WO2020179433A1

WO2020179433A1 - Laminated glass

Info

Publication number: WO2020179433A1
Application number: PCT/JP2020/006213
Authority: WO
Inventors: 時彦青木; 裕平儀間; 宮坂　誠一
Original assignee: Ａｇｃ株式会社
Priority date: 2019-03-04
Filing date: 2020-02-18
Publication date: 2020-09-10
Also published as: JPWO2020179433A1; DE112020001086T5; CN113518711A

Abstract

The present invention provides laminated glass having: a pair of glass sheets facing each other; a pair of intermediate adhesive layers located between the pair of glass sheets so as to contact the pair of glass sheets in respective fashion; and a light control film, which is positioned between the pair of intermediate adhesive layers and in which the visible light transmittance can be switched, wherein the laminated glass is characterized in that: the laminated glass is substantially polygonal in plan view; on at least one side of the outer periphery part of the laminated glass, the outer periphery of the light control film is positioned a distance of w [mm] inwards from the outer periphery of the laminated glass in plan view; w, ti, and ts satisfy formula 1: 0 < w/ti < 7/ts, where ts [mm] represents the thickness of the light control film, and ti [mm] represents the total thickness of the pair of intermediate adhesive layers; and the pair of intermediate adhesive layers are in contact with each other in the region from the outer periphery of the laminated glass to the outer periphery of the light control film.

Description

Laminated glass

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

As a window glass for vehicles, smart glass is known in which the transmittance can be electrically switched by turning the power switch on / off by enclosing a light control film inside the laminated glass.

In smart glass, for the purpose of protecting the edge of the light control film from the external environment, the light control film is cut smaller than the size of the glass plate or the intermediate adhesive layer, and the edge is covered with the intermediate adhesive layer. Often enclosed in glass. Specifically, it is general that a frame-shaped intermediate adhesive layer is arranged in the peripheral portion of the light control film, and the intermediate adhesive layer sandwiched by two intermediate adhesive layers is further sandwiched by a pair of glass plates ( For example, see Patent Document 1).

However, when a frame-shaped intermediate adhesive layer is used, there are problems such as deterioration of workability in the laminating process and cost increase due to an increase in the amount of the intermediate adhesive layer used.

As an existing technique, when a thin functional film, for example, an infrared reflective film is encapsulated in a laminated glass, it is common to encapsulate it without using a frame-shaped intermediate adhesive layer (for example, Patent Document). 2). However, in the case of a light control film, the light control material is usually sandwiched between two plastic films, and the thickness tends to be thicker than other functional films, and a frame-shaped intermediate adhesive layer is used. Otherwise, there will be appearance defects such as air remaining and foaming. As a result of diligent studies by the present inventor, it has been found that the above problems can be solved by controlling the thickness of the light control film and the positional relationship in the laminated glass.

Japanese Patent No. 5666128 JP, 2017-186179, A

An object of the present invention is to provide a laminated glass including a light control film, which is capable of protecting the end portion of the light control film without impairing its appearance, and which has improved productivity.

The laminated glass of the present invention is
A pair of glass plates facing each other,
A pair of intermediate adhesive layers located between the pair of glass plates and in contact with the pair of glass plates respectively;
A laminated glass having a dimming film capable of switching the visible light transmittance located between the pair of intermediate adhesive layers, wherein the laminated glass is substantially polygonal in plan view, At least one side of the outer peripheral portion is characterized by satisfying the following requirements (i-1) to (i-3).
(I-1) The outer periphery of the light control film is located inside the outer periphery of the laminated glass by a distance w [mm] in plan view.
(I-2) When the thickness of the light control film is ts [mm] and the total thickness of the pair of intermediate adhesive layers is ti [mm], w, ti and ts are expressed by the following formula 1 To be satisfied.

0 <w / ti <7 / ts formula 1
(I-3) The 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 control film.

According to the present invention, in a laminated glass including a light control film, a laminated glass in which an end portion of the light control film is protected can be provided with good productivity without impairing the appearance of the laminated glass.

It is a front view of an example of an embodiment of a laminated glass of the present invention. FIG. 2 is a cross-sectional view taken along line XX of the laminated glass shown in FIG. 1. 9 is a table showing the evaluation results of examples and comparative examples.

An embodiment of the present invention will be described below. It should be noted that the present invention is not limited to these embodiments, and these embodiments can be changed or modified without departing from the spirit and scope of the present invention.

The laminated glass of the present invention includes a pair of glass plates facing each other, a pair of intermediate adhesive layers located between the pair of glass plates and respectively in contact with the pair of glass plates, and the pair of intermediate bonds. A laminated glass having a dimming film located between layers and capable of switching the visible light transmittance, wherein the laminated glass is substantially polygonal in a plan view and at least one side of an outer peripheral portion of the laminated glass. It is characterized in that the following requirements (i-1) to (i-3) are satisfied.
(I-1) The outer circumference of the light control film is located inside a distance w [mm] from the outer circumference of the laminated glass in a plan view.
(I-2) When the thickness of the light control film is ts [mm] and the total thickness of the pair of intermediate adhesive layers is ti [mm], w, ti and ts are expressed by the following formula 1 To be satisfied.

In the present specification, the end portion means a ridge line formed by joining the faces, and the peripheral edge portion means a region having a certain width from the end portion of the surface toward the center portion of the surface. means. In the laminated glass, the end means the outer periphery of the main surface of the laminated glass. The thickness of the laminated glass measured at the end is the distance from the end of one main surface of the laminated glass at the measurement position to the end of the other main surface. The thickness of the laminated glass measured at the edges is also referred to as the thickness of the edges of the laminated glass.

