JP2020011502A - Molding film and method for producing the same, and molded body and method for producing the same - Google Patents

Abstract

To provide a molding film in which lowering of conductivity by tensile force is suppressed.SOLUTION: A molding film has a conductive layer on a base film and forms the conductive layer on a base material surface having an uneven surface and a three-dimensional curved surface, in which a relationship between breaking elongation rates of each of the layers in a softening point temperature of the base film satisfies a breaking elongation rate of the base film>a breaking elongation rate of the conductive layer, the conductive layer is a cured product of a conductive composition containing a resin (A) and conductive fine particles (B), a ratio of the conductive fine particles (B) is 50-85 wt.% in the conductive layer, and the conductive fine particles (B) contain one or more conductive fine particles that are selected from silver powder, copper powder, silver coat powder, copper alloy powder, conductive oxide powder and carbon fine particles and have any one shape of a flat shape, a needle shape, a dendritic shape and a wire shape.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a molded film and a method for producing the same, a molded product, and a method for producing the same.

Patent Literature 1 discloses a resin molded body, a base film embedded so as to be flush with one surface of the resin molded body, and a conductive circuit disposed between the resin molded body and the base film. A specific conductive circuit integrated molded product having the following is disclosed.
Patent Literature 1 discloses a method for manufacturing a molded article integrated with a conductive circuit, in which a base film on which a specific conductive circuit is formed is placed on a cavity surface of an injection mold, and then molten resin is injected. Injection molding of a molded article is described.
In Patent Document 1, a conductive circuit is formed by etching a specific transparent metal thin film.

As a method of forming a conductive circuit instead of the etching method, a printing method using conductive ink is being studied. According to the method of printing a conductive ink, a conductive circuit can be easily formed without a complicated process as compared with the etching method, and productivity can be improved and cost can be reduced.
For example, Patent Document 2 discloses a low-temperature processing type conductive ink capable of forming a high-definition conductive pattern by screen printing, a specific conductive particle containing specific conductive fine particles and a specific epoxy resin. A water-soluble ink is disclosed. According to screen printing, it is said that the thickness of the conductive pattern can be increased and the resistance of the conductive pattern can be reduced.

  Patent Document 3 discloses a laminated sheet having a printed layer printed in a pattern on a transparent resin layer and a base film as a method of manufacturing a decorative sheet capable of expressing a three-dimensional effect. There is disclosed a method in which the decorative layer is formed into a concavo-convex shape along the pattern of the print layer by thermocompression bonding a laminated sheet having a decorative layer thereon.

JP 2012-11691 A JP 2011-252140 A JP 2007-296848 A

  According to the method of Patent Document 1, a conductor can be easily provided on the surface of a molded body. On the other hand, there is an increasing demand for forming a conductive circuit on the surface of a substrate having various shapes such as a substrate having an uneven surface or a curved surface. When a conductive circuit is formed by laminating a film having a conductive layer on such a substrate surface, the film needs to be deformed according to the surface shape of the substrate. When the film is deformed, a large tensile force may be partially generated in the conductive layer. The tensile force caused the conductive layer to break or the like, resulting in a problem of a decrease in conductivity.

  The present invention has been made in view of such circumstances, and it is an object of the present invention to provide a molded film in which a decrease in conductivity due to a tensile force is suppressed, a molded body having excellent conductivity, and a method for producing the same. And

The formed film according to the present embodiment has a conductive layer on the base film, and the relationship of the elongation at break of each layer at the softening point temperature of the base film satisfies the elongation at break of the base film> the elongation at break of the conductive layer. A molded film for forming a conductive layer on the surface of a substrate having an uneven surface or a three-dimensional curved surface,
The conductive layer is a cured product of a conductive composition containing a resin (A) and conductive fine particles (B),
The ratio of the conductive fine particles (B) in the conductive layer is 50 to 85% by weight, and the conductive fine particles (B) are silver powder, copper powder, silver coating powder, copper alloy powder, conductive oxide. It contains at least one type of conductive fine particles selected from powder, carbon fine particles, and having any shape of flat, needle, dendritic, and wire shapes.

One embodiment of the molded film of the present embodiment has a decorative layer and a conductive layer on a base film, and the relationship between the elongation at break of each layer at the softening point temperature of the base film is the elongation at break of the base film. > Elongation at break of decorative layer> Satisfies the elongation at break of conductive layer, is a molded film for forming a conductive layer on the surface of a substrate having an uneven surface or a three-dimensional curved surface,
The conductive layer is a cured product of a conductive composition containing a resin (A) and conductive fine particles (B),
The ratio of the conductive fine particles (B) in the conductive layer is 50 to 85% by weight, and the conductive fine particles (B) are silver powder, copper powder, silver coating powder, copper alloy powder, conductive oxide. It contains at least one type of conductive fine particles selected from powder, carbon fine particles, and having any shape of flat, needle, dendritic, and wire shapes.

One embodiment of the formed film of the present embodiment has an insulating layer and a conductive layer on a base film, and the relationship between the elongation at break of each layer at the softening point temperature of the base film is the elongation at break of the base film> Elongation at break of insulating layer> Satisfies the elongation at break of conductive layer, a molded film for forming a conductive layer on the surface of a substrate having an uneven surface or a three-dimensional curved surface,
The conductive layer is a cured product of a conductive composition containing a resin (A) and conductive fine particles (B),
The ratio of the conductive fine particles (B) in the conductive layer is 50 to 85% by weight, and the conductive fine particles (B) are silver powder, copper powder, silver coating powder, copper alloy powder, conductive oxide. It contains at least one type of conductive fine particles selected from powder, carbon fine particles, and having any shape of flat, needle, dendritic, and wire shapes.

One embodiment of the formed film of the present embodiment is a formed film having an insulating layer, a decorative layer, and a conductive layer on a base film,
The relationship between the elongation at break of each layer at the softening point temperature of the base film is as follows: elongation at break of base film> elongation at break of decorative layer> elongation at break of conductive layer elongation at break of base film> elongation at break of insulating layer> Simultaneously satisfying the elongation at break of the conductive layer, a molded film for forming the conductive layer on the surface of the substrate having an uneven surface or a three-dimensional curved surface,
The conductive layer is a cured product of a conductive composition containing a resin (A) and conductive fine particles (B),
The ratio of the conductive fine particles (B) in the conductive layer is 50 to 85% by weight, and the conductive fine particles (B) are silver powder, copper powder, silver coating powder, copper alloy powder, conductive oxide. It contains at least one type of conductive fine particles selected from powder, carbon fine particles, and having any shape of flat, needle, dendritic, and wire shapes.

  In one embodiment of the formed film of the present embodiment, the base film is a film selected from polycarbonate, polymethyl methacrylate, polypropylene, and polyethylene terephthalate, or a laminated film thereof.

  The molded article according to the present embodiment is a molded article in which the molded film is laminated on a substrate.

A first method for manufacturing a molded article according to the present embodiment includes a step of arranging the molded film of the present embodiment,
Integrating the molded film and the base material by an overlay molding method.

A second method for manufacturing a molded article according to the present embodiment includes a step of molding the molded film of the present embodiment into a predetermined shape,
A step of arranging the molded film after molding in a mold for injection molding,
Forming the base material by injection molding, and integrating the formed film and the base material.

A third manufacturing method of a molded article according to the present embodiment includes a step of disposing the molded film of the present embodiment in a mold for injection molding;
Forming the base material by injection molding and transferring at least the conductive layer in the formed film to the base material side.

  Advantageous Effects of Invention According to the present invention, it is possible to provide a molded film in which a decrease in conductivity due to tensile force is suppressed, a molded body having excellent conductivity, and a method for producing the same.

FIG. 1 is a schematic cross-sectional view illustrating an example of a formed film of the present embodiment. It is a typical sectional view showing another example of the cast film of this embodiment. It is a schematic process drawing which shows an example of the 1st manufacturing method of a molded object. It is a schematic process drawing which shows another example of the 2nd manufacturing method of a molded object. It is a schematic process drawing which shows another example of the 3rd manufacturing method of a molded object.

Hereinafter, the molded film, the molded body, and the manufacturing method thereof according to the present embodiment will be sequentially described in detail.
In the present embodiment, the cured product includes not only a product cured by a chemical reaction but also a product cured without a chemical reaction, for example, a product hardened by the evaporation of a solvent.

