated glass of the present invention will be described with reference to the drawings. Fig. 1 is a front view showing an example of the embodiment of the laminated glass of the present invention, and fig. 2 is a cross-sectional view of the laminated glass shown in fig. 1 taken along the X-X line.

The laminated glass 10A shown in fig. 1 and 2 includes 1 pair of

glass plates

1A and 1B facing each other, and 1 pair of intermediate

adhesive layers

2A and 2B in contact with facing surfaces of the 1 pair of

glass plates

1A and 1B, respectively. In the laminated glass 10A, 1 pair of

glass plates

1A and 1B and 1 pair of intermediate

adhesive layers

2A and 2B are substantially quadrangular in plan view, and have main surfaces of substantially the same shape and the same size.

The shape of the laminated glass of the embodiment in a plan view is an approximately polygonal shape. Being approximately polygonal includes shapes where corners may have a radius of curvature of about 1000mm or less. The number of the polygonal corners is 3 to 8, and is appropriately selected according to the use of the laminated glass. The shape of the laminated glass of the embodiment in a plan view is preferably substantially quadrangular.

The laminated glass 10A further has a light adjusting film 3 capable of switching the visible light transmittance between the pair of intermediate

adhesive layers

2A, 2B 1. The light adjusting film 3 is disposed between the intermediate

adhesive layers

2A, 2B so that the area of the main surface is smaller than that of the

glass plates

1A, 1B, and the outer periphery of the main surface is located inside the outer periphery of the main surface of the

glass plates

1A, 1B.

The outer periphery of the laminated glass 10A coincides with the outer periphery of the

glass plates

1A, 1B. In the laminated glass 10A, the outer periphery of the light adjusting film 3 is located inward from the outer periphery of the laminated glass 10A by a distance of w [ mm ] in a plan view (the requirement (i-1) is satisfied). In a frame-like region from the outer periphery of the laminated glass 10A to the outer periphery of the light adjusting film 3, the opposing main surfaces of the intermediate adhesive layer 2A and the intermediate adhesive layer 2B are in contact with each other (requirement (i-3)) to form a display. That is, in the laminated glass 10A, the picture frame layer formed of the 3 rd intermediate adhesive layer does not exist outside the dimming film 3. The width of this region corresponds to the distance w.

In the laminated glass 10A, ts [ mm ] represents the thickness of the light adjusting film 3, ti1[ mm ] and ti2[ mm ] represent the thicknesses of the intermediate

adhesive layers

2A and 2B, respectively, and tg1[ mm ] and tg2[ mm ] represent the thicknesses of the

glass plates

1A and 1B, respectively. The total thickness of the thicknesses of the intermediate

adhesive layers

2A and 2B is denoted as ti [ mm ].

The thickness of each component of the laminated glass is substantially constant in the plane, and the position of measurement of the thickness is not particularly limited. However, as described later, the thickness of the intermediate adhesive layer at the end portion may be reduced depending on the manufacturing method. Therefore, the measurement position of the thickness of each component of the laminated glass is located at a position 50mm or more inward from the end of the laminated glass. The thickness is measured by a usual method, for example, using a slide caliper or a micrometer. The micrometer may be a digital straight micrometer (デジマチック, straight style ミクロンマイクロメーター)406 and 250OMV25M, available from Sanfeng corporation (ミツトヨ).

W, ti, and ts of the laminated glass 10A as the laminated glass of the embodiment of the present invention satisfy the following formula 1 (satisfy the requirement (i-2)).

W/ti < 7/ts 0, 1

In the laminated glass of the embodiment, the relationship of w, ti, and ts preferably satisfies the following formula 2. However, ts in this case is 0.25mm or more. Hereinafter, this requirement is also referred to as requirement (i-4).

W/ti < 4.5/ts formula 2

In the laminated glass of the embodiment, all of the requirements (i-1) to (i-3) can be satisfied on at least 1 side of the outer peripheral portion. In the laminated glass of the embodiment, it is preferable that all of the requirements (i-1) to (i-3) are satisfied on at least 2 sides of the outer peripheral portion, and it is preferable that all of the requirements (i-1) to (i-3) are satisfied on the entire periphery. In either case, it is further preferable that the requirement (i-4) is satisfied.

The laminated glass 10A shown in fig. 1 and 2 is an example in which all of the requirements (i-1) to (i-3), preferably (i-4), are satisfied over the entire circumference of the outer peripheral portion. W in the laminated glass 10A satisfies formula 1, preferably formula 2, with respect to w corresponding to the entire outer periphery of the laminated glass and the entire outer periphery of the light adjusting film. As long as w satisfies formula 1, preferably formula 2, it may be different on each outer periphery of the laminated glass 10A, and there may be a portion where w is different in one side. The same applies to the above-described embodiment, even if the laminated glass is a polygon other than the approximate quadrangle shown in fig. 1, for example.

In the laminated glass of the embodiment, w is preferably 100mm or less, more preferably 50mm or less, further preferably 20mm or less, and further preferably 10mm or less on at least 1 side, preferably all sides satisfying the requirements (i-1) to (i-3). When w is equal to or more than the above value, the area occupied by the light adjusting film is large, and not only can the visible light transmittance be controlled over a large area, but also the appearance design is excellent. Further, in the laminated glass of the embodiment, w is preferably 1mm or more, more preferably 3mm or more, and particularly preferably 5mm or more on at least 1 side, preferably all sides satisfying the requirements (i-1) to (i-3), from the viewpoint of protecting the end portion of the light adjusting film.

