WO2019103115A1 - Laminated glass and liquid crystal film - Google Patents

Abstract

Provided are a liquid crystal film and laminated glass that are capable of reducing liquid crystal accumulation and the occurrence of air gaps. This laminated glass (1) has a form in which a light-modulating film (10) is sandwiched between a first glass sheet (33A) and a second glass sheet (33B), and the light-modulating film (10) is provided with, in order in the thickness direction, a first base material layer (21A), a first transparent electrode layer (22A), a liquid crystal layer (14), a second transparent electrode layer (22B), and a second base material layer (21B). The liquid crystal layer (14) is provided with, within the layer, a plurality of spacers (24) for maintaining the thickness thereof. The first base material layer (21A) and the second base material layer (21B) each satisfy t×Y≥215 (μm×GPa), with t (μm) being the thickness thereof and Y (GPa) being the Young's modulus. The spacers (24) are provided in an amount of at least 60 spacers per 1 mm².

Description

Laminated glass, liquid crystal film

Embodiments of the present disclosure relate to a laminated glass provided with a liquid crystal film, and a liquid crystal film.

Conventionally, for example, a light control member that can be used as an electronic blind or the like that is provided in a window to control transmission of extraneous light has been proposed. One of such light control members is a light control film (liquid crystal film) using liquid crystal.
The liquid crystal film is produced, for example, by holding a film-like member in which a liquid crystal material is held by a transparent plate material including a transparent electrode with a linear polarizing plate. The liquid crystal film changes the orientation of the liquid crystal by changing the electric field applied between the transparent electrodes, and controls the amount of transmitted extraneous light.

Further, it has been proposed to manufacture a laminated glass by further sandwiching the above-described liquid crystal film with glass (see, for example, Patent Document 1).
However, conventionally, laminated glass sandwiching a liquid crystal film has never been actually manufactured. Therefore, there is a case where the laminated glass sandwiching the liquid crystal film can not be correctly manufactured only by applying the same method as the conventional laminated glass configured by sandwiching the interlayer film as it is.

As a case where the laminated glass sandwiching the liquid crystal film can not be manufactured properly, there is a phenomenon that a large amount of liquid crystal is accumulated in the liquid crystal film in the process of manufacturing the laminated glass (hereinafter referred to as "liquid crystal reservoir"). Moreover, an air gap may be generated in a part of the laminated glass.

JP, 2016-164617, A

An object of the embodiments of the present disclosure is to provide a liquid crystal film and a laminated glass that can reduce the occurrence of liquid crystal accumulation and voids.

The embodiment of the present disclosure solves the problem by the following solutions. In addition, although the code | symbol corresponding to embodiment of this indication attaches and demonstrates for ease of understanding, it is not limited to this.

The embodiment of the first disclosure is a laminated glass including a first glass plate (33A), a second glass plate (33B), and a liquid crystal film (10), and the liquid crystal film is sequentially formed in the thickness direction The liquid crystal comprising the one substrate layer (21A), the first transparent electrode layer (22A), the liquid crystal layer (14), the second transparent electrode layer (22B), and the second substrate layer (21B) The layer comprises a plurality of spacers (24) in the layer to maintain its thickness, said spacers comprising at least pillared spacers, said first and second substrate layers being of their thickness Where t (μm) and Young's modulus Y (GPa), t × Y ≧ 215 (μm × GPa) is satisfied, and the number of the spacers disposed per 1 mm ² is 60 or more Is a laminated glass (1) characterized by .

An embodiment of the second disclosure is the laminated glass according to the embodiment of the first disclosure, wherein the spacer (24) includes both the columnar spacer and the bead spacer, and the columnar spacer includes side surfaces, It is a laminated glass (1) which has a flat top surface and the angle between the top surface and the side surface has no curvature.

An embodiment of the third disclosure is a laminated glass including a first glass plate (33A), a second glass plate (33B), and a liquid crystal film (10), and the liquid crystal film is sequentially formed in the thickness direction The liquid crystal comprising the one substrate layer (21A), the first transparent electrode layer (22A), the liquid crystal layer (14), the second transparent electrode layer (22B), and the second substrate layer (21B) The layer is provided with a plurality of bead spacers (24) in the layer to maintain its thickness, and the first base layer and the second base layer have a thickness of t (μm), and the Young's modulus Where Y (GPa) satisfies t × Y ≧ 215 (μm × GPa), and the number of the bead spacers is 60 or more and 220 or less per 1 mm ^{2 of} laminated glass (1 ).

An embodiment of the fourth disclosure is the laminated glass of the first disclosure embodiment, wherein the average pitch between the spacers (24) is 130 μm or less, and the spacers are locally gathered so as to contact each other It is laminated glass (1) which does not have a part.

The embodiment of the fifth disclosure relates to the first base material layer (21A) and the second base material layer (22B) in any of the first to third embodiment disclosed embodiments. The material of is a laminated glass (1) which is any of polyethylene terephthalate, polycarbonate, and cycloolefin polymer.

In the embodiment of the sixth disclosure, the first base material layer (21A), the first transparent electrode layer (22A), the liquid crystal layer (14), and the second transparent electrode layer (22B) are sequentially arranged in the thickness direction. And a second base material layer (21B), wherein the liquid crystal layer includes a plurality of spacers (24) for maintaining its thickness in the layer, and the first base material layer and the above The second base material layer satisfies t × Y ≧ 215 (μm × GPa) when the thickness is t (μm) and the Young's modulus is Y (GPa), and the spacer has a thickness of 1 mm ² Is a liquid crystal film (10) having 60 or more pieces.