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

In the present specification, "substantially the same shape, same size" means having the same shape and the same size in terms of human appearance. For example, two people having "substantially the same shape, same size" have one outer circumference. The case where the shape does not have irregularities such as notches and the other is an outer peripheral shape having a fine notch or the like in a part is also included in the category. In other cases, "substantially" has the same meaning as described above. Further, in the present specification, "-" representing a numerical range includes upper and lower limit 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 of an example of an embodiment of the laminated glass of the present invention, and FIG. 2 is a sectional view taken along line XX of the laminated glass shown in FIG.

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

glass plates

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

adhesive layers

2A and 2B contacting the facing surfaces of the pair of

glass plates

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

glass plates

1A and 1B and the pair of intermediate

adhesive layers

2A and 2B are substantially quadrilateral in a plan view, and have main surfaces having substantially the same shape and the same size.

The shape of the laminated glass of the embodiment in a plan view is substantially polygonal. The term "substantially polygonal" means that the corner portion includes a shape that may have a radius of curvature of approximately 1000 mm or less. The number of corners of the polygon is 3 to 8, and it 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 a substantially quadrilateral shape.

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

adhesive layers

2A and 2B. The area of the main surface of the light control film 3 is smaller than the area of the main surfaces of the

glass plates

1A and 1B, so that the outer periphery of the main surface of the light control film 3 is located inside the outer periphery of the main surfaces of the

glass plates

1A and 1B. Is disposed between the intermediate

adhesive layers

2A and 2B.

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

glass plates

1A and 1B. In the laminated glass 10A, the outer circumference of the light control film 3 is located inside a distance w [mm] from the outer circumference of the laminated glass 10A in a plan view (satisfies the requirement (i-1)). In the intermediate adhesive layer 2A and the intermediate adhesive layer 2B, main surfaces facing each other are in contact with each other in a frame-shaped region from the outer periphery of the laminated glass 10A to the outer periphery of the light control film 3 (requirement (i-3) is satisfied). .. That is, in the laminated glass 10A, the frame layer composed of the third intermediate adhesive layer does not exist on the outside of the light control film 3. The width of the region corresponds to the distance w.

In the laminated glass 10A, the thickness of the light control film 3 is ts [mm], the thickness of the intermediate

adhesive layers

2A and 2B is ti1 [mm] and ti2 [mm], and the thickness of the

glass plates

1A and 1B is tg1 [mm]. And tg2 [mm]. The total thickness of the intermediate

adhesive layers

2A and 2B is ti [mm].

The thickness of each component of the laminated glass is substantially constant in the plane, and the measurement position of the thickness is not particularly limited. However, as described later, the thickness of the intermediate adhesive layer may decrease depending on the manufacturing method for the end portion. Therefore, the measurement position of the thickness of each component of the laminated glass is set to a position 50 mm or more inside from the end portion of the laminated glass. The thickness is measured by a usual method, for example, a caliper or a micrometer. Examples of the micrometer include Mitutoyo's Digimatic straight advance micron micrometer 406-250 OMV25M.

In the laminated glass 10A which is the laminated glass of the embodiment of the present invention, w, ti and ts satisfy the following formula 1 (satisfies the requirement (i-2)).

0 <w / ti <7 / ts formula 1
In the laminated glass of the embodiment, the relationship between w, ti and ts preferably satisfies the following expression 2. However, in this case, ts is 0.25 mm or more. Hereinafter, the requirement is also referred to as a requirement (i-4).

0 <w / ti <4.5 / ts formula 2
In the laminated glass of the embodiment, at least one side of the outer peripheral portion may satisfy all the requirements (i-1) to (i-3). The laminated glass of the embodiment preferably satisfies all of the requirements (i-1) to (i-3) on at least two sides of the outer peripheral portion, and meets the requirements (i-1) to (i-3) on the entire circumference. It is preferable to satisfy all of them. In any case, it is more preferable that the requirement (i-4) is further satisfied.

The laminated glass 10A shown in FIGS. 1 and 2 is an example that satisfies all the requirements (i-1) to (i-3), preferably the requirement (i-4), in the entire circumference of the outer peripheral portion. As for w in such a laminated glass 10A, w corresponding to the entire outer circumference of the laminated glass and the entire outer circumference of the light control film satisfies Expression 1, preferably Expression 2. As long as Expression 1 is satisfied, Expression 2 is preferably satisfied, and w may be different on each side of the outer periphery of the laminated glass 10A, and there may be a portion where w is different within one side. The same applies to the above aspect when the laminated glass is, for example, a polygon other than the substantially quadrilateral shown in FIG.

In the laminated glass of the embodiment, w is preferably 100 mm or less, more preferably 50 mm or less on at least one side that satisfies the requirements (i-1) to (i-3), preferably on all sides. 20 mm or less is more preferable, and 10 mm or less is further preferable. When w is at least the above value, the area occupied by the light control film is large, the visible light transmittance of a wide area can be controlled, and the design is excellent. Further, in the laminated glass of the embodiment, in at least one side satisfying the requirements (i-1) to (i-3), preferably in all sides, w is from the viewpoint of protecting the edge portion of the light control film. 1 mm or more is preferable, 3 mm or more is more preferable, and 5 mm or more is particularly preferable.

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

adhesive layers

2A and 2B is 0.8 mm and the thickness ts of the light control film 3 is 0.35 mm, w satisfying Equation 1 is 16. W that is less than 0 mm and that satisfies Expression 2 is less than 11.4 mm.

The laminated glass of the embodiment satisfies the requirements (i-1) to (i-3), preferably further the requirement (i-4), whereby the end portion of the light control film is protected from the external environment. At the same time, it is possible to suppress appearance defects due to air remaining inside the laminated glass. As a result, deterioration of the peripheral edge of the light control film is suppressed when used for a long period of time, and a highly reliable laminated glass is obtained. Further, since the frame-shaped intermediate adhesive layer is not used, the workability is good and the productivity is good because it is economical.