[Molded film]
The formed film of the present embodiment is a formed film for forming a conductive layer on the surface of a base material having an uneven surface or a three-dimensional curved surface having a conductive layer on a base film, and each layer at a softening point temperature of the base film. A molded film in which the relationship of the elongation at break satisfies the elongation at break of the base film> the elongation at break of the conductive layer, wherein the conductive layer contains a resin (A) and conductive fine particles (B). The conductive fine particles (B) occupy 50 to 85% by weight of the conductive layer, and the conductive fine particles (B) are silver powder, copper powder, silver-coated powder, copper Includes one or more conductive fine particles selected from an alloy powder, a conductive oxide powder, and a carbon fine particle, the shape being any one of flat, needle, dendritic, and wire shapes.

  According to the molded film of the present embodiment, it is possible to produce a molded film in which a decrease in conductivity due to a tensile force is suppressed.

The present inventors, as a conductive composition for forming a conductive layer for producing a molded film applicable to a non-flat substrate surface, as a result of variously selecting and examining conductive fine particles of different materials and shapes, The knowledge that the magnitude of the change in the resistance value of the conductive layer that occurs when the obtained molded film is pulled at a high temperature at which it can be molded is different depending on the type and amount of the conductive fine particles contained in the conductive composition is obtained. Was. The present inventors have conducted a study based on such knowledge, and as a result, a flat powder selected from silver powder, copper powder, silver coat powder, copper alloy powder, conductive oxide powder, and carbon fine particles on a resin film. , Needles, dendrites, conductive film containing no conductive fine particles of any shape of wire shape or conductive composition containing conductive fine particles in a specific ratio, when printed and heated and dried, molded film It was clarified that, when the resin composition was deformed by stretching at a high temperature corresponding to its softening point, the adhesion between the layer of the conductive composition and the resin film was reduced, or the conductive layer was cracked.
Even if it is a molded film having a conductive layer that causes a decrease in adhesion at the contact surface with the resin film when the film is deformed by pulling at such a high temperature, or cracks of the conductive layer occur, the single film is flat. When used as a flexible film circuit board, etc., or when used in a state of being bent on a two-dimensional curved surface, there has been a problem. However, when used as a molded film that follows and integrates the shape of a non-flat substrate surface, for example, an uneven shape or a three-dimensional curved surface shape, the molded film is accompanied by deformation. For this reason, it is expected that the conductivity of the conductive layer is reduced because the conductive layer cannot follow the deformation of the resin film and peeling or disconnection occurs.
In addition, the uneven surface and the three-dimensional curved surface in the present invention mean not only a surface having a gentle curved cross section, but also a general three-dimensional surface having an acute corner or a rectangular shape. That is, it refers to a three-dimensional shape that cannot be achieved only by deforming a plane without expanding and contracting, for example, a three-dimensional shape such as a hemispherical shape, a conical shape, a cylindrical shape, and a quadrangular prism shape. When a certain three-dimensional shape has both the above-described plane or two-dimensional curved surface and three-dimensional curved surface elements in a continuous three-dimensional surface, for example, one or more partial hemispherical shapes are combined with the planar shape. The obtained three-dimensional shape is a three-dimensional shape that cannot be established by deforming the plane as a whole without expanding and contracting, and thus is also assumed to be a three-dimensional curved surface. That is, the uneven surface and the three-dimensional curved surface in the present invention cannot be realized by bending a flexible substrate or the like, and have a shape that can be realized by, for example, shaping by three-dimensional molding under heating of a moldable film.
The present inventors have conducted intensive studies based on these findings, and as a result, the compounding ratio of the conductive fine particles in the conductive layer is 50 to 85% of the total solid content of the composition, and the conductive fine particles are silver powder. One or more conductivity selected from flat, needle, dendritic, and wire shapes selected from copper powder, silver-coated powder, copper alloy powder, conductive oxide powder, and carbon fine particles. Including fine particles, in addition to the above specific ratio and type, in addition to containing the conductive fine particles of the shape, the relationship between the elongation at break of the layer of the conductive composition at the softening point temperature of the base film, When satisfying the relationship of elongation at break of base film> elongation at break of conductive layer, it was found that the change in resistance value generated when the molded film was pulled was particularly remarkably small. Reached. Although the reason why such an effect can be obtained is unclear, there is a higher elongation at break of the base film in contact with the conductive layer as described above, and the conductive layer has a deformed shape with low symmetry as described above. By containing a filler, it suppresses the application of excessive stress to the network of conductive particles in the conductive layer during deformation of the molded film, and diffuses the stress efficiently, thereby exhibiting excellent conductivity maintenance characteristics. It is inferred.
That is, the molded film of the present invention uses the above resin (A) as a conductive composition for forming a conductive layer, and the conductive fine particles (B) having a specific material and shape with respect to the resin at a specific ratio, When the relationship between the elongation at break of each layer at the softening point temperature of the base film satisfies a specific order, a decrease in conductivity is suppressed even when used on an uneven substrate surface. Furthermore, by using the formed film, a formed body having a conductive circuit formed on an arbitrary surface such as an uneven surface or a curved surface can be obtained.

[Molded film]
The formed film of the present embodiment is a formed film having a conductive layer on a base film,
The conductive layer is a cured product of a conductive composition for forming a conductive layer of the molded film.
According to the molded film of the present embodiment, it is possible to obtain a molded body in which a conductive circuit is formed on an arbitrary substrate surface such as an uneven surface or a curved surface.
The layer structure of the molded film of the present embodiment will be described with reference to FIGS. 1 and 2 are schematic cross-sectional views showing an example of the formed film of the present embodiment.
A molded film 10 shown in the example of FIG. 1 has a conductive layer 2 on a base film 1. The conductive layer 2 may be formed on the entire surface of the base film 1 or may be formed in a desired pattern as in the example of FIG.
The molded film 10 shown in the example of FIG. 2 has the decorative layer 3 on the base film 1, has the conductive layer 2 on the decorative layer 3, and further has the conductive layer 2 and the decorative layer 3. Is provided with an insulating layer 6 on a part of. Further, as shown in the example of FIG. 2, the molded film 10 may include, on the conductive layer 2, the electronic component 4 and the pins 5 for connecting to a takeout circuit.
Although not shown, a resin layer for protecting the conductive layer or the electronic component may be provided on the conductive layer 2 or the electronic component 4, and the resin layer may be provided with a base material described later. May be a pressure-sensitive adhesive layer or an adhesive layer for improving the adhesion. Further, the insulating layer 6 may also serve as a pressure-sensitive adhesive layer or an adhesive layer for improving the adhesion to such a base material.
Although not shown, when the molded film 10 of the present embodiment includes the decorative layer 3, in addition to the example of FIG. 2, the base film 1 has the decorative layer 3 on one surface and the conductive film on the other surface. A layer configuration including the layer 2 may be used.
The molded film of the present embodiment has at least a base film and a conductive layer, and may have another layer as necessary. Hereinafter, each layer of such a formed film will be described.

<Conductive layer>
In the formed film of the present embodiment, the conductive layer is a cured product of a conductive composition described later. The conductive layer may be a patterned conductive layer or a solid conductive layer.
The method for forming the conductive layer is not particularly limited, but in this embodiment, a screen printing method, a pad printing method, a stencil printing method, a screen offset printing method, a dispenser printing method, a gravure offset using a fluid conductive composition is used. It is preferably formed by a printing method, a reverse offset printing method, or a microcontact printing method, and more preferably by a screen printing method.
In the screen printing method, it is preferable to use a screen having a fine mesh, particularly preferably a fine mesh of about 300 to 650 mesh, in order to cope with higher definition of the conductive circuit pattern. At this time, the open area of the screen is preferably about 20 to 50%. The screen wire diameter is preferably about 10 to 70 μm.
Examples of the type of the screen plate include a polyester screen, a combination screen, a metal screen, and a nylon screen. When printing a paste having a high viscosity, a high-tensile stainless steel screen can be used.
The screen printing squeegee may be any of a round shape, a rectangular shape, and a square shape, and a polishing squeegee may be used to reduce the attack angle (the angle between the printing plate and the squeegee). Other printing conditions may be appropriately designed based on conventionally known conditions.

After printing the conductive composition by screen printing, the conductive composition is heated and dried and crosslinked to cure.
For sufficient volatilization of the solvent and the crosslinking reaction, the heating temperature is preferably from 80 to 230 ° C, and the heating time is preferably from 10 to 120 minutes. Thus, a patterned conductive layer can be obtained.
The pattern of the conductive layer is not particularly limited. For example, a solid pattern such as a straight line, a curve, a mesh, a partial square, a circle, a diamond-shaped pattern, a solid pattern, and any combination thereof, or the entire conductive layer is entirely solid. It may be a pattern, and is not limited as long as the conductive layer functions as a conductive circuit or a part of the conductive circuit.