According to the embodiments of the present disclosure, it is possible to provide a liquid crystal film and a laminated glass capable of reducing the generation of liquid crystal reservoirs and voids.

It is a figure which shows the laminated glass 1 of embodiment. FIG. 5 is a cross-sectional view showing a layer configuration of laminated glass 1 using a bead spacer as spacer 24. It is sectional drawing which shows the laminated constitution of the laminated glass 1 which used the 1st columnar spacer as the spacer 24. FIG. It is sectional drawing which shows the laminated constitution of the laminated glass 1 which contains a 2nd columnar spacer and a bead spacer as the spacer 24. As shown in FIG. FIG. 7 is a partial cross-sectional perspective view showing a second columnar spacer 242. It is a figure which shows the modification of the 2nd columnar spacer 242. As shown in FIG. It is a figure which shows the modification of the 2nd columnar spacer 242. As shown in FIG. It is a figure which shows the modification of the 2nd columnar spacer 242. As shown in FIG. It is a figure which shows the modification of the 2nd columnar spacer 242. As shown in FIG.

Hereinafter, embodiments of the present disclosure will be described with reference to the drawings and the like. In addition, each figure shown below including FIG. 1 is a figure shown typically, and the magnitude | size of each part and the shape are suitably exaggerated in order to make an understanding easy.
In the present specification, specific numerical values, shapes, materials, and the like are shown and described, but these can be changed as appropriate.
In addition, in the present specification, terms specifying shape and geometrical conditions, such as terms such as parallel and orthogonal, have similar optical functions in addition to strictly meaning, and can be regarded as parallel or orthogonal. It also includes conditions with a degree of error.

In this specification, the terms plate, sheet, film, etc. are used, but as a general usage, these are used in the order of thickness, in order of plate, sheet, film I use it according to it even in writing. However, there is no technical meaning to such proper use, and these terms can be replaced as appropriate.
In the embodiment of the present disclosure, “transparent” refers to one that transmits light of at least the wavelength to be used. For example, even if it does not transmit visible light, if it transmits infrared light, it shall be treated as transparent when used for infrared applications.
The specific numerical values specified in the present specification and the claims should be treated as including general error ranges. That is, those whose numerical value is set in a range slightly beyond the numerical range of the present case should be construed as substantially within the scope of the embodiments of the present disclosure.

(Embodiment)
FIG. 1 is a view showing a laminated glass 1 of the present embodiment.
In the description of the present embodiment, one in which the respective constituent members of the laminated glass 1 are stacked and arranged is referred to as a laminated body 30. The laminated body 30 refers to a state before the respective members of the laminated glass 1 are joined, so that the shape, size, arrangement, and the like of the respective constituent members are equivalent to that of the laminated glass 1.
The laminate 30 of the present embodiment includes the first glass plate 33A, the first intermediate film 31A, the light control film (liquid crystal film) 10, the second intermediate film 31B, and the second glass plate 33B, and they are combined. The layers are arranged in this order along the thickness direction of the glass 1.

FIG. 2 is a cross-sectional view showing the layer structure of the laminated glass 1 using a bead spacer as the spacer 24. As shown in FIG.
The light control film (liquid crystal film) 10 is a film capable of controlling the amount of transmitted light by changing an applied voltage. As shown in FIG. 1, the light control film 10 of the present embodiment is sandwiched between two glass plates via an intermediate film, and used as laminated glass.
The laminated glass 1 provided with the light control film 10 is, for example, a portion to be subjected to light control such as window glass of a building, a showcase, an indoor transparent partition, a window of a vehicle, etc. It is disposed on the front, windows, such as the side, the rear, the roof, etc., and can control the light quantity of the incident light to the inside of a building or a vehicle.
In addition, in FIG.1 and FIG.2, although the example which is a planar shape was shown in the laminated glass 1, two-dimensional shape (two-dimensional curved surface) and three-dimensional shape (three-dimensional curved surface) may be sufficient. Here, the three-dimensional shape is not a simple cylindrical surface, but a curved surface that can not be configured only by deforming a plane without expansion and contraction, and a two-dimensional shape (two-dimensional) bent around a single axis It can be distinguished from a curved surface) or a two-dimensional shape (two-dimensional curved surface) which is bent in a two-dimensional manner with different curvatures around a plurality of parallel axes.

The light control film (liquid crystal film) 10 is a member that includes a guest-host liquid crystal layer 14 using a dichroic dye, and the amount of transmitted light is changed by an electric field applied to the liquid crystal of the liquid crystal layer 14. The light control film 10 is configured by sandwiching the liquid crystal layer 14 by a first laminate 12 and a second laminate 13 which are first and second laminates in the form of a film.
The first laminate 12 of the present embodiment is formed, for example, by laminating the first transparent electrode layer 22A and the first alignment layer 23A on the first base material layer 21A. The second laminate 13 of the present embodiment is formed, for example, by laminating the second transparent electrode layer 22B, the second alignment layer 23B, and the spacer 24 on the second base material layer 21B. The spacer 24 may be stacked on the first laminate 12 side. In each laminate, the first alignment layer 23A and the second alignment layer 23B can be omitted.
The light control film 10 is a liquid crystal based on the guest host liquid crystal composition of the liquid crystal layer 14 by driving the first transparent electrode layer 22A and the second transparent electrode layer 22B provided on the first laminate 12 and the second laminate 13. The orientation of the material is changed, thereby changing the amount of transmitted light.