For example, in the laminated glass 10A, when the total thickness ti of the thicknesses of the intermediate

adhesive layers

2A and 2B is 0.8mm and the thickness ts of the light adjusting film 3 is 0.35mm, w satisfying the formula 1 is less than 16.0mm, and w satisfying the formula 2 is less than 11.4 mm.

Since the laminated glass of the embodiment satisfies the requirements (i-1) to (i-3), and preferably further satisfies the requirement (i-4), not only the end portion of the light-adjusting film is protected from the external environment, but also the appearance defect caused by the air remaining in the laminated glass and the like can be suppressed. Thus, deterioration of the peripheral edge portion of the light adjusting film is suppressed during long-term use, and a highly reliable laminated glass is obtained. Further, since the frame-shaped intermediate adhesive layer is not used, the workability is good, the cost is reduced, and the productivity is good.

Here, as shown in fig. 1 and 2, when the thickness of the laminated glass 10A measured at the end portion indicated by the measurement point E in fig. 1 of the laminated glass 10A is represented as T1 and the thickness of the laminated glass 10A measured at a position 50mm inward from the end portion indicated by the measurement point E (measurement point I in fig. 1) is represented as T2, T2 to T1 are preferably 0.28mm or less. When T2-T1 is within the above range, residual stress in the laminated glass is small, and defects such as peeling and foaming are unlikely to occur. T2-T1 is more preferably 0.2mm or less, still more preferably 0.15mm or less.

The thickness T1, T2 is measured by a usual method, for example, with a slide caliper or a micrometer. The micrometer may be a digital straight micrometer (デジマチック, straight style ミクロンマイクロメーター)406 and 250OMV25M, available from Sanfeng corporation (ミツトヨ).

As described later, in the process of manufacturing the laminated glass 10A, since the process of degassing from the periphery of the laminate of the

glass plates

1A, 1B, the intermediate

adhesive layers

2A, 2B, and the light adjusting film 3 or the process of thermally pressing the laminate is performed, the end portions of the laminate receive a large compressive force, and the thickness of the end portions of the laminated glass is reduced. Therefore, in the obtained laminated glass 10A, the

glass sheets

1A and 1B tend to have the same thickness as the inner thickness due to the existence of the restoring force, and thus are subjected to a force in the direction in which the end portions are expanded (the direction indicated by the arrow in fig. 2), and the thickness increases from the time of manufacture. In addition, for convenience of explanation, fig. 2 depicts features more exaggerated than an actual product.

The thickness of the laminated glass obtained through the above-described manufacturing process is substantially uniform over the entire periphery of the laminated glass so as to be smaller than the inside. Therefore, in the laminated glass according to the embodiment of the present invention, as exemplified by the laminated glass 10A, the thickness may be measured at any point 1 at least at the end portion (measurement point E in the laminated glass 10A) and at 2 points 50mm inward from the end portion (measurement point I in the laminated glass 10A). Any 1 point of the end portion may be any 1 point on the outer periphery of the laminated glass.

For example, when the measurement point is located on one linear side of the outer periphery of the laminated glass, the point 50mm inward from the measurement point on the line where the measurement points on the side intersect perpendicularly is the point 50mm inward from the measurement point. When the outer circumference is curved, the outer circumference is located 50mm inward from the measurement point on a normal line to a tangent line to the measurement point. In fig. 1, a position 50mm inward from the outer periphery of the laminated glass 10A is indicated by a frame line M. In the laminated glass 10A, when an arbitrary 1 point on the outer periphery is taken as the measurement point E of the end thickness, the 1 point on the frame line M which satisfies the above-described relationship with respect to the measurement point E is the measurement point I which is 50mm inward from the end.

Hereinafter, each element constituting the laminated glass 10A will be described.

[ glass plate ]

As the material of the

glass plates

1A, 1B used for the laminated glass 10A according to the embodiment of the present invention, transparent inorganic glass or organic glass (resin) can be cited. As the inorganic glass, for example, soda lime glass (also referred to as soda lime silicate glass), borosilicate glass, alkali-free glass, quartz glass, and the like can be used without particular limitation. Among them, soda lime glass is particularly preferable. The forming method is not particularly limited, but float plate glass formed by a float process or the like is preferable. In the case of inorganic glass, it can have a surface stress by a strengthening treatment such as physical strengthening or chemical strengthening.

Examples of organic glass (resin) include polycarbonate resin, polystyrene resin, aromatic polyester resin, acrylic resin, polyester resin, polyarylate resin, polycondensate of halogenated bisphenol a and ethylene glycol, acrylic urethane resin, and acrylic resin containing halogenated aryl groups. Among them, polycarbonate resins such as aromatic polycarbonate resins and acrylic resins such as polymethyl methacrylate acrylic resins are preferable, and polycarbonate resins are more preferable. Further, bisphenol a-based polycarbonate resins are particularly preferable among the polycarbonate resins. The glass plate may be formed of 2 or more kinds of the above-described resins.

As the glass, a colorless and transparent material to which no coloring component is added or a colored and transparent material after coloring may be used within a range not impairing the effect of the present invention. These glasses may be used in 1 kind or in a combination of 2 or more kinds, and may be a laminated substrate laminated with 2 or more layers, for example. Although it depends on the application site of the laminated glass, inorganic glass is preferable as the glass.