Here, as shown in FIGS. 1 and 2, the laminated glass 10A has a thickness T1 measured at an end portion indicated by the measurement point E in FIG. 1 of the laminated glass 10A, and is 50 mm inside from the end portion indicated by the measurement point E. When the thickness of the laminated glass 10A measured at the position (measurement point I in FIG. 1) is T2, T2-T1 is preferably 0.28 mm or less. When T2-T1 is within the above range, the residual stress inside the laminated glass is small, and problems such as peeling and foaming hardly occur. T2-T1 is more preferably 0.2 mm or less, and further preferably 0.15 mm or less.

The thicknesses T1 and T2 are measured by a usual method, for example, a caliper or a micrometer. Examples of the micrometer include Mitutoyo's Digimatic straight advance type micron micrometer 406-250 OMV25M.

As will be described later, the phenomenon that the thickness of the laminated glass is reduced in thickness at the edge of the laminated glass is removed from the periphery of the laminated body of the

glass plates

1A and 1B, the intermediate

adhesive layers

2A and 2B, and the light control film 3 in the manufacturing process of the laminated glass 10A. This is a phenomenon that occurs because a greater compressive force is applied to the end portion of the laminated body due to the steps of care and thermocompression bonding of the laminated body. Therefore, in the obtained laminated glass 10A, due to the restoring force of the

glass plates

1A and 1B, a force acts in the direction in which the end portion expands so as to have the same thickness as the inner thickness (direction shown by an arrow in FIG. 2), The thickness increases from the time of manufacturing. For the sake of explanation, FIG. 2 shows the features exaggerated as compared with the actual product.

The thickness of the laminated glass obtained through the above-mentioned manufacturing process is substantially evenly smaller at the edges than on the inside over the entire outer circumference of the laminated glass. Therefore, in the laminated glass of the embodiment of the present invention, the thickness is measured from at least one arbitrary point (measurement point E in the laminated glass 10A) at at least one end, as exemplified by the laminated glass 10A. It may be performed at two points on the inside at a position of 50 mm (measurement point I in the laminated glass 10A). Any one point on the edge may be any one point on the outer circumference of the laminated glass.

The position 50 mm inward from the measurement point of the thickness of the end portion is, for example, on a line perpendicularly intersecting the measurement points of the side when the measurement point is on one linear side of the outer periphery of the laminated glass. It is located 50 mm inward from the above measurement point. When the outer circumference is curved, the position is 50 mm inward from the measurement point on the perpendicular line of the tangent line of the measurement point. In FIG. 1, a position 50 mm inward from the outer circumference of the laminated glass 10A is indicated by a frame line M. In the laminated glass 10A, when an arbitrary point on the outer circumference is set as a measurement point E for the thickness of the end portion, one point on the frame line M for which the above relationship holds with respect to the measurement point E is 50 mm inward from the end portion. Measurement point I of.

Hereinafter, each element that constitutes the laminated glass 10A will be described.
[Glass plate]
Examples of the material of the

glass plates

1A and 1B used for the laminated glass 10A of the embodiment of the present invention include transparent inorganic glass and organic glass (resin). As the inorganic glass, ordinary soda-lime glass (also referred to as soda-lime silicate glass), borosilicate glass, non-alkali glass, quartz glass and the like are used without particular limitation. Of these, soda lime glass is particularly preferable. Although the forming method is not particularly limited, for example, a float plate glass formed by the float method or the like is preferable. Inorganic glass may have surface stress by strengthening treatment such as physical strengthening and chemical strengthening.

Examples of the 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, halogenated aryl group. Examples include contained acrylic resin. Among these, polycarbonate resins such as aromatic polycarbonate resins and acrylic resins such as polymethylmethacrylate acrylic resins are preferable, and polycarbonate resins are more preferable. Further, among the polycarbonate resins, bisphenol A-based polycarbonate resins are particularly preferable. The glass plate may be configured to contain two or more of the above resins.

As the glass, a colorless and transparent material to which no coloring component is added may be used, or a colored and transparent material that is colored within a range that does not impair the effects of the present invention may be used. Further, these glasses may be used alone or in combination of two or more types, and may be, for example, a laminated substrate in which two or more layers are laminated. Inorganic glass is preferable as the glass, although it depends on the location where the laminated glass is applied.

The pair of

glass plates

1A and 1B used for the laminated glass 10A may be made of different kinds of materials. When the laminated glass 10A is attached to a vehicle or a building, the glass plate located inside or inside the vehicle is soda lime glass, and iron in the composition is 0 in terms of Fe ₂ O _{3 in} terms of total iron based on oxides. It is preferably contained in an amount of 4% by mass or more. When the iron content of the glass plate inside or inside the vehicle is in the above range, the haze of the light control film is high. For example, even when the haze is 5% or more, the haze is visually recognized from the inside or the inside of the vehicle. It becomes difficult and is preferable.

The plate thicknesses tg1 and tg2 of the

glass plates

1A and 1B can be appropriately selected depending on the application location of the laminated glass 10A, but in general, they are preferably 0.2 to 5 mm independently. From the viewpoint of achieving both weight reduction and rigidity of the laminated glass, 0.5 to 5 mm is more preferable, 1.1 to 3.5 mm is further preferable, and 1.6 to 3.0 mm is particularly preferable. The

glass plates

1A and 1B may have a three-dimensional curvature in terms of the design or functionality of the place where they are installed.

The plate thicknesses tg1 and tg2 of the pair of

glass plates

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

glass plates

1A and 1B have different thicknesses, the glass plate located inside when the laminated glass 10A is installed on a window or the like, for example, the inside of a car in the case of a window glass of an automobile, or the window glass of a building. If so, it is preferable that the thickness of the glass plate located on the indoor side is smaller than the thickness of the glass plate located on the outside. When the thickness of the glass plate has the above relationship, the heat generated from the light control film or the heat due to sunlight is likely to be released to the inside of the vehicle or the indoor side, so that the deterioration of the light control film due to heat can be suppressed.

