ES2952765T3 - Liquid crystal light regulating organ and liquid crystal light regulating element - Google Patents

Abstract

A liquid crystal light adjusting member provided, in the following order, with a transparent substrate, a transparent conductive layer and a liquid crystal light adjusting layer, the transparent conductive layer being provided, in the following order, with a first layer of inorganic oxide, a layer of metal and a second layer of inorganic oxide. (Automatic translation with Google Translate, without legal value)

Description

DESCRIPTION

Liquid crystal light regulating organ and liquid crystal light regulating element

TECHNICAL FIELD

The present invention relates to a liquid crystal light regulation member and a liquid crystal light regulation element that includes the liquid crystal light regulation member.

PREVIOUS TECHNIQUE

Recently, in view of the reduction of cooling and heating load, and design property, the demand for a liquid crystal light dimming element represented by smart windows or the like has increased. The liquid crystal dimming element is used for various uses, such as window glass for buildings and vehicles, partitions, and interior decoration.

As a liquid crystal dimming element, for example, a liquid crystal dimming element has been proposed that sequentially includes a substrate, an electrically conductive film, and a liquid crystal and resin composite (referred to, for example, to the following Patent Document 1).

Appointment list:

Patent document

Patent Document 1: Japanese Unexamined Patent Publication No. 2009-133921

SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION

On the other hand, in the liquid crystal light regulation element of Patent Document 1, an oxide composed of indium and tin (Indium Tin composite Oxide, ITO) is used as an electrically conductive film. Indium tin oxide (ITO) has low near-infrared reflectance properties, so it has poor heat shielding properties. There is, therefore, the disadvantage that, when the liquid crystal light regulation element of Patent Document 1 is used in an environment influenced by sunlight (outdoors or the like), the crystal resin compound The liquid of the liquid crystal light regulating element of Patent Document 1 is deteriorated by the heat of sunlight.

To eliminate this drawback, it has been considered to attach, to the surface of a substrate, an infrared reflective layer to shield a heat ray such as sunlight. However, in this case, there is a drawback that the thickness of the liquid crystal light regulation element increases corresponding to the thickness of the infrared ray reflective layer, and also increases the production costs.

Document KR 2015 0105249 A describes a liquid crystal light regulation member ("light modulation device") that sequentially comprises a transparent substrate ("base layer" which may be a "glass film"), an electrically light transmission conductive layer ("multilayer"), and a liquid crystal light regulation layer ("light modulation layer"), wherein the electrically conductive light transmission layer sequentially includes a first oxide layer inorganic ("first oxide layer"), a metal layer ("metallic layer"), and a second inorganic oxide layer ("second oxide layer"), and wherein the first inorganic oxide layer includes compound oxide of Indian. According to document KR 2015 0105249 A, the first oxide layer and the second oxide layer, in one example, may have the metal oxide including the metal including antimony (Sb), barium (Ba), gallium (Ga), germanium (Ge), hafnium (H), indium (In), lanthanum (La), magnesium (Mg), selenium (Se), silicon (Si), tantalum (Ta), titanium (Ti), vanadium (V), yttrium (Y), zinc (Zn), and at least one type selected from the group consisting of zirconium (Zr). KR 2015 0105249 A also describes controlling the degree of crystallization of the inorganic oxide layers by controlling the deposition conditions for each layer, so that the refractive indices of the layers can be different even with the same thickness and material.

JP 2004 050643 A refers to an infrared reflective composite electrode for an LC element. This has three layers, with a transparent metal oxide-based conductive layer arranged on both sides of a metal-based conductive layer. According to JP 2004050643 A, as a metal oxide-based transparent conductive layer, an amorphous indium oxide containing at least one selected from tungsten, silicon and germanium (Examples 1-36; Tables 1-6) is preferred over indium tin oxide. (Comparative Examples 1-16; Tables 7, 8) in terms of electrical resistance and corrosivity.

EP 2985145 A1 also refers to an infrared reflective composite sheet for a window, consisting of three layers, with a transparent metal oxide-based conductive layer on both. sides of a metal-based conductive layer. Document EP 2 985 145 A1 clarifies that ITO as a conductive layer based on metal oxide (Comparative Example 7) is at a disadvantage compared to other metal oxides such as an oxide composed of indium and zinc (Indium-Zinc composite Oxide, IZO ) (Invention Example 1) or a zinc-tin composite oxide (Zinc-Tin composite Oxide, ZTO) (Invention Example 2) in terms of visible ray transmittance and durability.

An object of the present invention is to provide a liquid crystal light regulating member that has excellent near-infrared reflectance properties without attaching an infrared reflective layer to the surface of a transparent substrate, an electrically conductive film of light transmission used for the liquid crystal light regulation member, and a liquid crystal light regulation member including the liquid crystal light regulation member.

MEANS TO SOLVE THE PROBLEM

The present invention presents a liquid crystal light regulation member according to the attached independent claim 1.

In the liquid crystal light regulating member, the electrically conductive light transmission layer includes the metal layer having high reflectance in a near-infrared ray region. Thus, the electrically conductive light transmission layer has, for example, a higher average reflectance of the near infrared ray compared to the case of being made only of an electrically conductive oxide; it is capable of efficiently shielding a heat ray such as sunlight from the liquid crystal light regulating layer; and can be used in an environment influenced by sunlight (outdoors or similar).

The liquid crystal light regulating member exhibits excellent near-infrared ray reflectance properties without attaching an infrared ray reflective layer to the surface of the transparent substrate. Therefore, the thickness of the liquid crystal light regulating member can be reduced and the production costs can also be reduced.

The present invention further presents a liquid crystal light regulation element according to the attached claim 2.

The liquid crystal light regulation element according to the attached claim 2 includes the liquid crystal light regulation member according to the attached claim 1. Therefore, the liquid crystal dimming element according to the attached claim 2 is capable of efficiently shielding a heat ray such as sunlight from the liquid crystal dimming layer and can be used in an environment influenced by sunlight (outdoors or similar).

The liquid crystal light regulation element according to the attached claim 2 includes the liquid crystal light regulation member according to the attached claim 1. Therefore, the thickness of the liquid crystal light regulation element according to the attached claim 2 can be reduced and the production costs can also be reduced.

EFFECT OF THE INVENTION

According to the liquid crystal light regulating member and the liquid crystal light regulating element including the liquid crystal light regulating member of the present invention, excellent reflectance properties of near-infrared rays can be obtained without attaching an infrared reflective layer to the surface of a transparent substrate. In this way, the thickness of the liquid crystal light regulating member can be reduced, and the production costs can also be reduced.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 shows a cross-sectional view of an embodiment of a liquid crystal light regulating member of the present invention.

Figures 2A to 2B show partially enlarged views of an electrically conductive light transmission film shown in Figure 1.

Figure 2A illustrates a schematic diagram when a second inorganic oxide layer is a perfect crystalline film and

Figure 2B illustrates a schematic diagram when the second inorganic oxide layer is a semicrystalline film.

Figure 3 shows a cross-sectional view of an embodiment of an electrically conductive light transmission film of the present invention that constitutes the liquid crystal light regulation member shown in Figure 1.

Figure 4 shows a cross-sectional view of an embodiment of a liquid crystal light regulation member of the present invention including the liquid crystal light regulation member shown in Figure 1.

Figure 5 shows a modified example of the liquid crystal light regulating member, and shows a cross-sectional view of the liquid crystal light regulating member in which a first layer of inorganic oxide is arranged directly on the upper surface of a transparent substrate.

Figure 6 shows a modified example of the liquid crystal light regulation member, and shows a cross-sectional view of the liquid crystal light regulation member in which an inorganic layer is interposed between a protective layer and the first layer of inorganic oxide.

DESCRIPTION OF IMPLEMENTATIONS

In Figure 1, the direction from top to bottom in the plane of the sheet is called the top-bottom direction (thickness direction, first direction), the upper side in the plane of the sheet is called the top side (one side in the direction of thickness, one side in the first direction), and the lower side in the plane of the sheet is called the lower side (the other side in the thickness direction, the other side in the first direction). In Figure 1, the direction from right to left in the plane of the sheet is called the right-left direction (width direction, second direction, perpendicular to the first direction), the left side in the plane of the sheet is called left (one side in the second direction), and the right side in the plane of the sheet is called the right side (the other side in the second direction). In Figure 1, the direction of paper thickness is called the front-back direction (third direction perpendicular to the first and second directions), the near side in the plane of the sheet is called the front side (one side in the third direction ), and the far side in the plane of the sheet is called the rear side (the other side in the third direction). Specifically, the directions are according to the direction arrows in each figure.

1. Liquid crystal light regulating organ

A liquid crystal light regulating member is in the form of a film (including a sheet form) having a predetermined thickness, extending in a predetermined direction perpendicular to the thickness direction (the front-back direction and the right-left direction). , i.e. one direction of the plane), and has a flat top surface and a flat bottom surface (two main surfaces). The liquid crystal light regulation member is, for example, a component of a light regulation panel or the like arranged in a light regulation device, that is, not the light regulation device. That is to say, the liquid crystal light regulation member is a component for manufacturing a light regulation device or the like, it does not include a light source such as LED and an external power supply, and it is a device available in the industry whose component can be distributed alone.