  The thickness of the conductive layer may be appropriately adjusted according to the required conductivity and the like, and is not particularly limited. For example, the thickness is 0.5 μm to 20 μm, and preferably 1 μm to 15 μm.

<Conductive composition>
The conductive composition for forming the conductive layer of the molded film of the present embodiment contains at least the resin (A) and the conductive fine particles (B), and further includes a crosslinking agent (C) if necessary. And other components may be contained. Hereinafter, each component of the conductive composition for forming a conductive layer of such a formed film will be described.

<Resin (A)>
The conductive composition of the present embodiment contains a resin (A) having a binder property in order to impart film formability and adhesion to a base film or a decorative layer. Further, in the present embodiment, by containing the resin (A), flexibility can be imparted to the conductive layer. Therefore, disconnection of the conductive layer due to stretching is suppressed by containing the resin (A).

The resin (A) can be appropriately selected and used from resins used for conductive composition applications.
As the resin (A), for example, acrylic resin, vinyl ether resin, polyether resin, polyester resin, polyurethane resin, epoxy resin, phenoxy resin, polycarbonate resin, polyvinyl chloride resin, polyolefin resin, styrene Examples include a system block copolymer resin, a polyamide system resin, and a polyimide system resin, which may be used alone or in combination of two or more.

In this embodiment, the resin (A) preferably has a substituent selected from a hydroxy group, an amino group, a carboxyl group, and an acid anhydride group. By having the substituent, affinity with the conductive fine particles (B) described below is improved, and adhesion to a base film or the like is also improved.
Furthermore, in this embodiment, the resin (A) preferably has two or more substituents selected from a hydroxy group, an amino group, a carboxyl group, and an acid anhydride group in one molecule. In this case, the resin (A) can be three-dimensionally cross-linked by being combined with a cross-linking agent (D) described later, and can be suitably used in applications where hardness is required for the conductive layer.

When the resin (A) has a functional group selected from a hydroxy group, an amino group, a carboxyl group, and an acid anhydride group, the functional group value is preferably from 1 mgKOH / g to 400 mgKOH / g, It is preferably from 2 mgKOH / g to 350 mgKOH / g. The details of the method for calculating the functional group value will be described in Examples described later.
When the resin (A) has a plurality of types of functional groups, the functional group value is the sum of the functional groups. For example, when the resin (A) has a hydroxy group and a carboxyl group, the functional group value represents the sum of the hydroxyl value and the acid value of the resin (A).

  The glass transition temperature (Tg) of the resin (A) is not particularly limited, but the glass transition temperature (Tg) of the resin (A) is 0 ° C or more and 150 ° C or less from the viewpoint of easy handling of the conductive layer. Is preferably 5 ° C. or more and 120 ° C. or less.

  In the present embodiment, the resin (A) may be used by synthesizing it according to Examples described later or other known methods, or a commercially available product having desired physical properties may be used. In this embodiment, the resin (A) can be used alone or in combination of two or more.

  The content ratio of the resin (A) in the conductive composition for forming the conductive layer of the molded film of the present embodiment is not particularly limited as long as it is appropriately adjusted according to the use and the like, but the solid content contained in the conductive composition is not particularly limited. The total amount is preferably 5% by mass or more and 50% by mass or less, more preferably 8% by mass or more and 40% by mass or less. When the content ratio of the resin (A) is equal to or more than the lower limit, film formability and adhesion to a base film or the like are improved, and flexibility can be imparted to the conductive layer. When the content of the resin (A) is equal to or less than the upper limit, the content of the conductive fine particles (B) can be relatively increased, and a conductive layer having excellent conductivity can be formed.

<Conductive fine particles (B)>
The conductive fine particles (B) are those in which a plurality of conductive fine particles come into contact in the conductive layer to exhibit conductivity. In the present embodiment, the conductive fine particles (B) are appropriately selected from those which can obtain conductivity without heating at a high temperature. Used selectively.
Examples of the conductive fine particles used in the present embodiment include metal fine particles, carbon fine particles, and conductive oxide fine particles.
Examples of the metal fine particles include, for example, simple metal powders such as gold, silver, copper, nickel, chromium, palladium, rhodium, ruthenium, indium, aluminum, tungsten, morbutene, and platinum, as well as copper-nickel alloy, silver-palladium alloy, Alloy powders such as copper-tin alloys, silver-copper alloys, and copper-manganese alloys, and metal coating powders obtained by coating the surface of the above-mentioned metal simple powder or alloy powder with silver or the like are included. Examples of the carbon fine particles include carbon black, graphite, and carbon nanotube. In addition, examples of the conductive oxide fine particles include silver oxide, indium oxide, tin oxide, zinc oxide, ruthenium oxide, and the like.

  In the present embodiment, it is particularly preferable to include one or more kinds of conductive fine particles selected from silver powder, copper powder, silver-coated powder, copper alloy powder, conductive oxide powder, and carbon fine particles. By using these conductive fine particles (B), a conductive layer having excellent conductivity can be formed without sintering.

  The shape of the conductive fine particles (B) is not particularly limited, and irregular shapes, aggregates, scales, microcrystals, spheres, flakes, wires, and the like can be appropriately used. From the viewpoint of maintaining conductivity during molding and the adhesion of the conductor pattern to the substrate, scaly, needle-like, aggregated, tree-like, and wire-like ones are preferred.

The average particle diameter of the conductive fine particles is not particularly limited, but from the viewpoint of the dispersibility in the conductive composition and the conductivity when the conductive layer is formed, is preferably 0.1 μm or more and 50 μm or less, more preferably 0.5 μm or more. It is more preferably 30 μm or less.
In the present embodiment, the average particle diameter of the conductive fine particles (B) is calculated as follows. According to the laser diffraction / scattering method described in JIS M8511 (2014), a commercially available surfactant polyoxyethylene octylphenyl is used as a dispersant using a laser diffraction / scattering particle size distribution analyzer (Microtrack 9220FRA manufactured by Nikkiso Co., Ltd.). An appropriate amount of the conductive fine particles (B) was added to an aqueous solution containing 0.5% by volume of ether (manufactured by Roche Diagnostics, Inc .: Triton X-100), and a 40 W ultrasonic wave was irradiated for 180 seconds with stirring. Then, the measurement was performed. The value of the obtained median diameter (D50) was defined as the average particle diameter of the conductive fine particles (B).

In this embodiment, the conductive fine particles (B) can be used alone or in combination of two or more.
The content ratio of the conductive fine particles (B) in the conductive composition for forming the conductive layer of the molded film of the present embodiment is not particularly limited as long as it is appropriately adjusted depending on the use and the like, but is included in the conductive composition. It is preferably from 45% by mass to 95% by mass, and more preferably from 50% by mass to 85% by mass, based on the total solid content. When the content ratio of the conductive fine particles (B) is at least the lower limit, a conductive layer having excellent conductivity can be formed. Further, when the content ratio of the conductive fine particles (B) is equal to or less than the above upper limit, the content ratio of the resin (A) can be increased, and the film formability and adhesion to a base film or the like are improved, and In addition, flexibility can be given to the conductive layer.

<Optional components>
The conductive composition for forming a conductive layer of the molded film of the present invention may further contain other components as necessary. Such other components include, in addition to the crosslinking agent (C) and the solvent (D), a dispersant, a friction resistance improver, an infrared absorber, an ultraviolet absorber, a fragrance, an antioxidant, an organic pigment, and an inorganic pigment. , An antifoaming agent, a silane coupling agent, a plasticizer, a flame retardant, a humectant, and the like.

<Crosslinking agent (C)>
The crosslinking agent (C) is used for crosslinking the resin (A). The cross-linking agent (C) can be appropriately selected from those having two or more reactive functional groups capable of forming a cross-link with the reactive functional group of the resin (A) in one molecule. Examples of such a reactive functional group include an epoxy group, an isocyanate group, a blocked isocyanate group, an alkyloxyamino group, an aziridinyl group, an oxetanyl group, a carbodiimide group, and a β-hydroxyalkylamide group.
The crosslinking agent (C) is preferably used in an amount of 0.05 to 30 parts by mass, more preferably 0.3 to 25 parts by mass, based on 100 parts by mass of the resin (A).

The solvent (D) is not particularly limited, but preferably has a boiling point of 180 ° C or more and 270 ° C or less from the viewpoint of continuous screen printability. Examples of the solvent include, but are not limited to, diethylene glycol monoethyl ether acetate, gamma-butyrolactone, and isophorone.

<Method for producing conductive composition for forming conductive layer of molded film>
The method for producing a conductive composition for forming a conductive layer of a molded film according to the present embodiment comprises the step of mixing the resin (A), the conductive fine particles (B), the crosslinking agent (C), and other components used as necessary. Any method can be used as long as it dissolves or disperses, and can be produced by mixing with a known mixing means.