Various transparent resin films can be applied to the first base layer 21A and the second base layer 21B, but the optical anisotropy is small, and the transmittance in the visible wavelength range (380 to 800 nm) is sufficient. It is desirable to apply a transparent resin film that is 80% or more.
Examples of the material of the transparent resin film include acetyl cellulose-based resins such as triacetyl cellulose (TAC), polyester-based resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene (PE), polypropylene (PP) Polyolefin resins such as polystyrene, polymethylpentene and EVA, vinyl resins such as polyvinyl chloride and polyvinylidene chloride, acrylic resins, polyurethane resins, polysulfone (PEF), polyether sulfone (PES), polycarbonate Mention may be made of resins such as PC), polysulfone, polyether (PE), polyether ketone (PEK), (meth) acronitrile, cycloolefin polymer (COP), cycloolefin copolymer and the like.
In particular, resins such as polycarbonate, cycloolefin polymer and polyethylene terephthalate are preferable.

The thickness of the first base material layer 21A and the second base material layer 21B may be selected in accordance with the Young's modulus and the like of the material from the viewpoint of reducing the liquid crystal pool and the voids in the laminated glass 1. preferable. Details of the material, thickness, and the like of the first base material layer 21A and the second base material layer 21B will be described later.
In the present embodiment, the first base material layer 21A and the second base material layer 21B use, for example, a polycarbonate film having a thickness of 100 μm.

The first transparent electrode layer 22A and the second transparent electrode layer 22B are each formed of a transparent conductive film laminated on the first base layer 21A and the second base layer 21B (transparent resin film).
As the transparent conductive film, various transparent electrode materials applied to this kind of transparent resin film can be applied, and a transparent metal thin film having an oxide-based total light transmittance of 50% or more can be mentioned. . For example, tin oxide type, indium oxide type and zinc oxide type can be mentioned.

Examples of tin oxide (SnO ₂ ) include nesa (tin oxide SnO ₂ ), ATO (Antimony Tin Oxide: antimony-doped tin oxide), and fluorine-doped tin oxide.
Examples of indium oxide (In ₂ O ₃ ) -based materials include indium oxide, ITO (Indium Tin Oxide: Indium Tin Oxide), and IZO (Indium Zinc Oxide).
Examples of zinc oxide (ZnO) -based include zinc oxide, AZO (aluminum-doped zinc oxide), and gallium-doped zinc oxide.
In the present embodiment, the transparent conductive film constituting the first transparent electrode layer 22A and the second transparent electrode layer 22B is formed of ITO (Indium Tin Oxide).

The spacer 24 is a member provided to define the thickness (cell gap) of the portion of the liquid crystal layer 14 excluding the outer peripheral portion.

(Bead spacer)
For example, as shown in FIG. 2, as an example, the spacer 24 can use a spherical bead spacer. The diameter of the bead spacer may be in the range of 1 μm to 20 μm, preferably 3 μm to 15 μm. The bead spacer can be widely applied to the configuration of an inorganic material such as silica, the configuration of an organic material, the configuration of a core-shell structure combining these, and the like. Further, the bead spacer may be configured by a rod shape by a cylindrical shape, a prismatic shape or the like, in addition to the configuration by the spherical shape. In addition, although the bead spacer is manufactured by a transparent member, a colored material may be applied as needed to adjust the color. When a bead spacer is used as the spacer 24 as in the present embodiment, it may be dispersed on the second alignment layer 23B of the second stack 13 and on the first alignment layer 23A of the first stack 12, respectively. It may be spread on only one or the other.

(First columnar spacer)
Further, the spacer 24 is not limited to the bead spacer, but may be produced, for example, by coating a photoresist on the first transparent electrode layer 22A or the second transparent electrode layer 22B, exposing and developing, etc. It may be a spacer having a pillar shape, a polygon shape or the like (for example, a columnar spacer made of a photoresist such as a photocurable acrylic resin and provided on the first transparent electrode layer 22A or the second transparent electrode layer 22B is described below) , And appropriately referred to as a first columnar spacer). The first columnar spacers can be, for example, cylindrical with a diameter of 5 to 40 μm, and can be regularly arranged at intervals of 100 to 300 μm. The height of the first columnar spacer is 2 to 20 μm, preferably 3 to 12 μm. Further, the spacer 24 may be a columnar spacer having an amorphous cross-sectional shape perpendicular to the height direction. That is, the cross-sectional shape of the columnar spacer orthogonal to the height direction is not particularly limited. When such spacers 24 are used, they may be arranged irregularly or regularly.
FIG. 3 is a cross-sectional view showing the layer structure of the laminated glass 1 using the first columnar spacer as the spacer 24. As shown in FIG.
As shown in FIG. 3, when the spacer 24 is a first columnar spacer, the surface on the side subjected to development processing in the preparation process (in FIG. 3, a photoresist is coated on the second laminate 13 side) Since exposure and development are performed from the upper surface, that is, the first laminated body 12 side, in FIG. 3, the upper surface of the spacer 24 and the surface on the first laminated body side has a curvature.

