JP2022151701A - Curved surface resin structure, electronic dimming lens and method for manufacturing curved surface resin structure - Google Patents

Abstract

To provide a curved surface resin structure which has excellent curved surface shape accuracy and can suppress damage of a conductive layer.SOLUTION: A curved surface resin structure has a support, and a laminated part in which at least a conductive layer and an electronic material layer are laminated on a surface of the support, wherein a radius of curvature of the surface of one end of the laminated part is represented by rA1(mm), a radius of curvature of the surface of the other end facing the one end around a central region of the laminated part is represented by rA2(mm), an average radius of curvature of the surface of the laminated part is represented by rB(mm), and the rA1, rA2 and rB satisfy the following inequality expression (1) or inequality expression (2). Inequality expression (1): rA1,rA2<rB, and inequality expression (2): rA1,rA2>rB.SELECTED DRAWING: Figure 1A

Description

The present invention relates to a curved resin structure, an electronic light control lens, and a method for manufacturing a curved resin structure.

Insert molding technology using a decorative film is known as a technology for decorating the surface of plastic products. In this technology, a decorative film with a design printed in advance is set in an injection mold, and resin is injected and welded to the back of the decorative film to create a plastic product that has a decorative film on its surface. integrally molded.
Compared to the method of attaching a decorative film to the surface of the product, insert molding technology can improve the design and productivity of products in terms of seamless surfaces, reduction of parts due to integration, space saving, etc. It is used in the manufacture of car interior parts, smartphone covers, etc.

In recent years, attempts have been made to manufacture electronic devices such as touch panels and displays for wearable applications by performing insert molding using an insert sheet corresponding to a decorative film, which has a conductive layer. In such an electronic device, it may be preferable to use a conductive layer having high translucency (transparency) depending on the application of the electronic device.

Further, in wearable applications, a curved resin structure having a three-dimensional shape such as a curved shape is preferable because the electronic device is lightweight, resistant to cracking, and excellent in design and wearability.
For the curved resin structure, for example, the object is to be able to suppress damage to the conductive layer in a high-temperature environment. and a resin layer containing, in this order, a third resin that is at least one of the same type of resin as the second resin and a resin having a softening temperature equal to or lower than the softening temperature of the second resin. A resin structure has been proposed (see Patent Document 1, for example).

SUMMARY OF THE INVENTION An object of the present invention is to provide a curved resin structure having excellent curved surface shape accuracy and capable of suppressing damage to a conductive layer.

A curved resin structure of the present invention as a means for solving the above problems has a support, and a laminated portion in which at least a conductive layer and an electronic material layer are laminated within the surface of the support,
The surface curvature radius of one end of the laminated portion is rA1 (mm), the surface curvature radius of the other end facing the one end centered on the central region of the laminated portion is rA2 (mm), and the surface average of the laminated portion is is rB (mm), and rA1, rA2 and rB satisfy the following inequality (1) or (2).
rA1, rA2<rB inequality (1)
rA1, rA2>rB inequality (2)

ADVANTAGE OF THE INVENTION According to this invention, the curved-surface resin structure which has the outstanding curved-surface shape accuracy and can suppress the damage of a conductive layer can be provided.

1A is a schematic side view showing an example of a curved resin structure according to a first embodiment; FIG. 1B is a schematic top view showing an example of the curved resin structure according to the first embodiment; FIG. 2A is a schematic top view showing an example of a resin structure (insert sheet) according to the first embodiment; FIG. 2B is a schematic top view showing an example of the resin structure (insert sheet) according to the first embodiment; FIG. 2C is a schematic top view showing an example of the resin structure (insert sheet) according to the first embodiment; FIG. FIG. 3 is a schematic side view showing an example of the curved resin structure according to the second embodiment. FIG. 4 is a schematic side view showing an example of a curved surface forming apparatus according to one embodiment of the present invention. FIG. 5A is a diagram showing an example of a three-dimensional curved surface forming method using a curved surface forming apparatus according to an embodiment of the present invention in order of steps. FIG. 5B is a diagram showing an example of a three-dimensional curved surface forming method using a curved surface forming apparatus according to an embodiment of the present invention in order of steps. FIG. 6 is a diagram showing another example of a three-dimensional curved surface forming method using a curved surface forming apparatus according to an embodiment of the present invention in order of steps. FIG. 7 is an explanatory diagram showing an embodiment of an insert injection molding apparatus for producing a spherical molded body, which is an example of the curved resin structure of the present invention. FIG. 8A is a diagram showing an example of an insert sheet integral molding method using an insert injection molding apparatus in order of steps. FIG. 8B is a diagram showing an example of an insert sheet integral molding method using an insert injection molding apparatus in order of steps. FIG. 8C is a diagram showing an example of an insert sheet integrated molding method using an insert injection molding apparatus in order of steps. FIG. 9 is a schematic side view showing an example of the shape of the curved resin structure of the present invention using an insert injection molding apparatus. 10A is a convex surface curved surface displacement profile (amount of displacement from the radius of curvature) of the curved resin structure in Example 1. FIG. 10B is a convex surface curved surface displacement profile (amount of displacement from the radius of curvature) of the curved resin structure in Example 2. FIG. 10C is a convex surface curved surface displacement profile (amount of displacement from the radius of curvature) of the curved resin structure in Example 5. FIG. 10D is a convex surface curved surface displacement profile (amount of displacement from the radius of curvature) of the curved resin structure in Comparative Example 1. FIG. FIG. 11 is a photograph of cracks occurring in the laminated portion of the curved resin structure.

(Curved surface resin structure)
The curved resin structure of the present invention preferably has a support and a laminated portion in which at least a conductive layer and an electronic material layer are laminated within the surface of the support, and preferably has a sealing member and a base layer. It has other members as needed.

In the curved resin structure of the present invention, the support has a curved shape.
The conventional curved resin structure is based on the knowledge that the conductive layer and the electronic material layer may be damaged if it is manufactured with high curved surface accuracy.

Since the coating of the decorative film used for insert molding is carried out on a flat plate-shaped film, it does not require special equipment compared to coating on the surface of a product with a three-dimensional shape such as a curved surface. low cost from Furthermore, since dipping coating is not required for coating the stepped portion, there is also the advantage that the amount of coating solvent used is small.

In this way, by manufacturing an electronic device by insert molding, mass production with low cost and high productivity becomes possible.
However, in the conventional insert molding technology, for example, the same resin material as the resin material forming the support is applied to the support on which the conductive layer is formed, at a high temperature (for example, 200 ° C. There is a problem that the electronic device is likely to be destroyed by heat and shear stress of the injected resin because the injection welding is performed in the state of about 100 degrees. Specifically, in the conventional insert molding technology, there are problems such as cracks in the conductive layer formed on the support due to thermal deformation of the support, and the conductive layer may be damaged. There is

With conventional insert molding technology, the conductive layer made of inorganic oxide has a high Young's modulus and lacks toughness, so it is brittle and easily broken. Taking into account the difficulty of molding, a specific underlayer was formed between the support and the conductive layer in order to suppress crack damage.
However, since the laminated part where the conductive layer and the electronic material layer are laminated is relatively softer than the area other than the laminated part such as the sealing member, high curved surface accuracy (for example, surface displacement of 20 μm or less) like an optical lens is not possible. If required, there is a problem that the load of heat and pressure during curved surface processing increases, the lamination portion is distorted, and the conductive layer and the electronic material layer are damaged.

As described above, the curved resin structure in the conventional technology, when using a conductive layer with excellent transparency and conductivity, is exposed to a high-temperature and high-pressure environment such as during manufacture by insert molding. There is a problem that the material layer is damaged and it is difficult to achieve excellent curved surface shape accuracy.

A curved resin structure of the present invention comprises a support, and a laminated portion in which at least a conductive layer and an electronic material layer are laminated within the surface of the support,
Let rA1 (mm) be the surface curvature radius of one end of the laminated portion, rA2 (mm) be the surface curvature radius of the other end facing the one end around the central region of the laminated portion, and rA2 (mm) be the average radius of the laminated portion surface. The radius of curvature is rB (mm), and rA1, rA2 and rB satisfy the following inequality (1) or (2).
rA1, rA2<rB inequality (1)
rA1, rA2>rB inequality (2)

The radius of curvature of the surface can be measured, for example, using a surface roughness measuring instrument (Form TalySurf Series 2, manufactured by Taylor Hobson).

The central region may be the center of gravity or the geometric center, and the size of the central region is preferably 1/10 or less of the area of the laminated portion.

Further, the curved resin structure of the present invention has a support and a laminated portion in which at least a conductive layer and an electronic material layer are laminated in the plane of the support, and the support does not have the laminated portion. The surface displacement in the vertical direction is 0.8 μm or more at the boundary between the and laminated portions.
Since the curved resin structure of the present invention has a curved surface that is substantially uniformly displaced with respect to the center of the laminated portion, better optical characteristics can be obtained in the center portion, which is frequently used.
In the present invention, surface displacement of 0.8 μm or more is formed at the boundary between the support and the laminated portion where the laminated portion is not formed, so that excessive pressure on the laminated portion can be suppressed. It is possible to obtain a curved resin structure that can prevent damage such as cracking in the conductive layer of the laminated portion.
The surface displacement refers to a step or unevenness at the boundary between the laminated portion and the non-laminated portion. Since the deformed portion is closer to the center of the laminated portion, the optical properties of the frequently used central portion tend to deteriorate.

The inside of the laminate where the conductive layer and the electronic material layer are formed is generally softer than the outside of the laminate where the protective sealing material is formed. and gaps are likely to occur. When high curved surface precision is required, such as an optical lens, the application of heat and pressure during curved surface processing becomes strong, which may distort the laminated portion and damage the conductive layers and functional layers.
Therefore, in the present invention, even when a conductive layer having excellent transparency and conductivity is used in the laminated portion, damage to the conductive layer due to formation of curved surfaces can be suppressed. The electronic material layer is laminated in contact with the conductive layer, and the electronic material layer of the laminated portion reacts with a voltage or current applied between one conductive layer or two conductive layers sandwiching the electronic material layer.