<Base film>
In the present embodiment, the base film can be appropriately selected from those having flexibility and stretchability that can follow the shape of the substrate surface under the molding temperature conditions at the time of forming the molded body. It is preferable to select according to the production method of the molded article.
For example, when an overlay molding method or a film insert method described later is used as a method for manufacturing a molded body, it is considered that the base film remains in the molded body, and has a function as a protective layer of the conductive layer. To select the base film.
On the other hand, when the in-mold transfer method described below or the like is employed as a method for manufacturing a molded product, it is preferable to select a base film having releasability.

Base film can be appropriately selected from the above viewpoint, for example, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polystyrene, polyimide, polyamide, polyether sulfone, polyethylene naphthalate, polybutylene terephthalate, polyvinyl chloride, polyethylene, polypropylene , Cycloolefin polymer, ABS (acrylonitrile-butadiene-styrene copolymer resin), AES (acrylonitrile-ethylene-styrene copolymer resin), Kaidac (acrylic modified vinyl chloride resin), modified polyphenylene ether, and two or more of these resins A film such as a polymer alloy or a laminated film thereof may be used. Among them, a film selected from polycarbonate, polymethyl methacrylate, polypropylene, and polyethylene terephthalate, or a laminated film thereof is preferable. As the laminated film, a laminated film of polycarbonate and polymethyl methacrylate is particularly preferable.
The method for producing a laminated film of polycarbonate and polymethyl methacrylate is not particularly limited, and may be laminated by laminating a polycarbonate film and a polymethyl methacrylate film, or may be formed as a laminated film by co-extrusion of polycarbonate and polymethyl methacrylate. Good.
It is also preferable that the surfaces of these base films have been subjected to a modification treatment such as a corona treatment.

Further, if necessary, an anchor coat layer may be provided on a base film for the purpose of improving the printability of the conductive composition, and the conductive composition may be printed on the anchor coat layer. The anchor coat layer is not particularly limited as long as it adheres to the base film, and furthermore, adheres well to the conductive composition and follows the film at the time of molding. An inorganic filler such as a metal oxide may be added as necessary. The method for providing the anchor coat layer is not particularly limited, and it can be obtained by applying, drying and curing by a conventionally known coating method.
Further, if necessary, a hard coat layer may be provided on the base film in order to prevent the surface of the molded product from being damaged, and the conductive composition and, if necessary, a decorative layer may be printed on the opposite surface. The hard coat layer is not particularly limited as long as it has good adhesion to the base film and further has good surface hardness and follows the film at the time of molding, and is also an inorganic filler such as an organic filler such as resin beads or a metal oxide. May also be added as needed. The method for providing the hard coat layer is not particularly limited, and can be obtained by applying, drying, and curing by a conventionally known coating method.

  When the formed film of the present embodiment has a decorative layer, it is preferable to select a transparent base film.

  Although the thickness of the base film is not particularly limited, it can be, for example, 10 μm or more and 500 μm or less, and preferably 20 μm or more and 450 μm or less.

<Decoration layer>
The molded film of the present embodiment may have a decorative layer from the viewpoint of the design of the obtained molded body.
The decorative layer may be a layer having a single color, or may be a layer having an arbitrary pattern.
The decorative layer can be formed, for example, by preparing a decorative ink containing a coloring material, a resin, and a solvent, and then applying the decorative ink to a base film by a known printing means. .
The coloring material can be appropriately selected from known pigments and dyes. Further, as the resin, it is preferable to appropriately select and use the same resin as the resin (A) in the conductive composition for forming the conductive layer of the molded film of the present embodiment.
The thickness of the decorative layer is not particularly limited, but may be, for example, 0.5 μm or more and 10 μm or less, and preferably 1 μm or more and 5 μm or less.

<Insulating layer>
If necessary, an insulating layer may be provided on the patterned conductive layer so as to cover part or all of the conductive pattern. By providing the insulating layer, the reliability of the wiring formed by the conductive layer, particularly, the resistance to ion migration is improved. In addition, by preventing the concentration of stress on the wiring, it is possible to suppress a decrease or breakage of the conductivity due to a tensile force. Can be. In addition, in the production of a molded body described later, by providing an insulating layer on the outermost surface of the molded film on the side of the substrate, the adhesion between the molded film and the substrate can be improved.
The insulating layer is not particularly limited, and a known insulating layer can be applied. However, curing of a screen-printable insulating ink is preferable in terms of a film thickness capable of sufficiently covering the conductive layer and simple patterning. It is preferably formed of a material. As the screen-printable insulating ink, for example, a solvent-drying screen insulating ink using the resin (A) and a solvent having a boiling point of 180 to 270 ° C. and, if necessary, a crosslinking agent (C) can be used. An ultraviolet-curable screen insulating ink containing an ultraviolet-curable resin and a photoinitiator can also be suitably used. The insulating ink may contain a colorant such as a pigment or a dye, an inorganic filler, or an organic filler, if necessary, and may contain an antifoaming agent, a leveling agent, and the like.
The insulating property required for the insulating layer is not particularly limited, as long as short-circuiting and ion migration when the conductive layer is used as a circuit or the like can be suppressed, and the volume resistivity is about 10 ⁸ to 10 ¹⁶ Ω · cm. Preferably,
The thickness of the insulating layer is not particularly limited, but may be, for example, 0.5 μm or more and 40 μm or less, and preferably 1 μm or more and 30 μm or less.

When the formed film of the present embodiment has a base film and a conductive layer, the relationship of the elongation at break of each layer at the softening point temperature of the base film satisfies the relation of elongation at break of base film> elongation at break of conductive layer. preferable.
Further, when the formed film of the present invention has a base film, a decorative layer, and a conductive layer in this order, the relationship between the elongation at break of each layer at the softening point temperature of the base film is as follows: elongation at break of base film> It is preferable that the elongation at break of the decoration layer> the elongation at break of the conductive layer is satisfied.
Furthermore, when the formed film of the present invention has a base film, a conductive layer, and an insulating layer in this order, or has a base film, a decorative layer, a conductive layer, and an insulating layer in this order, The relationship between the elongation at break of each layer at the softening point temperature of the base film is as follows: elongation at break of base film> elongation at break of insulating layer> elongation at break of conductive layer. It is preferable that elongation> elongation at break of decorative layer> elongation at break of conductive layer.
By satisfying such a relationship, it is possible to prevent a tensile force from being concentrated on the conductive layer and to apply a large mechanical load, thereby further suppressing a decrease in conductivity due to the tensile force.

[Molded body]
The molded article of the present embodiment is a molded article in which the molded film is laminated on a base material. Since the molded article of the present embodiment is formed from the molded film of the present embodiment, the molded article has a conductive circuit formed of a cured product of the conductive composition formed on an arbitrary surface such as an uneven surface or a curved surface.
Hereinafter, three embodiments of the manufacturing method of the molded article of the present embodiment will be described. The molded article of the present embodiment is not limited to these methods as long as it is manufactured using the molded film of the present embodiment.

<First manufacturing method>
A first method for producing a molded article according to the present embodiment includes a step of arranging the molded film of the present embodiment on a substrate,
Integrating the molded film and the base material by an overlay molding method.
Hereinafter, a description will be given with reference to FIG. 3, but since the method of manufacturing a molded film is as described above, description thereof will be omitted.

FIG. 3 is a schematic process diagram illustrating an example of a first method for manufacturing a molded body. FIGS. 3A to 3C respectively show the molded film 10 and the base material 20 arranged in a chamber box of a TOM (Three Dimension Overlay Method) molding machine, and FIG. 3B and FIG. In), the chamber box is omitted.
In the first manufacturing method, first, the base material 20 is set on a table of the lower chamber box 22. Next, the molded film 10 of the present embodiment is passed between the upper chamber box 21 and the lower chamber box 22 and placed on the base material 20. At this time, the molded film 10 may be disposed so that the conductive layer faces either the base material 20 side or the side opposite to the base material 20, and is selected according to the use of the final molded body. Next, after the upper and lower chamber boxes are evacuated, the formed film is heated. Next, the base material 20 is raised 15 by raising the table. Next, only the inside of the upper chamber box 21 is opened to the atmosphere (FIG. 3B). At this time, the molded film is pressurized 16 on the substrate side, and the molded film 10 and the substrate 20 are bonded and integrated (FIG. 3C). Thus, the molded body 30 can be obtained.