(2nd column spacer)
Furthermore, the spacer 24 may be formed in a columnar shape using printing using a thermosetting resin such as an epoxy resin or an acrylic resin, an ultraviolet curable resin, or the like (hereinafter referred to as a second columnar spacer as appropriate). Also, the material of the second columnar spacer may be the same as the material of the sealing material 32 described later. In addition, the second columnar spacer is manufactured by an opaque member colored in black, gray or the like, but a transparent material may be used. The second columnar spacers can be, for example, cylindrical with a diameter of 20 to 100 μm, and can be regularly arranged at intervals of 115 to 2000 μm. However, they may be arranged irregularly. The height of the second columnar spacer is 2 to 20 μm, preferably 3 to 12 μm. The first columnar spacer is provided on the first transparent electrode layer 22A or the second transparent electrode layer 22B, whereas the second columnar spacer is provided on the first alignment layer 23A or the second alignment layer 23B.

(Mixed with bead spacer and second columnar spacer)
In the case of employing the second columnar spacer, it is possible to easily manufacture the second columnar spacer with high accuracy by mixing the bead spacers.

FIG. 4 is a cross-sectional view showing the layer structure of the laminated glass 1 including the second columnar spacer and the bead spacer as the spacer 24. As shown in FIG.
In the example shown in FIG. 4, the spacer 24 includes a bead spacer 241 and a second columnar spacer 242. In order to produce the spacer 24 configured as shown in FIG. 4, first, the bead spacer 241 is disposed on the second alignment layer 23B. The arrangement of bead spacers 241 can be widely applied to various arrangement methods in addition to wet / dry spraying. For example, after partially applying a coating liquid prepared by dispersing the bead spacer 241 in the solvent together with the resin component, the drying and baking processes are sequentially performed to randomly arrange the beads on the second alignment layer 23B. The spacer 241 may be arranged to keep it difficult to move. The outer periphery of the bead spacer 241 may be covered with the second alignment layer 23B. Specifically, the bead spacer 241 is thinly covered and held by the second alignment layer 23B by forming the second alignment layer 23B by mixing the bead spacer 241 with the coating liquid related to the second alignment layer 23B. Form.

Next, a second columnar spacer 242 is formed on the second alignment layer 23B. First, a printing layer for forming the second columnar spacer 242 is formed on the second alignment layer 23B by printing. The print layers are arranged in the form of dots at positions corresponding to the respective second columnar spacers 242, and are adhered onto the second alignment layer 23B. The thickness of the print layer is formed to be slightly larger than the thickness of the second columnar spacer 242. There is no limitation on the method of forming the printing layer, but for example, the printing layer may be formed by a rotary screen printing method using a cylindrical plate. The printing layer is made of a thermosetting resin such as an epoxy resin or an acrylic resin, an ultraviolet curable resin, or the like. The printing layer formed in this way is rounded at its top by surface tension, and the corner of the rim of the top has a curvature.

Next, a cylindrical roller is provided, which is used to crush and flatten the top of the uncured print layer. Simultaneously with this crushing operation, the crushed printing layer is cured by heat or ultraviolet light. The crushing by the roller forms a flat top surface on top of the print layer. In addition, in the crushing operation by this roller, since the bead spacer 241 is disposed in advance, the printed layer is not crushed more than necessary, and the second columnar spacer 242 with high height dimension accuracy can be easily It can be made.

FIG. 5 is a partial cross-sectional perspective view showing the second columnar spacer 242. As shown in FIG.
As shown in FIG. 5, each second columnar spacer 242 is printed directly on the second alignment layer 23B, and the second alignment layer 23B is laminated on the surface opposite to the printed side. It does not have a solid cylinder shape of a roughly stump shape as a whole. In addition, since the second columnar spacer 242 is printed directly on the second alignment layer 23B, the liquid crystal directly contacts the side portions of the second columnar spacer 242 without the adhesion of the material constituting the alignment layer. ing. Each second columnar spacer 242 has a top surface 243, a side surface 245 connected to the top surface 243, and a bottom surface 244 connected to the side surface 245. Among these, the bottom surface 244 is bonded to the second alignment layer 23 B of the second laminate 13. The bottom surface 244 has a shape surrounded by a curve, such as a substantially circular shape or a substantially elliptical shape in a plan view. The width (maximum width) w1 of the bottom surface 244 may be 20 μm or more and 100 μm or less.

The top surface 243 is in surface contact with the first alignment layer 23A without being bonded to the first alignment layer 23A. The top surface 243 is a flat surface, and the flat surface is substantially parallel to the first alignment layer 23A and the second alignment layer 23B. The top surface 243 has a shape surrounded by a curve, such as a substantially circular shape or a substantially elliptical shape in a plan view. The width (maximum width) w2 of the top surface 243 may be 20 μm or more and 100 μm or less. In the present embodiment, the top surface 243 is smaller than the bottom surface 244 in plan view, but may be the same as the bottom surface 244 or larger than the bottom surface 244.

Further, the side surface 245 is located between the top surface 243 and the bottom surface 244. The side surface 245 has a curved surface curved from the outside to the inside. The side surface 245 has a shape in which a horizontal cross section (a cross section parallel to the first alignment layer 23A and the second alignment layer 23B) is surrounded by a curve, such as a substantially circular shape or a substantially elliptical shape. Further, the side surface 245 has an upper curved portion 245a, a reduced diameter portion 245b, and a skirt portion 245c.