<Conductive layer>
The conductive layer is not particularly limited as long as it has conductivity, and can be appropriately selected according to the purpose. It can generate heat using Joule heat and may function as a heater.
The conductive layer may be divided into a plurality of pieces. The form in which the conductive layer is divided into a plurality of parts is not particularly limited, and can be appropriately selected according to the purpose. ) may be arranged in a matrix.

The conductive layer preferably contains a conductive material, and more preferably contains a transparent conductive material.

The conductive material is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include conductive materials such as opaque materials and transparent materials. Among these materials, transparent materials are preferable for display applications or dimming applications where visibility is required.
The opaque material is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include metal materials such as Au, Ag, Cu, Al, Ni, W, and Mo.
Examples of the transparent material include inorganic oxides, carbon (CNT, graphene), metal nanowires, metal grids, and conductive polymers. Among these, inorganic oxides are preferable because they have electrical conductivity as a dense film and are excellent in electrical conductivity, transparency (transmittance and haze) and reliability.

The inorganic oxide is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include oxide materials such as In, Sn, Zn and Al. Further, examples of additive materials in the conductive layer containing the inorganic oxide include W, Ti, Zr, Zn, Sb, Ga, Ge, F, and the like.

The conductive layer containing the inorganic oxide preferably contains indium oxide. By including indium oxide in the conductive layer, crystallinity can be controlled, and a transparent conductive layer that is less susceptible to damage such as cracks during heat processing can be obtained.

Examples of the indium oxide include tin (Sn), tungsten (W), titanium (Ti), zirconium (Zr), zinc (Zn), aluminum (Al), antimony (Sb), gallium (Ga) and fluorine (F). other oxides, such as, may be included in the conductive layer either singly or in combination. Inclusion of such other oxides can improve the carrier density and mobility of indium oxide, and can change the crystallization temperature. In this case, the conductive layer preferably contains tin-doped indium oxide (hereinafter referred to as “ITO”).
The content of the other oxide in the conductive layer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 80% by mass or less. As the other oxides, tin oxide and zirconium oxide are particularly preferable from the viewpoint of conductivity, and the content of these oxides in the conductive layer is particularly preferably, for example, 15% by mass or less.

Examples of the transparent conductive material include a layer containing highly elastic carbon such as carbon nanotubes (CNT) and graphene, metal nanowires, metal grids, and conductive polymers, and a layer containing an inorganic oxide. It may be a composite layer.

The average thickness of the conductive layer is not particularly limited and can be appropriately selected depending on the intended purpose. When the average thickness of the conductive layer is 50 nm or more and 500 nm or less, it is possible to suppress the occurrence of damage such as cracks during curved surface formation processing. The average thickness of the conductive layer is preferably adjusted according to the amount of current required for the electronic device.

The sheet resistance of the conductive layer is not particularly limited and can be appropriately selected according to the purpose, but is preferably 300Ω/□ or less.

The visible light transmittance of the conductive layer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 70% or more. The transmittance can be appropriately adjusted by changing the average thickness of the conductive layer and the oxygen ratio of the inorganic oxide such as indium oxide.

The conductive layer can be formed, for example, by a vacuum film formation method, and the crystallinity of the indium oxide layer, that is, the crystal peak shape (height H/width W) value depends on the substrate temperature and film formation rate during vacuum film formation. , gas pressure, etc. Heat treatment after film formation is also effective for adjusting the H/W value. Examples of the vacuum film forming method include a vacuum deposition method, a sputtering method, an ion plating method, a chemical vapor deposition (CVD) method, and the like. Among these, the sputtering method capable of high-speed film formation is preferable. In the case of the sputtering method, the H/W value of the crystal peak can be easily controlled by adjusting the sputtering power.
The conductive layer used in the present invention preferably has a crystal peak shape H/W value of (222) plane of indium oxide of 6 or less. The measurement conditions are radiation source: Cu tube. 50 kV, 1000 μm, incident angle: 3°, slit width: 1 mm, collimator diameter: 1 mm. This is because if the crystallinity is too high, cracks tend to occur from the crystal planes.
The method for forming the conductive layer is not particularly limited and can be appropriately selected according to the purpose. and a method of forming a film.
The method for applying the conductive layer is not particularly limited and can be appropriately selected depending on the purpose. Examples include spin coating, casting, micro gravure coating, gravure coating, bar coating, and roll coating. method, wire bar coating method, dip coating method, slit coating method, capillary coating method, spray coating method, nozzle coating method, gravure printing method, screen printing method, flexographic printing method, offset printing method, reverse printing method, inkjet printing method and various other printing methods.

<Electronic material layer>
The electronic material layer is preferably laminated on the conductive layer in the plane of the support, and more preferably sandwiched between two conductive layers. The electronic material layers of the laminate react with the voltage or current applied to the conductive layer.

The electronic material layer is not particularly limited as long as it exhibits functions such as color development, light emission, polarization, deformation, and heat generation when electricity (voltage/current) is applied. It can be selected as appropriate.

The electronic material layer preferably contains an electronic material, and more preferably contains an inorganic material.
Examples of the electronic materials include electrochromic materials, electroluminescence materials, chemical luminescence materials, electroforetic materials, electrowetting materials, liquid crystal materials, piezoelectric materials, storage materials, electrolytes, electrothermal conversion materials, solar cell materials, and the like. mentioned. Among these, electrochromic materials are preferred. That is, it is preferable that the electronic material layer includes an electrochromic layer. Moreover, it is preferable that the electronic material layer includes an electrolytic layer and an electrochromic layer.
As the electrolytic layer, a solid electrolyte layer containing at least one of an ionic liquid and a polymer is preferable from the viewpoint of excellent workability during bending and heating. This makes it possible to use the curved resin structure of the present invention, for example, as photochromic spectacles (photochromic sunglasses).

The inorganic material is included to provide strength, thickness uniformity, and thermal expansion control to the electronic material layer.
The inorganic material is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include inorganic nanoparticles. The electronic material layer may be composed of inorganic nanoparticles.

The average thickness of the electronic material layer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 100 μm or less from the viewpoint of material cost and workability.
The electronic material layer is preferably a layer formed of an organic material that is resistant to processing and has excellent flexibility.

The method of coating the electronic material layer is not particularly limited and may be appropriately selected depending on the intended purpose. Coating method, wire bar coating method, dip coating method, slit coating method, capillary coating method, spray coating method, nozzle coating method, gravure printing method, screen printing method, flexographic printing method, offset printing method, reverse printing method, inkjet printing various printing methods such as printing method.

<<Electrochromic layer>>
The electrochromic layer contains an electrochromic material and optionally other ingredients.
The electrochromic material is not particularly limited as long as it exhibits electrochromism, and can be appropriately selected depending on the purpose. Examples thereof include inorganic electrochromic compounds, organic electrochromic compounds, and conductive polymers.

The inorganic electrochromic compound is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include tungsten oxide, molybdenum oxide, iridium oxide and titanium oxide. The inorganic electrochromic compound is used by forming a film as a particle layer such as nanoparticles or a dense layer.

The organic electrochromic compound is not particularly limited and can be appropriately selected depending on the intended purpose. type, dipyridine type, styryl type, styrylspiropyran type, spirooxazine type, spirothiopyran type, thioindigo type, tetrathiafulvalene type, terephthalic acid type, triphenylmethane type, benzidine type, triphenylamine type, naphthopyran type, viologen type, Low-molecular-weight organic electrochromic compounds such as pyrazoline, phenazine, phenylenediamine, phenoxazine, phenothiazine, phthalocyanine, fluorane, fulgide, benzopyran, and metallocene; conductive polymers such as polyaniline and polythiophene compound and the like. These may be used individually by 1 type, and may use 2 or more types together. A monomer having a reactive group may be polymerized and used.

The electrochromic layer preferably has a structure in which conductive or semiconducting fine particles carry an organic electrochromic compound. Specifically, a structure in which fine particles having a particle size of about 5 nm to 50 nm are bound to the electrode surface and an organic electrochromic compound having a polar group such as phosphonic acid, carboxyl group, or silanol group is adsorbed on the surface of the fine particles is preferable. In this structure, electrons are efficiently injected into the organic electrochromic compound by utilizing the large surface effect of the fine particles, so that the responsiveness can be improved compared to conventional electrochromic devices. Furthermore, since a transparent film can be formed as a display layer by using fine particles, a high color density of the electrochromic compound can be obtained.
Moreover, as an electrochromic layer, a plurality of kinds of organic electrochromic compounds can be supported on conductive or semiconducting fine particles. Furthermore, the conductive particles can also serve as a conductive layer as an electrode layer.

The electrochromic layer has two electrochromic portions, one electrochromic portion being a first electrochromic portion containing an electrochromic material capable of developing color in an oxidized state, and the other electrochromic portion being a reduced electrochromic portion. A second electrochromic portion comprising an electrochromic material capable of developing color in a state is preferred. Details of this form will be described later.

The average thickness of the electrochromic layer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.2 μm or more and 5.0 μm or less. When the average thickness of the electrochromic layer is 0.2 μm or more, the color density can be improved. Visibility can be improved.

The electrochromic layer is preferably formed by dissolving an electrochromic material in a solvent, coating the solution to form a film, and then solidifying the solution by heating, or by polymerizing the solution with light or heat. Examples of coating methods include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, slit coating, capillary coating, and spray coating. printing method, nozzle coating method, gravure printing method, screen printing method, flexographic printing method, offset printing method, reversal printing method, inkjet printing method and the like.

<<<electrolyte layer>>>
The electrolyte layer is used for an electronic material layer that undergoes an electrochemical reaction such as electrochromic, and is preferably a solid electrolyte layer containing at least one of an ionic liquid and a polymer. In addition to electrochromic devices, such electrochemical devices include primary batteries, secondary batteries, capacitors, solar cells, and the like.
Moreover, the electrochromic layer in the curved resin structure of the present invention preferably has two electrochromic portions as described above. In this case, the electrochromic layer preferably has an electrochromic portion and a solid electrolyte portion, and preferably has a solid electrolyte portion between the two electrochromic portions.
Here, the electrochromic portion means a portion containing an electrochromic material, and the solid electrolyte portion means a portion formed of a solid electrolyte.
The solid electrolyte part is preferably formed as a film in which an electrolyte is held in a photocurable or thermosetting resin. Furthermore, it is preferable to mix inorganic particles for controlling the layer thickness of the electrolyte portion.