The pair of

glass plates

1A, 1B used for the laminated glass 10A may be made of different types of materials from each other. When the laminated glass 10A is mounted on a vehicle or a building, it is preferable that the glass plate located on the vehicle interior side or the building interior side is soda lime glass, and the total amount of iron in the composition based on iron as an oxide is converted into Fe₂O₃When the content is 0.4% by mass or more. When the iron content of the glass sheet on the vehicle interior side or the house interior side is within the above range, the haze is not easily seen from the vehicle interior side or the house interior side even when the haze of the light-adjusting film is high (for example, the haze is 5% or more), which is preferable.

The thicknesses tg1 and tg2 of the

glass sheets

1A and 1B may be appropriately selected depending on the application site of the laminated glass 10A, but generally, they are preferably 0.2 to 5mm, respectively. From the viewpoint of ensuring both the weight reduction and rigidity of the laminated glass, the thickness is more preferably 0.5 to 5mm, still more preferably 1.1 to 3.5mm, and particularly preferably 1.6 to 3.0 mm. The

glass plates

1A, 1B may have a 3-dimensional curvature in terms of design or functionality of the installation site.

The plate thicknesses tg1 and tg2 of the 1 pair of

glass plates

1A, 1B may be the same as or different from each other. When the

glass sheets

1A and 1B have different sheet thicknesses, when the laminated glass 10A is provided in a window or the like, the sheet thickness of the glass sheet positioned on the inner side (for example, the vehicle inner side in the case of automotive window glass and the house inner side in the case of building window glass) is preferably smaller than the sheet thickness of the glass sheet positioned on the outer side. When the thickness of the glass plate is in the above-described relationship, heat generated by the light-adjusting film or heat generated by sunlight is easily released to the inside of the vehicle or the inside of the house, and therefore deterioration due to heat of the light-adjusting film can be suppressed.

Further, the

glass sheets

1A and 1B may be coated to impart a water repellent function, a hydrophilic function, an antifogging function, low emissivity, ultraviolet absorption, and the like to the exposed surface exposed to the atmosphere. Further, functional coating such as infrared shielding coating and conductive coating may be applied to the opposing surfaces of the

glass plates

1A and 1B that face each other. If the laminated glass 10A has a low reflection film on the vehicle interior side or the house interior side, reflection on the glass surface can be particularly prevented at night, and the design is good, which is preferable.

In the case where the facing surfaces of the

glass plates

1A and 1B have the functional coatings, the following intermediate

adhesive layers

2A and 2B are in contact with the functional coatings on the facing surfaces of the

glass plates

1A and 1B.

[ intermediate adhesive layer ]

The pair of intermediate

adhesive layers

2A, 2B of the laminated glass 10A has main surfaces having substantially the same shape and size as the main surfaces of the

glass plates

1A, 1B. The intermediate

adhesive layers

2A and 2B are provided so as to contact the facing surfaces of the

glass plates

1A and 1B, respectively, with the light adjusting film 3 interposed therebetween. In this way, the intermediate

adhesive layers

2A and 2B have a function of integrating the laminated glass 10A by bonding the pair of

glass plates

1A and 1B with the light adjusting film 3 interposed therebetween 1 through the intermediate

adhesive layers

2A and 2B.

Here, as the intermediate

adhesive layers

2A and 2B, specifically, there can be mentioned an intermediate adhesive layer obtained by forming a composition containing the following thermoplastic resin as a main component into a sheet-like film having a main surface having substantially the same shape and size as the main surface of the

glass plates

1A and 1B.

The thermoplastic resin is not particularly limited as long as it is a resin which can be integrated when a sheet-like film made of a composition containing a thermoplastic resin as a main component is inserted between 1 pair of

glass plates

1A and 1B with the light adjusting film 3 interposed therebetween, and the laminated glass 10A is formed by heating and pressing. The required optical performance varies depending on the characteristics of the light-adjusting film sealed in the laminated glass, but the transmittance of the intermediate adhesive layer is preferably 80% or more of the visible light transmittance in a state where the laminated glass is combined with only a normal colorless and transparent glass.

Specific examples of the thermoplastic resin include thermoplastic resins conventionally used as an intermediate adhesive layer, such as polyvinyl acetal resin (e.g., polyvinyl butyral resin (PVB)), polyvinyl chloride resin, saturated polyester resin, polyurethane resin, ethylene-vinyl acetate copolymer resin (EVA), ethylene-ethyl acrylate copolymer resin, ionomer resin, and cycloolefin polymer (COP). Among them, PVB, EVA, urethane resins, ionomer resins, and COP are preferable. These thermoplastic resins may be used alone or in combination of 2 or more.

The thermoplastic resin used for the intermediate adhesive layer of the laminated glass can be selected in consideration of the balance of various properties such as transparency, weather resistance, strength, adhesive strength, penetration resistance, impact energy absorption, moisture resistance, heat insulation, and sound insulation depending on the application. From the viewpoint of these conditions, among the thermoplastic resins, preferred are a resin composition obtained by saponifying vinyl acetate units in an ethylene-vinyl acetate copolymer, and an ethylene-vinyl acetate copolymer resin composition characterized in that an ethylene-vinyl acetate copolymer described in japanese patent No. 5625781 contains an organized layered clay, a silane coupling agent, and the like. By incorporating the organized layered clay, the moisture permeability can be significantly reduced as compared with a conventional ethylene-vinyl acetate copolymer resin composition. Further, a resin composition containing a modified block copolymer hydride described in Japanese patent laid-open No. 2015-821 can also be advantageously used.