Among these, the upper curved portion 245 a extends from the reduced diameter portion 245 b to the top surface 243 side. The horizontal cross section of the upper curved portion 245a gradually widens from the reduced diameter portion 245b toward the top surface 243 (first laminated body 12). The upper curved portion 245a is formed together with the top surface 243 by being crushed by a roller. The reduced diameter portion 245 b is the portion of the side surface 245 that is the narrowest in horizontal cross section, and is located closer to the top surface 243 than the intermediate portion between the top surface 243 and the bottom surface 244. The skirt portion 245c extends from the reduced diameter portion 245b to the bottom surface 244 side. The horizontal cross section of the skirt portion 245c gradually widens from the reduced diameter portion 245b toward the bottom surface 244 (second laminated body 13). The horizontal cross section of the side surface 245 is largest at the bottom surface 244 side of the skirt portion 245 c.

In the present embodiment, the angle θ1 between the top surface 243 and the side surface 245 is shaped to have no curvature. That is, the angle θ1 between the top surface 243 and the side surface 245 is not rounded, and the top surface 243 and the side surface 245 are not connected by one continuous curved surface.

Here, although it has been described that the angle θ1 between the top surface 243 and the side surface 245 does not have a curvature, for example, a minute curved surface is formed in a magnified view using a scanning electron microscope (SEM) or the like Although it may be possible to confirm, it does not exclude it. That is, in the present embodiment, when it is considered that the angle between the top surface 243 and the side surface 245 can be enlarged and regarded as an arc if it does not have a curvature, a minute circle of radius r of the circle regarded as the arc. In the case where the curvature k of is expressed by 1 / r, the radius of curvature r <0.5 μm, that is, the curvature k> 1 / (0.5 μm) is referred to.

In the first columnar spacer, the corner between the top surface and the side surface has a curvature of about 1 μm.
On the other hand, in the second columnar spacer, the angle between the top surface and the side surface has a curvature sufficiently smaller than 0.5 μm, and has a curvature radius of about 0.1 μm or less. So it can be said that it has virtually no curvature.

The angle θ1 is the angle between the top surface 243 and the portion of the upper curved portion 245a that is closest to the top surface 243. Specifically, θ1 is in the range of 75 ° to 105 °. preferable. By setting θ1 in this range, it is possible to suppress the bending of the first stacked body 12 along the top surface 243 during laminated glass processing, and the pressure applied to the light control cell 10 can be uniformly dispersed.
Further, the angle θ2 between the bottom surface 244 and the side surface 245 is formed to be an acute angle, and has a shape having a curvature. The angle θ2 is the angle between the bottom surface 244 and the portion of the bottom portion 245c of the skirt portion 245c, and specifically, it is preferable that θ2 be in the range of 60 ° to 90 °.

The measurement of the angles θ1 and θ2 is performed by cutting the second columnar spacer 242 in the light control cell 10 in a direction perpendicular to the top surface 243 or the bottom surface 244 or without cutting the second columnar spacer 242. The angle can be measured by photographing the shape of the column with using a scanning electron microscope (SEM).

6 to 9 are diagrams showing modifications of the second columnar spacer 242. FIG.
As shown in FIG. 6, the center of the top surface 243 of the second columnar spacer 242 and the center of the bottom surface 244 are offset in the plane direction (the plane direction parallel to the first alignment layer 23A and the second alignment layer 23B) It is also good. In this case, the side surface 245 of the second columnar spacer 242 has a non-rotationally symmetrical shape in the circumferential direction.

As shown in FIG. 7, the side surface 245 of the second columnar spacer 242 may have a curved surface that is curved outward from the inside. In this case, the horizontal cross section of the side surface 245 is the smallest on the top surface 243 side. Further, a portion of the side surface 245 having the largest horizontal cross section is located between the top surface 243 and the bottom surface 244.

As shown in FIG. 8, the side surface 245 of the second columnar spacer 242 is the smallest at the reduced diameter portion 245 b, and the portion on the top surface 243 side of the reduced diameter portion 245 b in the side surface 245 has a uniform diameter. You may have.

As shown in FIG. 9, the top surface 243 and the bottom surface 244 of the second columnar spacer 242 may have substantially the same shape. In this case, the reduced diameter portion 245 b having the narrowest horizontal cross section among the side surfaces 245 is located at an intermediate portion between the top surface 243 and the bottom surface 244.

As described above, the spacer 24 can take various forms, and may be provided to the first laminate 12 and the second laminate 13 or the first laminate 12 and the second laminate 13. It may be provided only on one side. Further, the spacer 24 may be fixed to either one of the laminates or may be fixed to both laminates, and is attached to the surface of each laminate, in the case of using a bead spacer, etc. It is good also as a form which is not fixed.

The first alignment layer 23A and the second alignment layer 23B are formed of a photo alignment layer. As the photo alignment material applicable to the photo alignment layer, various materials to which the photo alignment method can be applied can be widely applied. For example, photo decomposition type, photo dimerization type, photo isomerization type, etc. may be mentioned. it can.
In the present embodiment, a light dimerization type material is used. Examples of the photo-dimerization type material include cinnamate, coumarin, benzylidene phthalimidine, benzylidene acetophenone, diphenyl acetylene, stilbazole, uracil, quinolinone, maleimide, or a polymer having a cinnamylidene acetic acid derivative. Among them, a polymer having one or both of cinnamate and coumarin is preferably used in that it has a good alignment control force. As specific examples of such photo-dimerization type materials, compounds described in, for example, JP-A-9-118717, JP-A-10-506420, JP-A-2003-505561 and WO2010 / 150748 are disclosed. Can be mentioned.