The solid electrolyte part is preferably formed into a film by coating the electrochromic part with a solution obtained by mixing a curable resin, electrolyte inorganic fine particles, and inorganic fine particles as necessary, and then curing the solid electrolyte part by light or heat. After forming a fine inorganic fine particle layer, a mixed solution of a curable resin and an electrolyte is applied so as to permeate the inorganic fine particle layer, and then cured by light or heat to form a film.
Furthermore, when the electrochromic part is a layer in which an electrochromic compound is supported on conductive or semiconducting nanoparticles, after applying a solution in which a curable resin and an electrolyte are mixed so as to permeate the electrochromic part, It can also be formed as a film cured by light or heat.

As the electrolyte in the solid electrolyte portion, a liquid electrolyte such as an ionic liquid, a solution obtained by dissolving a solid electrolyte in a solvent, or the like is used. An electrochromic material can also be mixed in the solid electrolyte portion.

The average thickness of the solid electrolyte portion is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 5 μm or more and 500 μm or less, more preferably 10 μm or more and 100 μm or less. When the average thickness of the solid electrolyte portion is within the above preferred range, it is possible to suppress the manufacturing cost while preventing current short circuit.

<Support>
The support contains a resin and, if necessary, other materials.
The resin material is not particularly limited and can be appropriately selected according to the purpose. For example, known thermoplastic resins can be used.

Examples of thermoplastic resins include polycarbonate, polyethylene terephthalate, polyethylene naphthalate, acrylic (polymethyl methacrylate), polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene-acrylonitrile copolymer. Examples include polymers, polyethylene, ethylene-vinyl acetate copolymer, polypropylene, polyacetal, cellulose acetate, polyamide (nylon), polyurethane, fluorine-based (Teflon (registered trademark)), and the like.

The support resin includes at least one selected from polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, polyethylene, polypropylene, acrylonitrile-butadiene-styrene (PBS), polyoxymethylene, polyolefin and urethane. From the standpoint of moldability, it is preferable to use any one of these materials and copolymer materials. Furthermore, since these materials are suitable as injection molding materials, which will be described later, they are excellent in weldability with the resin forming the resin layer. Furthermore, among these, polycarbonate or polyethylene terephthalate is more preferable.
When expressing the relationship between resins, resins classified into the same classification may be referred to as "same type" resins. Examples of classification include polycarbonate, polyester, acrylic resin, polyethylene, polypropylene, PBS, polyacetal, polyolefin, and urethane resin.

The softening temperature of the resin of the support is, for example, preferably 80° C. or higher and 300° C. or lower, more preferably 100° C. or higher and 200° C. or lower.

The visible light transmittance of the support is preferably 70% or more.
In addition, when a plurality of supports are provided and the curved resin structure is used for viewing from one side, for example, one support has a visible light transmittance of 70% or more, and the other supports are opaque. may be
The average thickness of the support is not particularly limited and can be appropriately selected according to the purpose. .

The support is integrated by bonding or welding a resin layer to the surface of the support as a molding process or a thick plate.
The interface between the surface of the support and the resin layer can be welded or bonded by various methods such as injection molding, ultrasonic welding, laser welding, thermal welding, vibration welding, and cast molding. Injection molding for integral molding and cast molding are preferable in terms of productivity. Specifically, a resin support having a laminated portion in which at least a conductive layer and an electronic material layer are laminated in the plane is placed in a mold as an insert sheet, and the resin is injected or cast (injection molding) insert. It is preferable to form a resin layer and manufacture a curved resin structure by molding.
In cast molding, after an insert sheet is placed in a mold, a cured resin is injected into the mold and cured by heat or light to form an integral mold.

The shape of the resin layer is not particularly limited and can be appropriately selected depending on the intended purpose. Among these, optical lenses are preferred. That is, an optical lens is preferable as the resin layer. By using the resin layer as an optical lens, for example, the curved resin structure of the present invention can be used as a lens of a spectacle-type wearable device. In this case, since the curved resin structure has an electrochromic layer as an electronic material layer, the curved resin structure of the present invention can be used as a lens of photochromic spectacles (photochromic sunglasses), which is particularly preferable.

The resin for the resin layer is not particularly limited and can be appropriately selected depending on the intended purpose, and is preferably the same kind of resin as the resin material for the support. The "same type" resin is as described for the support. As a result, the welding strength between the support and the resin layer can be improved, the refractive indices of the support and the resin layer can be made uniform, and the transparency (visibility) of the curved resin structure can be improved.
Furthermore, the resin layer is more preferably at least one selected from polycarbonates and polycarbonate copolymers in terms of moldability, transparency, and cost, as with the material of the support.
As polycarbonate copolymer materials, copolymer materials containing various different monomer components have been developed from the viewpoint of improving the refractive index of polycarbonate, reducing birefringence, and imparting flame retardancy. Polycarbonate copolymers, UV curable resins, and thermosetting resins can be used.
Examples of the polycarbonate include Iupilon CLS3400S (manufactured by Mitsubishi Engineering-Plastics Corporation), Iupilon H-4000 (manufactured by Mitsubishi Engineering-Plastics Corporation), AD5503 (manufactured by Teijin Limited), L-1225LM (manufactured by Teijin Limited), TR -0601A (Sumika Polycarbonate SD) and the like.
Examples of the polycarbonate copolymer include SH1126Z (manufactured by Teijin Limited), Iupilon KH3310UR (manufactured by Mitsubishi Engineering-Plastics Corporation), SP5570 (manufactured by Teijin Limited), SP5580 (manufactured by Teijin Limited), SP1516 (manufactured by Teijin Limited). made), etc.
Examples of the UV curable resin include SK6500 and SK3200 (manufactured by Dexerials).
Examples of the thermosetting resin include MR8, MR7 and MR10 (manufactured by Mitsui Chemicals, Inc.).

As for the properties of the resin layer, it is preferable that the resin layer has high fluidity when in contact with the support during production. For example, for injection molding resins, it is preferable that the melt volume flow rate according to ISO 1133 is large. More specifically, the melt volume flow rate of the resin layer material conforming to ISO 1133 is preferably 14 cm ³ /10 min or more. Here, in injection molding, the higher the fluidity of the resin to be injected, the more the damage to the insert sheet (especially the conductive layer) due to the shear stress can be reduced. Therefore, by setting the melt volume flow rate of the resin layer material to 14 cm ³ /10 min or more, damage such as cracking in the conductive layer can be further suppressed.
Examples of devices for measuring the melt volume flow rate of resins conforming to ISO 1133 include Melt Indexer F-F01 (manufactured by Toyo Seiki Seisakusho Co., Ltd.) and Melt Indexer D4003 (manufactured by Nippon Dainisco Co., Ltd.). . The melt volume flow rate of polycarbonate is generally measured under conditions of a measurement temperature of 300° C. and a measurement load of 1.20 kgf.

If it is difficult to obtain sufficient welding strength between the support and the resin layer when welding or bonding, an adhesive layer may be provided between the support and the resin layer.

<Seal member>
Preferably, the curved resin structure of the present invention further has a sealing member.
The sealing member is not particularly limited and can be appropriately selected according to the purpose.
The sealing member is formed, for example, to physically and chemically protect the periphery of the laminated portion of the curved resin structure and the surface and side portions of the structure. In particular, when forming a curved resin structure by laminating two supports, it is preferable to have a sealing member on the outside of the edge around the laminated portion formed between the two supports.

The sealing member is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include photocurable resins, thermosetting resins, and materials obtained by adding inorganic particles to these.
By adding the inorganic particles, the film thickness of the seal layer can be controlled, and the coefficient of thermal expansion and moisture permeability can be reduced.
The sealing member is preferably insulating.
As a method for forming the sealing member, for example, a photocurable or thermosetting insulating resin is applied so as to cover at least one of the periphery of the laminated portion of the curved resin structure and the side surface and top surface of the curved resin structure. and then cured.
The method of applying the sealing member is not particularly limited and can be appropriately selected depending on the purpose. Examples include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating method, dip coating method, slit coating method, capillary coating method, spray coating method, nozzle coating method, gravure printing method, screen printing method, flexographic printing method, offset printing method, reverse printing method, inkjet printing method, etc. Examples include various printing methods.

The average thickness of the sealing member is preferably equal to or greater than the thickness of the laminated portion from the viewpoint of protecting the laminated portion. The average thickness of the sealing member when the sealing member is formed on the surface or the side surface of the laminated portion of the curved resin structure is not particularly limited and can be appropriately selected according to the purpose, but is 0.5 μm or more. 100 μm or less is preferable.

The content of the inorganic particles is not particularly limited and can be appropriately selected according to the purpose, but is preferably 10 wt % or more and 200 wt % or less with respect to the sealing member. When the content is 10 wt% or more, the film thickness can be easily controlled, and the coefficient of thermal expansion and moisture permeability can be reduced. It has high density and improves its function as a barrier layer that suppresses physical or chemical damage.

<Underlayer>
The underlying layer is formed between the support and the conductive layer to physically and chemically protect the support and to suppress thermal expansion of the conductive layer-forming surface during heat processing. By forming a layer with a smaller thermal expansion than the support as the underlayer, thermal deformation of the surface on which the conductive layer is formed is suppressed during heat processing. It is possible to suppress damage caused by cracks even when a
As the material of the underlayer, it is preferable to use a resin layer containing inorganic particles.
By containing the inorganic particles, the coefficient of thermal expansion can be suppressed more than a general resin base layer made of a single resin.