The minimum value of the storage modulus of the intermediate adhesive layer in the dynamic viscoelasticity measurement at the measurement frequency of 10Hz in the temperature range of 90-120 ℃ is preferably 2.0 x 10⁶Pa or less (hereinafter referred to as requirement (ii-1)). If the intermediate bonding layer satisfiesThe requirement (ii-1) is that the temperature range in which the hot press bonding is performed has a predetermined flexibility. Accordingly, the intermediate adhesive layer 1 has shape conformity in the frame-like region having the width w from the outer periphery of the laminated glass to the outer periphery of the light adjusting film from the region in contact with the peripheral edge portion of the light adjusting film to the region in contact with each other, and therefore, sufficient adhesion is facilitated without leaving air.

The minimum value of the storage modulus of the intermediate adhesive layer is more preferably 8.0 × 10⁵Pa or less, more preferably 5.0X 10⁵Pa or less. In addition, from the viewpoint of ensuring a predetermined rigidity in the temperature range in which the thermal compression bonding is performed, the maximum value of the storage modulus of the intermediate adhesive layer is preferably 2.0 × 10⁵Pa or above.

In order to adjust the storage modulus of the intermediate adhesive layer, among the thermoplastic resins constituting the intermediate adhesive layer, for example, in the case of EVA, the storage modulus can be reduced by increasing the amount of vinyl acetate units. Likewise, for PVB, the composition can be adjusted to increase the amount of plasticizer to reduce the storage modulus.

Further, in the case of an ionomer resin, for example, an ionomer resin in which a copolymer of ethylene and (meth) acrylic acid, (meth) acrylate ester, or the like is bridged by metal ions, the storage modulus can be decreased by increasing the ratio of (meth) acrylic acid or (meth) acrylate ester to ethylene.

For example, when the COP is composed of at least 2 polymer blocks [ a ] containing a repeating unit derived from an aromatic vinyl compound as a main component and at least 1 polymer block [ B ] containing a repeating unit derived from a chain-like conjugated diene compound as a main component, and the weight fraction of all the polymer blocks [ a ] to the entire block copolymer is denoted as wA and the weight fraction of all the polymer blocks [ B ] to the entire block copolymer is denoted as wB, the COP has a ratio of wA to wB (wA: wB) of 30: 70-60: 40 [1] in the block copolymer [1] all unsaturated bonds are hydrogenated to obtain a block copolymer hydride [2] and introducing alkoxysilyl groups into the modified block copolymer hydride [3] resin composition, the storage modulus can be reduced by reducing the wA ratio.

By adjusting the storage modulus of the thermoplastic resin constituting the intermediate adhesive layer in this manner, an intermediate adhesive layer satisfying the requirement (1) can be obtained.

The intermediate adhesive layer is preferably a material that does not affect the function of the light adjusting film during production or use. Therefore, it may be a thermoplastic resin containing no plasticizer, or a plasticizer-containing thermoplastic resin containing a plasticizer which does not affect the light-modulating film.

Further, the heating temperature at the time of molding the laminated glass is set in accordance with the thermoplastic resin used for the intermediate adhesive layer, but if the heating temperature is equal to or higher than the heat-resistant temperature of the light-adjusting film, the light-adjusting film may not function sufficiently when the laminated glass is produced. Therefore, the thermoplastic resin used for the intermediate adhesive layer is preferably selected under the condition that the molding temperature of the laminated glass is equal to or lower than the heat-resistant temperature of the light-adjusting film to be used.

As described above, the thermoplastic resin-containing composition containing the thermoplastic resin as a main component is used for the production of the intermediate

adhesive layers

2A and 2B. The thermoplastic resin-containing composition may contain 1 or 2 or more of various additives such as an infrared absorber, an ultraviolet absorber, a fluorescent agent, an adhesion regulator, a coupling agent, a surfactant, an antioxidant, a heat stabilizer, a light stabilizer, a dehydrating agent, an antifoaming agent, an antistatic agent, and a flame retardant, depending on the purpose, within the range not to impair the effects of the present invention. These additives are contained uniformly throughout the intermediate

adhesive layers

2A, 2B.

The thicknesses ti1 and ti2 of the intermediate

adhesive layers

2A and 2B may be set such that the relationship between the total thickness ti and the thicknesses w and ts satisfies expression 1. Specifically, the thickness of each 1 layer is preferably 0.3 to 0.8mm, and the total thickness of 2 layers is preferably 0.6 to 1.6mm, as in the case of an intermediate adhesive layer generally used for laminated glass or the like. If the thicknesses ti1 and ti2 of the intermediate adhesive layers per 1 layer are respectively less than 0.3mm, or the total thickness ti of the 2 layers is less than 0.6mm, the strength may be insufficient, and if the glass misalignment is serious, peeling may easily occur. On the other hand, if the total thickness ti of the intermediate

adhesive layers

2A and 2B is greater than 1.6mm, the weight increases, which may cause a problem when the intermediate adhesive layers are mounted on a vehicle.