Specifically, as shown in Figure 1, a liquid crystal light regulating member 1 is a laminated film that sequentially includes a transparent substrate 2, a protective layer 3, an electrically conductive light transmission layer 4 and a layer 5 liquid crystal light dimming in the thickness direction. That is, the liquid crystal light regulation member 1 includes the transparent substrate 2, the protective layer 3 which is arranged on the upper side of the transparent substrate 2, the electrically conductive light transmission layer 4 which is arranged on the side top of the protective substrate 3, and the liquid crystal light regulation layer 5 which is arranged on the upper side of the electrically conductive light transmission layer 4. Preferably, the liquid crystal light regulation member 1 is formed only by the transparent substrate 2, the protective layer 3, the electrically conductive light transmission layer 4, and the liquid crystal light regulation layer 5. Below, each of the layers is described in detail.

2. Transparent substrate

The transparent substrate 2 forms part of an electrode substrate of the liquid crystal light regulation member 1, the lowest layer of the liquid crystal light regulation member 1, and a support material that ensures the mechanical resistance of the control member. liquid crystal light regulation 1. The transparent substrate 2, together with the protective layer 3, supports the electrically conductive light transmission layer 4 and the liquid crystal light regulation layer 5.

The transparent substrate 2 is formed, for example, of a polymer film.

The polymer film has transparency and flexibility. Examples of polymeric film material include polyester resins such as polyethylene terephthalate (pEt), polybutylene terephthalate, and polyethylene naphthalate; (meth)acrylic resins (acrylic resin and/or methacrylic resin) such as polymethacrylate; olefin resins such as polyethylene, polypropylene and cycloolefin polymer; polycarbonate resin; polyethersulfone resin; polyarylate resin; melamine resin; polyamide resin; polyimide resin; cellulose resin; polystyrene resin; and norbornene resin. These polymeric films can be used alone or in combination of two or more. In view of the transparency, flexibility, heat resistance, and mechanical properties, an olefin resin and a polyester resin are preferably used, more preferably, a cycloolefin polymer and a PET are used.

The thickness of the transparent substrate 2 is, for example, 2 μm or more, preferably 20 μm or more and, for example, 300 μm or less, preferably 200 μm or less, more preferably 150 μm or less.

In order to preserve the amorphous properties of a first inorganic oxide layer 6, preferably the transparent substrate 2 contains a small amount of water. That is, in the transparent substrate 2, preferably, the polymer film contains the water.

3. Protective layer

The protective layer 3 forms part of the electrode substrate of the liquid crystal light regulating member 1, and a scratch protective layer to prevent scratches (i.e., to obtain excellent scratch resistance) on the upper surfaces of the electrically conductive light transmission layer 4 and the liquid crystal light regulation layer 5. The protective layer 3 is also an optical regulation layer that regulates the optical properties of the liquid crystal light regulation member 1 to suppress recognition visual of a pattern, when the electrically conductive light transmission layer 4 has the shape of a pattern, such as a wire pattern.

The protective layer 3 is in the form of a film (including sheet form), and is arranged on the entire upper surface of the transparent substrate 2 to be in contact with the upper surface of the transparent substrate 2. The protective layer 3 is formed of a composition of resin.

The resin composition contains, for example, a resin, particles, or the like. The resin composition preferably contains a resin, more preferably is formed from only a resin.

Examples of resin include curable resin and thermoplastic resin (e.g., polyolefin resin). Preferably, a curable resin is used.

Examples of curable resin include active energy beam curable resin that cures by the application of an active energy beam (namely, ultraviolet rays, electron beams or the like) and thermosetting resin that cures by heating. Preferably, a resin curable by active energy rays is used.

An example of an active energy beam curable resin includes a polymer having a functional group having a polymerizable carbon-carbon double bond in a molecule. Examples of the functional group include vinyl group and (meth)acrylol group (methacrylol group and/or acrylol group).

An example of an active energy beam curable resin includes a (meth)acrylic resin (acrylic resin and/or methacrylic resin) having a functional group on a side chain.

These resins can be used alone or in combination of two or more.

Examples of the particles include inorganic particles and organic particles. Examples of the inorganic particles include silica particles, metal oxide particles formed by zirconium oxide, titanium oxide, or the like, and carbonate particles such as calcium carbonate. Examples of the organic particles include cross-linking acrylic resin particles.

The thickness of the protective layer 3 is, for example, 0.01 μm or more, preferably 1 μm or more and, for example, 10 μm or less, preferably 5 μm or less. The thickness of the protective layer 3 is measured, for example, by observing the cross section with a transmission electron microscope (TEM).

4. Electrically conductive light transmission layer

The electrically conductive light transmission layer 4 forms part of the electrode substrate of the liquid crystal light regulation member 1, and an electrically conductive layer for generating an electric field in the liquid crystal light regulation layer 5 by applying an electric current from an external power supply (not shown). The light transmission electrically conductive layer 4 is also a transparent electrically conductive layer.

As shown in Figure 1, the electrically conductive light transmission layer 4 is in film form (including sheet form), and is arranged on the entire upper surface of the protective layer 3 to contact the upper surface. of the protective layer 3.

The electrically conductive light transmission layer 4 sequentially includes the first inorganic oxide layer 6, a metal layer 7, and a second inorganic oxide layer 8 from the side of the transparent substrate 2 in the thickness direction. That is, the electrically conductive light transmission layer 4 includes the first inorganic oxide layer 6 disposed on the protective layer 3, the metal layer 7 disposed on the first inorganic oxide layer 6, and the second layer of inorganic oxide 8 that is arranged on the metal layer 7. Preferably, the electrically conductive light transmission layer 4 is formed only by the first inorganic oxide layer 6, the metal layer 7, and the second inorganic oxide layer 8.

The surface resistance value of the electrically conductive light transmission layer 4 is, for example, 40 Q/ ^d or less, preferably 30 Q/ ^d or less, more preferably 20 Q/ ^d or less, more preferably 15 Q/ ^d or less and, for example, 0.1 Q/ ^d or more, preferably 1 Q/ ^d or more, more preferably 5 Q/ ^d or more.

The value of the surface resistance of the electrically conductive light transmission layer 4 with respect to the surface of the electrically conductive light transmission layer 4 of an electrically conductive light transmission film 9 is obtained, for example, through a measurement according to a four-point probe method of JIS K 7194 (in 1994).

The specific resistance of the electrically conductive light transmission layer 4 is, for example, 2.5 * 10-4 Qcm or less, preferably 2.0 * 10-4 Qcm or less, more preferably 1.1 * 10-4 Qcm or less and, for example, 0.01 * 10-4 Q cm or more, preferably 0.1 * 10-4 Q cm or more, more preferably 0.5 * 10-4 Q cm or more.

The specific resistance of the electrically conductive light transmission layer 4 is calculated using the thickness of the electrically conductive light transmission layer 4 (the total thickness of the first inorganic oxide layer 6, the metal layer 7 and the second layer of inorganic oxide 8) and the value of the surface resistance of the electrically conductive light transmission layer 4.

The average reflectance of the near infrared ray (wavelength of 850 to 2500 nm) of the electrically conductive light transmission layer 4 is, for example, 10% or more, preferably 20% or more, more preferably 50% or more and, for example, 95% or less, preferably 90% or less.

The thickness of the electrically conductive light transmission layer 4, that is, the total thickness of the first inorganic oxide layer 6, the metal layer 7, and the second inorganic oxide layer 8 is, for example, 20 nm or more, preferably 40 nm or more, more preferably 60 nm or more, more preferably 80 nm or more and, for example, 150 nm or less, preferably 120 nm or less, more preferably 100 nm or less.

5. First layer of inorganic oxide

In the following paragraphs under the chapter "First inorganic oxide layer" a large number of different materials are mentioned to form the first inorganic oxide layer, but only those containing an oxide composed of indium and tin are within the scope of protection. of the attached claims.

The first inorganic oxide layer 6 is a barrier layer that prevents the entry into the metal layer 7 of hydrogen derived from water contained in the transparent substrate 2 and carbon derived from an organic substance contained in the protective layer 3. Furthermore, the first inorganic oxide layer 6, together with the second inorganic oxide layer 8 which will be described later, is also an optical regulation layer to suppress the reflectance of visible rays of the metal layer 7 and improve the transmittance of visible rays of the electrically conductive light transmission layer 4. The first inorganic oxide layer 6, together with the metal layer 7 to be described later, is preferably an electrically conductive layer that imparts electrically conductive properties to the electrically conductive transmission layer of light 4, more preferably a transparent electrically conductive layer.