The softening temperature of the resin contained in the underlayer is preferably 100° C. or higher, and more preferably higher than the softening temperature of the resin constituting the support. By using a material with a high softening temperature as the resin contained in the underlayer, it is possible to suppress the thermal expansion of the surface on which the conductive layer is formed (the surface in contact with the conductive layer) during heating, resulting in cracks and damage to the conductive layer. can be more restrained.

The resin contained in the underlayer is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include ultraviolet (UV) curable resin materials and thermosetting resin materials.
Examples of the resin include acrylic resin, epoxy resin, urethane resin, silicone resin, and melamine resin. These materials are preferred in terms of moldability, transparency, and cost.
As the resin contained in the underlayer, a cured product of an oligomer having a plurality of unit structures with respect to the reactive group is preferable. If the resin contained in the underlayer is a monomer having a single unit structure with respect to the reactive group, the underlayer may crack during heat processing of the cured product. As the resin contained in the underlayer, it is preferable to use an oligomer having a plurality of unit structures with respect to the reactive group, because the cured product thereof has higher flexibility than the cured product of the monomer and is less prone to cracks.

-Inorganic particles-
The inorganic particles in the underlayer are not particularly limited and can be appropriately selected according to the intended purpose. For example, commonly used inorganic fillers can be used. More specifically, examples of inorganic particles include silicon oxide, zirconia oxide, aluminum oxide, tin oxide, various mica, Ag, Cu, Au, and Ni. These may be used individually by 1 type, and may use 2 or more types together.

The number average particle diameter of the primary particle diameter of the inorganic particles is not particularly limited and can be appropriately selected according to the purpose. When the number average particle size of the primary particle size of the inorganic particles is 1 nm or more and 50 μm or less, the transparency of the underlayer can be ensured.

The content of the inorganic particles in the underlayer is not particularly limited, and can be appropriately selected according to the properties of the underlayer (transparency, film thickness, coefficient of thermal expansion, etc.). 10% by mass or more is preferable, and 10% by mass or more and 200% by mass or less is more preferable. When the content of the inorganic particles in the underlayer is 10% by mass or more with respect to the total amount of the resin, the effect of suppressing thermal expansion can be improved. This is preferable because an underlying layer can be obtained.

The thickness of the underlayer is not particularly limited and can be appropriately selected according to the purpose.
The visible light transmittance of the underlying layer is preferably 70% or more.

The softening temperature and thermal expansion coefficient of the underlayer can be adjusted by changing the types of resins and inorganic materials used in the underlayer, their contents, crosslink density, amount of reaction initiator, and the like.

Here, the softening temperature of the resin can be measured using, for example, thermomechanical analysis (Thermo Mechanical Analysis: TMA, Dynamic Mechanical Analysis: DMA, Differential scanning calorimetry: DSC).

The method for forming the underlayer is not particularly limited and can be appropriately selected according to the purpose. For example, a mixture of at least an organic monomer material having a reactive group and an initiator and an inorganic material are supported. It can be formed by coating on the body and performing solidification or curing treatment such as UV irradiation, heat treatment, dehydration treatment, and the like.
Examples of coating methods include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, slit coating, capillary coating, and spraying. Various printing methods such as a coating method, a nozzle coating method, a gravure printing method, a screen printing method, a flexographic printing method, an offset printing method, a reverse printing method and an inkjet printing method can be used.
<Other parts>
Other members are not particularly limited and can be appropriately selected according to the purpose.
For example, a conductive portion for connecting to a power source, an antireflection layer for adjusting optical transmittance, a polarizing layer, and the like may be formed.

(Manufacturing method of curved resin structure)
In the method for producing a curved resin structure of the present invention, a resin structure is prepared by forming a conductive layer and an electronic material layer in this order on at least the surface of a resin support to form a laminated portion, and the resin structure is placed in a mold as an insert sheet. Then, a resin layer is integrally formed on the back surface by insert molding. In addition, in order to improve the ease of installation in the mold and to reduce the expansion and contraction of the support during insert molding, the surface of the support is pressed against a curved mold that is heated and temperature-controlled before insert molding to form a curved shape. It is preferable to keep Furthermore, other steps may be included as necessary.
The method for manufacturing a curved resin structure according to the present invention can be suitably performed, for example, by a manufacturing apparatus (insert injection molding apparatus) described later.

In insert injection molding, it is preferable to integrally form a resin layer by injecting molten resin from a direction substantially parallel to the surface of a support (insert sheet). By doing so, the surface accuracy of the front and back surfaces of the molded body can be improved, and the fluidity and filling speed of the ejected resin can be improved. damage can be suppressed.
The shape of the resin injection part (gate) of the mold is preferably a shape that is narrow in the thickness direction of the curved resin structure and does not face the side surface of the insert sheet. This is because the wider the gate shape is in the thickness and width directions, the more the fluidity and filling speed of the injected resin are improved.

The thickness of the shape of the resin injection portion of the mold is equal to or less than the average thickness of the curved resin structure, and the width of the shape of the resin injection portion of the mold is greater than the thickness of the shape of the resin injection portion. preferable. Thereby, the curved resin structure of the present invention can be obtained.

Furthermore, in the method of manufacturing a curved resin structure of the present invention, the melt volume flow rate of the injected resin according to ISO 1133 is preferably 14 cm ³ /10 min or more. In injection molding, the higher the fluidity of the resin to be injected, the more the damage to the insert sheet (support), particularly the conductive layer, due to shear stress can be reduced. Therefore, by setting the melt volume flow rate of the resin to 14 cm ³ /10 min or more, damage such as cracking in the conductive layer can be further suppressed.
In particular, when the thickness of the curved resin structure to be molded is small, the insert sheet is likely to be affected by the shear stress caused by the injected resin. Therefore, for example, when the average thickness of the resin layer is 2 mm or less, the melt volume flow rate is preferably 24 cm ³ /10 min or more.

In insert injection molding, the temperature of the mold is preferably 10° C. or more lower than the softening temperature of the resin, more preferably 30° C. or more and 150° C. or less.
Moreover, the temperature of the mold is preferably a temperature equal to or lower than the softening temperature of the support. By doing so, softening of the support can be suppressed, and damage to the conductive layer can be suppressed.
In insert injection molding, the pressure (holding pressure) is preferably 100 MPa or more and 150 MPa or less. As a result, the entire laminated portion of the curved resin structure can be uniformly pressurized, and the curved resin structure of the present invention can be obtained.
When the polycarbonate resin or polycarbonate copolymer resin is injection-molded, the mold temperature is preferably 40° C. or higher and 120° C. or lower, and the pressure (holding pressure) is preferably 100 MPa or higher and 150 MPa or lower. By heating and pressurizing in this range, distortion of the laminated portion is reduced even in the case where high curved surface accuracy is required, such as an optical lens, so that the conductive layer and the electronic material layer are less likely to be damaged.

The curved resin structure of the present invention can be used, for example, as a component of an electrochromic device, an electronic light control lens, and the like.

Embodiments of the present invention will be described below, but the present invention is not limited to these embodiments.
The number, position, shape, and the like of the following constituent members are not limited to those of the present embodiment, and the number, position, shape, and the like can be set to be preferable in carrying out the present invention.

<First embodiment>
First, the curved resin structure according to the first embodiment will be described. The curved resin structure according to the first embodiment is an embodiment related to an electrophoretic (electrophoretic) display element. 1A and 1B are schematic side views showing an example according to the first embodiment.

The curved resin structure 10 according to the first embodiment includes supports 11a and 11b, base layers 13a and 13b on the supports 11a and 11b, and a conductive layer 12a between the base layers 13a and 13b. , an electronic material layer 15 and a conductive layer 12b; a sealing member 14 surrounding the laminate 19 and covering the outside of the edge of the laminate; and a resin layer 17 formed on the back surface of the support 11a. have

Further, in this embodiment, the electronic material layer 15 is an electrophoretic ink layer that reversely displays black and white particles.
A portion of the conductive layer 12a and a portion of the conductive layer 12b are exposed from the sealing member 14 as lead portions 16a and 16b. At least one of a conductive paste and a metal electrode is formed on the lead portion.

2A to 2C are schematic top views showing an example of the resin structure (insert sheet) according to the first embodiment. FIG. The contours of the supports 11a and 11b are formed by a linear portion including two substantially parallel straight lines and a curved portion including two arcuate curves connecting both ends of the straight portions. Underlayers 13a and 13b also have similar contours. 2A shows an example of the positional relationship between the sealing member 14 and the conductive layer 12b, FIG. 2B shows an example of the positional relationship between the sealing member 14 and the conductive layer 12a, and FIG. 2C shows the sealing member 14 and the electronic material. An example of the positional relationship with the layer 15 is shown.

The curved resin structure 10 shown in FIG. By sandwiching the material layer 15 (electrophoretic ink layer) and the sealing member 14 and bonding them together, a resin structure in the form of a flat sheet is formed. As a method for processing the curved surface shape, after setting a flat sheet resin structure or a curved surface resin structure (insert sheet) that has been curved in advance in a molding die, the back surface of the insert sheet (the support body 11a side) is removed from the gate portion 18. ) is injection-molded or cast-molded with a resin material for forming the resin layer 17, and then cured to form an integrally molded curved resin structure.
In the curved resin structure of the present invention, inflection points of the same phase of surface displacement in the longitudinal direction of the laminated portion are present on both sides of the center of the laminated portion, satisfying the relationship rA1, rA2<rB or rA1, rA2>rB.
The surface curvature displacement at the boundary between the laminated portion and the non-laminated portion is 0.8 μm or more.
The main component of the electrophoretic ink layer is a layer in which positively charged oxide particles such as titanium oxide and negatively charged organic particles such as carbon are dispersed in a solvent. Thus, white or black is displayed.

<Second embodiment>
Next, a curved resin structure according to a second embodiment will be described. The curved resin structure according to the second embodiment is an embodiment related to an electrochromic device. FIG. 3 is a schematic side view showing an example according to the second embodiment.

In the curved resin structure 20 according to the second embodiment, the electronic material layer 15 includes a reduced electrochromic (EC) portion as the electronic material layer 15a, an oxidized EC portion as the electronic material layer 15b, and a solid EC portion as the electronic material layer 15c. It differs from the curved surface resin structure according to the first embodiment in that it has an electrolyte portion.