In addition, it may replace with a photo alignment layer, an alignment layer may be produced by a rubbing process, and a fine line-shaped uneven | corrugated shape may be formed and processed to produce an alignment layer.
In the present embodiment, an example in which a photo alignment layer is used as the first alignment layer 23A and the second alignment layer 23B has been described. However, the present invention is not limited thereto. Alignment which does not perform alignment processing such as photo alignment or rubbing processing It may be a layer. Moreover, although the light control film 10 showed the form provided with 1st orientation layer 23A and 2nd orientation layer 23B in this embodiment, it does not restrict to this but is provided with 1st orientation layer 23A and 2nd orientation layer 23B. It is good also as a form without.

A guest host liquid crystal composition using a dichroic dye can be widely applied to the liquid crystal layer 14. The guest host liquid crystal composition may be made to contain a chiral agent, and when the liquid crystal material is horizontally aligned, it may be aligned in a spiral shape in the thickness direction of the liquid crystal layer 14.
The sealing material 25 is disposed in an annular frame shape in plan view so as to surround the liquid crystal layer 14 between the first laminate 12 and the second laminate 13 of the light control film 10. The first stacked body 12 and the second stacked body 13 are integrally held by the sealing material 25, and the liquid crystal material is prevented from leaking. For example, a thermosetting resin such as an epoxy resin or an acrylic resin, an ultraviolet curable resin, or the like can be used as the sealing material 25.

The light control film (liquid crystal film) 10 is subjected to an alignment control that pre-tilts the first alignment layer 23A and the second alignment layer 23B in a predetermined direction so that the alignment of the guest host liquid crystal composition at the time of light shielding becomes an electric field application. It is comprised by the vertical alignment layer which set the force, and, thereby, is comprised by a normally clear. In addition, the setting at the time of light transmission may be configured by the normally dark when the electric field is applied.
Here, the normally dark is a structure in which the transmittance is minimized when no voltage is applied to the liquid crystal, and a black screen is obtained. Normally clear is a structure in which the transmissivity is maximized and the liquid crystal is transparent when no voltage is applied to the liquid crystal.

Although the light control film 10 of the present embodiment is configured to include the guest-host liquid crystal layer 14, a TN (Twisted Nematic) system, a VA (Vertical Alignment) system, and a IPS that do not use a dichroic dye composition The liquid crystal layer 14 of the (In-Plane-Switching) system or the like may be provided. In the case of the light control film 10 provided with such a liquid crystal layer 14, it is possible to function as a light control cell by further providing a linear polarization layer on the surface of each of the first base layer 21A and the second base layer 21B. it can.

The first glass plate 33A and the second glass plate 33B are respectively disposed on the front and back surfaces of the laminated glass 1 and are light-transmissive plate glass.
In the present embodiment, each of the first glass plate 33A and the second glass plate 33B uses a plate glass having a thickness of 2 mm.

The first intermediate film 31A is a member for bonding the first glass plate 33A and the light control film 10. Similarly, the second intermediate film 31B is a member for bonding the second glass plate 33B and the light control film 10.
In the present embodiment, as the first intermediate film 31A and the second intermediate film 31B, a sheet of 760 μm in thickness made of PVB (polyvinyl butyral) resin is used.
As materials of the first intermediate film 31A and the second intermediate film 31B, EVA (ethylene-vinyl acetate copolymer), COP (cycloolefin polymer) or the like may be used. Further, the thickness of the first intermediate film 31A and the second intermediate film 31B may be appropriately selected according to the material and the like.
When the light control film 10 is smaller than the first glass plate 33A and the second glass plate 33B in plan view, the first intermediate film 31A and the second intermediate film 31B are around the light control film 10. A ring-shaped, frame-shaped intermediate film may be further provided in a portion corresponding to the thickness between them.

Hereinafter, the manufacturing method of the laminated glass 1 of this embodiment is demonstrated.
First, a lamination step of sequentially laminating the first glass plate 33A, the first intermediate film 31A, the light control film 10, the second intermediate film 31B, and the second glass plate 33B is performed. The lamination body 30 is created by the lamination process.
Next, a bonding process for bonding the stacked body 30 integrally is performed. In the present embodiment, as the bonding step, a preliminary pressure bonding step and an autoclave step are performed.
In the preliminary pressure-bonding step, the laminate 30 is heated and pressurized to bond the members of the laminate 30. The preliminary pressure-bonding step is preferably performed by, for example, a vacuum bag method, a vacuum laminating method, a roll press method, a tube method, or the like.

After the pre-pressing process, an autoclave process is performed. In this autoclave step, the laminate 30 after the preliminary pressure bonding step is transferred to a pressure vessel for an autoclave, and bonding of the members of the laminate 30 is strengthened after leaving the laminate 30 for a predetermined time under a high pressure and high temperature environment.
When the autoclave process is completed, the laminated glass 1 is completed. In addition, if necessary, a part of the laminated glass 1 may be cut away to perform a cutting step of adjusting the shape of the outer shape.

