JP2022001414A - Molded film, molded body, and method for manufacturing the same - Google Patents

Abstract

To provide a molded film in which reduction of conductivity due to tensile force in a molding process and stress under high temperature is suppressed, and which has excellent ion migration resistance between conductive patterns even after molding.SOLUTION: A molded film for forming a printed conductive circuit coated by an insulator layer on a substrate surface having an uneven surface or a three-dimensional curved surface, in which the molded film is a molded film including a conductive layer and an insulator layer on a base film, the conductive layer is a cured product of a conductivity resin composition including resin (A1), conductive particles (D), and cross-linking agent (C1) if required, the insulator layer is a cured product of an insulating resin composition including the resin (A2) and the cross-linking agent (C2), the volume resistivity of the insulator layer is 1×1010 Ω cm or more and less than 1×1017 Ω cm, and the resin (A1) and the resin (A2) have a cross-linkable functional group that can react with the cross-linking agent (C2).SELECTED DRAWING: Figure 1

Description

The present invention relates to a molded film, a molded body, and a method for manufacturing the same, for forming a printed conductive circuit coated with an insulating layer on the surface of a base material having an uneven surface or a three-dimensional curved surface.

Patent Document 1 describes 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 arranged between the resin molded body and the base film. A specific conductive circuit integrated molded product having the above is disclosed.
In Patent Document 1, as a method for manufacturing the conductive circuit integrated molded product, a base film on which a specific conductive circuit is formed is placed on the cavity surface of an injection molding die, and then a molten resin is injected to form a resin. It is described that the molded body is injection-molded.
In Patent Document 1, the conductive circuit is formed by etching a specific transparent metal thin film.

As a method for forming a conductive circuit instead of the etching method, a printing method using conductive ink has been studied. According to the method of printing the conductive ink, as compared with the etching method, there is no complicated process, the conductive circuit can be easily formed, the productivity can be improved, and the cost can be reduced.
For example, Patent Document 2 describes a conductive ink containing specific conductive fine particles and a specific epoxy resin as a low-temperature treatment type conductive ink capable of forming a high-definition conductive pattern by screen printing. Is disclosed. According to screen printing, it is possible to increase the thickness of the conductive pattern, and it is said that the resistance of the conductive pattern can be reduced.

Further, in Patent Document 3, as a method for manufacturing a decorative sheet capable of expressing a three-dimensional three-dimensional effect, a laminate having a printed layer printed in a pattern on a transparent resin layer and a base film are provided. A method of forming the decorative layer into an uneven shape along the pattern of the printed layer by thermocompression bonding with a laminated sheet having a decorative layer on the top is disclosed.

Further, in Patent Document 4, the resin molded body and the base film are described by thermoforming the molded film in which the conductive pattern is formed by printing the conductive ink on the base film and integrating the resin molded body. Disclosed is a method for obtaining a conductive circuit integrated molded product having a conductive circuit between the two.

Japanese Unexamined Patent Publication No. 2012-11691 Japanese Unexamined Patent Publication No. 2011-252140 Japanese Unexamined Patent Publication No. 2007-296884 Japanese Unexamined Patent Publication No. 2019-189680

According to the method of Patent Document 1, a conductive circuit can be easily provided on the surface of the molded product. On the other hand, there is an increasing demand for forming a conductive circuit on the surface of a base material having various shapes such as a base material having an uneven surface or a curved surface. When a film having a conductive layer is laminated on the surface of such a base material to form a conductive circuit, the film needs to be deformed according to the surface shape of the base material. When the film is deformed, a large tensile force may be partially generated on the conductive layer. The tensile force causes breakage of the conductive layer, which causes a problem of deterioration of conductivity. Further, when forming a conductive circuit on a base material having such an uneven surface or a curved surface, the film having the conductive layer is deformed or deformed, and at the same time, the film and the base material are integrated. However, in this integration process, stress stress due to friction with the plastic substrate under high temperature is applied to the conductive circuit. The stress stress under high temperature also causes breakage of the conductive layer, which causes a problem of deterioration of conductivity.
On the other hand, in the method of Patent Document 4, since the conductive ink material is imparted with resistance to the thermoforming process, the decrease in conductivity due to the above-mentioned stress stress under high temperature is solved. However, on the other hand, in the conductive circuit formed on the surface of the three-dimensional base material by this method, the resin molded body and the conductive layer are in direct contact with each other, and the adhesion at the boundary portion is not always sufficient, and in reality, In some cases, extremely fine voids were formed. Therefore, when this conductive circuit integrated molded product is used as a practical device under harsh conditions for a long period of time, a short circuit between circuits due to ion migration has become a problem with the passage of time.