For example, the curved resin structure 20 shown in FIG. A sheet 2 having an oxidized electrochromic (EC) portion formed as a conductive layer 12b and an electronic material layer 15b is prepared, and the electronic material layer 15c (solid electrolyte portion) and the sealing member 14 are sandwiched and bonded together to form a flat sheet resin structure. Formed as a body.

As a method of insert molding as a welding or bonding process, after setting a flat sheet resin structure or a curved surface molded resin structure (insert sheet) in a molding die, the back surface of the resin structure ( A resin material forming the resin layer 17 is injection-molded or cast-molded on the support 11a side), and then cured to form an integrally molded curved resin structure.

In the curved resin structure of the present invention, the inflection points of the same phase of surface displacement in the longitudinal direction of the laminate are on both sides of the center of the laminate, satisfying the relationship rA1, rA2<rB or rA1, rA2>rB.
The surface curvature displacement at the boundary between the laminated portion and the non-laminated portion is 0.8 μm or more.
In applications where the color development or color change of the electronic material layers 15a and 15b is visible only from one of the supports 11a and 11b, the support on the side to be viewed is transparent, while the other support is transparent. It doesn't have to be.
Further, either one of the electrochromic layers 15a and 15b may be replaced by a deterioration prevention layer that does not change color with applied voltage/current.
The material of the deterioration prevention layer is not particularly limited as long as it can prevent corrosion due to irreversible oxidation-reduction reaction of the conductive layer, and can be appropriately selected according to the purpose.
As a material for the deterioration prevention layer, for example, antimony tin oxide, nickel oxide, titanium oxide, zinc oxide, tin oxide, or a conductive or semiconducting metal oxide containing a plurality thereof can be used.
Among these, when an electrochromic device is produced as an optical element such as a lens that requires transparency, it is preferable to use a highly transparent material as the deterioration prevention layer.
As a highly transparent material, it is preferable to use n-type semiconducting oxide fine particles (n-type semiconducting metal oxide). As the n-type semiconducting metal oxide, titanium oxide, tin oxide, zinc oxide, or compound particles containing a plurality thereof, or a mixture thereof, which are composed of particles having a primary particle diameter of 100 nm or less can be used.
On the other hand, as a material for the highly transparent p-type semiconducting layer as the deterioration preventing layer, an organic material having a nitroxyl radical (NO radical) can be mentioned. -tetramethylpiperidine-N-oxyl (TEMPO) derivatives, or derivative polymer materials.

<Embodiment of Method for Manufacturing Curved Resin Structure>
When insert molding is performed as a welding process, preforming (preforming) of the insert sheet is performed for the purpose of improving processing accuracy, suppressing sheet damage, and improving processing yield. Here, a curved surface forming method for preforming suitable for the present invention will be described.

FIG. 4 is a schematic side view showing an example of a curved surface forming apparatus according to one embodiment of the present invention. 5A and 5B are diagrams showing an example of a three-dimensional curved surface forming method using a curved surface forming apparatus according to an embodiment of the present invention in order of steps.

As shown in FIG. 4 , the curved surface forming apparatus 100 includes a concave mold 111 and a temperature control section 116 that adjusts the temperature of the concave mold 111 . The concave mold 111 is formed with a hole 115 that connects the bottom and back of a three-dimensional (3D) curved, for example spherical, concave surface 112 , and an intake/exhaust pump 117 is connected to the hole 115 . The curved surface forming apparatus 100 includes an elastic sheet 131 arranged on the flat surface 113 around the concave surface 112 of the concave mold 111 so as to cover the concave surface 112 . The elastic sheet 131 is formed with holes 132 passing through the front and back.

When processing a laminated sheet into a 3D curved surface as an insert sheet using the curved surface forming apparatus 100, first, an insert sheet 151 is prepared as shown in FIG. 5A. Further, the concave mold 111 is heated and temperature-controlled to the vicinity of the softening temperature (Tg) of the support of the insert sheet by the temperature control unit 116 . Then, the insert sheet 151 is placed on the elastic sheet 131 so as to close the hole 132 . For example, the temperature for temperature control is in the range from 20° C. higher than the softening temperature (Tg) to 20° C. lower than the softening temperature (Tg), preferably lower than the softening temperature.

Next, the suction/exhaust pump 117 is operated to evacuate the space between the concave surface 112 and the elastic sheet 131 . As a result, the elastic sheet 131 stretches and adheres to the concave surface 112 . In addition, since the insert sheet 151 is in close contact with the elastic sheet 131 and approaches the concave mold 111 as the elastic sheet 131 deforms, heat is transferred from the concave mold 111 to the insert sheet 151 and the support included in the insert sheet 151 is reduced. Body softens. Then, as shown in FIG. 5B , the insert sheet 151 is brought into close contact with the concave mold 111 and is plastically deformed so as to follow the concave surface 112 .

After that, by stopping the operation of the intake and exhaust pump 117 and opening the hole 115 to the atmosphere, the elastic sheet 131 returns to its original shape and the insert sheet 151 can be released from the concave mold 111 . Since the support is plastically deformed, the insert sheet 151 permanently maintains the shape following the concave surface 112 even after being released from the concave mold 111 .
In this manner, the insert sheet 151 can be processed into a 3D curved surface.

In this processing method, since the elastic sheet 131 expands and contracts isotropically during processing, the insert sheet 151 is uniformly pressed against the concave mold 111 and adheres thereto. In addition, the support included in the insert sheet 151 is not softened by heating in advance, but is brought into close contact with the temperature-controlled concave mold 111 and is gradually softened by receiving heat.
Therefore, according to this processing method, the conductive layer included in the insert sheet 151 can be deformed while suppressing distortion and cracks in the direction along the curved surface. can also suppress distortion and cracking of electronic material layers. Even when the mechanical characteristics are uneven in the conductive layer, such as when the conductive layer is divided or when a plurality of TFTs are arranged in a matrix, the variation in distortion of the electronic material layer is suppressed. , uniform performance can be obtained.

FIG. 6 is a diagram showing another example of a three-dimensional curved surface forming method using a curved surface forming apparatus according to an embodiment of the present invention in order of steps.
The curved surface forming apparatus 100 may include a convex mold 121 fitted to the concave mold 111 and a temperature control section 126 for adjusting the temperature of the convex mold 121, as shown in FIG. When using this curved surface forming apparatus 100, after the insert sheet 151 is brought into close contact with the concave mold 111, the insert sheet 151 is pressed with the convex mold 121 whose temperature is controlled by the temperature control unit 126, thereby further improving the surface precision. It is possible to

In this processing method, the range of the concave surface of the concave mold is preferably wider than the insert sheet to be processed in plan view. In this case, the entire insert sheet can be brought into close contact with the concave surface without restraint, and the 3D curved surface can be processed while further suppressing distortion.

The temperature of the concave mold and the convex mold is adjusted, for example, in a range from the softening temperature (Tg) of the support to a temperature 20° C. lower than the softening temperature (Tg), and the flat plate before being brought into close contact with the concave mold. The temperature of the insert sheet is preferably adjusted to room temperature or a temperature 20° C. or more lower than the softening temperature.

Here, the members of the curved surface forming apparatus 100 will be described in more detail.

[Elastic sheet 131]
The elastic sheet 131 expands and contracts when decompressed or pressurized, and has a function of bringing the insert sheet into close contact with the mold. The elastic sheet 131 also has a function of transferring the heat of the mold to the insert sheet.
The material of the elastic sheet is not particularly limited and can be appropriately selected according to the purpose. For example, a known elastic rubber material can be used. Examples of elastic rubber materials include natural rubber, styrene-butadiene rubber (SBR), isoprene rubber (IR), butadiene rubber (BR), chloroprene rubber (CR), acrylonitrile-butadiene rubber (NBR), butyl rubber (isobutene-isoprene rubber (IIR)), ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), urethane rubber (U), silicone rubber (silicone rubber (Si, Q)), fluororubber (FKM), etc. .
Silicone rubber and fluororubber are particularly preferable as the material for the elastic sheet.

As the material of the elastic sheet, for example, thermoplastic elastomer such as styrene, olefin, ester, urethane, amide, polyvinyl chloride (PVC), and fluorine can be used. The material of the elastic sheet is preferably selected according to conditions such as temperature and pressure when forming the curved surface on the insert sheet. For example, it is preferable to select the material in consideration of heat resistance, elasticity, etc., depending on the conditions.

The average thickness of the elastic sheet is not particularly limited and can be appropriately selected depending on the intended purpose.
If the elastic sheet has stickiness, the insert sheet can be held without forming holes.

From the viewpoint of uniform deformation of the insert sheet, it is preferable that the elastic sheet is less likely to adhere to the insert sheet and the mold, and that the surface of the elastic sheet that contacts the insert sheet or the mold is slippery. After the curved surface is formed, the elastic sheet is peeled off from the mold and the insert sheet is removed from the elastic sheet.

The holes 132 of the elastic sheet 131 are provided to attract and hold the insert sheet 151 to the elastic sheet 131, and the number of holes 132 may be one or more. The position of the hole 132 can be arbitrarily set according to the shape of the insert sheet 151 .

[Molds 111, 121]
General molds can be used for the concave mold and the convex mold as long as they have a curved surface suitable for the 3D curved shape to be formed on the insert sheet, such as a spherical shape, and a heat capacity suitable for processing.
The material of the mold is not particularly limited and can be appropriately selected according to the purpose. Glass, ceramics, etc. can be used.
The temperature control part has a temperature control heater attached to the inside of the mold or the outer surface of the mold. The surface of the mold may be subjected to general heat resistance treatment or mold release treatment, or both.

The number and positions of the holes 115 in the concave mold 111 can be arbitrarily set according to the shape of the insert sheet 151 .

Next, a method of insert injection molding will be described as an example of the method of manufacturing the curved resin structure of the present invention.