Further, the

glass plates

1A and 1B may be coated on the exposed surface exposed to the atmosphere to impart water-repellent function, hydrophilic function, anti-fog function, low radiation, ultraviolet absorption and the like. Moreover, functional coatings such as an infrared shielding coating and a conductive coating may be applied to the facing surfaces of the

glass plates

1A and 1B that face each other. It is preferable to provide a low-reflection film on the inside or the indoor side of the laminated glass 10A because it can prevent reflection on the glass surface especially at night and has good design.

When the facing surfaces of the

glass plates

1A and 1B have the above-mentioned functional coating, 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 and 2B in the laminated glass 10A has a main surface having substantially the same shape and size as the main surfaces of the

glass plates

1A and 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, while sandwiching the light control film 3. In this way, the intermediate

adhesive layers

2A and 2B are bonded together so as to sandwich the light control film 3 between the pair of

glass plates

1A and 1B via the intermediate

adhesive layers

2A and 2B, and integrated as a laminated glass 10A. Have a function.

Here, as the intermediate

adhesive layers

2A and 2B, specifically, a sheet having a main surface having substantially the same shape and the same size as the main surfaces of the

glass plates

1A and 1B, containing a composition containing the following thermoplastic resin as a main component. An example is a film-formed product.

As the thermoplastic resin, a composition containing this as a main component is formed into a sheet, and as a pair of intermediate

adhesive layers

2A and 2B, a light control film 3 is sandwiched between a pair of

glass plates

1A and 1B. It is not particularly limited as long as it can be integrated when the laminated glass 10A is formed by inserting, heating, and pressurizing the laminated glass 10A. The required optical performance differs depending on the characteristics of the light control film enclosed in the laminated glass, but the transmittance of the intermediate adhesive layer is the visible light transmittance when combined with only ordinary colorless transparent glass to make the laminated glass. Is preferably 80% or more.

Specific examples of the thermoplastic resin include polyvinyl acetal resin such as polyvinyl butyral resin (PVB), polyvinyl chloride resin, saturated polyester resin, polyurethane resin, ethylene-vinyl acetate copolymer resin (EVA), and ethylene-ethyl acrylate. Examples thereof include thermoplastic resins conventionally used for intermediate adhesive layers such as copolymer resins, ionomer resins, and cycloolefin polymers (COPs). Among these, PVB, EVA, polyurethane resin, ionomer resin, and COP are preferable. These thermoplastic resins may be used alone or in combination of two or more.

Thermoplastic resin for the intermediate adhesive layer of laminated glass has 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. Is selected in consideration of the balance of. From the viewpoint of these conditions, among the above-mentioned thermoplastic resins, a resin composition obtained by saponifying a vinyl acetate unit in an ethylene-vinyl acetate copolymer and an ethylene-vinyl acetate copolymer as described in Japanese Patent No. 5625781 are used. An ethylene-vinyl acetate copolymer resin composition characterized by containing an organic layered clay, a silane coupling agent, or the like in the polymer is preferable. By containing the organic layered clay, the moisture permeability can be significantly reduced as compared with a normal ethylene-vinyl acetate copolymer resin composition. Further, a resin composition containing a modified block copolymer hydride described in JP-A-2015-821 can also be preferably used.

The intermediate adhesive layer has a storage elastic modulus minimum value of 2.0×10 ⁶ Pa or less in a temperature range of 90 to 120° C. in the dynamic viscoelasticity measurement at a measurement frequency of 10 Hz (hereinafter, the requirement (ii- 1)) is preferable. By satisfying the requirement (ii-1) for the intermediate adhesive layer, the intermediate adhesive layer has a predetermined flexibility in the temperature range where thermocompression bonding is performed. As a result, the pair of intermediate adhesive layers each have a frame-shaped region having a width w from the region in contact with the peripheral portion of the light control film to the region in which they are in contact with each other, that is, from the outer periphery of the laminated glass to the outer periphery of the light control film. By having shape conformability over the entire length, sufficient adhesion becomes easy without leaving air.

The minimum value of the storage elastic modulus in the intermediate adhesive layer is more preferably 8.0×10 ⁵ Pa or less, further preferably 5.0×10 ⁵ Pa or less. Further, the storage elastic modulus in the intermediate bonding layer, from the viewpoint of securing a predetermined rigidity in a temperature range of performing thermocompression bonding, preferably at maximum 2.0 × 10 5 ^Pa or more.

In order to adjust the storage elastic modulus of the intermediate adhesive layer, the storage elastic modulus of the thermoplastic resins constituting the intermediate adhesive layer can be lowered by increasing the unit amount of vinyl acetate, for example, for EVA. .. Similarly, for PVB, the storage elastic modulus can be lowered by adjusting the composition so as to increase the amount of the plasticizer.

Regarding the ionomer resin, for example, in the ionomer resin in which a copolymer of ethylene with (meth) acrylic acid, (meth) acrylic acid ester or the like is crosslinked with metal ions, the (meth) acrylic acid or (meth) acrylic acid with respect to ethylene is used. The storage elastic modulus can be lowered by increasing the ratio of (meth)acrylic acid ester.

In COP, for example, at least two polymer blocks [A] containing a repeating unit derived from an aromatic vinyl compound as a main component and at least one polymer block containing a repeating unit derived from a chain conjugated diene compound as a main component. The weight fraction of all polymer blocks [A] in the whole block copolymer is wA, and the weight fraction of all polymer blocks [B] in the whole block copolymer is When wB, the block copolymer [1] in which the ratio of wA to wB (wA:wB) is 30:70 to 60:40 is obtained by hydrogenating 90% or more of all unsaturated bonds. In the resin composition containing the modified block copolymer hydride [3] in which an alkoxysilyl group is introduced into the polymer hydride [2], the storage elastic modulus can be reduced by lowering the wA ratio.