The first inorganic oxide layer 6 is the bottommost layer of the electrically conductive light transmission layer 4, is in film form (including sheet form), and is arranged on the entire upper surface of the protective layer 3 to be in contact with the top surface of the protective layer 3.

An example of an inorganic oxide forming the first inorganic oxide layer 6 includes a metal oxide formed from at least one type of metal selected from the group consisting of In, Sn, Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd, W, Fe, Pb, Ni, Nb, and Cr. The metal oxide may also be additionally doped with a metal atom represented by the group described above as necessary.

As the inorganic oxide, in view of reducing the surface resistance value and ensuring excellent transparency, an oxide containing an indium oxide (indium oxide containing oxide) is preferably used. The oxide containing indium oxide may contain only indium (In) as a metallic element, or may contain a (semi)metallic element other than indium (In). In the oxide containing indium oxide, a main metallic element is preferably indium (In). The oxide containing indium oxide in which the main metal element is indium has an excellent barrier function and preferably easily suppresses the corrosion of the metal layer 7 influenced by water or the like.

By containing one or more (semi)metallic elements as an impurity element, the oxide containing indium oxide can also improve electrically conductive properties, transparency, and durability. The ratio between the number of atoms contained in the impurity metal element and the number of atoms of the main metal element In in the first inorganic oxide layer 6 (number of atoms of impurity metal element/number of In atoms) is, for example, less than 0.50, preferably 0.40 or less, more preferably 0.30 or less, more preferably 0.20 or less and, for example, 0.01 or more, preferably 0.05 or more, more preferably 0.10 or more. In this way, an inorganic oxide layer can be obtained that has excellent transparency and excellent wet heat durability.

Specifically, examples of the oxide containing indium oxide include indium zinc composite oxide (IZO), indium gallium composite oxide (IGO), indium gallium zinc composite oxide (IGZO), and indium tin composite oxide (ITO), but the claimed invention is limited to the use of a compound indium tin oxide (ITO). "ITO" herein may be a compound oxide containing at least indium (In) and tin (Sn), and may also contain an additional component to these. An example of the additional component includes a metallic element other than In and Sn, and a metallic element represented by the group described above and a combination thereof may be used. The content of the additional component is not particularly limited and is, for example, 5% by weight or less.

The tin oxide (SnO ₂ ) contained in the ITO with respect to the total amount of tin oxide and indium oxide (In ₂ O ₃ ) is, for example, 0.5% by mass or more, preferably 3 % by mass or more, more preferably 6% by mass or more, even more preferably 8% by mass or more, particularly preferably 10% by mass or more and, for example, 35% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, more preferably 13% by mass or less. The indium oxide (In ₂ O ₃ ) contained is the remaining part of the tin oxide (SnO ₂ ) contained.

The ratio (Sn/In) between the number of Sn atoms and that of In atoms contained in the ITO is, for example, 0.004 or more, preferably 0.02 or more, more preferably 0.03 or more, even more preferably 0. .04 or more, particularly preferably 0.05 or more and, for example, 0.4 or less, preferably 0.3 or less, more preferably 0.2 or less, still more preferably 0.10 or less. The relationship between the number of Sn and In atoms can be obtained by X-ray photoelectron spectroscopy (ESCA: Electron Spectroscopy for Chemical Analysis). By adjusting the ratio between the number of Sn and In atoms within the range described above, a film quality having excellent environmental reliability can be easily obtained.

The first inorganic oxide layer 6 preferably does not contain glass particles. That is, the first inorganic oxide layer 6 is preferably amorphous. In this way, the wettability of the surface of the first inorganic oxide layer 6 is improved, and the metal layer 7 to be described later can be formed more thinly and uniformly on the upper surface of the first inorganic oxide layer 6. In this way, the film quality of the electrically conductive light transmission layer 4 is excellent, and the damp heat durability can be improved.

In the present invention, “does not contain glass particles” means that, when observing the first inorganic oxide layer 6 using a cross-sectional TEM image at 200,000x magnification, glass particles are not observed in the range of 500 nm. in the direction of the plane perpendicular to the thickness direction (the right-left direction or the front-back direction).

The content ratio of the inorganic oxide in the first inorganic oxide layer 6 is, for example, 95 mass% or more, preferably 98 mass% or more, more preferably 99 mass% or more and, for example , 100% by mass or less.

A thickness T1 of the first inorganic oxide layer 6 is, for example, 5 nm or more, preferably 20 nm or more, more preferably 30 nm or more and, for example, 100 nm or less, preferably 60 nm or less, more preferably 50 nm or less. When the thickness T1 of the first inorganic oxide layer 6 is within the range described above, the visible ray transmittance of the electrically conductive light transmission layer 4 can be easily adjusted to a high level. The thickness T1 of the first inorganic oxide layer 6 is measured, for example, by observing the cross section with a transmission electron microscope (TEM).

6. Metal layer

The metal layer 7, together with the first inorganic oxide layer 6 and the second inorganic oxide layer 8, is an electrically conductive layer that imparts electrically conductive properties to the light transmitting electrically conductive layer 4. The metal layer 7 is also a resistance reduction layer that reduces the surface resistance value of the electrically conductive light transmission layer 4. The metal layer 7 is also an infrared ray reflective layer to impart high reflectance of infrared rays (mean reflectance of the near infrared ray).

The metal layer 7 is in film form (including sheet form) and is arranged on the upper surface of the first inorganic oxide layer 6 to contact the upper surface of the first inorganic oxide layer 6.

The metal forming the metal layer 7 is not particularly limited as long as the metal has a small surface resistance, and examples thereof include a type of metal selected from the group consisting of Ti, Si, Nb, In, Zn, Sn, Au, Ag, Cu, Al, Co, Cr, Ni, Pb, Pd, Pt, Cu, Ge, Ru, Nd, Mg, Ca, Na, W, Zr, Ta, and Hf and an alloy containing two or more types of metals.

As the metal, silver (Ag) and a silver alloy are preferably used, more preferably, a silver alloy is used. If the metal is silver or a silver alloy, the resistance value of the electrically conductive light transmission layer 4 can be reduced and, in addition, the electrically conductive light transmission layer 4 is obtained has a particularly high average reflectance in a near-infrared ray region (wavelength 850 to 2500 nm), so it can preferably be used for liquid crystal light dimming element used outdoors.

Silver alloy contains silver as the main component and another metal as an auxiliary component. The metal element of the auxiliary component is not limited. Examples of silver alloy include Ag-Cu alloy, Ag-Pd alloy, Ag-Pd-Cu alloy, Ag-Pd-Cu-Ge alloy, Ag-Cu-Au alloy, Ag-Cu-alloy. In, Ag-Cu-Sn alloy, Ag-Ru-Cu alloy, Ag-Ru-Au alloy, Ag-Nd alloy, Ag-Mg alloy, Ag-Ca alloy, Ag-Na alloy, Ag-Ni alloy, Ag-Ti alloy, Ag-In alloy, and Ag-Sn alloy. In view of the durability to moist heat, an Ag-Cu alloy, an Ag-Cu-In alloy, an Ag-Cu-Sn alloy, an Ag-Pd alloy, and an Ag-Pd-Cu alloy. The proportion of silver content in the silver alloy is, for example, 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more and, for example, 99, 9% by mass or less. The content ratio of the other metal in the silver alloy is the remaining part of the silver content ratio described above.

In view of the improvement of the transmittance of the electrically conductive light transmission layer 4, the thickness T3 of the metal layer 7 is, for example, 1 nm or more, preferably 5 nm or more, and, for example, 30 nm or less, preferably 20 nm or less, more preferably 10 nm or less. The thickness T3 of the metal layer 7 is measured, for example, by observing the cross section with a transmission electron microscope (TEM).

7. Second layer of inorganic oxide

In the following paragraphs under the chapter "Second inorganic oxide layer" a large number of different layers are mentioned, but only those that form a semicrystalline film that has an amorphous part and a crystalline part are within the scope of protection of the claims attached.

The second inorganic oxide layer 8 is a barrier layer that prevents the entry of water (described below) or the like, contained as a solvent in the liquid crystal light regulation layer 5, to the metal layer 7, and a barrier layer that suppresses discoloration of the metal layer 7 particularly due to water over time. The second inorganic oxide layer 8 is also an optical regulation layer to suppress the reflectance of visible rays of the metal layer 7 and improve the transmittance of visible rays of the electrically conductive light transmission layer 4. The second layer of inorganic oxide 8, together with the metal layer 7, is preferably an electrically conductive layer that imparts electrical conduction properties to the light transmission electrically conductive layer 4, more preferably a transparent electrically conductive layer.

The second inorganic oxide layer 8 is the upper layer of the electrically conductive light transmission layer 4, is in film form (including sheet form), and is arranged on the entire upper surface of the metal layer 7 to be in contact with the top surface of the metal layer 7.