The present invention has been made in view of such circumstances, and the decrease in conductivity due to the tensile force in the molding process and the stress stress at high temperature is suppressed, and the ion migration resistance between the conductive patterns is improved even after molding. It is an object of the present invention to provide an excellent molded film, a molded body having excellent conductivity and capable of maintaining circuit characteristics even when used under harsh conditions for a long period of time, and a method for producing the same.

The molded film of the present invention is a molded film for forming a printed conductive circuit coated with an insulating layer on a substrate surface having an uneven surface or a three-dimensional curved surface, and the molded film has a conductive layer on a base film. A molded film with an insulating layer,
The conductive layer is a cured product of a conductive resin composition containing a resin (A1), a cross-linking agent (C1) if necessary, and conductive particles (D).
The insulating layer is a cured product of an insulating resin composition containing a resin (A2) and a cross-linking agent (C2).
The volume resistivity of the insulating layer is 1 × 10 ¹⁰ Ω · cm or more ^{and less than 1 × 10 17} Ω · cm.
The resin (A1) and the resin (A2) have a crosslinkable functional group capable of reacting with the crosslinker (C2).

In the molded film of the present invention, the resin (A1) and the resin (A2) each independently have one or more bonds selected from the group consisting of an ester bond portion, a carbonate bond portion, and an amide bond portion in the main chain.

The molded film of the present invention has at least one kind of the joint portion of the resin (A1) and at least one kind of the joint portion of the resin (A2) having the same kind of joint portion.

In the molded film of the present invention, the base film is a film selected from polycarbonate, polymethylmethacrylate, polypropylene, and polyethylene terephthalate, or a laminated film thereof.

In the molded film of the present invention, the cross-linking agent (C2) is a blocked isocyanate according to any one of the following i) to iii).
i) Block isocyanate with a number average molecular weight of 700 to 1300 having an isocyanurate structure ii) Block isocyanate with a number average molecular weight of 700 to 1300 having a biuret structure iii) Trimethylolpropane ester structure with a number average molecular weight of 1000 to 3000 Block isocyanate

In the molded film of the present invention, the crosslinkable functional group of the resin (A1) and the resin (A2) is a hydroxyl group or an amino group.

The molded film of the present invention is provided with a conductive layer and an insulating layer in this order on both surfaces of the base film, respectively.

The molded film of the present invention further includes a second conductive layer and a second insulating layer on the insulating layer in this order.

In the molded body of the present invention, a molded film molded into a predetermined shape is laminated on the base material so that the insulating layer surface and the base material surface are in contact with each other, or the base film surface and the base material surface are in contact with each other, and the uneven surface is formed. It is a molded body in which a printed conductive circuit coated with an insulating layer is formed on the surface of a base material having a three-dimensional curved surface.

The method for producing a molded film of the present invention includes a step of arranging the molded film on a substrate and a step of arranging the molded film.
A step of integrating the molded film and the base material by an overlay molding method is included.

The method for producing a molded film of the present invention includes a step of molding the molded film into a predetermined shape, a step of arranging the molded film after molding in a mold for injection molding, and molding of a base material by injection molding. In addition, the step of integrating the molded film and the base material is included.

In the method for producing a molded film of the present invention, the molding film described in the previous term is placed in a mold for injection molding, the base material is molded by injection molding, and the conductive layer in the molded film is placed on the base material side. Including the step of transferring to.

According to the present invention, a molding film in which a decrease in conductivity due to tensile force in a molding process and stress stress under high temperature is suppressed, and excellent ion migration resistance between conductive patterns even after molding, and excellent conductivity. Moreover, it is possible to provide a molded body capable of maintaining circuit characteristics even when used under harsh conditions for a long period of time, and a method for manufacturing the same.

It is a schematic cross-sectional view which shows an example of the molded film of this embodiment. It is a schematic cross-sectional view which shows another example of the molded film of this embodiment. It is a schematic cross-sectional view which shows another example of the molded film of this embodiment. It is a schematic cross-sectional view which shows another example of the molded film of this embodiment. It is a schematic process diagram which shows an example of the 1st manufacturing method of a molded body. It is a schematic process diagram which shows another example of the 2nd manufacturing method of a molded body. It is a schematic process diagram which shows another example of the 3rd manufacturing method of a molded body.