(Regarding the reduction of liquid crystal reservoir and air gap)
As described above, in the laminated glass 1 including the light control film 10, liquid crystal stagnation in the liquid crystal layer 14 and voids in the laminated glass 1 may occur in the step of bonding the laminate 30. Such liquid crystal stagnation and air gaps are not preferable because they cause deterioration of the optical performance and the appearance of the light control film 10.
In order to reduce such liquid crystal reservoirs and voids, the inventors of the present invention are important to select the physical properties and thickness of the first base layer 21A and the second base layer 21B, the arrangement density of the spacers, and the like. I found it to be.
That is, from the viewpoint of reducing liquid crystal stagnation and voids in the laminated glass 1, the thickness of the first base material layer 21A and the second base material layer 21B is t (μm), and the Young's modulus is Y (GPa) It is preferable that the value of the product t × Y is 215 (μm · GPa) or more (that is, satisfy t × Y ≧ 215 (μm · GPa)), and the spacer 24 It is preferable to arrange 60 or more per 1 mm ² .
The average pitch between the spacers 24 is preferably 130 μm or less.
In addition, it is preferable that the spacers 24 be arranged regularly or irregularly and without deviation in arrangement.

(Evaluation test with samples)
Hereinafter, a plurality of light control films 10 are prepared by changing the material and thickness of the first base material layer 21A and the second base material layer 21B, the shape and arrangement density of the spacers 24, etc. It manufactured and investigated about the presence or absence of generation | occurrence | production of a liquid crystal reservoir and a space | gap. In addition, in the light control film 10 of the sample used, all except 1st base material layer 21A, 2nd base material layer 21B, and the spacer 24 presuppose that it is the form described in the above-mentioned embodiment. In addition, the laminated glass 1 of each sample is a rectangular shape of 262 mm x 328 mm.
In this evaluation test, in the manufacturing process of the laminated glass 1 as a sample, the preliminary pressure bonding step was performed at a temperature equal to or lower than the glass transition temperature of the first base layer 21A and the second base layer 21B using a bag method. . In the autoclave process, the laminated body 30 after the preliminary pressure bonding process was placed in an environment of 120 ° C. and 8 atm.

Each sample and evaluation result are shown in Table 1 shown below. Samples 1 to 8, 11, 12, 16 to 21 and 24 to 31 shown in Table 1 correspond to the examples of the embodiment of the present invention, and samples 9, 10, 13 to 15, 22, 23, 32 and 33 are compared. It corresponds to an example.
In the laminated glass of each sample, the Young's modulus of the polyethylene terephthalate film used for the first base material layer 21A and the second base material layer 21B is 4.3 GPa, the Young's modulus of the polycarbonate film is 2.3 GPa, and the cycloolefin polymer is used. Young's modulus is 2.5 GPa.

The spacers of samples 1, 2 and 3 use a first columnar spacer. The spacers of the samples 17 to 23 mix the bead spacer and the second columnar spacer.
In Table 1, the diameter of the spacer of sample 17 to sample 23, for example, what is described as 9/70 in sample 17 is that the diameter of the bead spacer is 9 μm and the diameter of the second columnar spacer is 70 μm It is shown that. In addition, although the diameter of a 2nd columnar spacer changes a little with positions as mentioned above, it was set as the average value measured in multiple by each in the position of the largest outer diameter.

In Table 1, the density of the spacers is the number of spacers 24 disposed per 1 mm ² . Further, the pitch is an average pitch between the spacers 24 calculated from the number of the spacers 24 arranged per 1 mm ² (average value of the distance between the centers of the spacers 24 when the laminated glass 1 is viewed in plan) . In addition, aggregation means "presence" when there is at least one state in which three or more particles are solidified in the bead-like spacer, and "no" when no such state exists.
When the density and the average pitch are calculated, in the sample in which the bead spacer and the second columnar spacer are mixed, the calculation is performed similarly without distinction between the bead spacer and the second columnar spacer.

In Table 1, evaluation of the liquid crystal reservoir and evaluation of the air gap are regarded as "excellent" when there is no defect (liquid crystal reservoir or air gap) at all. Those that are good are marked as "good", those that are partially defective but have no problem in use are marked as "acceptable" and those that are not suitable for use due to significant defects etc are marked as "bad".

From the results shown in Table 1 and the like, the following can be said for the first base material layer 21A, the second base material layer 21B, and the spacer 24 from the viewpoint of reducing the generation of liquid crystal reservoirs and voids.
The Young's modulus Y of the first base material layer 21A and the second base material layer 21B is preferably larger, and the thickness is also preferably thicker. When the thickness is t (μm) and the Young's modulus is Y (GPa), It is preferable that the value of txY which is these products is 215 (μm x GPa) or more.
The spacer 24 preferably has a large density, and the number of the spacers 24 arranged per 1 mm ² is preferably 60 or more. However, in the case of using a bead spacer, when the number is too large, aggregation occurs and a good result is not obtained. When using a bead spacer, it is desirable to set the number arranged per 1 mm ² to 220 or less. In addition, in this connection, it is preferable that the spacers 24 have a smaller average pitch between the disposed spacers 24 and be 130 μm or less.
Even if the density is high, it is not preferable that the spacer 24 has a biased arrangement such as aggregation. Also, the arrangement may be regular or irregular.