In addition, the thicknesses ti1 and ti2 of the intermediate

adhesive layers

2A and 2B may be the same as or different from each other. When the intermediate

adhesive layers

2A and 2B have different thicknesses, when the laminated glass 10A is provided in a window or the like, the thickness of the intermediate adhesive layer on the inner side, for example, the vehicle inner side in the case of a window glass of an automobile, and the thickness of the intermediate adhesive layer on the house inner side in the case of a window glass of a building is preferably smaller than the thickness of the intermediate adhesive layer on the outer side. When the thickness of the intermediate adhesive layer is in the above-described relationship, heat generated from the light-adjusting film or heat generated from sunlight is easily released to the inside of the vehicle or the inside of the house, and therefore deterioration due to heat of the light-adjusting film can be suppressed.

The intermediate

adhesive layers

2A, 2B are not limited to a single-layer structure. The intermediate

adhesive layers

2A, 2B may be the same, but need not be the same, and may be independently selected to have a single-layer structure or a multi-layer structure.

In addition, when an intermediate adhesive layer is prepared as an adhesive film or the like in the production of a laminated glass, it is preferable to have emboss. In general, a material film to be an intermediate adhesive layer of a laminated glass has embossments, and after a laminate is formed by sandwiching between glass plates, the embossments function as air passages when heat press bonding is performed, and heat press bonding is performed under a condition that air between layers of the laminate is sufficiently exhausted, and finally the embossments of the material film disappear to form the intermediate adhesive layer, and a high-quality laminated glass free from residual air bubbles is obtained.

[ light adjusting film ]

As the light-adjusting film 3, a light-adjusting film used for a smart glass or the like is preferably used, which has a thickness ts of 0.1mm to 1mm, preferably 0.1mm to 0.7mm, and more preferably 0.1mm to 0.4 mm. This is because generally, if the thickness is less than 0.1mm, handling in the production of a laminated glass is difficult, and if it exceeds 1mm, the rigidity of the substrate increases and it becomes difficult to follow a curved surface. If ts is within this range, w satisfying formula 1 or formula 2 in the above ti range may be set as a preferable range.

Here, in the laminated glass of the embodiment, from the viewpoint of design, the ratio of the area of the light adjusting film to the area of the laminated glass in a plan view is preferably 0.7 or more. If it is less than 0.7, the picture frame-like region becomes too large, and the appearance may be impaired.

As the light adjusting film 3, for example, a Suspended Particle Device (SPD) film can be used. As the SPD film, a general SPD film can be used which is configured by sandwiching a polymer layer containing suspended particles that can be oriented by applying a voltage between 2 pieces of electrically insulating films each having a transparent conductive film applied to the inside. When a power switch is turned on to apply a voltage between the transparent conductive films to orient suspended particles in the polymer layer, the SPD film exhibits a high visible light transmittance and high transparency. When the power switch is turned off, the suspended particles in the polymer layer are not oriented, and the visible light transmittance and transparency are low.

As the SPD film, for example, a commercially available product such as LCF-1103DHA (trade name, manufactured by hitachi chemical corporation) can be used. Further, since such a commercially available product is provided in a predetermined size, it is cut into a desired size and used. The thickness of the SPD film used for the laminated glass is preferably within the range of the thickness ts of the light adjusting film described above, and is preferably 0.2 to 0.4mm from the viewpoint of handling and easiness of acquisition.

By using the SPD film, the visible light transmittance can be electrically switched to a high state and a low state. In a state where the visible light transmittance of the SPD film is low, the contrast ratio of the HUD image to the background can be improved by projecting the HUD image on the HUD display region where the SPD film is present.

Further, even when a Polymer Dispersed Liquid Crystal (PDLC) is used as the light adjusting film 3 instead of the SPD film, the contrast ratio between the HUD image and the background can be improved. The prepolymer, the column liquid crystal, and the spacer material may be mixed in a specific ratio to produce a PDLC film, and then disposed between 2 soft transparent conductive films. The working principle includes the following. Without the application of an electric field, the liquid crystal droplets may be randomly distributed in the polymer material with their aligners in a free-alignment state.

In this case, the refractive index of the liquid crystal with respect to the normal light is different from that of the polymer material, resulting in a relatively strong scattering effect of light, and as a result, the PDLC film appears to be translucent or opaque "milky" in appearance. Under an electric field, liquid crystal droplets can align their directors along the direction of an external electric field due to the characteristic of positive dielectric constant anisotropy. In the case where the refractive index of liquid crystal with respect to normal light is the same as that of the polymer material, light can pass through the PDLC film, and thus the PDLC film has a transparent appearance. Specifically, the higher the voltage supplied to the PDLC film, the more transparent the PDLC film becomes.

As the PDLC film, commercially available products such as MIYO film (manufactured by kyushu nano-technologies optical co., ltd. (kyushu ナノテック optical corporation)) can be used. Further, since such a commercially available product is provided in a predetermined size, it is cut into a desired size and used. The thickness of the PDLC film used for the laminated glass is preferably within the range of the thickness ts of the light-adjusting film described above, and is preferably 0.1 to 0.4mm from the viewpoint of handling and easiness of acquisition.

In addition, when any one of Polymer Network Liquid Crystal (PNLC), guest-host effect liquid crystal, va (vertical alignment) liquid crystal, tn (twisted nematic) liquid crystal, photochromic substance, electrochromic substance, and electrodynamic substance is used as the light adjusting film 3, the contrast ratio between the HUD image and the background can be increased.