In the first manufacturing method, the base material 20 can be prepared in advance by any method. In the first manufacturing method, the material of the base material 20 is not particularly limited, and may be made of resin or metal.

<Second manufacturing method>
A second method for manufacturing a molded article according to the present embodiment includes a step of molding the molded film of the present embodiment into a predetermined shape,
A step of arranging the molded film after molding in a mold for injection molding,
Forming the base material by injection molding, and integrating the formed film and the base material. Hereinafter, description will be made with reference to FIG. Note that the second manufacturing method may be referred to as a film insert method.

  FIG. 4 is a schematic process diagram illustrating an example of a second method for manufacturing a molded body. In the second manufacturing method, the formed film 10 is formed into a predetermined shape by a mold 11 in advance (FIG. 4A). After the molded film 10 is softened by heating or while being softened, the film is sucked into the mold by vacuum or pressed against the mold by compressed air, or both, and molded by the mold 11 (FIG. 4). (B)). At this time, the molded film 10 may be molded so that the conductive layer faces either the side of the base material 20 described later or the side opposite to the base material 20, and is selected depending on the use of the final molded body. . Next, the molded film 10 after molding is placed in the mold 12 for injection molding (FIGS. 4C to 4D). Next, the resin is injected 14 from the opening 13 to form the base material 20, and the molded film 10 and the base material 20 are integrated to obtain a molded body 30 (FIG. 4E). .

  In the second manufacturing method, it is not necessary to prepare the substrate 20 in advance, and the molding of the substrate and the integration with the molded film can be performed simultaneously. The material of the base material 20 can be appropriately selected and used from known resins used for injection molding.

<Third manufacturing method>
A third manufacturing method of a molded article according to the present embodiment includes a step of disposing the molded film of the present embodiment in a mold for injection molding;
Forming the base material by injection molding and transferring at least the conductive layer in the formed film to the base material side.
Hereinafter, description will be made with reference to FIG. Note that the third manufacturing method may be referred to as an in-mold transfer method.

  FIG. 5 is a schematic process diagram illustrating an example of a third method for manufacturing a molded body. In the third manufacturing method, as the molded film 10, a film having releasability is selected and used as a base film. The molded film 10 is disposed in the injection molding die 12 such that the conductive layer faces the base material 20 described later (FIG. 5A). Next, the resin is injected 14 from the opening 13 to form the base material 20, and at the same time, the molded film 10 and the base material 20 adhere to each other, and at least the conductive layer is transferred to the base material 20 side (see FIG. B)), and a molded body 30 is obtained (FIG. 5C). When the molded film 10 has a decorative layer, the decorative layer and the conductive layer are transferred, and when the molded film 10 has an insulating layer, the insulating layer and the conductive layer are transferred. When a decorative layer and an insulating layer are provided, the decorative layer, the insulating layer, and the conductive layer are simultaneously transferred.

  In the third manufacturing method, since it is not necessary to cut the base film, a long base film can be arranged as shown in the example of FIG. The material of the base material 20 can be appropriately selected and used from known resins used for injection molding.

The molded body thus obtained enables mounting of circuits, touch sensors, and various electronic components on plastic housings of home electric appliances, automobile parts, robots, drones, and the like. Further, it is extremely useful for reducing the size and weight of electronic devices, improving design flexibility, and increasing the number of functions.

Hereinafter, the present invention will be described in more detail with reference to examples, but the following examples do not limit the present invention in any way. In the examples, “parts” represents “parts by mass”, and “%” represents “% by mass”.
Further, the weight average molecular weight in the examples is a molecular weight in terms of polystyrene measured by using GPC (gel permeation chromatography) “HLC-8320” manufactured by Tosoh Corporation.

The “functional group value” in the examples is based on the molecular weight per functional group of each raw material (this is referred to as functional group equivalent), and the functional group amount per 1 g of raw material is equimolar by the following formula. In terms of potassium hydroxide equivalent mass (mg).
(Functional group value) [mgKOH / g] = (56.1 × 1000) / (functional group equivalent)
The functional group value is, for example, an acid value when the functional group is a carboxyl group, a hydroxyl value when the functional group is a hydroxy group, or an amine value when the functional group is an amino group. When comparing the functional group ratio between substances having different functional groups, it may be considered that the substances have the same molar amount if the functional group values are the same.

In the case where potassium hydroxide titration is used for quantification of a functional group such as a carboxyl group or a hydroxy group, for example, the water used for neutralization using a known and official measurement method defined in JIS K 0070 is used. The measured values (acid value and hydroxyl value) can also be directly obtained from an appropriate amount of potassium oxide, and can be treated in the same manner as the values calculated by the above formula.
In addition, even when the titration with potassium hydroxide is not used for the quantification of the functional group value, such as the isocyanate group, using the above functional group equivalent and the above calculation formula derived from the respective measured values representing the functional group amount, For convenience, it can be calculated as an equivalent amount of potassium hydroxide. A specific calculation example is shown below.

Calculation Example: As a compound having an isocyanate group, an isocyanate amount measured by a method specified in JIS K 6806 (a method in which an isocyanate group is reacted with n-dibutylamine and the remaining n-dibutylamine is titrated with an aqueous hydrochloric acid solution). Is calculated for a trifunctional isocyanate compound “X” in which is 23%. The functional group equivalent of the trifunctional isocyanate compound “X” is derived from the above isocyanate amount (%) and the molecular weight of the isocyanate group (NCO = 44 g / mol) as follows.
(Functional group equivalent of “X”) = 1 / (0.23 / 44) = 191.3
From the functional group equivalent of the trifunctional isocyanate compound “X” and the above formula for calculating the functional group value, the functional group value of the trifunctional isocyanate compound “X” can be calculated as follows.
(Functional value of trifunctional isocyanate compound "X") [mgKOH / g]
= (56.1 × 1000) /191.3=293.3

<Resins (A1), (A2)>
The following resins were used as the resins (A1) and (A2).
-Resin (A1): phenoxy resin manufactured by Mitsubishi Chemical Corporation, jER-4275, weight average molecular weight 60,000, glass transition point 73 ° C, hydroxy group (hydroxyl value 213 mgKOH / g) and epoxy group (epoxy value 5 mgKOH / g) Are contained two or more in one molecule.
-Resin (A2): Mitsubishi Chemical's acrylic resin, Dianal BR-84, weight average molecular weight 120,000, glass transition point 105 ° C, carboxyl group (acid value 6.5 mg KOH / g) 2 or more per molecule contains.

<Synthesis Example 1: Synthesis of resin (A3)>
In a reactor equipped with a stirrer, a thermometer, a rectification tube, a nitrogen gas introduction tube, and a decompression device, 10.1 parts of dimethyl terephthalate, 30.5 parts of dimethyl isophthalate, 12.9 parts of ethylene glycol, 1,5- 18.2 parts of pentanediol and 0.03 part of tetrabutyl titanate were charged and gradually heated to 180 ° C. while stirring under a nitrogen stream to carry out a transesterification reaction at 180 ° C. for 3 hours. Next, 28.3 parts of sebacic acid was charged and gradually heated to 180 to 240 ° C. to carry out an esterification reaction. The reaction was carried out at 240 ° C. for 2 hours, and the acid value was measured. When the acid value became 15 or less, the pressure in the reactor was gradually reduced to 1 to 2 Torr. When the viscosity reached a predetermined value, the reaction was stopped and the surface was removed. By transferring to a fluorinated pallet and cooling, the polyester resin (A3) having a weight average molecular weight of 45,000, a glass transition point of 58 ° C., and containing two or more hydroxy groups (hydroxyl value of 5 mg KOH / g) in one molecule. A solid was obtained.

<Synthesis Example 2: Synthesis of resin (A4)>
In a reactor equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube, a polycarbonate polyol obtained from 1,6-hexanediol and 3-methyl-1,5 pentanediol (“Kuraray polyol C” manufactured by Kuraray Co., Ltd.) -2090 ") 127.4 parts, 4.2 parts of dimethylolbutanoic acid, 19.2 parts of isophorone diisocyanate, and 32.5 parts of diethylene glycol monoethyl ether acetate were charged and reacted at 90 ° C. for 3 hours under a nitrogen stream. Then, by adding 193.7 parts of diethylene glycol monoethyl ether acetate, a weight average molecular weight of 34,000, a glass transition point of 2 ° C., a hydroxyl group (hydroxyl value of 4 mg KOH / g), and a carboxyl group (acid value of 10 mg KOH / g) were respectively obtained. Urethane resin (A3) 4 containing 2 or more in one molecule % To obtain a non-volatile content of 40% urethane resin (A4) a solution of 60% diethylene glycol monoethyl ether acetate solvent.