An example of the inorganic oxide forming the second inorganic oxide layer 8 includes an inorganic oxide illustrated in the first inorganic oxide layer 6. Preferably, an indium oxide is used, more preferably, an oxide containing indium oxide is used, more preferably, an oxide containing indium oxide having indium (In) as the main metallic element is used, more preferably, an ITO is used. The inorganic oxide forming the second inorganic oxide layer 8 may be the same or different from the inorganic oxide forming the first inorganic oxide layer 6. In view of the etching properties and durability to moist heat, the same oxide is preferably used. inorganic than that of the first inorganic oxide layer 6. If the second inorganic oxide layer 8 is formed of the oxide containing indium oxide, the ratio between the number of atoms contained in the impurity metallic element and those of the main metallic element In in the second inorganic oxide layer 8 (number of impurity metal element atoms/number of In atoms) is equal to or not less than "the number of impurity metal element atoms/the number of In atoms" in the first inorganic oxide layer 6 (for example, 0.001 or more).

If the second layer of inorganic oxide 8 is formed of ITO, the content of tin oxide (SnO ₂ ) in the ITO, and the ratio between the number of Sn atoms and that of In are the same as those of the first layer inorganic oxide 6.

If both the first inorganic oxide layer 6 and the second inorganic oxide layer 8 are formed of ITO, the tin oxide (SnO ₂ ) contained in the second inorganic oxide layer 8 is preferably equal to or not less than the oxide content of tin (SnO ₂ ) in the first layer of inorganic oxide 6 (for example, 0.1% by mass or more). In particular, the ratio (S2/S1) between the content (S2) of tin oxide (SnO ₂ ) in the second layer of inorganic oxide 8 and the content (S1) of tin oxide (SnO ₂ ) in the first layer of inorganic oxide 6 is, for example, 1.0 or more, preferably 1.2 or more and, for example, 3.0 or less, preferably 2.5 or less.

By setting the content of tin oxide (SnO ₂ ) in the ITO within the range described above, a degree of crystallization of the ITO film can be adjusted. In particular, by increasing the content of tin oxide in the ITO film, perfect crystallization of the ITO film by heating can be suppressed and a semi-crystalline film can be easily obtained.

The ratio (Sn/In) between the number of Sn atoms and those of In contained in the second inorganic oxide layer 8 is preferably equal to or not less than the ratio between the number of Sn atoms and those of In contained in the first layer of inorganic oxide 6 (specifically, 0.001 or more). By setting the tin oxide (SnO ₂ ) content and the number of Sn to In atoms in the second inorganic oxide layer 8 to be equal to or not less than those of the first inorganic oxide layer 6, a degree of crystallization of the second inorganic oxide layer 8.

The content ratio of the inorganic oxide in the second inorganic oxide layer 8 is, for example, 95% by mass or more, preferably 98% by mass or more, more preferably 99% by mass or more and, for example , 100% by mass or less.

The second inorganic oxide layer 8 contains a glass particle 10 (see Figures 2A and 2B). In this way, a film structure of the crystal particle 10 is stable, and hardly transmits water, so that the ingress of water (described below) contained as a solvent in the crystal light regulating layer can be suppressed. liquid 5 to the metal layer 7 by passing through the second inorganic oxide layer 8. Therefore, the wet heat durability of the electrically conductive light transmission layer 4 can be excellent. Specifically, but not according to the present invention, the second inorganic oxide layer 8 is a crystalline film. The crystalline film may be, for example, but not according to the present invention, as shown in Figure 2A, in a side cross-sectional view (in particular, TEM image of the cross section), a perfect crystalline film which continuously contains the crystal particle 10 in the entire direction of the plane. According to the claimed invention, however, as shown in Figure 2B, the second inorganic oxide layer 8 is a semi-crystalline film containing an amorphous part 11 (part that is not crystallized) and a crystalline part 12 (i.e. that is, part formed from the crystal particle 10). Since it contains a second glass particle 10b which will be described later and, in addition, has excellent durability to moist heat, a semi-crystalline film is preferably used.

In the present invention, "contains glass particles" means that, when the second inorganic oxide layer 8 is observed using a TEM image of the cross section at 200,000 times magnification, at least one or more glass particles 10 are observed in a range of 500 nm in the direction of the plane. In the range described above, the number of crystal particles 10 is preferably 2 or more, more preferably 3 or more, more preferably 5 or more, and preferably 50 or less, more preferably 40 or less, more preferably 30 or more less.

When the top surface of the second inorganic oxide layer 8 is observed using a planar TEM image at 100,000 times magnification, the area ratio of the crystal particle 10 is, for example, 5% or more, preferably 10%. or more, more preferably 20% or more and, for example, 100% or less, preferably 90% or less, more preferably 80% or less, still more preferably 70% or less, particularly preferably 60% or less.

When the area ratio of the crystal particle is calculated with the flat TEM image, the TEM image of the cross section of the first inorganic oxide layer 6 under the conditions described above, the absence of the crystal particle is confirmed. in the first inorganic oxide layer 6 and, subsequently, the flat TEM image is observed. Only from the planar TEM image it can be difficult to judge whether the glass particle is in the first inorganic oxide layer 6 or the second inorganic oxide layer 8. Therefore, in the present invention, after confirming the absence of the crystal particle in the first inorganic oxide layer 6 with the cross-sectional TEM image, by observing the flat TEM image, it is considered that the crystalline particle 10 in the second inorganic oxide layer 8 can be observed.

The size of the crystal particle 10 contained in the second inorganic oxide layer 8 is, for example, 3 nm or more, preferably 5 nm or more, more preferably 10 nm or more and, for example, 200 nm or less, preferably 100 nm or less, more preferably 80 nm or less, more preferably 50 nm or less. A crystal particle other than the range described above may be contained in the observed area of the second inorganic oxide layer 8, and the area ratio thereof is preferably 30% or less, more preferably 20% or less. . More preferably, all of the glass particles 10 contained in the second inorganic oxide layer 8 are formed by glass particles having a size within the range described above. When the second inorganic oxide layer 8 is observed using a TEM image of the cross section at 200,000 times magnification, the size of the crystal particle 10 is the maximum value of the length that can be obtained for each of the crystal particles 10.

The size of the largest crystal particle 10 (maximum crystal particle) of the crystal particles 10 contained in the second inorganic oxide layer 8 is, for example, 10 nm or more, preferably 20 nm or more and, for example , 200 nm or less, preferably 100 nm or less.

The shape of the crystal particle is not limited, and examples thereof include a substantially triangular shape as seen in cross section and a substantially rectangular shape as seen in cross section.

Examples of the glass particle 10 include a first glass particle 10a that passes through the second inorganic oxide layer 8 in the thickness direction and the second glass particle 10b that does not pass through the second inorganic oxide layer 8 in the thickness direction .

The first glass particle 10a is a glass particle grown such that its upper end is exposed from the upper surface of the second inorganic oxide layer 8 and its lower end is exposed from the lower surface of the second inorganic oxide layer 8. The length in the thickness direction of the first glass particle 10a is the same as the thickness of the second inorganic oxide layer 8.

The second glass particle 10b is a glass particle that grows such that at least one end of the upper end and the lower end is not exposed from the surface (the upper surface or the lower surface) of the second inorganic oxide layer 8. The second glass particle 10b is formed such that, preferably, its upper end is exposed from the upper surface of the second inorganic oxide layer 8, and its lower end is not exposed from the lower surface of the second layer inorganic oxide 8.

The average length in the thickness direction of the second glass particle 10b is less than the thickness (T2) of the second inorganic oxide layer 8 and, with respect to 100% of the thickness of the second inorganic oxide layer 8 is , for example, 98% or less, preferably 90% or less, more preferably 80% or less, and, for example, 5% or more, preferably 10% or more, more preferably 20% or more .

The second inorganic oxide layer 8 preferably contains the second glass particle 10b. In this way, a particle boundary of the glass particle 10 does not pass through in the thickness direction, so water can be prevented from passing through the second inorganic oxide layer 8 in the thickness direction along of the particle boundary.

The amount of the first crystal particle 10a is, for example, 0 or more, preferably 1 or more and, for example, 30 or less, preferably 10 or less.

The amount of the second crystal particle 10b is preferably greater than that of the first crystal particle 10a and, in particular, preferably 1 or more, more preferably 2 or more, even more preferably 3 or more, and preferably 50 or less, more preferably 40 or less, more preferably 30 or less.

The thickness T2 of the second inorganic oxide layer 8 is, for example, 5 nm or more, preferably 20 nm or more, more preferably 30 nm or more and, for example, 100 nm or less, preferably 60 nm or less, more preferably 50 nm or less. If the thickness T2 of the second inorganic oxide layer 8 is within the range described above, the visible ray transmittance of the electrically conductive light transmission layer 4 can be easily adjusted to a high level. The thickness T2 of the second inorganic oxide layer 8 is measured, for example, by observing the cross section with a transmission electron microscope (TEM).