In the present invention, an insert sheet 151 is installed on one side of a mold that can be opened and closed, and after the mold is closed, molten resin is injected and filled on the back of the support, and then cooled and solidified to form a welded resin portion (resin layer). Form.
In the present invention, an electric, hydraulic, or hybrid hydraulic injection molding machine can be used.

FIG. 7 is an explanatory diagram showing an embodiment of an insert injection molding apparatus for manufacturing a curved resin structure, which is an example of the present invention. 8A to 8C are diagrams showing the order of steps of a method for integrally molding an insert sheet using an insert injection molding apparatus.
As shown in FIG. 7, the insert injection molding apparatus 200 has an injection unit 230 and a mold clamping unit 240. As shown in FIG. The insert injection molding apparatus 200 injects the resin material heated and melted by the injection unit 230 into the mold of the mold clamping unit 240 with an injection nozzle or the like, and opens and closes the mold to form a resin molded body (curved resin structure). make.

The mold clamping unit 240 has a movable mold 221 and a fixed mold 211 , and the temperature of each mold is controlled by a temperature control section 226 and a temperature control section 216 .
One mold is provided with a sheet suction hole 212 and/or a step for positioning in order to install the insert sheet 151 if necessary. The sheet suction holes 212 are connected to an intake/exhaust pump 217 to suck the insert sheet 151 when fixing it, and eject gas such as air when removing the insert sheet 151 . The sheet suction hole 212 and the positioning step are formed to increase the positional accuracy of the insert sheet, and are not required if high positioning accuracy is not required.

When the insert sheet 151 is integrally molded with the resin (welding resin) forming the resin layer using the insert injection molding apparatus 200, first, the insert sheet 151 is prepared as shown in FIG. 8A. Further, the heating conditions are controlled by adjusting the temperature of the mold below the softening temperature (Tg) of the welding resin by means of the temperature controllers 216 and 226 .
Then, the insert sheet 151 is set in the mold 211 so as to close the suction holes 212 , and the insert sheet 151 is fixed by exhausting the air with the intake/exhaust pump 217 . The fixing of the insert sheet 151 by suction may be performed before injection of the welding resin.

The insert sheet 151 is preferably preformed as described above, but if the insert sheet is sufficiently fixed, preforming may be omitted. Although the insert sheet 151 is set in the fixed mold, it may be set in the movable mold 221 by changing the mold structure.

Next, as shown in FIG. 8B, the movable mold 221 is moved to close the mold, and the injection unit 230 injects molten welding resin into the resin injection part 213 to fill the resin.
The injection pressure (holding pressure) of the resin is preferably 100 MPa or more and 150 MPa or less when the resin to be injected is a polycarbonate resin or polycarbonate copolymer having a softening temperature of 110° C. or more and 150° C. or less. When the injection pressure (holding pressure) is 100 MPa or more, good curved surface accuracy can be obtained. layer) can be suppressed from being damaged by the injection pressure.

After the resin is cooled and solidified, as shown in FIG. 8C, the movable mold 221 is moved to open the mold, and the integrated laminate (curved surface resin structure) as shown in FIG. 9 is taken out.
In this manner, a curved resin structure in which the insert sheet 151 and the resin layer (welding resin) are integrally molded can be produced.

As the movable mold 221 and the fixed mold 211, general molds can be used as long as they match the shape of the laminate such as a flat surface, a curved surface, or a spherical surface and have a heat capacity suitable for processing.
Specifically, metal materials such as aluminum (Al) and nickel (Ni), steel materials for molds such as NAK80 and STAVAX, glass, and ceramics can be used as materials for the mold. The temperature control part has a temperature control heater attached to the inside of the mold or the outer surface of the mold. The surface of the mold may be subjected to general heat resistance treatment or mold release treatment, or both.
Furthermore, the movable mold 221 and the fixed mold 211 may be provided with an ejection mechanism such as an ejector pin for ejecting the molded body from the mold.

Further, in the present embodiment, the temperatures of the movable mold 221 and the fixed mold 211 are lower than the softening temperature of the resin support 11 . By doing so, softening of the support can be suppressed, and damage to the conductive layer can be suppressed. The temperature of the movable mold 221 and the fixed mold 211 is preferably 30° C. or higher and 150° C. or lower, for example. When the resin to be injected is a polycarbonate resin or a polycarbonate copolymer having a softening temperature of 110° C. or higher and 150° C. or lower, the temperature of the mold is preferably 40° C. or higher and 120° C. or lower. When the temperature of the mold is 30° C. or higher, good curved surface accuracy can be obtained. ) can suppress thermal damage.

Furthermore, in this embodiment, as shown in FIGS. 8A to 8C, a resin layer is integrally formed on the exposed back surface of the insert sheet by injecting from a direction substantially parallel to the front surface of the insert sheet. As a result, it is possible to improve the curved surface accuracy of the front and back surfaces of the molded product, and to improve the fluidity and filling speed of the resin to be discharged. Moreover, damage to the conductive layer, the electronic material layer, and the support due to the shear stress of the injected resin can be suppressed.
Further, the shape of the molten resin injection part (gate) of the mold is preferably a shape that is narrow in the thickness direction of the curved resin structure and does not face the side surface of the insert sheet. As the shape of the gate increases in the thickness and width directions, the fluidity of the injected resin and the filling speed are improved.

In this embodiment, it is preferable that the melt volume flow rate of the injected resin conforming to ISO 1133 is 14 cm ³ /10 min or more. In injection molding, damage to the insert sheet 151 due to shear stress can be reduced as the fluidity of the injected resin increases.

Examples of the present invention will be described below, but the present invention is not limited to these examples.

(Example 1)
In Example 1, an example of the curved resin structure 20 (electronic device substrate) described in the second embodiment was produced. The produced curved resin structure is useful as an electrochromic device component, and can also be used as it is as an electronic photochromic lens.

In Example 1, polycarbonate sheets (PC2151, manufactured by Teijin Limited, average thickness: 0.3 mm) were prepared as the supports 11a and 11b.
Materials for the underlayers 13a and 13b include an inorganic particle propylene glycol monomethyl ether dispersion (PGM-AC4120Y, manufactured by Nissan Chemical Industries, Ltd., methacrylic surface treatment, average particle size 10 nm to 15 nm, SiO ₂ ) as inorganic particles, and acid as resin. A modified epoxy acrylate oligomer resin (ZCR6002H, manufactured by Nippon Kayaku Co., Ltd.) was used. The content of the inorganic particles is adjusted to 150% by mass with respect to the total amount of the resin, and Omnirad TPO H (manufactured by IGM Resins B.V.) as a photoinitiator is added to 4% by mass with respect to the total amount of the resin. % and diluted with 1-methoxy-2-propanol was coated with a bar coater, dried at 80° C. for 120 sec, and cured by UV irradiation to form an underlayer A having an average thickness of 2 μm.
Next, an inorganic oxide conductive layer was formed on the underlayer by sputtering using an ITO target of 90% by mass In ₂ O ₃ and 10% by mass SnO ₂ . The sputtering power during film formation was set to 6.5 kW, the oxygen/argon flow ratio (O ₂ flow ratio) was set to 3.6%, and the average thickness of the conductive layer was adjusted to 110 nm during film formation. As a sputtering device, Solaris manufactured by Oerlikon was used.

A conductive layer was formed on one support in the region shown in FIG. 2A and on the other support in the region shown in FIG. 2B using a mask. The average thickness of the conductive layer was measured with an α-step D-500 manufactured by KLA-Tenchore.

Next, in the support on which the conductive layer is formed in the region shown in FIG. 2A, the region shown in FIG. 2C has (a) a triarylamine represented by the following structural formula A as the electronic material layer (oxidized EC layer) 15b. A radically polymerizable compound, (b) polyethylene glycol diacrylate, (c) a photopolymerization initiator, and (d) tetrahydrofuran were mixed with a:b:c:d=10:5:0.15:85 (mass ratio). The mixed solution was applied by an inkjet device and UV-cured in a nitrogen atmosphere to form an oxidation-reactive electrochromic layer having an average thickness of 1.5 μm.

<<Structural Formula A>>

KAYARAD PEG400DA manufactured by Nippon Kayaku Co., Ltd. was used as polyethylene glycol diacrylate. As a photopolymerization initiator, IRGACURE 184 (manufactured by IGM Resins B.V.) was used.

In addition, in the support on which the conductive layer was formed in the region shown in FIG. 2B, the reduced EC layer 15a was formed in the region shown in FIG. 2C. In the formation of the reduction-reactive electrochromic layer, a solution obtained by adding 1% by mass of polyvinyl butyral to a methanol dispersion of titanium oxide was applied and annealed at 100° C. for 5 minutes to form a nanoparticle titanium oxide layer having a thickness of 3 μm. formed.
Next, a solution obtained by dissolving 2% by mass of a compound represented by the following structural formula B in 2,2,3,3-tetrafluoropropanol was applied to the surface of the nanoparticle titanium oxide layer, and then subjected to adsorption treatment at 100°C. Annealed for 5 minutes.

<<Structural Formula B>>

(a) the (FSO ₂ ) ₂ N-salt of 1-ethyl-3-methylimidazolium, (b) polyethylene glycol diacrylate, and (c) a photoinitiator were then added to a:b:c=2: An electrolyte solution was prepared by mixing them at a ratio of 1:0.01 (mass ratio). After filling this electrolyte solution between the oxidation-reactive electrochromic layer and the reduction-reactive electrochromic layer, annealing treatment is performed at 60° C. for 1 minute, and the layers are cured by ultraviolet irradiation and bonded together. made the body. At this time, the filling amount of the electrolyte solution was adjusted so that the solid electrolyte layer 15c had an average thickness of 30 μm.

KAYARAD PEG400DA manufactured by Nippon Kayaku Co., Ltd. was used as polyethylene glycol diacrylate. As a photopolymerization initiator, IRGACURE 184 (manufactured by IGM Resins B.V.) was used. Further, the periphery of the electronic material layer was filled with a UV-curable acrylic material to which inorganic particles (oxide) were added and UV-cured to form a sealing portion (protective layer). TB3050B manufactured by ThreeBond Co., Ltd. was used as the inorganic particle-containing UV curable acrylic material.