The following were used as the conductive fine particles, the solvent, and the crosslinking agent.
<Conductive fine particles (B1) to (B5)>
-Conductive fine particles (B1): Fukuda Metal Foil Powder Co., Ltd., flaky silver powder, average particle size 5.2 μm
-Conductive fine particles (B2): manufactured by Fukuda Metal Foil Powder Co., Ltd., aggregated silver powder, average particle size 1.7 μm
-Conductive fine particles (B3): manufactured by Mitsui Kinzoku Mining Co., Ltd., dendritic silver-coated copper powder, silver coverage 10%, average particle diameter 2 µm
Conductive fine particles (B4): manufactured by Ishihara Sangyo Co., Ltd., acicular conductive tin oxide powder, average particle diameter 1 μm
-Conductive fine particles (B5): manufactured by Ito Graphite, wire-shaped expanded graphite, average particle diameter 15 µm
-Conductive fine particles (B6): Dowa Electronics Co., Ltd., spherical silver powder, average particle diameter of 3.9 µm

<Crosslinking agent (C1), (C2)>
-Crosslinking agent (C1):
Baxeneden Chemicals' blocked isocyanate solution, Trixene BI7992, contains three blocked isocyanate groups in one molecule, nonvolatile content 70% (solvent (D2): 2-methoxypropanol)
-Crosslinking agent (C2):
Glycidylamine manufactured by Mitsubishi Chemical Corporation, jER604, containing four epoxy groups in one molecule, 100% non-volatile content

<Solvent>
-Solvent (D1): diethylene glycol monoethyl ether acetate, boiling point 217 ° C
-Solvent (D2): 2-methoxypropanol, boiling point 120 ° C

<Production Example 1: Preparation of decorative ink (F1)>
To 175 parts of the resin solution (A4) (70 parts as the resin (A4) alone), 10 parts of a phthalocyanine blue pigment (LIONOL BLUE FG7351 manufactured by Toyo Color Co., Ltd.) and 20 parts by mass of a titanium oxide pigment (TIPAQUE CR-93 manufactured by Ishihara Sangyo Co., Ltd.) After stirring and mixing and kneading with a three-roll mill (manufactured by Kodaira Seisakusho), a decorative ink (F1) was obtained by adding 5 parts of a crosslinking agent (C2) and 90 parts of a solvent (C1) and uniformly stirring and mixing. .

<Production Example 2: Preparation of decorative ink (F2)>
After 175 parts of the resin solution (A4) (70 parts as the resin (A4) alone) and 13 parts of carbon black pigment (MA-100 manufactured by Mitsubishi Chemical Corporation) were stirred and mixed, and kneaded with a three-roll mill (manufactured by Kodaira Seisakusho). A decorative ink (F1) was obtained by adding 5 parts of an isocyanate curing agent (Desmodur N3300, manufactured by Sumika Kovestoururethane Co., Ltd., 100% non-volatile content) and 90 parts of a solvent (C1) and uniformly stirring and mixing.

<Production Example 3: Preparation of insulating ink (G1)>
A resin solution comprising 70 parts of the resin (A3) and 130 parts of the solvent (C1) is prepared, and 5 parts of an isocyanate curing agent (Duranate 24A-100, manufactured by Asahi Kasei Corporation, 100% non-volatile content) and an antifoaming agent (manufactured by BYK-Chemie) are prepared. , BYK-1790), and uniformly stirred and mixed to obtain an insulating ink (G1).

<Production Example 4: Preparation of insulating ink (G2)>
50 parts of a urethane acrylate resin (manufactured by Nippon Soda Co., Ltd., TEAI-1000, nonvolatile content: 100%), 20 parts of isodecyl acrylate, 5 parts of a photoinitiator (manufactured by BASF, Darocur 1173, nonvolatile content: 100%), and an antifoaming agent (Big Chemie) (BYK-1790, non-volatile content: 100%), and the mixture was uniformly stirred and mixed to obtain an insulating ink (G2).

<Production Example 5: Preparation of conductive composition (E1) for forming conductive layer of molded film>
20.0 parts of the resin (A1) is dissolved in 30.0 parts of the solvent (C1), 80.0 parts of the conductive fine particles (B1) are stirred and mixed, and kneaded by a three-roll mill (manufactured by Kodaira Seisakusho) to form. A conductive composition (E1) for forming a conductive layer of a film was obtained.

<Production Examples 6 to 12: Preparation of conductive compositions (E2) to (E8) for forming conductive layer of molded film>
In Production Example 5, the types and amounts of the resin, the solvent, and the conductive fine particles were changed as shown in Tables 1 and 2, and as necessary, the same procedures as in Production Example 5 were carried out except that a crosslinking agent was further blended. Thus, conductive compositions (E2) to (E8) for forming a conductive layer of a molded film were obtained.
The numerical values of each material in Tables 1 and 2 are parts by mass.

<Comparative Production Examples 1 and 2: Preparation of conductive compositions (E9) and (E10) for forming conductive layer of molded film>
In Production Example 5, a conductive composition for forming a conductive layer of a molded film was prepared in the same manner as in Production Example 5 except that the types and amounts of the resin, the solvent, and the conductive fine particles were changed as shown in Table 3. E9) and (E10) were obtained. The numerical values of each material in Table 3 are parts by mass.

<Examples 1 to 8 and Comparative Example 1>
Polycarbonate (PC) film (manufactured by Teijin Limited, Panlite 2151, thickness 300 μm, softening point temperature 160 ° C.) On a substrate (300 mm × 210 mm), a conductive composition (E1) to (E1) to form a conductive layer of a molded film E10) was printed using a screen printing machine (Minomat SR5575 semi-automatic screen printing machine, manufactured by MinoScreen Inc.). Next, by heating in a hot air drying oven at 120 ° C. for 30 minutes, a conductive layer having a rectangular solid shape having a width of 15 mm, a length of 30 mm, and a thickness of 10 μm and a linear pattern having a line width of 3 mm, a length of 60 mm, and a thickness of 10 μm were formed. The resulting molded film was obtained.

<Examples 9, 10 and Comparative Example 2>
On a polycarbonate film (manufactured by Teijin Limited, Panlite 2151, thickness 300 μm, softening point temperature 160 ° C.), a decorative ink (F1) or (F2) is dried on a substrate (300 mm × 210 mm) using a blade coater. Coating was performed so that the thickness became 2 μm, and heating was performed at 120 ° C. for 30 minutes to form a decorative layer.
Next, in the above Examples 1 to 8, a polycarbonate film was prepared in the same manner as in Examples 1 to 8 except that the film with a decorative layer was used instead of the polycarbonate film and a conductive layer was formed on the decorative layer. Thus, a molded film in which the decorative ink layer and the conductor were laminated in this order was obtained.

<Examples 11 and 12, and Comparative Example 3>
A linear conductive layer pattern having a line width of 3 mm, a length of 60 mm, and a thickness of 10 μm was formed on the formed film on which the polycarbonate film, the decorative ink layer, and the conductor obtained in Examples 9 and 10 were laminated in this order. A screen printing machine (MinoScreen Co., Ltd.) is used to cover a part of the insulating ink (G1) in a rectangular shape having a length of 30 mm, a width of 20 mm, and a thickness of 15 μm based on the center of the linear conductive layer pattern. (Minomat SR5575 semi-automatic screen printer). Next, by heating in a hot air drying oven at 120 ° C. for 30 minutes, a molded film in which a polycarbonate film, a decorative ink layer, a conductor, and an insulating ink layer were laminated in this order was obtained.

<Examples 13 and 14>
Instead of using the insulating ink (G1) instead of the insulating ink (G2), a screen printing machine (manufactured by Minoscreen, Minomat SR5575 semi-automatic screen printing machine) is used, and then a conveyor is used instead of heating in a hot air drying oven at 120 ° C. for 30 minutes. Using the same type of UV irradiation apparatus (manufactured by Toshiba Lighting & Technology Co., Ltd., high-pressure mercury lamp, 120 W / cm), the integrated exposure amount was 1,500 mJ / cm2, except that UV irradiation was performed in the same manner as in Examples 11 and 12, A molded film in which a polycarbonate film, a decorative ink layer, a conductor, and an insulating ink layer were laminated in this order was obtained.
<Examples 15 and 16>
Instead of the molded film obtained by laminating the polycarbonate film, the decorative ink layer, and the conductor obtained in Examples 9 and 10 in this order, the molding provided with the conductive layer obtained in Examples 2 and 4. Except that a film was used, a molded film in which a polycarbonate film, a decorative ink layer, a conductor, and an insulating ink layer were laminated in this order was obtained in the same manner as in Example 12 or Example 13.