The ratio (T2/T1) between the thickness T2 of the second inorganic oxide layer 8 and the thickness T1 of the first inorganic oxide layer 6 is, for example, 0.5 or more, preferably 0.75 or more, and for example, 1.5 or less, preferably 1.25 or less. If the ratio (T2/T1) is the lower limit described above or more and the upper limit described above or less, the deterioration of the metal layer 7 can further be suppressed under the humid heat environment.

The ratio (T2/T3) between the thickness T2 of the second inorganic oxide layer 8 and the thickness T3 of the metal layer 7 is, for example, 2.0 or more, preferably 3.0 or more and, for example , 10 or less, preferably 8.0 or less. 8. Liquid crystal dimming layer

The liquid crystal light regulation layer 5 is a light regulation layer that varies the light transmittance and color by applying an electric field to the electrically conductive light transmission layer 4.

The liquid crystal light regulation layer 5 is the uppermost layer of the liquid crystal light regulation member 1, is in film form (including sheet form), and is arranged on the entire upper surface of the electrically conductive layer of light transmission 4 to come into contact with the upper surface of the electrically conductive light transmission layer 4.

The liquid crystal light regulation layer 5 contains a liquid crystal material, and preferably contains a liquid crystal capsule.

As the liquid crystal material, a known material is used, and examples thereof include nematic liquid crystal molecule, smectic liquid crystal molecule, and cholesteric liquid crystal molecule.

These liquid crystal materials can be used alone or in combination of two or more.

The liquid crystal capsule is a tiny particle and includes the liquid crystal material described above. The liquid crystal material and the liquid crystal capsule are dispersed by a transparent resin and/or a dispersant. That is, the liquid crystal material and the liquid crystal capsule are preferably dispersed by a polymer emulsion.

The transparent resin is a matrix resin that disperses the liquid crystal material and the liquid crystal capsule, and a known resin material is used. The transparent resin is not particularly limited, and examples thereof include acrylic resin, epoxy resin and urethane resin. These transparent resins can be used alone or in combination of two or more.

Examples of the solvent include water; aromatic hydrocarbon compounds such as benzene, toluene, xylene, methoxybenzene and 1,2-dimethoxybenzene; halogenated hydrocarbon compounds such as chloroform, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloroethane, trichloroethylene, tetrachloroethylene, chlorobenzene and orthodichlorobenzene; phenolic compounds such as phenol and parachlorophenol; ether compounds such as diethyl ether, dibutyl ether, tetrahydrofuran, anisole, dioxane, and tetrahydrofuran; ketone compounds such as acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-pentanone, 3-pentanone, 2-hexanone, 3 hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2,6-dimethyl-4-heptanone, 2-pyrrolidone and N-methyl-2-pyrrolidone; and alcoholic compounds such as n-butanol, 2-butanol, cyclohexanol, isopropyl alcohol, t-butyl alcohol, glycerin, ethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol, dipropylene glycol and 2-methyl-2,4 -pentanediol. Of these, in view of emulsion formation, preferably an alcoholic compound and water are used, more preferably water is used. These solvents can be used alone or in combination of two or more.

These transparent resins and solvents can be used alone or in combination of two or more, and preferably water is used as a solvent.

In the liquid crystal light regulating layer 5, preferably, the refractive index of the transparent resin and/or the solvent is adjusted to be the same as that of a liquid crystal molecule in the direction of the main axis.

When the electric field is not applied, the liquid crystal molecule included in the liquid crystal capsule is aligned along the inner wall of the liquid crystal capsule. Therefore, the orientation direction of the liquid crystal molecule is not uniform and an inconsistency of refractive index occurs at the interface between the liquid crystal capsule and the transparent resin and/or the solvent, so that the light is reflected. disperses. In this way, the liquid crystal light regulation layer 5 becomes opaque.

When the electric field is applied, the liquid crystal molecule included in the liquid crystal capsule is aligned parallel to the direction of the electric field. The refractive index of the transparent resin and/or the solvent is adjusted to be the same as that of the liquid crystal molecule in the direction of the main axis, so that the inconsistency of the refractive index does not occur at the interface between the liquid crystal capsule and transparent resin. In this way, the liquid crystal light regulation layer 5 becomes transparent.

The thickness of the liquid crystal light regulation layer 5 is, for example, 0.1 μm or more and 5000 μm or less. 9. Electrically conductive light transmission film

Of the elements constituting the liquid crystal light regulation member 1, the transparent substrate 2, the protective layer 3 and the electrically conductive light transmission layer 4 constitute an embodiment of the electrically conductive light transmission film 9 of the present invention.

That is, as shown in Figure 3, the electrically conductive light transmission film 9 is a laminated film that sequentially includes the transparent substrate 2, the protective layer 3, and the electrically conductive light transmission layer 4 on the thickness direction. That is, the electrically conductive light transmission film 9 includes the transparent substrate 2, the protective layer 3 which is arranged on the upper side of the transparent substrate 2, and the electrically conductive light transmission layer 4 which is arranged on the upper side. top of the protective layer 3. Preferably, the electrically conductive light transmission film 9 is formed only by the transparent substrate 2, the protective layer 3 and the electrically conductive light transmission layer 4.

The electrically conductive light transmission film 9 takes the form of a film (including sheet form) having a predetermined thickness, extending in the direction of the plane, and having a flat top surface and a flat bottom surface. The electrically conductive light transmission film 9 is a component for manufacturing the liquid crystal light regulation member 1, and specifically, an electrode substrate used for the liquid crystal light regulation member 1. The electrically conductive light transmission film light transmission 9 does not include the liquid crystal light regulation layer 5, and is an industry-available device whose component can be distributed alone. The electrically conductive light transmission film 9 is a film through which the visible ray is transmitted, and includes a transparent electrically conductive film.

The electrically conductive light transmission film 9 may be the electrically conductive light transmission film 9 that is thermally contracted, or it may be the electrically conductive light transmission film 9 that is not heated, that is, it is not contracted. In view of the excellent bending resistance, preferably, the light transmission electrically conductive film 9 and which is thermally shrunk is used.

The total thickness of the electrically conductive light transmission film 9 is, for example, 2 μm or more, preferably 20 μm or more and, for example, 300 μm or less, preferably 200 μm or less, more preferably 150 μm or less .

10. Production method of liquid crystal light regulating organ

Next, a method for producing the liquid crystal light regulating member 1 is described.

To produce the liquid crystal light regulating member 1, first, the electrically conductive light transmission film 9 is manufactured, and then the liquid crystal light regulating layer 5 is placed on the electrically conductive film of light transmission 9.

The electrically conductive light transmission film 9 is obtained, for example, by arranging the protective layer 3 and the electrically conductive light transmission layer 4 on the transparent substrate 2 in the order described above.

In this method, as indicated in Figure 1, firstly, the transparent substrate 2 is prepared.

The water content of the transparent substrate 2 (polymeric film) is not limited and is, for example, 10 |jg/cm2 or more, preferably 15 jg/cm2 or more and, for example, 200 jg/cm2 or less, preferably 170 jg/cm2 or less. If the water content is the lower limit described above or more, a hydrogen atom or the like is imparted to the first inorganic oxide layer 6, the crystallization of the first inorganic oxide layer 6 is suppressed by heating to be described further. forward, and the amorphous properties of the first inorganic oxide layer 6 can be easily preserved. If the water content is the upper limit described above or less, the second inorganic oxide layer 8 containing the crystal particle 10 can certainly be obtained by a heating step or the like. The water content of the transparent substrate 2 is measured according to JIS K 7251 (in 2002) B-moisture vaporization method.

The water content in the transparent substrate 2 (polymer film) relative to the content of the transparent substrate 2 is, for example, 0.05% by mass or more, preferably 0.1% by mass or more and, for example, 1.5% by mass or less, preferably 1.0% by mass or less, more preferably 0.5% by mass or less.

Some or all of the water described above is released to the outside through a degassing treatment which will be described later.

Next, for example, a resin composition is placed on the upper surface of the transparent substrate 2 by a wet process.

Specifically, the resin composition is first applied to the upper surface of the transparent substrate 2. Subsequently, if the resin composition contains a resin curable by active energy rays, an active energy beam is applied.

In this way, the protective layer 3 in the form of a film is formed on the entire upper surface of the transparent substrate 2. That is, a protective layer including a transparent substrate including the transparent substrate 2 and the protective layer 3 is obtained.

Subsequently, the transparent substrate including the protective layer is subjected to degassing treatment as necessary.

To subject the protective layer including the transparent substrate to the degassing treatment, the protective layer including the transparent substrate is allowed to stand under a reduced pressure atmosphere of, for example, 1*10-1 Pa or less, preferably 1*10 -2 Pa or less and, for example, 1 * 10-6 Pa or more. The degassing treatment is carried out, for example, using an extractor (to be more specific, a turbomolecular pump or the like) arranged in a dry process member.

Through the degassing treatment, a part of the water contained in the transparent substrate 2 and a part of an organic substance contained in the protective layer 3 are emitted to the outside.

The electrically conductive light transmission layer 4 is then arranged, for example, on the upper surface of the protective layer 3 by a dry process.