Hereinafter, the molded film, the molded body, and the manufacturing method thereof according to the present invention will be described in detail in order.
In the present invention, the cured product includes not only a product cured by a chemical reaction but also a product cured by a chemical reaction, for example, a product hardened by volatilization of a solvent.

[Molded film]
The molded film of the present invention is a molded film provided with a conductive layer and an insulating layer on a base film.
The conductive layer is a cured product of a conductive resin composition containing a resin (A1) and conductive particles (D), and the insulating layer contains a resin (A2) and a cross-linking agent (C2). It is a cured product of an insulating resin composition.
According to the molded film of the present invention, it is possible to obtain a molded body in which a conductive circuit is formed on an arbitrary base material surface such as an uneven surface or a curved surface.

The present inventors have a conductive resin composition that can be screen-printed or the like in order to produce a molded film that is applicable to an uneven substrate surface and has process suitability for an integration process with a plastic substrate. The material and the insulating resin composition were examined. In order to apply it to the production of molded films, the volume specific resistance of the conductive resin composition and the insulating resin composition, the resin skeleton, and the cross-linking agent component were examined. A molded film cross-linked by the cross-linking functional group of the resin contained in the conductive / insulating resin composition and the cross-linking agent contained in the insulating resin composition, and the affinity due to the difference in the type of the bonding portion of the resin. The difference between the presence or absence of disconnection and the magnitude of the resistance value change when pulled under a moldable high temperature and the ion migration characteristics over time when the conductive circuit integrated product is energized and used under harsh conditions for a long period of time. I found it.
As a result of studies based on such findings, the present inventors, when an insulating layer having a low volume resistivity is laminated on a conductive layer, is compared with a flat film circuit board or the like in a conductive circuit integrally formed product. , Confirmed that a significantly large ion migration occurs. Further, when the insulating layer formed on the conductive layer does not have a crosslinkable reactive group or does not have a crosslinking agent (C2), the insulating layer infiltrates the conductive layer and is pulled at a high temperature. It was found that the conductivity of the conductive layer was significantly deteriorated when the conductive layer was deformed.

When such an insulating layer having a slightly low resistivity is laminated on the conductive layer, or when the conductive layer is deformed by pulling at a high temperature, more cracks or local deformation of the conductive layer and accompanying ion migration occur. Even a molded film having a conductive layer and an insulating layer has become a problem when it is used alone as a flat film circuit board or the like, or when it is used in a state of being bent on a two-dimensional curved surface. However, when it is used as a molded film that follows and integrates the shape of the surface of a non-flat base material, for example, an uneven shape or a three-dimensional curved surface shape, the molded film is accompanied by deformation. Therefore, with respect to the deformation of the base film, the deformation stress generated for the conductive layer and the insulating layer is concentrated on the conductive layer and the conductive layer / insulating layer interface, causing peeling or disconnection, and the conductivity of the conductive layer is lowered. It is expected that there will be.
The uneven surface and the three-dimensional curved surface in the present invention refer not only to a surface having a gentle curved cross section but also to a general three-dimensional surface having acute-angled corners and a rectangular shape. That is, it refers to a three-dimensional shape that cannot be established only by deforming the plane without expanding and contracting, and refers to a three-dimensional shape such as a hemispherical shape, a conical shape, a columnar shape, or a square columnar shape. When a certain three-dimensional shape has elements of both the above-mentioned plane or two-dimensional curved surface and a three-dimensional curved surface in a continuous three-dimensional surface, for example, one or more partial hemispherical shapes are combined with the plane shape. As for the formed three-dimensional shape, since it is a three-dimensional shape that cannot be established by deforming the plane without expanding and contracting, it 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 are shapes that can be realized by, for example, shaping by three-dimensional molding under heating of a moldable film.

As a result of diligent studies based on these findings, the present inventors have found that the volume resistivity of the insulating layer is 1 × 10 ¹⁰ Ω · cm or more ^{and less than 1 × 10 17} Ω · cm, and the resin of the conductive layer. When a molded film having a crosslinkable reactive group capable of reacting (A1) and the resin (A2) of the insulating layer with the crosslinker (C2) is used, the occurrence of ion migration is suppressed in the conductive circuit integrated molded body. I found that. Further, by using the film, it is possible to obtain a molded body in which a conductive circuit having an insulating coating is formed on an arbitrary surface such as an uneven surface or a curved surface on a three-dimensional shaped base material having practical strength.