In this way, by adjusting the storage elastic modulus of the thermoplastic resin forming the intermediate adhesive layer, the intermediate adhesive layer satisfying the requirement (1) can be obtained.

For the intermediate adhesive layer, a material that does not affect the function of the light control film during manufacturing and use is preferable. Therefore, it is preferable that the thermoplastic resin does not contain a plasticizer, or that the thermoplastic resin containing a plasticizer contains a plasticizer that does not affect the light control film.

Further, the heating temperature at the time of forming the laminated glass is set according to the thermoplastic resin for the intermediate adhesive layer, but if the heating temperature is equal to or higher than the heat resistant temperature of the light control film, the light control film is formed when the laminated glass is formed. May not work well. From this point of view, it is preferable to select the thermoplastic resin for the intermediate adhesive layer so that the molding temperature of the laminated glass is equal to or lower than the heat resistant temperature of the light control film used.

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

adhesive layers

2A and 2B. The thermoplastic resin-containing composition can be used for various purposes within a range that does not impair the effects of the present invention, for example, an infrared absorber, an ultraviolet absorber, a fluorescent agent, an adhesive modifier, a coupling agent, a surfactant, and an oxidation. It may contain one or more of various additives such as an inhibitor, a heat stabilizer, a light stabilizer, a dehydrating agent, a defoaming agent, an antistatic agent, and a flame retardant. These additives are uniformly contained in the intermediate

adhesive layers

2A and 2B.

The thicknesses ti1 and ti2 of the intermediate

adhesive layers

2A and 2B may satisfy the formula 1 in relation to the total thickness ti of w and ts. Specifically, the thickness per layer is preferably 0.3 to 0.8 mm, and the total film thickness of the two layers is 0.6, as in the case of the intermediate adhesive layer usually used for laminated glass. It is preferably about 1.6 mm. If the thicknesses ti1 and ti2 per layer of the intermediate adhesive layer are less than 0.3 mm, respectively, or if the total thickness ti of the two layers is less than 0.6 mm, the strength may be insufficient, and the strength may be insufficient. If the glass mismatch is large, peeling is likely to occur. If the total thickness ti of the intermediate

adhesive layers

2A and 2B exceeds 1.6 mm, the weight becomes large and a problem may occur when assembling to the vehicle.

The thicknesses ti1 and ti2 of the intermediate

adhesive layers

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

adhesive layers

2A and 2B are different, a glass plate located inside when the laminated glass 10A is installed in a window or the like, for example, in the case of a window glass of an automobile, the inside of the vehicle or a window glass of a building. If so, it is preferable that the thickness of the intermediate adhesive layer located on the indoor side is smaller than the thickness of the intermediate adhesive layer located on the outer side. When the thickness of the intermediate adhesive layer has the above relationship, the heat generated from the light control film or the heat due to sunlight is likely to be released to the inside of the vehicle or the indoor side, so that the deterioration of the light control film due to heat can be suppressed.

Each of the intermediate

adhesive layers

2A and 2B is not limited to a single layer structure. The intermediate

adhesive layers

2A and 2B may be the same, but they do not necessarily have to be the same, and a single-layer structure or a multi-layer structure can be selected independently of each other.

The intermediate adhesive layer preferably has embossing when it is prepared as an adhesive film or the like during the production of laminated glass. Normally, the material film that becomes the intermediate adhesive layer of laminated glass has embossing, and when it is sandwiched between glass plates to form a laminate and then heat-bonded, the embossing functions as an air passage. Heat crimping is performed while the air between the layers of the laminate is sufficiently exhausted, and finally the embossing in the material film disappears to form an intermediate adhesive layer, and a high-quality laminated glass without residual bubbles can be obtained.
[Light control film]
As the light control film 3, among the light control films used for smart glass and the like, the thickness ts is 0.1 mm or more and 1 mm or less, preferably 0.1 mm or more and 0.7 mm or less, and more preferably 0.1 mm or more and 0. It is possible to use one having a size of 0.4 mm or less. In general, if the thickness is less than 0.1 mm, it is difficult to handle when producing laminated glass, and if it is more than 1 mm, the rigidity of the substrate increases and it is difficult to follow the curved surface. When ts is within this range, the range of w can be set to a preferable range so as to satisfy Expression 1 or Expression 2 within the above range of ti.

Here, in the laminated glass of the embodiment, it is preferable that the ratio of the area of the light control film to the area of the laminated glass is 0.7 or more in a plan view from the viewpoint of design. If it is less than 0.7, the frame-like area becomes too wide, which may spoil the appearance.

As the light control film 3, for example, a Suspended Particle Device (SPD) film can be used. The SPD film is a general SPD film in which a polymer layer containing suspended particles that can be oriented by applying a voltage is sandwiched between two electrically insulating films coated with a transparent conductive film inside. Film can be used. Such an SPD film is in a state of high visible light transmittance and high transparency by orienting suspended particles in the polymer layer by turning on the power switch and applying a voltage between the transparent conductive films. become. When the power switch is off, the suspended particles in the polymer layer are not oriented, the visible light transmittance is low, and the transparency is low.

As the SPD film, for example, a commercially available product such as LCF-1103DHA (trade name, manufactured by Hitachi Chemical Co., Ltd.) can be used. Since such a commercially available product is supplied in a predetermined size, it is cut into a desired size before use. The thickness of the SPD film used for the laminated glass is preferably within the range of the thickness ts of the light control film described above, and is preferably 0.2 to 0.4 mm from the viewpoint of handleability and availability.