Specifically, the first inorganic oxide layer 6, the metal layer 7, and the second inorganic oxide layer 8 are each removed sequentially by the dry process.

Examples of the dry process include vacuum deposition method, sputtering method, and ion coating method. Preferably, a sputtering method is used. Specifically, a magnetron sputtering method is used.

An example of a gas used in the sputtering method includes an inert gas such as Ar. Additionally, a reactive gas such as oxygen may be used in combination as necessary. If the reagent gas is used in combination, the flow rate of the reagent gas is not particularly limited, and the ratio between the flow rate of the reagent gas and that of the inert gas is, for example, 0.1/100 or more, preferably 1/100 or more and, for example, 5/100 or less.

Specifically, in the formation of the first inorganic oxide layer 6, the inert gas and the reactive gas are preferably used as the gas in combination. In forming the metal layer 7, preferably only the inert gas is used as the gas. In the formation of the second inorganic oxide layer 8, the inert gas and the reactive gas are preferably used as the gas in combination.

If the first inorganic oxide layer 6 and the second inorganic oxide layer 8 contain indium oxide, the resistance behavior of each of the layers varies depending on the amount of introduction of the reactive gas and, in a graph of the amount introduction of the reactive gas (x-axis) and the surface resistance value (y-axis), a downward convex parabola is represented. At this time, the amount of reactive gas contained in the first inorganic oxide layer 6 and the second inorganic oxide layer 8 is preferably an introduction amount in which the resistance value is approximately the minimum value (i.e., the inflection point of the parabola) and, specifically, it is preferably an introduction quantity of ± 20% of the introduction quantity at which the resistance value is the minimum value.

If the sputtering method is used, the inorganic oxide described above or the metal described above that constitutes each of the layers is used as the target material.

The power source used in the sputtering method is not limited and, for example, a direct current power source, a medium frequency/alternating current power source, and a radio frequency power source are used, alone or in combination of two or more. Preferably, a direct current power supply is used.

If the first inorganic oxide layer 6 is formed by the sputtering method, preferably, the transparent substrate 2 (and the protective layer 3) is cooled. Specifically, the bottom surface of the transparent substrate 2 is contacted with a cooling device (for example, a cooling roller) or the like, and the transparent substrate 2 (and the protective layer 3) are cooled. In this way, when the first inorganic oxide layer 6 is formed, a large amount of water contained in the transparent substrate 2 and a large amount of organic substance contained in the protective layer 3 are released by vapor deposition heat or the like generated. by sputtering, and excess water contained in the first inorganic oxide layer 6 can be prevented. The cooling temperature is, for example, -30 °C or more, preferably -10 °C or more, and, for example, 60°C or less, preferably 40°C or less, more preferably 30°C or less, more preferably 20°C or less, particularly preferably below 0°C. Preferably, the first inorganic oxide layer 6, the metal layer 7, and the second inorganic oxide layer 8 are formed by sputtering, while cooling within the temperature range described above. In this way, the aggregation of the metal layer 7, and the excessive oxidation of the second inorganic oxide layer 8, can be suppressed. In this way, the electrically conductive light transmission layer 4 in which the first layer is sequentially formed of inorganic oxide 6, the metal layer 7, and the second inorganic oxide layer 8 in the thickness direction, is formed on the protective layer 3, so that a light-transmitting electrically conductive laminate is obtained. At this time, both the first inorganic oxide layer 6 and the second inorganic oxide layer 8 immediately after the formation of the film (for example, within 24 hours after the formation of the laminate of the electrically conductive transmission layer of light) do not contain the crystal particle 10.

Next, if the second inorganic oxide layer 8 contains the crystal particle 10, a crystallization step is carried out to generate the crystal particle 10 in the second inorganic oxide layer 8. The crystallization step is not always limited. that the glass particle 10 can be formed and, for example, a heating step is used, that is, the light transmitting electrically conductive laminate is heated.

The heating step is not only heating in order to generate the glass particle 10 described above, but may also be a heating performed incidentally along with the removal of laminate waviness of the electrically conductive light transmission layer and the formation dry from a silver paste wire.

The heating temperature can be set appropriately and is, for example, 30°C or more, preferably 40°C or more, more preferably 80°C or more and, for example, 180°C or less, preferably 150°C or less .

The heating time is not limited and is adjusted according to the heating temperature. The heating time is, for example, 1 minute or more, preferably 10 minutes or more, more preferably 30 minutes or more and, for example, 4000 hours or less, preferably 100 hours or less.

The heating can be carried out under an air atmosphere, an inert atmosphere or a vacuum atmosphere and, in view of easy crystallization, preferably, the heating is carried out under an air atmosphere.

Through the heating step, the second inorganic oxide layer 8 is crystallized and the crystal particle 10 is present inside the second inorganic oxide layer 8. In particular, if the second inorganic oxide layer 8 contains the particle of glass 10, the metal layer 7 that is interposed between the transparent substrate 2 and the second layer of inorganic oxide 8 acts as a barrier for water from the transparent substrate 2 and the organic substance from the protective layer 3 that interrupt crystallization, and They easily incorporate the oxygen that is necessary for crystallization when they are exposed at the time of the heating step, so that the crystallization of the second inorganic oxide layer 8 can be easily carried out. The first inorganic oxide layer 6 is greatly influenced by water and organic substance, and cannot easily incorporate oxygen, so the growth of the crystalline particle 10 is interrupted and the amorphous properties are preserved.

In this way, as shown in Figure 1, the electrically conductive light transmission film 9 is obtained that sequentially includes the transparent substrate 2, the protective layer 3, and the electrically conductive light transmission layer 4 (the first inorganic oxide layer 6, the metal layer 7, and the second inorganic oxide layer 8) in the thickness direction, and in which only the second inorganic oxide layer 8 contains the glass particle 10.

Next, the liquid crystal light regulation layer 5 is arranged on the electrically conductive light transmission film 9.

A known material can be used for the liquid crystal light regulation layer 5.

The liquid crystal light regulating layer 5 is arranged on the upper surface of the electrically conductive light transmission film 9 so that the liquid crystal light regulating layer 5 is in contact with the second inorganic oxide layer 8 .

In this way, as shown in Figure 1, the liquid crystal light regulation member 1 is obtained that sequentially includes the transparent substrate 2, the protective layer 3, the electrically conductive light transmission layer 4, and the liquid crystal light regulation layer 5 in the thickness direction.

The production method described above can also be carried out by a roll-to-roll method. Additionally, some or all of the method may be performed using a batch method.

The electrically conductive light transmission layer 4 may also be in the form of a pattern, such as a wire pattern by etching, as necessary.

11. Function and effect

According to the liquid crystal light regulating member 1, the electrically conductive light transmission layer 4 includes the metal layer 7 having a high reflectance in the near infrared ray region. Thus, the electrically conductive light transmission layer 4 has, for example, a higher average reflectance of the near infrared ray compared to the case in which it is formed only of an electrically conductive oxide; is capable of efficiently shielding a heat ray such as sunlight from the liquid crystal light regulating layer 5; and can be used in an environment influenced by sunlight (outdoors or similar).

According to the liquid crystal light regulating member 1, the electrically conductive light transmission layer 4 has electrically conductive properties, so that it can be used as an electrode. Furthermore, the liquid crystal light regulating member 1 has excellent near-infrared ray reflectance properties without attaching an infrared ray reflective layer to the surface of the transparent substrate 2. Therefore, the thickness of the light regulating member liquid crystal light 1 can be reduced, and production costs can also be reduced.

The liquid crystal light regulating member 1 has excellent near-infrared ray reflectance properties without attaching an infrared ray reflective layer to the surface of the transparent substrate 2. Therefore, the thickness of the liquid crystal light regulating member 1 liquid crystal 1 can be reduced, and production costs can also be reduced.

According to the liquid crystal light regulating member 1, the electrically conductive light transmission layer 4 includes the second inorganic oxide layer 8 containing the crystal particle 10. Therefore, if the light regulating layer liquid crystal 5 contains water as a solvent, the entry of water into the metal layer 7 can be suppressed by passing through the second inorganic oxide layer 8 in the thickness direction.

According to the liquid crystal light regulating member 1, the second inorganic oxide layer 7 is the semi-crystalline film having the amorphous part 11 and the crystalline part 12. Thus, the durability to humid heat is furthermore excellent.

According to the electrically conductive light transmission film 9, the electrically conductive light transmission layer 4 includes the metal layer 7 having high reflectance in the near infrared ray region. Therefore, when the electrically conductive light transmission film 9 is used for the liquid crystal light regulating member 1 described above, the electrically conductive light transmission layer 4 has, for example, an average reflectance of the infrared ray higher proximity compared to the case in which it is formed only by an electrically conductive oxide; is capable of efficiently shielding a heat ray such as sunlight from the liquid crystal light regulating layer 5; and can be used in an environment influenced by sunlight (outdoors or similar).