The layer structure of the molded film of this embodiment will be described with reference to FIGS. 1 and 2. 1 and 2 are schematic cross-sectional views showing an example of the molded film of the present embodiment.
The molded film 10 shown in the example of FIG. 1 has a conductive layer 2 on the base film 1 and an insulating layer 3 on the conductive layer 2. 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. Further, the insulating layer 3 may be formed on the entire surface of the base film 1 and the conductive layer 2, and is formed in a desired pattern so as to cover a part of the conductive layer 2 as in the example of FIG. You may.
The molded film 10 shown in the example of FIG. 2 has a decorative layer 6 on the base film 1, a conductive layer 2 on the decorative layer 6, and an insulating layer on the conductive layer 2. It is equipped with 3. Further, as shown in the example of FIG. 2, the molded film 10 may include an electronic component 4 and a pin 5 for connecting to a take-out circuit on the conductive layer 2.
The molded film 10 shown in the example of FIG. 3 has a conductive layer 2 on the base film 1 and an insulating layer 3 on the conductive layer 2. Further, the second conductive layer 7 is provided on the surface opposite to the base film 1, and the second insulating layer 8 is provided on the second conductive layer 7. The second conductive layer 7 may also 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. Further, the second insulating layer 8 may also be formed on the entire surfaces of the base film 1 and the second conductive layer 7, and may cover a part of the second conductive layer 7 as in the example of FIG. It may be formed in a desired pattern.
The molded film 10 shown in the example of FIG. 4 has a conductive layer 2 on the base film 1, an insulating layer 3 on the conductive layer 2, and a second conductive layer on the insulating layer 3. 7 is provided, and a second insulating layer 8 is provided on the second conductive layer 7. In this case, the second conductive layer 7 may be formed on the entire surface of the base film 1 and the insulating layer 3, and is not covered with the insulating layer 3 of the conductive layer 2 as in the example of FIG. If there is a portion, it may be provided in a desired pattern so as to partially contact the conductive layer 2. Further, it is not necessary that any portion of the conductive layer 2 is in contact with the conductive layer 2. The second insulating layer 8 may also be formed on the entire surface of the base film 1, the conductive layer 2, the insulating layer 3, and the second conductive layer 7, and the second conductive layer 7 may be formed as in the example of FIG. It may be formed in a desired pattern so as to cover a part of the above.
Further, although not shown, when the molded film 10 of the present embodiment includes the decorative layer 6, in addition to the example of FIG. 2, the decorative layer 6 is provided on one surface of the base film 1 and the other surface is conductive. It may have a layer structure including the layer 2.
The molded film of this embodiment includes at least a base film, a conductive layer and an insulating layer, and may have other layers if necessary. Hereinafter, each layer of such a molded film will be described.

<Base film>
In this embodiment, the base film can be appropriately selected from those having flexibility and stretchability that can follow the shape of the surface of the base material under the molding temperature conditions at the time of molding the base material. , It is preferable to select according to the manufacturing method of the molded product and the like.
For example, when an overlay molding method or a film insert method, which will be described later, is adopted as a method for manufacturing a molded body, consideration is given to having a function as a protective layer for a conductive layer because the base film remains in the molded body. You can select the base film.
On the other hand, when an in-mold transfer method or the like, which will be described later, is adopted as a method for producing a molded product, it is preferable to select a base film having peelability.

The base film can be appropriately selected from the above viewpoints, for example, polycarbonate, polymethylmethacrylate, 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), Kaidak (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, polymethylmethacrylate, polypropylene, polyethylene terephthalate, or a laminated film thereof is preferable. As the laminated film, a laminated film of polycarbonate and polymethylmethacrylate is particularly preferable.
The method for producing the laminated film of polycarbonate and polymethylmethacrylate is not particularly limited, and the polycarbonate film and the polymethylmethacrylate film may be laminated and laminated, or the polycarbonate and polymethylmethacrylate may be co-extruded to form a laminated film. good.
It is also preferable that the surface of these base films is subjected to a modification treatment such as a corona treatment.