By using the SPD film, it is possible to electrically switch between a state in which the visible light transmittance is high and a state in which the visible light transmittance is low. By projecting the HUD image on the HUD display area where the SPD film is present while the visible light transmittance of the SPD film is low, the contrast ratio between the HUD image and the background can be improved.

Even when a polymer-dispersed liquid crystal (PDLC) is used as the light control film 3 instead of the SPD film, the contrast ratio between the HUD image and the background can be improved. PDLC films can be made by mixing prepolymers, nematic liquid crystals, and spacer materials in specific ratios and then placed between the two soft transparent conductive films. The principle of operation includes the following: When no electric field is applied, the liquid crystal droplets can be randomly distributed in the polymeric material with their directors freely oriented.

In such cases, the refractive index of the liquid crystal with respect to normal light does not match that of the polymer material, causing a relatively strong scattering effect with respect to light, resulting in the appearance of the PDLC film being translucent or opaque "milky white". Become. Under an electric field, the liquid crystal droplets can have their directors aligned along the direction of the external electric field due to their positive anisotropic dielectric properties. If the index of refraction of the liquid crystal with respect to normal light matches that of the polymeric material, the light can pass through the PDLC film and thus the PDLC film will have a transparent appearance. Specifically, the higher the voltage supplied to the PDLC film, the more transparent the PDLC film becomes.

As the PDLC film, for example, a commercially available product such as MIYO film (manufactured by Kyushu Nanotech Optical Co., Ltd.) can be used. Since such a commercially available product is supplied in a predetermined size, it is cut into a desired size before use. The thickness of the PDLC film used for the laminated glass is preferably within the range of the thickness ts of the light control film described above, and is preferably 0.1 to 0.4 mm from the viewpoint of handleability and availability.

When any one of polymer network liquid crystal (PNLC), guest host liquid crystal, VA (Vertical Alignment) type liquid crystal, TN (Twisted Nematic) type liquid crystal, photochromic, electrochromic, and electrokinetic is used as the light control film 3. Moreover, the contrast ratio between the HUD image and the background can be improved.
In addition, the laminated glass of the embodiment may optionally have other layers in addition to the above-described components within a range not impairing the effects of the present invention.
(Other layers)
In the laminated glass, for the purpose of concealing the mounting portion to the frame or the like, the wiring conductors, etc., the main part of the pair of glass plates constituting the laminated glass which is in contact with the intermediate adhesive layer of at least one of the glass plates A dark-colored concealing layer can be provided in a band shape on a part or all of the peripheral edge of the surface. In the laminated glass of the embodiment, such a dark color concealment may be provided as another layer.

Examples of the dark-colored concealing layer include a black ceramic layer. The black ceramic layer can be formed by using a known material such as a colored ceramic paste. As the ink used for forming the black ceramic layer, for example, an ink in which a resin such as a dark pigment, a glass frit, a refractory filler, and ethyl cellulose is dispersed in a solvent is used. Usually, ink is printed on a glass plate in a predetermined pattern, and the ink is temporarily baked by drying or irradiation with ultraviolet rays, and then fired at a high temperature to obtain a completely baked black ceramic layer on the glass plate. Further, an intermediate adhesive layer having a dark pigment, a colored film obtained by printing a dark color on a resin film, and the like can also be used to form a dark concealing layer.

From the viewpoint of design, the laminated glass may be provided with the width of the dark-colored concealing layer reduced, or the dark-colored concealing layer may not be provided. An example of not providing a dark concealing layer is a door glass for a vehicle.

In the laminated glass of the present invention, the requirements (i-1) to (i-3) are satisfied in the laminated glass of the present invention when the dark masking layer is provided with a small width at the peripheral edge or when the dark masking layer is not provided. By satisfying the above conditions, the distance w between the outer periphery of the light control film and the outer periphery of the laminated glass can be reduced without impairing the appearance of the laminated glass and while ensuring the durability of the laminated glass, which is preferable. In the case where the width of the dark-colored concealing layer is reduced, the width of the dark-colored concealing layer is specifically 100 mm or less, further 50 mm or less, and particularly 20 mm or less. The effect of can be remarkably enjoyed. Within the scope of the present invention, the w of the short side may be made relatively small with respect to the long side of the polygon in plan view from the viewpoint of designability. Then, the width of the concealing layer on the short side can be reduced.
[Manufacture of laminated glass]
The laminated glass of the embodiment of the present invention can be produced by a commonly used known technique. For example, in the laminated glass 10A, a laminated body in which the light control film 3 is arranged between the pair of intermediate

adhesive layers

2A and 2B so as to have a predetermined positional relationship is produced, and the laminated body is formed with the pair of glass plates 1A, A laminated glass precursor, which is a laminated glass before pressure bonding, is prepared by inserting the glass plate 1A, the intermediate adhesive layer 2A, the light control film 3, the intermediate adhesive layer 2B, and the glass plate 1B in this order. In the case of having other layers as well, a laminated glass precursor is prepared by laminating a glass plate and each layer in the same laminating order as the laminated glass obtained in the same manner.

The laminated glass precursor is placed in a vacuum bag such as a rubber bag, the vacuum bag is connected to the exhaust system, and vacuum suction is performed so that the pressure inside the vacuum bag is about -65 to -100 kPa. The laminated glass of the embodiment can be obtained by adhering at a temperature of about 70 to 110 ° C. while (degassing) (hereinafter, also referred to as “vacuum heating and crimping”). Further, for example, by performing a crimping treatment (hereinafter, also referred to as “pressurized heat crimping”) of heating and pressurizing under the conditions of 100 to 110 ° C. and a pressure of 0.6 to 1.3 MPa, the durability is further improved. A laminated glass can be obtained.