The laminated glass of the embodiment may have any other layer in addition to the above-described constituent elements within a range in which the effects of the present invention are not impaired.

(other layers)

In the laminated glass, a band-shaped dark-colored concealing layer may be provided in a part or all of the peripheral edge portion of the main surface on the side contacting the intermediate adhesive layer of at least one of the 1 pair of glass plates constituting the laminated glass, for the purpose of concealing the attached portion of the frame or the wiring conductor. In the laminated glass of the embodiment, such a dark-colored concealing layer may be provided as another layer.

As the dark color concealing layer, a black ceramic layer can be cited. The black ceramic layer may be formed of a known material such as a colored ceramic paste. As the ink for forming the black ceramic layer, for example, an ink in which a dark color pigment, glass frit, refractory filler, and a resin such as ethyl cellulose are dispersed in a solvent can be used. In general, a black ceramic layer that is completely sintered can be obtained on a glass plate by printing an ink on the glass plate in a predetermined pattern, quasi-sintering the ink by drying or ultraviolet irradiation, and then firing the ink at a high temperature. As a material for forming the dark color concealing layer, an intermediate adhesive layer having a dark color pigment, a colored film obtained by printing a dark color on a resin film, or the like can be used.

In view of design, there are laminated glasses in which the dark color masking layer is not provided or is formed to have a small width. As an example of not providing the dark color concealing layer, a door glass for a vehicle is cited.

In the laminated glass, when the dark color concealing layer having a small width is provided at the peripheral edge portion or the dark color concealing layer is not provided, if the laminated glass of the present invention satisfies the requirements (i-1) to (i-3), the durability of the light adjusting film can be ensured without impairing the appearance of the laminated glass, and the distance w between the outer periphery of the light adjusting film and the outer periphery of the laminated glass can be preferably made small. Specifically, the effect of the present invention is particularly remarkable when the width of the dark-color masking layer provided when the width of the dark-color masking layer is small, specifically, when the width is 100mm or less, further, when the width is 50mm or less, and particularly, when the width is 20mm or less. In the scope of the present invention, from the viewpoint of design, w of the short side of the polygon may be relatively small with respect to the long side in plan view. This makes it possible to make the width of the concealing layer of the short side smaller.

[ production of laminated glass ]

The laminated glass according to the embodiment of the present invention can be produced by a generally used known technique. For example, a laminated glass precursor as a laminated glass before pressure bonding, which is prepared by manufacturing a laminated body in which a light adjusting film 3 is disposed in a predetermined positional relationship between 1 pair of intermediate

adhesive layers

2A and 2B, inserting the laminated body between 1 pair of

glass plates

1A and 1B, and laminating the glass plate 1A, the intermediate adhesive layer 2A, the light adjusting film 3, the intermediate adhesive layer 2B, and the glass plate 1B in this order, is prepared for the laminated glass 10A. In the case of having other layers, a laminated glass precursor is prepared by laminating a glass sheet and each layer in the same lamination order as the obtained laminated glass.

The laminated glass precursor can be put into a vacuum bag such as a rubber bag, and the vacuum bag is connected to an exhaust system, and bonding (hereinafter, also referred to as "reduced-pressure heat-pressure bonding") is performed at a temperature of about 70 to 110 ℃ while performing reduced-pressure suction (degassing) so that the pressure in the vacuum bag becomes a vacuum degree of about-65 to-100 kPa, thereby obtaining the laminated glass of the embodiment. Further, a laminated glass having more excellent durability can be obtained by performing a pressure bonding treatment (hereinafter also referred to as "pressure heating and pressure bonding") under heating and pressure at, for example, 100 to 110 ℃ and a pressure of 0.6 to 1.3 MPa.

The pressure-heating crimping is generally performed using an autoclave. By performing the pressure-heat-pressure bonding after the reduced-pressure heat-pressure bonding, the reduction in the thickness of the end portion of the laminated glass obtained by the reduced-pressure heat-pressure bonding due to the reduction in the thickness ts portion of the light-adjusting film in the frame-like region of the laminate in which the width w of the light-adjusting film is not present is alleviated. Specifically, the above-mentioned T2-T1 can easily be 0.28mm or less, more preferably 0.2mm or less, still more preferably 0.15mm or less. This eliminates residual stress in the laminated glass, and suppresses occurrence of troubles such as peeling or foaming of the intermediate adhesive layer.

The present invention provides a laminated glass having a light adjusting film, which can protect the end of the light adjusting film without damaging the appearance and can improve the productivity. The laminated glass of the present invention can be advantageously used for a window glass for a vehicle, for example.

Examples

The present invention will be described in further detail below with reference to examples. The present invention is not limited to the following embodiments and examples. Examples 1 to 6, 9 to 22 and 25 to 42 are examples, and examples 7, 8, 23 and 24 are comparative examples.

[ examples 1 and 2]

(production of laminated glass)

A laminated glass having the same structure as the laminated glass 10A shown in fig. 1 and 2 was produced in the following manner. Hereinafter, the same reference numerals as in the laminated glass 10A are given to the respective members of the evaluation sample corresponding to the respective members of the laminated glass 10A, and the description will be given.