Thereafter, using the curved surface forming apparatus 100, the bonded EC sheet (hereinafter referred to as "EC sheet 1") was processed into a 3D curved surface. In this processing, a spherical concave mold with a radius of curvature of 131 mm and a diameter of 200 mm was prepared, and a silicone rubber sheet with an average thickness of 0.3 mm was used as the elastic sheet.
Mold steel NAK80 was used as the material for the spherical concave mold. After controlling the temperature of the spherical concave mold at 140° C., the EC sheet 1 was placed on the elastic sheet as an insert sheet, and the elastic sheet and the EC sheet 1 were brought into close contact with the concave mold for 90 seconds by pump suction to cause plastic deformation. rice field.
Subsequently, by stopping the operation of the intake and exhaust pump and opening the holes to the atmosphere, the elastic sheet and the EC sheet 1 were released from the mold, and the EC sheet 1 having a spherical 3D curved surface was produced. A preformed insert sheet 1 was prepared.

Next, using the insert injection molding device 200, the EC sheet 1 is set in a fixed mold, and after the mold is clamped, a polycarbonate resin is injected to integrally mold the resin layer, and the surface having the shape shown in FIG. A curved resin structure (electronic device substrate) 20 having an electrochromic laminate inside was produced.
As an injection molding machine, SE-D (clamping pressure: 1,765 kN) C510SHP 32φ (Sumitomo Heavy Industries) was used. As the fixed mold and the movable mold, mold steel material STAVAX was mirror-finished to produce a shape having a diameter of 75.5 mm, a radius of curvature of 129 mm, and an average thickness of 10 mm. The shape of the gate was 35 mm (width direction) x 3 mm (thickness direction) in contact with the concave and convex surfaces of the molded product.

Polycarbonate 1 (L1225, manufactured by Teijin Limited, softening temperature: 146° C.) was used as the injected resin (resin forming the resin layer), and was annealed at 100° C. for 5 hours before injection.
The melt volume flow rate of the resin was 24.0 cm ³ /10 min (measurement temperature 300° C., measurement load 1.20 kgf).

The injection molding conditions were set as follows. Also, the cooling time was set to 200 sec.
・Mold temperature: 70℃/70℃ (fixed mold/movable mold)
・Resin temperature: 280℃
・Holding pressure: 110 MPa Holding pressure time: 30 sec
・Injection time: 4 sec

The convex surface in the longitudinal direction (45 mm) of the laminated portion of the curved resin structure 20 thus produced was measured with a surface roughness measuring instrument (Form TalySurf Series 2, manufactured by Taylor Hobson), and the radius of curvature and the curved surface displacement profile (from the radius of curvature) were measured. Amount of displacement) was confirmed, and the radius of curvature was 128.4 mm. rice field. Moreover, the surface curvature displacement at the boundary between the laminated portion and the non-laminated portion was 7.3 μm at maximum, confirming that the molded product was a low-distortion molded product of 20 μm or less. The surface curvature displacement profile of Example 1 is shown in FIG. 10A.
Furthermore, six prototypes of the curved resin structure 20 were produced, and damage to the laminated portion was observed with a surface inspection light (CRLM LED light CSPV-1000).

Next, the electronic device substrate 20 was evaluated for color appearance and disappearance. In this evaluation, a voltage of 2.0 V was applied so that one lead portion of the electronic material layer exposed from the protective layer (sealing member) became a positive electrode and the other lead portion became a negative electrode, and a voltage of 7 mC/cm ² was applied. Charge injected. As a result, it was confirmed that the oxidation-reactive electrochromic layer developed a blue-green color, and the reduction-reactive electrochromic layer developed a blue color. In addition, it was confirmed that when −0.6 V was applied, the film became transparent and decolored, and that the coloring and decoloring operations were performed normally. The light transmittance was measured using an ultraviolet-visible-near-infrared spectrophotometer UH4150 (manufactured by Hitachi High-Tech Science Co., Ltd.). Table 1 shows the conditions and evaluation results in Example 1.

(Example 2)
In Example 2, a curved resin structure (electronic device substrate) 20 was produced in the same manner as in Example 1, except that the injection molding conditions in Example 1 were changed as follows. Moreover, it evaluated similarly to Example 1. As a result, as in Example 1, the inflection points of the same phase of surface displacement in the longitudinal direction of the laminated portion were on both sides of the center of the laminated portion, satisfying the relationship rA1, rA2<rB. In addition, it was confirmed that the surface curvature displacement at the boundary between the laminated part and the non-laminated part was 1.2 μm at maximum, and that it was a low-distortion molded product of 20 μm or less, that the laminated part was not damaged, and that coloring and decoloring were good. was done. The surface curvature displacement profile of Example 2 is shown in FIG. 10B. Table 1 shows the conditions and evaluation results in Example 2.
・Mold temperature: 80℃/80℃ (fixed mold/movable mold)
・Resin temperature: 280℃
・Holding pressure: 120 MPa Holding pressure time: 30 sec
・Injection time: 2 sec

(Example 3)
In Example 3, a curved resin structure (electronic device substrate) 20 was produced in the same manner as in Example 1, except that the injection molding conditions in Example 1 were changed as follows. Moreover, it evaluated similarly to Example 1. As a result, as in Example 1, the inflection points of the same phase of surface displacement in the longitudinal direction of the laminated portion were on both sides of the center of the laminated portion, satisfying the relationship rA1, rA2<rB. In addition, it was confirmed that the surface curvature displacement at the boundary between the laminated part and the non-laminated part was 3.7 μm at maximum, and that it was a low-distortion molded product of 20 μm or less, that the laminated part was not damaged, and that the coloring was good. was done. Table 1 shows the conditions and evaluation results in Example 3.
・Mold temperature: 40℃/40℃ (fixed mold/movable mold)
・Resin temperature: 280℃
・Holding pressure: 150 MPa Holding pressure time: 30 sec
・Injection time: 2 sec

(Example 4)
In Example 4, a curved resin structure (electronic device substrate) 20 was produced in the same manner as in Example 1, except that the injection molding conditions in Example 1 were changed as follows. Moreover, it evaluated similarly to Example 1. As a result, as in Example 1, the inflection points of the same phase of surface displacement in the longitudinal direction of the laminated portion were on both sides of the center of the laminated portion, satisfying the relationship rA1, rA2<rB. In addition, the surface curvature displacement at the boundary between the laminated part and the non-laminated part was a maximum of 0.9 μm, and it was confirmed that it was a low-distortion molded product of 20 μm or less, but the laminated part was damaged in 2/6 pieces. did. A photograph of the damage is shown in FIG. It was confirmed that the undamaged molded product was good in coloring and decoloring. Table 1 shows the conditions and evaluation results in Example 4.
・Mold temperature: 100℃/100℃ (fixed mold/movable mold)
・Resin temperature: 280℃
・Holding pressure: 110 MPa Holding pressure time: 30 sec
・Injection time: 2 sec

(Example 5)
In Example 5, the mold curvature radius of the curved surface forming apparatus in Example 1 was changed to 87 mm, the curvature radius of the stationary mold and the movable mold of the injection molding machine was changed to 87 mm, and the thickness was changed to 10 mm. Polycarbonate 2 (SH1126Z, manufactured by Teijin Limited, softening temperature: 131 ° C.) was used as the resin (resin forming the resin layer), and it was annealed at 100 ° C. for 5 hours before injection in the same manner as in Example 1. A curved resin structure (electronic device substrate) 20 was produced.
The melt volume flow rate of the resin was 26.0 cm ³ /10 min (measurement temperature 300° C., measurement load 1.20 kgf).
Moreover, it evaluated similarly to Example 4. As a result, as in Example 1, the inflection points of the same phase of surface displacement in the longitudinal direction of the laminated portion were located on both sides of the center of the laminated portion, and the relationship of rA1, rA2>rB was established. In addition, the surface curvature displacement at the boundary between the laminated part and the non-laminated part was 3 μm at maximum, and the surface displacement at the laminated part was 3.5 μm at maximum. Damage to the laminated portion occurred in 6 sheets. The state of damage was the same as in Example 4. It was confirmed that the undamaged molded product was good in coloring and decoloring. The surface curvature displacement profile of Example 5 is shown in FIG. 10C. Table 1 shows the conditions and evaluation results in Example 5.
・Mold temperature: 60℃/60℃ (fixed mold/movable mold)
・Resin temperature: 270°C
・Holding pressure: 140 MPa Holding pressure time: 30 sec
・Injection time: 1.3 sec

(Example 6)
In Example 6, NF-2000 (manufactured by Mitsubishi Engineering-Plastics Co., Ltd., average thickness: 0.3 mm) was prepared as the polycarbonate sheet in Example 4, and In ₂ O ₃ : 99% by mass and ZrO ₂ were added on the underlayer. : Using a 1% by mass ITO target, a conductive layer of inorganic oxide is formed by sputtering, the sputtering power during film formation is set to 6.5 kW, and the oxygen/argon (Ar) flow ratio is 2.5. %, and a curved resin structure (electronic device substrate) 20 was produced in the same manner as in Example 4, except that the average thickness of the conductive layer was adjusted to 110 nm by the film forming time. Moreover, it evaluated similarly to Example 1. As a result, the inflection points of the same phase of the surface displacement in the longitudinal direction of the laminate were on both sides of the center of the laminate, satisfying the relationship rA1, rA2<rB. In addition, it was confirmed that the surface curvature displacement at the boundary between the laminated part and the non-laminated part was 1.5 μm at maximum, and that it was a low-distortion molded product of 20 μm or less, that the laminated part was not damaged, and that the coloring was good. was done. Table 1 shows the conditions and evaluation results in Example 6.
・Mold temperature: 100℃/100℃ (fixed mold/movable mold)
・Resin temperature: 280℃
・Holding pressure: 110 MPa Holding pressure time: 30 sec
・Injection time: 2 sec