<Examples 17 to 32 and Comparative Examples 4 and 5>
In the above Examples 1 to 16, an acrylic resin film (Technoloy S001G, thickness 250 µm, softening point temperature 120 ° C) (300 mm x 210 mm) was used instead of the polycarbonate film substrate, and A molded film was obtained in the same manner as in Examples 1 to 16, except that each drying condition in a hot air drying oven was 80 ° C. for 30 minutes.

<Examples 33 and 34 and Comparative Example 6>
In Example 11, Example 14 and Comparative Example 1, instead of the acrylic resin film substrate, a polycarbonate resin / acrylic resin two-layer, two-layer co-extruded film (Technoloy C001, manufactured by Sumitomo Chemical Co., thickness 125 μm, softening point temperature) Example 11, Example 14, and Comparative Example 1 except that a conductive composition for forming a conductive layer of a molded film was printed on the polycarbonate resin side using a base material (300 mm x 210 mm) at 160 ° C). In the same manner as in the above, a molded film was obtained.

[(1) Volume resistivity measurement]
Regarding a square solid conductive layer of 15 mm × 30 mm formed on the molded films of Examples 1 to 34 and Comparative Examples 1 to 6, a resistivity meter (Loresta GP MCP-T610 manufactured by Mitsubishi Chemical Analytech Co., Ltd.) The volume resistivity (Ω · cm) was measured using a resistivity meter, JIS-K7194 compliant, 4-terminal 4-probe method, constant current application method (4-terminal probe at 0.5 cm intervals). The results are shown in Tables 1 to 3.

[(2) Evaluation of peel adhesion]
For a 15 mm × 30 mm square solid conductive layer formed on the molded films of Examples 1 to 34 and Comparative Examples 1 to 6, the above was performed with a cutter knife using a 1 mm interval cross cut guide manufactured by Gardner. A 10 × 10 square grid-like cut was made to penetrate the conductive layer, and a cellophane tape manufactured by Nichiban Co., Ltd. was adhered to the air, and the air that had been bitten was removed. The degree of peeling of the coating film was evaluated as follows in accordance with ASTM-D3519 standard. The results are shown in Tables 1 to 3.
(Peel adhesion evaluation criteria)
A: Evaluation 5B to 4B, excellent in adhesion B: Evaluation is 5B to 4B, but the coating film undergoes cohesive failure and a part of the coating film on the surface side is detached. C: Evaluation 3B or less, adhesion Inferior

[(3) Wiring resistance evaluation]
Cut and measure 70 mm in the longitudinal direction and 10 mm in the width direction so that the conductive layer of the linear pattern of 3 mm × 60 mm formed on the molded films of Examples 1 to 34 and Comparative Examples 1 to 6 is located in the middle, and measured. And a coupon. On the surface of the measurement coupon opposite to the conductive layer, two lines were added at 4 cm intervals with oily magic using a line perpendicular to the conductive layer from the longitudinal end as a mark. According to this mark, the resistance value was measured at a position at an interval of 40 mm using a tester, and the measured value was taken as the wiring resistance (Ω). The results are shown in Tables 1 to 3.

[(4) Thermal stretching evaluation 1]
The measuring coupons of Examples 1 to 16, 33, and 34 and Comparative Examples 1 to 3 and 6 were stretched in a heating oven at 160 ° C in the longitudinal direction at a pulling rate of 10 mm / min to an elongation of 50%. After removal from the oven and cooling, the presence or absence of disconnection was evaluated using an optical microscope. Further, the wiring resistance (Ω) at a position corresponding to the interval of 40 mm is measured based on the original mark in the same manner as the above-described measurement of the wiring resistance, and the wiring resistance after expansion / contraction / the wiring resistance before expansion / contraction is calculated as the resistance during thermal stretching. The rate of change (fold) was used, and each was evaluated according to the following criteria. The results are shown in Tables 1 and 3.
(Presence of disconnection)
A: No disconnection was observed.
B: One or two minor cracks were observed. C: Severe disconnection or peeling of the conductive coating film was observed (resistance change rate during hot stretching).
A: 5 times or more and less than 10 times B: 10 times or more and less than 100 times C: 100 times or more

The elongation rate is a value calculated as follows.
(Elongation ratio) [%] = {(length after stretching−length before stretching) / (length before stretching)} × 100

[(5) Thermal stretching evaluation 2]
In the heat stretching evaluation 1, except that the elongation rate was changed to 100%, the evaluation was performed in the same manner as the heat stretching evaluation 1 according to the following criteria. The results are shown in Tables 1 and 3.
(Presence of disconnection)
A: No disconnection was observed.
B: One or two minor cracks were observed. C: Severe disconnection or peeling of the conductive coating film was observed (resistance change rate during hot stretching).
A: 10 times or more and less than 100 times B: 100 times or more and less than 1000 times C: 1000 times or more

[(6) Thermal stretching evaluation 3]
The measurement coupons of Examples 17 to 32 and Comparative Examples 4 and 5 were stretched in a heating oven at 120 ° C. in a longitudinal direction at a pulling rate of 10 mm / min to an elongation of 50%. After removal from the oven and cooling, the presence or absence of disconnection was evaluated using an optical microscope. Further, the wiring resistance (Ω) at a position corresponding to the interval of 40 mm is measured based on the original mark in the same manner as the above-described measurement of the wiring resistance, and the wiring resistance after expansion / contraction / the wiring resistance before expansion / contraction is calculated as the resistance during thermal stretching. The rate of change (fold) was used, and each was evaluated according to the following criteria. The results are shown in Tables 2 and 3.
(Presence of disconnection)
A: No disconnection was observed.
B: One or two minor cracks were observed. C: Severe disconnection or peeling of the conductive coating film was observed (resistance change rate during hot stretching).
A: 5 times or more and less than 10 times B: 10 times or more and less than 100 times C: 100 times or more

[(7) Evaluation of hot stretching 4]
In the heat stretching evaluation 3, except that the elongation rate was changed to 100%, evaluation was performed in the same manner as the heat stretching evaluation 3 according to the following criteria. The results are shown in Tables 2 and 3.
(Presence of disconnection)
A: No disconnection was observed.
B: One or two minor cracks were observed. C: Severe disconnection or peeling of the conductive coating film was observed (resistance change rate during hot stretching).
A: 10 times or more and less than 100 times B: 100 times or more and less than 1000 times C: 1000 times or more

[(8) Measurement of elongation at break in Examples 1 to 34 and Comparative Examples 1 to 6]
The above conductive compositions (E1) to (E10) were dried on a base material of a release-treated PET film (manufactured by Lintec Corporation, CN100) by a screen printing machine (Minomat SR5575, a semi-automatic screen printing machine manufactured by MinoScreen). Was printed at 120 ° C. for 30 minutes in a hot-air drying oven to form a solid conductive layer of the conductive composition (E1). Next, the conductive layer was peeled from the release-treated PET film to obtain a conductive layer for elongation at break.
In addition, a polycarbonate film (manufactured by Teijin Limited, Panlite 2151, thickness 300 µm, softening point temperature 160 ° C) was prepared as a base film for elongation at break.
Further, for Examples 9 to 14, 25 to 30 and Comparative Examples 2, 3, and 5 using a decorative ink, a release-treated PET film substrate was separately prepared, and the decorative ink (F1) was formed on the substrate. To (F2) using a blade coater so that the dry film thickness becomes 5 μm.
Heating was performed at 20 ° C. for 30 minutes to form a decorative layer. Next, the decorative layer was peeled from the release-treated PET film to obtain a decorative layer for measuring the elongation at break.
In addition, for Examples 11 to 16, 27 to 34 and Comparative Example 3 using an insulating ink, a release-treated PET film base material was separately prepared, and the insulating inks (G1) to (G2) were formed on the base material. Using a blade coater, coating was performed so that the dry film thickness was 30 μm, and Examples 11, 12, 15, 27, 28, 31, and 33 were heated in a hot-air drying oven at 120 ° C. for 30 minutes, and For Examples 13, 14, 16, 29, 30, 32, and 34, an integrated exposure amount of 1,500 mJ / cm2 ultraviolet irradiation was performed using a conveyor type UV irradiation apparatus (manufactured by Toshiba Lighting & Technology Corp., high-pressure mercury lamp, 120 W / cm). As a result, an insulating layer was formed. Next, the insulating layer was peeled off from the release-treated PET film to obtain an insulating layer for measuring the elongation at break.
The conductive layer, decorative layer, insulating layer and base film for measuring the elongation at break were cut out into shapes each having a size of 60 mm × 10 mm. Examples 1 to 16, 33 and 34 and Comparative Examples 1 to 3 and 6, respectively, were used. The elongation at break was measured in a heating oven at 160 ° C. and in Examples 17 to 32 and Comparative Examples 4 and 5 in a heating oven at 120 ° C. at a tensile rate of 10 mm / min. The results are shown in Tables 1 to 3.