In the electrically conductive light transmission film 9, the electrically conductive light transmission layer 4 has electrically conductive properties, so that it can be used as an electrode. Furthermore, the light transmission electrically conductive film 9 exhibits excellent near-infrared ray reflectance properties without attaching an infrared ray reflective layer to the surface of the transparent substrate 2. Therefore, the thickness of the electrically conductive light transmission film 9 9 light transmission can be reduced, and production costs can also be reduced.

12. Liquid crystal dimming element

A liquid crystal light regulating element 13 has a film shape (including sheet shape) having a predetermined thickness, extending in a predetermined direction perpendicular to the thickness direction (the front-back direction and the right-left direction , that is, the direction of the plane), and has a flat top surface and a flat bottom surface (two main surfaces). The liquid crystal dimming element 13 is, for example, a component of a dimming panel or the like arranged in a dimming device, that is, not the dimming device. That is, the liquid crystal light dimming element 13 is a component for manufacturing the light dimming device or the like, does not include a light source such as an LED and an external power supply, and is a device available in the industry whose component can be distributed alone.

Specifically, as shown in Figure 4, the liquid crystal light regulation member 13 is a laminated film including the liquid crystal light regulation member 1 and an electrode substrate (upper side electrode substrate). 14. That is, the liquid crystal light regulating element 13 includes the liquid crystal light regulating member 1 and the electrode substrate 14 which is arranged on the upper side of the liquid crystal light regulating element 1. Preferably, the liquid crystal light regulation member 13 is formed only by the liquid crystal light regulation member 1 and the electrode substrate 14. Each layer is described in detail below.

The electrode substrate 14 is the electrically conductive light transmission film 9 described above, and sequentially includes the electrically conductive light transmission layer 4, the protective layer 3, and the transparent substrate 2 in the thickness direction. The electrode substrate 14 is arranged on the upper side of the liquid crystal light regulating member 1. Specifically, the electrode substrate 14 is arranged on the entire upper surface (opposite surface of the transparent substrate 2 of the electrically conductive transmission film light 9 on the lower side) of the liquid crystal light regulation layer 5 so that the upper surface of the liquid crystal light regulation layer 5 is in contact with the lower surface of the electrically conductive light transmission layer light 4.

That is, in the liquid crystal light regulation element 13, the two electrically conductive light transmission films 9 are arranged opposite each other so that each of the electrically conductive light transmission layers 4 is in contact with the surface (the bottom surface or the top surface) of the liquid crystal light regulation layer 5.

The liquid crystal light regulation member 13 includes the liquid crystal light regulation member 1 described above. Therefore, the liquid crystal light regulation element 13 is capable of effectively shielding a heat ray, such as sunlight, from the liquid crystal light regulation layer 5, and can be used in an environment influenced by sunlight (outdoors or similar).

The liquid crystal light regulation member 13 includes the liquid crystal light regulation member 1 described above. Therefore, the thickness of the liquid crystal dimming element 13 can be reduced and the production costs can also be reduced.

13. Modified example

In the modified example, the same reference numbers are given for the organs and scales corresponding to each of the embodiment described above, and their detailed description is omitted.

In one embodiment of the liquid crystal light regulation member 1, as shown in Figure 1, the protective layer 3 is interposed between the transparent substrate 2 and the first inorganic oxide layer 6. Alternatively, for example, such as shown in Figure 5, the first inorganic oxide layer 6 can also be arranged directly on the upper surface of the transparent substrate 2. That is, the liquid crystal light regulation member 1 sequentially includes the transparent substrate 2, the layer electrically light transmission conductive layer 4, and the liquid crystal light regulating layer 5 in the thickness direction. On the other hand, the liquid crystal light regulation member 1 does not include the protective layer 3.

In one embodiment of the liquid crystal light regulating member 1, as shown in Figure 1, the first inorganic oxide layer 6 is arranged directly on the upper surface of the protective layer 3. Alternatively, for example, as shown shown in Figure 6, a layer of inorganic substance 15 can also be interposed between the protective layer 3 and the first layer of inorganic oxide 6.

The inorganic substance layer 15, together with the protective layer 3, is also an optical regulation layer that adjusts the optical properties of the liquid crystal light regulation member 1 to suppress the visual recognition of the wire pattern in the electrically conductive layer. of light transmission 4. The inorganic substance layer 15 is in the form of a film (including sheet form), and is arranged on the entire upper surface of the protective layer 3 to be in contact with the upper surface of the protective layer 3. The inorganic substance layer 15 has predetermined optical properties and is prepared, for example, from an inorganic substance such as oxide and fluoride. The thickness of the inorganic substance layer 15 is, for example, 1 nm or more, preferably 5 nm or more, more preferably 10 nm or more and, for example, 200 nm or less, preferably 80 nm or less, more preferably 40 nm or less, more preferably 25 nm or less.

In one embodiment of the liquid crystal light regulating member 1, as shown in Figure 1, the electrically conductive light transmission layer 4 includes only the first inorganic oxide layer 6, the metal layer 7, and the second inorganic oxide layer 8. Alternatively, for example, although not shown, in addition, a second metal layer and a third inorganic layer may also be arranged sequentially on the upper surface of the second inorganic oxide layer 8. Additionally, A third metal layer and a fourth inorganic oxide layer are also arranged on the upper surface of the third inorganic oxide layer. Although not shown, on the top surface and/or on the bottom surface of the transparent substrate 2, for example, a functional layer such as an antifouling layer, an adhesive layer, a water-repellent layer, a layer that prevents reflections, and a layer that prevents oligomers.

The functional layer preferably contains the resin composition described above, more preferably it is formed by a resin composition.

In addition, an insulating layer (not shown) (preferably, the thickness thereof is 50 nm or less) may be arranged in the entire space or a part thereof between the electrically conductive light transmission layer 4 and the liquid crystal light regulation 5. The insulating layer is formed, for example, of a resin composition, an inorganic oxide, or the like.

In one embodiment of the liquid crystal light regulation member 1, as shown in Figure 1, the liquid crystal light regulation member 1 includes the transparent substrate 2, and the transparent substrate 2 can be attached to another colored substrate ( not shown). For example, a polarizer and a polarizing film can be arranged on the opposite side of the electrically conductive light transmission layer 4 of the transparent substrate 2. The polarizer and the polarizing film can be attached, for example, to the transparent substrate 2 through a pressure sensitive adhesive layer or an adhesive layer.

The functional layer can be selected appropriately according to a required function.

In the modified example described above, the liquid crystal light regulating member 1 is described, and the electrically conductive light transmission film 9 and the liquid crystal light regulating element 13 are the same.

In the liquid crystal light regulating element 13, as shown in Figure 3, the electrically conductive light transmission film 9 of the present invention is used as the upper side electrode substrate 14. Alternatively, for example, although not shown, the top side electrode substrate 14 may also be comprised of the transparent substrate 2 and a single electrically conductive layer. Examples of the single electrically conductive layer include ITO film (crystalline ITO film, amorphous ITO film), IGO film, and IGZO film.

Examples

Below, the present invention is further described based on Examples and Comparative Examples. However, only Example 1 and Production Example 1 fall within the scope of protection of the appended claims. On the other hand, Examples 2, 3 and Production Examples 2, 3, as well as the Comparative Examples, are not within the scope of protection of the attached claims. The present invention is limited, however, only by the appended claims. The specific numerical values of mixing ratio (content ratio), property value, and parameter used in the following description may be replaced by upper limit values (numerical values defined as "or less" or "lower") or lower limit values ( numerical values defined as "or more" or "higher") of the corresponding numerical values in mixing ratio (content ratio), property value, and parameter described in the "DESCRIPTION OF EMBODIMENTS" described above.

[Electrically conductive light transmission film]

Example 1

(Preparation of film substrate and formation of protective layer)

First, a transparent substrate was prepared which was formed by a long polyethylene terephthalate (PET) film and had a thickness of 50 μm.

Next, a UV-curable resin which was formed by an acrylic resin to be cured by applying UV rays was applied to the upper surface of the transparent substrate, so that a protective layer formed by a layer of curable resin was created. and that it had a thickness of 2 μm. In this way, a transparent substrate roll was obtained having a protective layer including the transparent substrate and the protective layer.

(Formation of the first inorganic oxide layer)

Next, the transparent substrate roll including the protective layer was placed in a vacuum device and then evacuated under vacuum until the atmospheric pressure at the time of no transport was 2 x 10 ^-3 Pa (treatment of degassing). At this time, in a state of no introduction of a spray gas (Ar and O ₂ ), a part of the protective layer including transparent substrate was transported, and it was confirmed that the atmospheric pressure increased to 1 x 10-2 Pa In this way, it was confirmed that a sufficient amount of gas remained on the roller of the protective layer including transparent substrate.

Then, a first inorganic oxide layer formed by an amorphous ITO and with a thickness of 40 nm was formed on the top surface of the sputter-curable resin layer, while the protective layer roller including transparent substrate was supplied. .