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

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

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

<Conductive layer>
In the molded film of this embodiment, the conductive layer is a cured product of the conductive resin composition described later.
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 printing method, a reverse offset printing method, and a microcontact printing method are used. It is preferably formed by a method, and more preferably formed by a screen printing method.
In the screen printing method, it is preferable to use a fine mesh, particularly preferably a screen having a fine mesh of about 300 to 650 mesh, in order to cope with high definition of the conductive circuit pattern. The open area of the screen at this time is preferably about 20 to 50%. The screen wire diameter is preferably about 10 to 70 μm.
Examples of the screen version include polyester screens, combination screens, metal screens, nylon screens and the like. Further, when printing a high-viscosity paste state, a high-tensile stainless steel screen can be used.
The screen-printed squeegee may have a round, rectangular or square shape, and a polished squeegee can also be used to reduce the attack angle (the angle between the plate and the squeegee at the time of printing). For other printing conditions and the like, conventionally known conditions may be appropriately designed.

After printing the conductive resin composition, it is heated and dried or subjected to a cross-linking reaction to be cured.
For sufficient volatilization and cross-linking reaction of the solvent, the heating temperature is preferably 80 to 230 ° C. and the heating time is preferably 10 to 120 minutes. Thereby, a patterned conductive layer can be obtained.

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

[Conductive resin composition]
The conductive resin composition used in the molded film of this embodiment contains a resin (A1) and conductive particles (D), and further contains a solvent (B1) and a cross-linking agent (C1) as needed. ) And other components may be contained.
Hereinafter, each component of such a conductive resin composition for a molded film will be described.

<Resin (A1)>
The conductive resin composition of the present embodiment contains a binder resin (A1) in order to impart film forming property and adhesion to the base film or the decorative layer. Further, in this embodiment, the conductive layer can be imparted with flexibility by containing the resin (A1). Therefore, by containing the resin (A1), disconnection of the conductive layer due to stretching is suppressed.

The resin (A1) can be appropriately selected and used from the resins used for the conductive resin composition application.
Examples of the resin (A1) include acrylic resin, vinyl ether resin, polyether resin, polyester resin, polyurethane resin, epoxy resin, phenoxy resin, polycarbonate resin, polyvinyl chloride resin, polyolefin resin, and styrene. Examples thereof include a block copolymer resin, a polyamide resin, and a polyimide resin, and one type can be used alone or two or more types can be used in combination.

In this embodiment, the resin (A1) may contain a bond selected from the group consisting of an ester bond, a carbonate bond and an amide bond in the main chain.

In this embodiment, the resin (A1) contains a crosslinkable functional group. The crosslinkable functional group may be any crosslinkable functional group that can react with the crosslinking agent (C2) described later. It is preferably a substituent selected from a hydroxy group, an amino group, a carboxyl group and an acid anhydride group, and among these, it is preferable to use a hydroxy group and an amino group. By combining with the cross-linking agent (C2), the interface between the conductive layer and the insulating layer containing the resin (A1) is three-dimensionally cross-linked, so that the interfacial stress of the conductive layer can be reduced. Further, when the resin (A1) contained in the conductive layer and the resin (A2) contained in the insulating layer have the same crosslinkable reactive group, they are three-dimensionally crosslinked at the interface between the conductive layer and the insulating layer to have an affinity. It can be further improved and stress relaxation during thermal stretching and generation of cracks and voids can be suppressed. Further, these crosslinkable functional groups can be used for three-dimensional cross-linking of the resin (A1) by combining with a cross-linking agent (C1) described later, if necessary, and are suitably used in applications where hardness is required for the conductive layer. Can be done.

In this embodiment, the resin (A1) may be synthesized and used by the following examples or other known methods, or a commercially available product having desired physical properties may be used. In this embodiment, the resin (A1) can be used alone or in combination of two or more.

The content ratio of the resin (A1) in the conductive resin composition of the present embodiment may be appropriately adjusted according to the intended use and is not particularly limited, but is 5% by mass with respect to the total amount of solid content contained in the conductive resin composition. % Or more and 50% by mass or less, and more preferably 10% by mass or more and 40% by mass or less. When the content ratio of the resin (A1) is at least the above lower limit value, the film forming property and the adhesion to the base film and the like can be improved, and the conductive layer can be imparted with flexibility. Further, when the content ratio of the resin (A1) is not more than the above upper limit value, the content ratio of the conductive fine particles (D) can be relatively increased, and a conductive layer having excellent conductivity can be formed.

<Solvent (B1)>
The solvent (B1) is not particularly limited, but the boiling point is preferably 180 ° C. or higher and 270 ° C. or lower from the viewpoint of printability. Examples of the solvent include, but are not limited to, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, gamma butyrolactone, isophorone, and tetralin. In this embodiment, the solvent (B1) can be used alone or in combination of two or more.