2

glass plates

1A and 1B (manufactured by AGC Co., Ltd., FL, 2mm thick, 150mm × 150mm square), 2 saponified EVA intermediate

adhesive layers

2A and 2B (MERSEN G (trade name) manufactured by Tosoh Japan K.K. (Dow. ソー K. ニッケミ Co.), 0.4mm thick, 150mm × 150mm square), and 1 dimming film 3 (LCF-1103 DHA90 (trade name) manufactured by Hitachi chemical Co., Ltd.), SPD dimming film, 0.35mm thick, 140mm × 140mm square) were prepared. These were laminated in this order of one glass plate 1A, one EVA intermediate adhesive layer 2A, SPD light adjusting film 3, another EVA intermediate adhesive layer 2B, and another glass plate 1B to obtain a laminate. The distance between the outer periphery of the SPD light-adjusting film 3 and the outer periphery of the laminate was 5mm on 4 sides.

The laminate obtained above was put into a rubber vacuum bag and degassed (reduced pressure: 90kPa), and then put into a furnace maintained at 100 ℃ for 60 minutes, and after pressure-reducing heating and pressure-bonding, it was taken out from the rubber vacuum bag to obtain a laminated glass 1A. The laminated glass 1A was pressure-heated and pressure-bonded in an autoclave at 110 ℃ and a pressure of 1.3MPa for 20 minutes to obtain a laminated glass 1B. In the laminated glass 1A and the laminated glass 1B, the thickness ts of the SPD light adjusting film 3, the total thickness ti of the intermediate

adhesive layers

2A and 2B, and the distance w between the outer periphery of the SPD light adjusting film 3 and the outer periphery of the laminated glass are all the same as those of the laminated body. The laminated glass 1A was example 1, and the laminated glass 1B was example 2.

In the laminated glass 1A and the laminated glass 1B, the thickness T1 at the 1 point (measurement point E) of the end portion and the thickness T2 at the position 50mm inward from the 1 point (measurement point E) of the end portion (measurement point I) were measured with a vernier caliper, and the difference between the thicknesses was calculated as the thickness T2[ mm ] at the position 50mm inward from the end portion of the laminated glass (measurement point I) and the thickness T1[ mm ] at the end portion of the laminated glass (measurement point E). In this example, the measurement point E is the center point of 1 side of the outer periphery of the laminated glass, and the measurement point I is a position 50mm inward from the measurement point E toward the center of the laminated glass. As a result, the thickness difference was recorded in fig. 3, with the laminated glass 1A being example 1 and the laminated glass 1B being example 2.

< evaluation >

(appearance)

The appearance of the laminated glass 1A and the laminated glass 1B was evaluated by visual observation according to the following criteria.

Good (good): no air residue and foaming were observed in the region 3mm inward from the end of the laminated glass.

Δ (general): less than 20mm was observed in the region 3mm inward from the end of the laminated glass²Air remains and foams.

X (poor): at least 20mm was confirmed in the region 3mm inward from the end of the laminated glass²One of the above air entrapment and foaming.

(evaluation of durability)

The laminated glass 1A and the laminated glass 1B were put into a constant temperature and humidity bath at 60 ℃ and a humidity of 95% RH for 500 hours. The intermediate adhesive layer was impregnated with water to generate an environment in which peeling easily occurs due to residual stress, and the presence or absence of peeling was evaluated visually. Will confirm to 20mm²When the peeling was observed as X, it was confirmed that the thickness was less than 20mm²The case of peeling was regarded as Δ, and the case where peeling was not observed was regarded as good.

The evaluation results are shown in FIG. 3 together with whether w, ti, and ts satisfy formula 1 (good when satisfied, "good" and poor when unsatisfied "×"), whether or not satisfy formula 2 (good when satisfied, "good" and poor when unsatisfied "×"), and the production method (A: performing only reduced pressure heat crimping, B: reduced pressure heat crimping + pressure heat crimping).

[ examples 3 to 16]

In examples 1 and 2, (1) the shape of the SPD light adjusting film 3 was changed to w shown in fig. 3 with the same holding material, (2) the total thickness ti of the intermediate

adhesive layers

2A and 2B was changed as shown in fig. 3 with the same holding material, and (3) as a manufacturing method, a or B was selected as shown in fig. 3, and laminated glasses of examples 3 to 16 were manufactured, and the same evaluations as described above were performed. The measurement results are shown in FIG. 3. In comparative examples 7, 8, 23 and 24, air residue was generated, and the appearance was evaluated as "x".

[ examples 17 to 32]

In examples 1 and 2, LCF-1103DHA30 (trade name, SPD light adjusting film, manufactured by hitachi chemical co., ltd., 0.28mm thick) was used as the light adjusting film 3 instead of LCF-1103DHA90 (trade name, hitachi chemical co., ltd., 0.28mm thick), (1) the shape of the light adjusting film 3 was changed to w shown in fig. 3, (2) the total thickness ti of the intermediate

adhesive layers

2A and 2B was changed as shown in fig. 3 while keeping the materials the same, (3) as the manufacturing method, a or B was selected as shown in fig. 3, and laminated glasses of examples 17 to 22 were manufactured, and the same evaluations as described above were performed. The measurement results are shown in FIG. 3.