▽Pressurization, heating and pressure bonding are typically performed using an autoclave. By performing pressure heat crimping after decompression heat crimping, the thickness of the light control film ts is small in the frame-like region having a width w where the light control film of the laminated body does not exist. The decrease in the thickness of the end portion of the laminated glass thus obtained can be alleviated. Specifically, the above T2-T1 can be easily set to 0.28 mm or less, more preferably 0.2 mm or less, and further preferably 0.15 mm or less. As a result, the residual stress in the laminated glass can be eliminated, and the occurrence of defects such as peeling and foaming of the intermediate adhesive layer can be suppressed.

In the present invention, in the laminated glass provided with the light control film, it is possible to protect the edge portion of the light control film without spoiling the appearance, and the laminated glass having improved productivity can be obtained. The laminated glass of the present invention is suitably used for, for example, a window glass for a vehicle.

Hereinafter, the present invention will be described in more detail with reference to Examples. The present invention is not limited to the embodiments and examples described below. Examples 1 to 6, Examples 9 to 22 and Examples 25 to 42 are Examples, and Examples 7, 8, 23 and 24 are Comparative Examples.
[Examples 1 and 2]
(Production of laminated glass)
Laminated glass having the same configuration as that of the laminated glass 10A shown in FIGS. 1 and 2 was produced as follows. Hereinafter, each member of the evaluation sample corresponding to each member of the laminated glass 10A will be described with the same reference numeral as in the laminated glass 10A.

Glass plates

1A and 1B (made by AGC, commonly known as FL, 2 mm thick, 150 mm x 150 mm size quadrangle) made of two soda lime glasses, two saponified EVA intermediate

adhesive layers

2A and 2B (made by Toso Nikkemi, Mercen) G (trade name), 0.4 mm thick, 150 mm×150 mm size square), one light control film 3 (manufactured by Hitachi Chemical Co., LCF-1103DHA90 (trade name), SPD light control film, 0.35 mm thickness, A square having a size of 140 mm × 140 mm) was prepared. These were laminated in order of one glass plate 1A, one EVA intermediate adhesive layer 2A, SPD light control film 3, another EVA intermediate adhesive layer 2B, and the other glass plate 1B to obtain a laminate. The distance w between the outer circumference of the SPD light control film 3 and the outer circumference of the laminated body was set to 5 mm on all four sides.

The laminate obtained above was placed in a rubber vacuum pack, degassed (decompression degree: -90 kPa), placed in an oven maintained at 100 ° C., left for 60 minutes, heat-pressed under reduced pressure, and then pressure-bonded. It was taken out from the rubber vacuum pack to obtain laminated glass 1A. Laminated glass 1A was pressure-heated and pressure-bonded in an autoclave at 110 ° C. and a pressure of 1.3 MPa for 20 minutes to obtain laminated glass 1B. In the laminated glass 1A and the laminated glass 1B, the thickness ts of the SPD light control 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 control film 3 and the outer periphery of the laminated glass are all the above-mentioned lamination. It is similar to the body value. The laminated glass 1A was used as Example 1 and the laminated glass 1B was used as Example 2.

For the laminated glass 1A and the laminated glass 1B, the thickness T1 of one point (measurement point E) at the end and the thickness T2 at a position (measurement point I) 50 mm inward from one point (measurement point E) of the end are set. The thickness difference=thickness T2 [mm] at a position (measurement point I) 50 mm inside from the edge of the laminated glass-thickness T1 [mm] of edge of the laminated glass (measurement point E) was calculated. In this example, the measurement point E was set as the center point of one side of the outer periphery of the laminated glass, and the measurement point I was set at a position 50 mm inward from the measurement point E toward the center of the laminated glass. The results are shown in FIG. 3 as a thickness difference, with laminated glass 1A as Example 1 and laminated glass 1B as Example 2.
<Evaluation>
(appearance)
The appearances of the laminated glass 1A and the laminated glass 1B were visually evaluated according to the following criteria.
◯ (Good): No air residue or foaming is confirmed in the area inside 3 mm from the edge of the laminated glass.
Δ (Fair): Air residue and foaming of less than 20 mm ² are confirmed in the area inside 3 mm from the edge of the laminated glass × (Poor): 20 mm ² or more in the area inside 3 mm from the edge of the laminated glass At least one of air retention and foaming is confirmed.
(Durability evaluation)
The laminated glass 1A and the laminated glass 1B were placed in a thermo-hygrostat at 60° C. and a humidity of 95% RH for 500 hours. Moisture was permeated into the intermediate adhesive layer to create an environment in which peeling due to residual stress was likely to occur, and the presence or absence of peeling was visually evaluated. The case where peeling of 20 mm ² or more was confirmed was evaluated as x, the case where peeling of less than 20 mm ² was confirmed was evaluated as Δ, and the case where peeling was not confirmed was evaluated as 〇.

Whether the evaluation result is w, ti, ts, whether expression 1 is satisfied (“◯” when satisfied, “x” when not satisfied), or whether expression 2 is satisfied (“◯” when satisfied, “x” when not satisfied), It is shown in FIG. 3 together with the manufacturing method (A: decompression heat crimping only, B: decompression heating crimping + pressure heating crimping).
[Examples 3 to 16]
In Examples 1 and 2, (1) the shape of the SPD light control film 3 was changed to the same material as shown in FIG. 3 with the same material, and (2) the intermediate