(Example 7)
In Example 7, NF-2000 (manufactured by Mitsubishi Engineering-Plastics Co., Ltd., average thickness: 0.3 mm) was used as the polycarbonate sheet in Example 1, and the injection molding conditions were changed as follows. A curved resin structure (electronic device substrate) 20 was produced and evaluated. As a result, as in Example 1, the inflection points of the same phase of surface displacement in the longitudinal direction of the laminated portion were on both sides of the center of the laminated portion, satisfying the relationship rA1, rA2<rB. In addition, the surface curvature displacement at the boundary between the laminated part and the non-laminated part was a maximum of 0.8 μm, and it was confirmed that it was a low-distortion molded product of 20 μm or less, but the laminated part was damaged in 4/6 pieces. did. The state of damage was the same as in Example 4. It was confirmed that the undamaged molded product was good in coloring and decoloring. Table 1 shows the conditions and evaluation results in Example 7.
・Mold temperature: 120°C/120°C (fixed mold/movable mold)
・Resin temperature: 280℃
・Holding pressure: 130 MPa Holding pressure time: 30 sec
・Injection time: 2 sec

(Comparative example 1)
In Comparative Example 1, a curved resin structure (electronic device substrate) was produced in the same manner as in Example 1, except that preforming using the curved surface forming apparatus 100 was not performed in Example 1, and the injection molding conditions were set as follows. 20 was made. Moreover, it evaluated similarly to Example 1. As a result, it was an asymmetrical shape with no inflection points of the same phase of surface displacement in the longitudinal direction of the laminated portion on both sides of the center of the laminated portion. Also, a strain exceeding 20 μm was confirmed. In addition, it was confirmed that there was no damage to the laminated portion and that the coloring was good. The curved surface displacement profile of Comparative Example 1 is shown in FIG. 10D. Table 1 shows the conditions and evaluation results in Comparative Example 1.
・Mold temperature: 100°C/100°C (fixed mold/movable mold)
・Resin temperature: 280℃
・Holding pressure: 90 MPa Holding pressure time: 30 sec
・Injection time: 2 sec

(Comparative example 2)
In Comparative Example 2, a curved resin structure (electronic device substrate) 20 was produced in the same manner as in Example 1 except that the injection molding conditions in Example 1 were changed as follows. Moreover, it evaluated similarly to Example 1. As a result, no clear inflection point was confirmed in the surface curvature displacement of the laminated part. In addition, the surface curvature displacement at the boundary between the laminated part and the non-laminated part was 0.5 μm at maximum, confirming that it was a low-distortion molded product of 10 μm or less, and the laminated part was damaged in 6 out of 6 pieces. The damage was the same as in Example 4. Table 1 shows the conditions and evaluation results in Comparative Example 2.
・Mold temperature: 110℃/110℃ (fixed mold/movable mold)
・Resin temperature: 280℃
・Holding pressure: 160 MPa Holding pressure time: 30 sec
・Injection time: 2 sec

Evaluation criteria for “presence or absence of cracks” in Table 1 are shown below.
"◎": 6 out of 6 sheets had no cracks in the laminated part / conductive layer "○": 4 out of 6 sheets had no cracks in the laminated part / conductive layer "△": 2 out of 6 sheets No cracks occurred in the laminated part or conductive layer of the sheet "×": Cracks occurred in the laminated part / conductive layer of 6 out of 6 sheets

The evaluation criteria for "driving of coloring and disappearing" in Table 1 are shown below.
“○”: The entire electrochromic layer develops and disappears “×”: The cracked area does not develop color

Embodiments of the present invention are, for example, as follows.
<1> having a support and a laminated portion in which at least a conductive layer and an electronic material layer are laminated in the plane of the support;
The surface curvature radius of one end of the laminated portion is rA1 (mm), the surface curvature radius of the other end facing the one end centered on the central region of the laminated portion is rA2 (mm), and the surface average of the laminated portion is is a radius of curvature of rB (mm), and rA1, rA2 and rB satisfy the following inequality (1) or (2).
rA1, rA2<rB inequality (1)
rA1, rA2>rB inequality (2)
<2> having a support and a laminated portion in which at least a conductive layer and an electronic material layer are laminated in the plane of the support;
In the curved resin structure, a vertical surface displacement is 0.8 μm or more at a boundary between an end portion of the support where the laminated portion is not formed and the laminated portion.
<3> The curved resin structure according to any one of <1> to <2>, wherein the electronic material layer includes an electrolyte layer.
<4> The curved resin structure according to <3>, wherein the electrolyte layer is a solid electrolyte layer containing at least one of an ionic liquid and a polymer.
<5> The curved resin structure according to any one of <3> to <4>, wherein the electronic material layer contains an electrochromic material.
<6> The curved resin structure according to any one of <1> to <5>, further comprising an underlying layer between the support and the conductive layer.
<7> The curved resin structure according to <6>, wherein the base layer contains an epoxy resin.
<8> An electronic light control lens comprising the curved resin structure according to any one of <1> to <7>.
<9> A method for manufacturing a curved resin structure according to any one of <1> to <7>, comprising:
disposing a support having in its plane a laminated portion in which at least a conductive layer and an electronic material layer are laminated on the mold so as to be in contact with the mold;
The method of manufacturing a curved resin structure is characterized by including an insert injection molding step of injecting a resin onto the exposed support to integrally form a resin layer.
<10> Before the insert injection molding step, a support having a laminated portion in which at least a conductive layer and an electronic material layer are laminated is pressed against a heated curved mold to plastically deform the curved surface shape. The method for producing a curved resin structure according to <9> above, which includes a step of forming a curved surface of the support.
<11> In the insert injection molding step, the thickness of the resin injection part shape of the mold is equal to or less than the average thickness of the curved resin structure according to any one of <1> to <7>, and The method for manufacturing a curved resin structure according to any one of <9> to <10>, wherein the width of the injection part is larger than the thickness.
<12> In the insert injection molding step, the temperature of the mold is set to a temperature lower than the softening temperature of the resin by 10° C. or more, and the holding pressure is 100 MPa or more and 150 MPa or less. The method for manufacturing a curved resin structure according to any one of <9> to <11>, wherein the resin layer is integrally formed by injecting a resin.
<13> The method for manufacturing a curved resin structure according to any one of <9> to <12>, wherein the resin is a polycarbonate resin, and the temperature of the mold is 40°C or higher and 120°C or lower.

The curved resin structure according to any one of <1> to <7>, the electronic light control lens according to <8>, and the curved resin structure according to any one of <9> to <13>. According to the production method of , the various problems in the prior art can be solved and the object of the present invention can be achieved.

JP 2020-157759 A

REFERENCE SIGNS LIST 1 sheet with oxidized electrochromic (EC) part 2 sheet with reduced electrochromic (EC) part 10, 20 curved resin structure 11a, 11b support 12a, 12b conductive layer 13a, 13b base layer 14 sealing member 15 Electronic material layer 15a electrochromic layer (electrochromic part)
15b Solid electrolyte layer (solid electrolyte part)
15c electrochromic layer (electrochromic part)
16a, 16b drawer section 17 resin layer 18 gate section 19 lamination section 100 curved surface forming apparatus 200 insert injection molding apparatus 211 fixed mold 213 resin injection section 221 movable mold 230 injection unit

Claims (13)

a support, and a laminated portion in which at least a conductive layer and an electronic material layer are laminated in the plane of the support,
The surface curvature radius of one end of the laminated portion is rA1 (mm), the surface curvature radius of the other end facing the one end centered on the central region of the laminated portion is rA2 (mm), and the surface average of the laminated portion is is a radius of curvature of rB (mm), and rA1, rA2 and rB satisfy the following inequality (1) or (2).
rA1, rA2<rB inequality (1)
rA1, rA2>rB inequality (2) a support, and a laminated portion in which at least a conductive layer and an electronic material layer are laminated in the plane of the support,
A curved resin structure, wherein a vertical surface displacement is 0.8 μm or more at a boundary between an end portion of the support where the laminated portion is not formed and the laminated portion. 3. The curved resin structure according to claim 1, wherein said electronic material layer includes an electrolyte layer. 4. The curved resin structure according to claim 3, wherein said electrolyte layer is a solid electrolyte layer containing at least one of an ionic liquid and a polymer. 5. The curved resin structure according to claim 3, wherein said electronic material layer contains an electrochromic material. 6. The curved resin structure according to claim 1, further comprising an underlying layer between said support and said conductive layer. 7. The curved resin structure according to claim 6, wherein said base layer contains an epoxy resin. An electronic light control lens comprising the curved resin structure according to any one of claims 1 to 7. A curved resin structure manufacturing method for manufacturing the curved resin structure according to any one of claims 1 to 7, comprising:
disposing a support having in its plane a laminated portion in which at least a conductive layer and an electronic material layer are laminated on the mold so as to be in contact with the mold;
A method of manufacturing a curved resin structure, comprising an insert injection molding step of injecting a resin onto the exposed support to integrally form a resin layer. Before the insert injection molding step, a support having a laminated portion in which at least a conductive layer and an electronic material layer are laminated is pressed against a heated curved mold to plastically deform the support into a curved shape. 10. The method for manufacturing a curved resin structure according to claim 9, further comprising a step of forming a curved surface. In the insert injection molding step, the thickness of the resin injection part shape of the mold is equal to or less than the average thickness of the curved resin structure according to any one of claims 1 to 7, and the width of the resin injection part shape is The method for manufacturing a curved resin structure according to any one of claims 9 to 10, wherein the shape is larger than the thickness. In the insert injection molding step, the temperature of the mold is set to a temperature lower than the softening temperature of the resin by 10° C. or more, and the holding pressure is 100 MPa or more and 150 MPa or less, and the resin is injected onto the exposed support. 12. The method for manufacturing a curved resin structure according to any one of claims 9 to 11, wherein the resin layer is integrally formed by pressing. The method for manufacturing a curved resin structure according to any one of claims 9 to 12, wherein the resin is a polycarbonate resin, and the temperature of the mold is 40°C or higher and 120°C or lower.

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