Examples 33 to 42

In examples 1 and 2, a MIYO film (trade name, PDLC film, manufactured by kyushu nano-technology optical co., ltd., 0.12mm thick) was used as the light adjusting film 3 instead of LCF-1103DHA90 (trade name, manufactured by hitachi chemical co., ltd.), (1) the shape of the light adjusting film 3 was changed to w shown in fig. 3, (2) the total thickness ti of the intermediate

adhesive layers

2A and 2B was changed as shown in fig. 3 while keeping the materials the same, (3) as a manufacturing method, a or B was selected as shown in fig. 3, and laminated glasses of examples 23 to 32 were manufactured and evaluated in the same manner as described above. The evaluation results are shown in FIG. 3.

As is clear from fig. 3, if the requirements (i-1) and (i-3) are satisfied and the relationship between w, ti, and ts satisfies the expression 1 (requirement (i-2)), that is, if all of the requirements (i-1) to (i-3) are satisfied, a laminated glass in which the end portion of the light-adjusting film is protected and the productivity is improved without impairing the appearance can be obtained.

The present invention has been described above based on the embodiments and examples, but the present invention is not limited to the embodiments and examples described above, and various modifications can be made within the scope described in the claims.

The present application claims priority to basic application No. 2019-038676, filed on 3/4/2019 to the present patent office, the entire contents of which are incorporated herein by reference.

Description of the symbols

10A laminated glass

1A, 1B glass plate

2A, 2B intermediate adhesive layer

3 light adjusting film

Claims

1. A laminated glass comprising:

1 pair of glass plates facing each other,

wherein the laminated glass is approximately polygonal in a plan view, and at least 1 side of the outer peripheral portion of the laminated glass satisfies the following requirements (i-1) to (i-3):

(i-1) the periphery of the light adjusting film is located inward from the periphery of the laminated glass by a distance of w [ mm ] in a plan view,

(i-2) when the thickness of the light adjusting film is ts [ mm ] and the total thickness of the 1 pair of intermediate adhesive layers is ti [ mm ], w, ti, and ts satisfy the following formula 1:

w/ti < 7/ts 0, 1

2. The laminated glass according to claim 1, wherein at least 2 sides of the outer peripheral portion of the laminated glass satisfy the requirements (i-1) to (i-3).

3. The laminated glass according to claim 2, wherein the whole circumference of the outer peripheral portion of the laminated glass satisfies the requirements (i-1) to (i-3).

4. The laminated glass according to any one of claims 1 to 3, wherein the side of the outer peripheral portion of the laminated glass satisfying the requirements (i-1) to (i-3) further satisfies the following requirement (i-4):

(i-4) ts is 0.25mm or more, w, ti, and ts satisfy the following formula 2:

w/ti is more than 0 and less than 4.5/ts formula 2.

5. The laminated glass according to any one of claims 1 to 4, wherein the laminated glass is substantially quadrangular in plan view, and the w is 100mm or less on at least 1 side satisfying the requirements (i-1) to (i-3).

6. The laminated glass according to any one of claims 1 to 5, wherein the material of the intermediate adhesive layer comprises at least 1 selected from the group consisting of a polyvinyl butyral resin, an ethylene vinyl acetate copolymer resin, a polyurethane resin, an ionomer resin, and a cyclic olefin polymer.

7. The laminated glass according to any one of claims 1 to 6, wherein the minimum value of the storage modulus of the intermediate adhesive layer in the dynamic viscoelasticity measurement at a measurement frequency of 10Hz in the temperature range of 90 to 120 ℃ is 2.0 x 10⁶Pa or less.

8. The laminated glass according to any one of claims 1 to 7, wherein T2-T1 is 0.28mm or less, where T1 represents the total thickness of the laminated glass at the end portion of the laminated glass, and T2 represents the total thickness of the laminated glass at the end portion of the laminated glass which is inward 50 mm.

9. The laminated glass according to any one of claims 1 to 8, wherein a peripheral portion is free from a dark-colored shielding layer.

10. The laminated glass according to any one of claims 1 to 9, wherein the light-adjusting film is a suspended particle device, a polymer dispersed liquid crystal, a polymer network liquid crystal, a guest-host effect type liquid crystal, a VA type liquid crystal, a TN type liquid crystal, a photochromic substance, an electrochromic substance, or an electrodynamic substance.

11. The laminated glass according to any one of claims 1 to 10, wherein the total thickness ti of the thicknesses of the 1 pair of intermediate adhesive layers is 1.6mm or less.

12. The laminated glass according to any one of claims 1 to 11, wherein the total thickness ti of the thicknesses of the 1 pair of intermediate adhesive layers is 0.6mm or more.

13. The laminated glass according to any one of claims 1 to 12, wherein the thickness ts of the light adjusting film is 1mm or less.

14. The laminated glass according to any one of claims 1 to 13, wherein a ratio of an area of the light adjusting film to an area of the laminated glass in a plan view is 0.7 or more.

15. The laminated glass according to any one of claims 1 to 14, wherein the laminated glass is a laminated glass to be mounted on a vehicle, and of the 1 pair of glass sheets, a glass sheet positioned on an inner side of the vehicle has a smaller sheet thickness than a glass sheet positioned on an outer side of the vehicle.

16. The laminated glass according to claim 15, wherein the total amount of iron in the composition of the glass sheet on the vehicle interior side, which is based on iron as an oxide, is converted into Fe₂O₃In the case, the content is 0.4% by mass or more.

17. The laminated glass according to claim 15 or 16, wherein the thickness of the intermediate adhesive layer positioned on the vehicle interior side is thinner than the thickness of the intermediate adhesive layer positioned on the vehicle exterior side, of the 1 pair of intermediate adhesive layers.