<Examples 35 to 37: Production of molded article>
A hemispherical ABS resin molded product having a radius of 3 cm is aligned so as to face the surface on the conductor side so as to overlap the position of the linear pattern of 3 mm × 60 mm of the molded films of Examples 1, 25 and 33, By performing overlay molding at a set temperature of 160 ° C. using a TOM molding machine (manufactured by Fuse Vacuum Co., Ltd.), a molded article in which a hemispherical molded film and an ABS resin molded product were integrated was obtained. As a result of checking the presence / absence of disconnection of the linear pattern and the rate of resistance variation during hot stretching, no disconnection was confirmed, and the variation of the resistance value was 10 times or more and less than 100 times. Was confirmed.

<Examples 38 to 40>
A hemispherical metal mold having a radius of 3 cm is placed so as to face the surface on the conductor side so as to overlap the position of the linear pattern of 3 mm × 60 mm of the molded films obtained in Examples 1, 25 and 33. Then, overlay molding was performed at a set temperature of 160 ° C. using a TOM molding machine (manufactured by Fuse Vacuum Co., Ltd.) to obtain a hemispherically shaped film for forming with a patterned conductor.
Next, the hemispherical molded film is set on an injection molding machine (IS170 (i5), manufactured by Toshiba Machine Co., Ltd.) to which a test mold for in-mold molding of a valve gate type is attached, and PC / ABS resin is set. (LUPOYPC / ABSHI5002, manufactured by LG Chemical Co., Ltd.) was injection-molded to obtain a molded body integrated with a molding film with a patterned conductor (injection conditions: screw diameter 40 mm, cylinder temperature 250 ° C., mold) Temperature (fixed side,
Movable side) 60 ° C, injection pressure 160MPa (80%), holding pressure 100MPa, injection speed 6
0 mm / sec (28%), injection time 4 sec, cooling time 20 sec). As a result of checking the presence / absence of disconnection of the linear pattern and the rate of resistance variation during hot stretching, no disconnection was confirmed, and the variation of the resistance value was 10 times or more and less than 100 times. Was confirmed.

[Summary of results]
The relationship between the elongation at break of each layer at the softening point temperature of the base film satisfies the elongation at break of the base film ≦ the elongation at break of the conductive layer. Occasionally, a break occurred and the resistance value was found to increase.

  On the other hand, from the results of Examples 1 to 34, the conductive composition of the present embodiment shows good adhesion of the obtained conductive layer and no disconnection or dropout due to stretching of the conductive layer at the time of molding, and the resistance value is also increased. Was kept in This is because the conductive path used in the conductive composition of the present embodiment has a high boiling point and specific types, shapes, and amounts of conductive fine particles are used. In addition, the relationship between the elongation at break of each layer at the softening point temperature of the base film satisfies a specific region, thereby suppressing excessive tensile stress concentration on the conductive layer during high-temperature molding, thereby maintaining conductivity. It is presumed that the stretching aptitude was exhibited.

  Also, from the results of Examples 35 to 40, according to the molded film provided with the conductive layer of the conductive composition of the present invention, even if the substrate surface is not a flat three-dimensional shape, an excellent wiring-integrated molded product was gotten.

  Thus, the molded film and the wiring-integrated molded body using the conductive composition of this embodiment can be directly designed into plastic housings and three-dimensional parts such as home appliances, automobile parts, robots and drones. It is possible to build a lightweight and space-saving circuit and to build touch sensors, antennas, planar heating elements, electromagnetic wave shields, inductors (coils), and resistors, and to mount various electronic components without compromising performance. To Further, it is extremely useful for reducing the size and weight of electronic devices, improving design flexibility, and increasing the number of functions.

DESCRIPTION OF SYMBOLS 1 Base film 2 Conductive layer 3 Decorative layer 4 Electronic component 5 Pin 6 Insulating layer 10 Molded film 11 Mold 12 Injection mold 13 Opening 14 Injection 15 Ascent 16 Pressurization 17 Resin 20 Base material 21 Upper chamber box 22 Lower chamber box 30 molded body

Claims (9)

Having a conductive layer on the base film, a molded film for forming a conductive layer on the surface of the substrate having an uneven surface or a three-dimensional curved surface,
A molded film, wherein the relationship of the elongation at break of each layer at the softening point temperature of the base film satisfies the elongation at break of the base film> the elongation at break of the conductive layer,
The conductive layer is a cured product of a conductive composition containing a resin (A) and conductive fine particles (B),
The ratio of the conductive fine particles (B) in the conductive layer is 50 to 85% by weight, and the conductive fine particles (B) are silver powder, copper powder, silver coating powder, copper alloy powder, conductive oxide. Powder, and at least one selected from the group consisting of flat, needle, dendritic, and wire-shaped, wherein the shape of the conductive fine particles (B) includes at least one selected from the group consisting of carbon fine particles. Molded film, including shape. On a base film, having a decorative layer and a conductive layer, a molded film for forming a conductive layer on the surface of the substrate having an uneven surface or a three-dimensional curved surface,
A relationship between the elongation at break of each layer at the softening point temperature of the base film, the elongation at break of the base film> the elongation at break of the decorative layer> the elongation at break of the conductive layer, a molded film,
The conductive layer is a cured product of a conductive composition containing a resin (A) and conductive fine particles (B),
The ratio of the conductive fine particles (B) in the conductive layer is 50 to 85% by weight, and the conductive fine particles (B) are silver powder, copper powder, silver coating powder, copper alloy powder, conductive oxide. Powder, and at least one selected from the group consisting of flat, needle, dendritic, and wire-shaped, wherein the shape of the conductive fine particles (B) includes at least one selected from the group consisting of carbon fine particles. Molded film, including shape. On a base film, having an insulating layer and a conductive layer, a molded film for forming a conductive layer on the surface of a substrate having an uneven surface or a three-dimensional curved surface,
A relationship between the elongation at break of each layer at the softening point temperature of the base film, elongation at break of base film> elongation at break of insulating layer> elongation at break of conductive layer, a molded film,
The conductive layer is a cured product of a conductive composition containing a resin (A) and conductive fine particles (B),
The ratio of the conductive fine particles (B) in the conductive layer is 50 to 85% by weight, and the conductive fine particles (B) are silver powder, copper powder, silver coating powder, copper alloy powder, conductive oxide. Powder, and at least one selected from the group consisting of flat, needle, dendritic, and wire-shaped, wherein the shape of the conductive fine particles (B) includes at least one selected from the group consisting of carbon fine particles. Molded film, including shape. On a base film, having an insulating layer, a decorative layer, and a conductive layer, a molded film for forming a conductive layer on the surface of a substrate having an uneven surface or a three-dimensional curved surface,
The relationship between the elongation at break of each layer at the softening point temperature of the base film is as follows: elongation at break of base film> elongation at break of decorative layer> elongation at break of conductive layer elongation at break of base film> elongation at break of insulating layer> A molded film that simultaneously satisfies the elongation at break of the conductive layer,
The conductive layer is a cured product of a conductive composition containing a resin (A) and conductive fine particles (B),
The ratio of the conductive fine particles (B) in the conductive layer is 50 to 85% by weight, and the conductive fine particles (B) are silver powder, copper powder, silver coating powder, copper alloy powder, conductive oxide. Powder, and at least one selected from the group consisting of flat, needle, dendritic, and wire-shaped, wherein the shape of the conductive fine particles (B) includes at least one selected from the group consisting of carbon fine particles. Molded film, including shape.   The molded film according to any one of claims 1 to 4, wherein the base film is a film selected from the group consisting of polycarbonate, polymethyl methacrylate, polypropylene, and polyethylene terephthalate, or a laminated film thereof.   A molded product in which the molded film according to any one of claims 1 to 5 is laminated on a substrate. A step of arranging the molded film according to any one of claims 1 to 5 on a substrate,
Integrating the molded film and the base material by an overlay molding method. Forming the molded film according to any one of claims 1 to 5 into a predetermined shape,
A step of arranging the molded film after molding in a mold for injection molding,
Molding a substrate by injection molding, and integrating the molded film with the substrate after the molding. A step of disposing the molded film according to any one of claims 1 to 5 in a mold for injection molding,
Molding a substrate by injection molding, and transferring at least the conductive layer in the molded film to the substrate side.