In particular, under a vacuum atmosphere at an atmospheric pressure of 0.2 Pa in which Ar and O ₂ were introduced (as flow ratio, Ar: O ₂ = 100: 3.8), sputtering was applied on a target formed by a sintered body of 12% by mass of tin oxide and 88% by mass of indium oxide using a direct current (DC) power supply.

When the first inorganic oxide layer was formed by sputtering, the bottom surface of the protective layer including the transparent substrate roller (specifically, the bottom surface of the transparent substrate) was contacted with a cooling roller at -5° C to cool the transparent substrate roller including the protective layer.

(Metal layer formation)

A metal layer made of an Ag alloy and with a thickness of 8 nm was formed on the upper surface of the first inorganic oxide layer by sputtering.

Specifically, in a vacuum atmosphere at an atmospheric pressure of 0.4 Pa in which Ar was introduced, sputtering was applied on an Ag alloy (manufactured by Mitsubishi Materials Corporation, part number: "No. 317") using a direct current (DC) power supply as a power supply.

(Formation of the second inorganic oxide layer)

A second inorganic oxide layer formed by an ITO and having a thickness of 38 nm was formed on the upper surface of the metal layer by sputtering.

In particular, under a vacuum atmosphere at an atmospheric pressure of 0.2 Pa in which Ar and O ₂ were introduced (as flow ratio, Ar: O ₂ = 100: 4.0), sputtering was applied to a ITO target formed by a sintered body of 12% by mass of tin oxide and 88% by mass of indium oxide using a direct current (DC) power supply.

Next, a heating step was carried out under air atmosphere conditions at 80°C for 12 hours. In this way, the second layer of inorganic oxide crystallized.

In this way, an electrically conductive light transmission film was obtained in which the protective layer, the first inorganic oxide layer, the metal layer, and the second inorganic oxide layer were sequentially formed on the transparent substrate in the direction of the thickness.

Example 2

A light transmission electrically conductive film of Example 2 was obtained in the same manner as that of Example 1, except that the flow ratio of Ar to O ₂ was changed to "Ar: O ₂ = 100: 3.1", and the second inorganic oxide layer was formed by sputtering an ITO target formed by a sintered body of 12 mass% tin oxide and 88 mass% indium oxide.

Example 3

An electrically conductive light transmission film of Example 3 was obtained in the same manner as that of Example 1, except that the heating step was not performed on the second inorganic oxide layer.

Comparative Example 1

An electrically conductive light transmission film of Comparative Example 1 was obtained in the same manner as that of Example 1, except that the flow ratio of Ar to O ₂ at the time of spraying was changed to "Ar:O ₂ = 100:1.0", the thickness of the second inorganic oxide layer was varied to that described in Table 1, an electrically conductive light transmission layer was formed without forming a first inorganic oxide layer and a metal layer, and Subsequently, a heating step was carried out under an air atmosphere at 140°C for 1 hour.

[Liquid crystal light dimming element]

(Production example 1)

The electrically conductive light transmission film of Example 1 and the electrically conductive light transmission film of Comparative Example 1 were prepared. Next, a coating liquid was prepared in which a nematic liquid crystal and a resin were mixed. Next, the coating liquid was applied to the top surface of the electrically conductive light transmission film of Example 1, and a liquid crystal light regulating layer was formed. Next, the electrically conductive light transmission film of Comparative Example 1 was laminated on the top surface of the liquid crystal light regulation layer, so that a liquid crystal light regulation element of the Production Example was produced. 1. After removing the liquid crystal light dimming layer from the end part of the obtained liquid crystal light dimming element, a pressure-sensitive electrically conductive copper foil adhesive tape (manufactured by Teraoka Seisakusho Co.) was attached ., Ltd., trade name: No. 8323) to a part in which the liquid crystal light regulation layer was removed, and an electric voltage was applied. A variation in transparency due to the presence or absence of an electric field was then visually recognized, and the liquid crystal dimming element was confirmed to function as a dimming element.

(Production example 2)

A liquid crystal light dimming element of Production Example 2 was produced in the same manner as that of Production Example 1, except that the light transmission electrically conductive film of Example 1 was changed to the transmission electrically conductive film of light from Example 2.

(Production example 3)

A liquid crystal light dimming element of Production Example 3 was produced in the same manner as that of Production Example 1, except that the light transmission electrically conductive film of Example 1 was changed to the transmission electrically conductive film of light from example 3.

(Comparative production example 1)

A liquid crystal light regulating element of Comparative Production Example 1 was produced in the same manner as that of Production Example 1, except that the two electrically conductive light transmission films of Comparative Example 1 were prepared to be laminated of so that each of the electrically conductive light transmission layers was in contact with the surface (the upper surface or the lower surface) of the liquid crystal light regulation layer.

(Measurement)

(1) Thickness

The thickness of the protective layer, the first inorganic oxide layer, the metal layer, and the second inorganic oxide layer was measured by observation of the cross section using a transmission electron microscope (manufactured by Hitachi, Ltd., HF- 2000). The thickness of the transparent substrate was measured using a film thickness gauge (manufactured by Ozaki MFG. CO., LTD., DG-205 digital indicator type gauge).

(2) Observation of crystal particles with cross section TEM

A cross section of the first inorganic oxide layer and the second inorganic oxide layer was observed using a transmission electron microscope (manufactured by Hitachi, Ltd., HF-2000, 200,000x magnification). The number of crystal particles per 500 nm at a distance from the plane direction of the cross-sectional view at this time was counted. The maximum crystal particle length of the crystal particle generated in the inorganic oxide layer was measured. The results are shown in Table 1.

(3) Observation of glass particles with planar TEM

In each of the light-transmitting electrically conductive films of the Examples and the Comparative Examples in which the glass particle was confirmed by TEM of the cross section, using a transmission electron microscope (manufactured by Hitachi, Ltd., "H -7650"), the upper surface of the second inorganic oxide layer was observed, and a flat image at 100,000x magnification was obtained. Next, the ratio of the area of the crystal particle (crystallized part) to that of the entire second inorganic oxide layer was measured. The results are shown in Table 1. In Example 1, the number of the second crystal particle was greater than that of the first crystal particle.

(4) Damp heat durability

Each of the electrically conductive light transmission films of the Examples and the Comparative Examples was cut into a piece having a size of 10 cm * 10 cm, a pressure sensitive adhesive layer was formed (manufactured by NITt O DENKO CORPORATION , "CS9904U") on the electrically conductive light transmission layer to bond it to a glass substrate and then the laminate obtained was allowed to rest under conditions of 60°C and 95% relative humidity for 240 hours. Next, the top surface of the electrically conductive light transmission layer of the 8 cm x 8 cm central portion was visually observed. At this time, the appearance evaluation was carried out based on the following criteria.

Excellent: No white point defect (aggregation, part in poor condition) was observed (0).

Good: The number of white point defects is greater than 0 and 5 or less.

Bad: The number of white point defects is more than 5.

The results are shown in Table 1.

(5) Reflectance properties of near-infrared rays

As for each of the light-transmitting electrically conductive films of the Examples and Comparative Examples, the average reflectance of the near-infrared ray (wavelength of 850 to 2500 nm) was measured.

At this time, the evaluation of the average reflectance was carried out based on the following criteria.

Good: The average reflectance is 30% or more.

Poor: The average reflectance is 15% or more and less than 30%.

Bad: Average reflectance is less than 15%.

The results are shown in Table 1.

[Table 1]

Although illustrative embodiments of the present invention are given in the foregoing description, this is for illustrative purposes only and should not be construed as limiting the scope of the present invention defined in the following claims.

Industrial Applicability

The liquid crystal light regulating member and the liquid crystal light regulating element of the present invention can be applied in various industrial products and can be used, for example, for various uses, such as window glass for buildings and vehicles, partitions, and interior decoration.

Description of reference numbers

1 Liquid crystal light regulation organ

2 Transparent substrate

4 Electrically conductive light transmission layer

5 Layer liquid crystal dimming

6 First layer of inorganic oxide

7 Metal layer

8 Second layer of inorganic oxide

9 Electrically conductive light transmission film

13 Liquid crystal dimming element

Claims (2)

1. Liquid crystal light regulation organ (1), which includes, sequentially: a transparent substrate (2), an electrically conductive light transmission layer (4), and a liquid crystal light regulation layer (5), in which The electrically conductive light transmission layer (4) sequentially includes a first inorganic oxide layer (6), a metal layer (7), and a second inorganic oxide layer (8), characterized by the fact that the first inorganic oxide (6) is an amorphous layer and includes oxide composed of indium and tin, and by the fact that the second inorganic oxide layer (8) is a semicrystalline film that has an amorphous part and a crystalline part. 2. Liquid crystal light regulation element (13), comprising: the liquid crystal light adjustment member (1) according to claim 1 and an electrode substrate (14) arranged on a surface opposite the liquid crystal light adjustment layer (5) with respect to the transparent substrate (2).