The samples 1 to 8, 11 12 and 16 which are examples have a value of product of thickness t (μm) and Young's modulus Y (GPa) of 215 (μm × GPa) or more, and with regard to the spacer 24, The arrangement density is 60 or more per 1 mm ² , the average pitch between the spacers 24 is 130 μm or less, and no aggregation or the like occurs. Therefore, the said preferable range was satisfy | filled, and the evaluation regarding a liquid crystal reservoir and space | gap was also "good" or "acceptable."
On the other hand, in the samples 9 and 10 in which the spacers 24 were agglutinated, and in the samples 13 whose density is smaller than the preferable range and the average pitch between the spacers 24 is larger than the preferable range, liquid crystal stagnation and voids occurred. Further, in Samples 14 and 15 in which the value of the product of the thickness t (μm) of the first base material layer 21A and the second base material layer 21B and the Young's modulus Y (GPa) is less than 215 (μm × GPa), Puddles and voids were created.

Furthermore, in the samples 17 to 21, the bead spacer and the second columnar spacer were mixed, and the evaluation results of these were “excellent”. However, even when the bead spacer and the second columnar spacer are mixed, as in Samples 22 and 23, the density of the spacer is lower than 60 pieces / mm ² or the value of t × Y is 215 If it is too low, the evaluation result is "bad".

From the above, the value of the product of the thickness t (μm) of the first base material layer 21A and the second base material layer 21B and the Young's modulus Y (GPa) from the viewpoint of reducing liquid crystal storage and voids in the laminated glass 1 Is preferably 215 (μm × GPa) or more, and 60 or more spacers 24 are preferably disposed per 1 mm ² . However, in the case of using a bead spacer, the number to be arranged per 1 mm ^2, it is desirable that the 220 or less.
Furthermore, the average pitch between the spacers 24 is preferably 130 μm or less.
Furthermore, the spacers 24 may be arranged regularly or irregularly, but if arranged irregularly, it is preferable that there is no deviation in arrangement such as aggregation.
Furthermore, it is desirable to mix the bead spacer and the second columnar spacer.

(Modified form)
Various modifications and changes are possible without being limited to the embodiments described above, which are also within the scope of the embodiments of the present disclosure.
(1) In the embodiment, as the method of manufacturing the laminated glass 1, after performing the preliminary pressure bonding step in the bonding step, the example in which the autoclave step is performed is described. However, the present invention is not limited thereto. For example, the autoclave process may be omitted if the laminate 30 can be sufficiently bonded in the process.

(2) In the embodiment, the laminated glass whose main purpose is the so-called dimming function, which controls the light amount of incident light to the inside of a building, a vehicle, etc., is described as an example. Embodiments of the present disclosure may be applied to laminated glass having a liquid crystal film that is not.

In addition, although this embodiment and a modification can also be combined and used suitably, detailed description is abbreviate | omitted. Further, the embodiments of the present disclosure are not limited by the embodiments described above.

1 Laminated glass 10 Light control film (Liquid crystal film)
12 first laminated body 13 second laminated body 14 liquid crystal layer 21A first base material layer 21B second base material layer 22A first transparent electrode layer 22B second transparent electrode layer 23A first alignment layer 23B second alignment layer 24 spacer 25 Sealing Material 30 Laminated Body 31A First Intermediate Film 31B Second Intermediate Film 33A First Glass Plate 33B Second Glass Plate

Claims (6)

A laminated glass comprising a first glass plate, a second glass plate, and a liquid crystal film,
The liquid crystal film includes, in order in the thickness direction, a first base layer, a first transparent electrode layer, a liquid crystal layer, a second transparent electrode layer, and a second base layer.
The liquid crystal layer comprises a plurality of spacers in the layer to maintain its thickness,
The spacer includes at least a columnar spacer
The first base material layer and the second base material layer satisfy t × Y (215 (μm × GPa) when the thickness is t (μm) and the Young's modulus is Y (GPa), and ,
The said spacer is a laminated glass whose number arrange | positioned per 1 mm ² is 60 or more. In the laminated glass according to claim 1,
The spacer includes both the columnar spacer and the bead spacer,
The columnar spacer is
With the side,
With a flat top surface,
Have
Laminated glass in which the corner between the top surface and the side surface has no curvature. A laminated glass comprising a first glass plate, a second glass plate, and a liquid crystal film,
The liquid crystal film includes, in order in the thickness direction, a first base layer, a first transparent electrode layer, a liquid crystal layer, a second transparent electrode layer, and a second base layer.
The liquid crystal layer comprises a plurality of bead spacers in the layer to maintain its thickness,
The first base material layer and the second base material layer satisfy t × Y (215 (μm × GPa) when the thickness is t (μm) and the Young's modulus is Y (GPa), and ,
The said bead spacer is a laminated glass whose number arrange | positioned per 1 mm ² is 60 or more and 220 or less. In the laminated glass according to claim 1,
An average pitch between the spacers is 130 μm or less, and the laminated glass does not have a portion locally gathered such that the spacers contact each other. In the laminated glass according to any one of claims 1 to 3,
The material of the first substrate layer and the second substrate layer is any one of polyethylene terephthalate, polycarbonate and cycloolefin polymer. A liquid crystal film comprising a first base material layer, a first transparent electrode layer, a liquid crystal layer, a second transparent electrode layer, and a second base material layer in order in the thickness direction,
The liquid crystal layer comprises a plurality of spacers in the layer to maintain its thickness,
The first base material layer and the second base material layer satisfy t × Y (215 (μm × GPa) when the thickness is t (μm) and the Young's modulus is Y (GPa), and ,
The said spacer is a liquid crystal film whose number arrange | positioned per 1 mm ² is 60 or more.

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