adhesive layers

2A and 2B were made of the same material and had a total thickness ti. 3 was changed as shown in FIG. 3, and (3) A or B was selected as the manufacturing method as shown in FIG. 3, laminated glass of Examples 3 to 16 was prepared, and the same evaluation as described above was performed. The measurement results are shown in FIG. In Comparative Examples 7, 8, 23, and 24, residual air was generated, and the appearance evaluation was “x”.
[Examples 17 to 32]
In Examples 1 and 2, LCF-1103DHA30 (trade name, manufactured by Hitachi Kasei Co., Ltd., SPD dimming film, 0.28 mm thickness) was used as the dimming film 3 instead of LCF-1103DHA90 (trade name, manufactured by Hitachi Kasei Co., Ltd.). , (1) the shape of the light control film 3 is changed so as to have w shown in FIG. 3, (2) the total thickness ti is changed as shown in FIG. 3) A or B was selected as the manufacturing method as shown in FIG. 3, the laminated glass of Examples 17 to 22 was produced, and the same evaluation as above was performed. The measurement results are shown in FIG.
[Examples 33 to 42]
In Examples 1 and 2, MIYO film (trade name, manufactured by Kyushu Nanotech Optical Co., Ltd., PDLC film, 0.12 mm thick) was used as the dimming film 3 instead of LCF-1103DHA90 (trade name, manufactured by Hitachi Kasei Co., Ltd.). 1) The shape of the light control film 3 is changed so as to have w shown in FIG. 3, and (2) the total thickness ti is changed as shown in FIG. 3 with the same materials for the intermediate

adhesive layers

2A and 2B, and (3) As the manufacturing method, A or B was selected as shown in FIG. 3, the laminated glasses of Examples 23 to 32 were manufactured, and the same evaluation as above was performed. The evaluation result is shown in FIG.

From FIG. 3, if the requirements (i-1) and (i-3) are satisfied and the relationship between w, ti and ts satisfies the equation 1 (requirement (i-2)), that is, the requirements (i-1) to ( It can be seen that if all of i-3) are satisfied, a laminated glass can be obtained in which the edge of the light control film can be protected without spoiling the appearance and the productivity is improved.

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

This application claims the priority of the basic application 2019-038676 filed on Mar. 4, 2019 to the Japan Patent Office, the entire contents of which are incorporated herein by reference.

10A Laminated

glass

1A,

1B Glass plate

2A, 2B Intermediate adhesive layer 3 Light control film.

Claims

A pair of glass plates facing each other,
A pair of intermediate adhesive layers located between the pair of glass plates and in contact with the pair of glass plates respectively;
A laminated glass having a dimming film capable of switching the visible light transmittance located between the pair of intermediate adhesive layers, wherein the laminated glass is substantially polygonal in plan view, Laminated glass that meets the following requirements (i-1) to (i-3) on at least one side of the outer peripheral portion.
(I-1) The outer circumference of the dimming film is located inside a distance w [mm] from the outer circumference of the laminated glass in a plan view.
(I-2) When the thickness of the light control film is ts [mm] and the total thickness of the pair of intermediate adhesive layers is ti [mm], w, ti and ts are expressed by the following formula 1 Satisfied,
0<w/ti<7/ts Expression 1
(I-3) The 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 control film.
The laminated glass according to claim 1, wherein the requirements (i-1) to (i-3) are satisfied on at least two sides of the outer peripheral portion of the laminated glass.
The laminated glass according to claim 2, which satisfies the requirements (i-1) to (i-3) on the entire circumference of the outer peripheral portion of the laminated glass.
The laminated glass according to any one of claims 1 to 3, wherein a side that satisfies the requirements (i-1) to (i-3) in the outer peripheral portion of the laminated glass further satisfies the following requirement (i-4). ..
(I-4) The ts is 0.25 mm or more, and the w, the ti, and the ts satisfy the following Expression 2.
0 <w / ti <4.5 / ts formula 2
5. The laminated glass is substantially quadrilateral in plan view, and the w is 100 mm or less on at least one side satisfying the requirements (i-1) to (i-3). Laminated glass according to item.
6. The material of the intermediate adhesive layer contains at least one selected from the group consisting of polyvinyl butyral resin, ethylene vinyl acetate copolymer resin, polyurethane resin, ionomer resin and cycloolefin polymer. Laminated glass according to.
The minimum value of the storage elastic modulus of the intermediate adhesive layer in the dynamic viscoelasticity measurement at a measurement frequency of 10 Hz in the temperature range of 90 to 120° C. is 2.0×10 6 Pa or less. The laminated glass according to any one item.
T2-T1 is 0.28 mm or less, where T1 is the total thickness of the laminated glass at the edge of the laminated glass and T2 is the total thickness of the laminated glass at 50 mm inside from the edge. The laminated glass according to any one of 7 to 7.
The laminated glass according to any one of claims 1 to 8, which does not have a dark shielding layer on the peripheral edge.
10. The light control film is a suspended particle device, polymer dispersed liquid crystal, polymer network liquid crystal, guest-host liquid crystal, VA liquid crystal, TN liquid crystal, photochromic, electrochromic, or electrokinetic. Laminated glass given in any 1 paragraph.
The laminated glass according to any one of claims 1 to 10, wherein a total thickness ti of the pair of intermediate adhesive layers is 1.6 mm or less.
The laminated glass according to any one of claims 1 to 11, wherein a total thickness ti of the pair of intermediate adhesive layers is 0.6 mm or more.
The laminated glass according to any one of claims 1 to 12, wherein the thickness ts of the light control film is 1 mm or less.
The laminated glass according to any one of claims 1 to 13, wherein the ratio of the area of the light control film to the area of the laminated glass in plan view is 0.7 or more.
The laminated glass is a laminated glass to be attached to a vehicle, and among the pair of glass plates, the thickness of the glass plate located inside the vehicle is thinner than the thickness of the glass plate located outside the vehicle. The laminated glass according to any one of 14.
The laminated glass according to claim 15, wherein the glass plate located inside the vehicle has 0.4% by mass or more in terms of Fe 2 O 3 in terms of total iron content based on oxide in the composition.
The laminated glass according to claim 15 or 16, wherein the thickness of the intermediate adhesive layer located inside the vehicle is thinner than the thickness of the intermediate adhesive layer located outside the vehicle among the pair of intermediate adhesive layers.