<Conductive fine particles (D)>
The conductive fine particles (D) are those in which a plurality of conductive fine particles come into contact with each other in the conductive layer to develop conductivity. Selected and used.
Examples of the conductive fine particles used in this embodiment include metal fine particles, carbon fine particles, and conductive oxide fine particles.
Examples of the metal fine particles include single metal powders such as gold, silver, copper, nickel, chromium, palladium, rhodium, ruthenium, indium, aluminum, tungsten, morphten, and platinum, as well as copper-nickel alloys and silver-palladium alloys. Examples thereof include alloy powders such as copper-tin alloys, silver-copper alloys, and copper-manganese alloys, and metal-coated powders obtained by coating the surface of the metal single powder or the alloy powder with silver or the like. Examples of carbon fine particles include carbon black, graphite, and carbon nanotubes. Examples of the conductive oxide fine particles include silver oxide, indium oxide, tin oxide, zinc oxide, ruthenium oxide and the like.

In this embodiment, it is preferable to include one or more 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 (D), it is possible to form a conductive layer having excellent conductivity without sintering, and further, the stretchability and conductivity when molded into a three-dimensional shape as a molding film described later. It is possible to form a conductive layer having excellent property retention performance.

The shape of the conductive fine particles (D) is not particularly limited, but is preferably flake-shaped or chain-aggregated. In the case of a flake shape, the shape is not particularly limited as long as it is a flat shape having a two-dimensional plane shape. The "flake-like" in the present invention refers to a general flat shape of a two-dimensional plane called a scale-like, a scale-like, a plate-like, a flat-like, a sheet-like, or the like. Above all, the aspect ratio is 3 or more and 500 or less from the viewpoint of maintaining printability, maintaining conductivity during molding tension, and friction stress stress resistance with the base plastic at high temperature in the process of integrating with the plastic base material. Those are particularly preferable. Further, in the case of chain agglutination, it is not particularly limited as long as it has an indefinite shape in which fine spherical particles are bound to each other. The term "chain-aggregated" in the present invention refers to all irregular shapes formed by the settlement of spherical particles called bound spheres, chained spheres, agglutinated particles, and the like. The chain-aggregated form also maintains printability, maintains conductivity during molding tension, and is resistant to frictional stress and stress with the base plastic at high temperatures in the process of integrating with the plastic base material. Is particularly preferable.

The average particle size of the conductive fine particles is not particularly limited, but the dispersibility and printability in the conductive resin composition are maintained, the conductivity is maintained during molding, and the injection molding process resistance by the molten resin or the molded resin is obtained. From the viewpoint of high temperature tensile resistance, 0.5 μm or more and 30 μm or less are preferable, and 1 μm or more and 15 μm or less are more preferable.
In this implementation, the average particle size of the conductive fine particles (D) is calculated as follows. A commercially available surfactant polyoxyethylene octylphenyl is used as a dispersant using a laser diffraction / scattering type particle size distribution measuring device (Microtrac 9220FRA manufactured by Nikkiso Co., Ltd.) in accordance with the laser diffraction / scattering method described in JIS M8511 (2014). An appropriate amount of conductive fine particles (D) was added to an aqueous solution containing 0.5% by volume of ether (manufactured by Roche Diffractives Co., Ltd .: Triton X-100), and 40 W ultrasonic waves were irradiated for 180 seconds while stirring. After that, the measurement was performed. The value of the obtained median diameter (D50) was taken as the average particle size of the conductive fine particles (D).

In this embodiment, the conductive fine particles (D) can be used alone or in combination of two or more.
The content ratio of the conductive fine particles (D) in the conductive resin composition of the present embodiment may be appropriately adjusted according to the intended use and the like, and is not particularly limited. It is preferably 50% by mass or more and 85% by mass or less, and preferably 55% by mass or more and 80% by mass or less. When the content ratio of the conductive fine particles (D) is at least the above lower limit value, a conductive layer having excellent conductivity can be formed. Further, when the content ratio of the conductive fine particles (D) is not more than the above upper limit value, the content ratio of the resin (A1) can be increased, the film forming property and the adhesion to the base film or the like are improved, and also. , Flexibility can be imparted to the conductive layer.

<Arbitrary ingredient>
The conductive resin composition of the present invention may further contain other components, if necessary. In addition to the cross-linking agent (C1), such other components include dispersants, friction improvers, infrared absorbers, ultraviolet absorbers, fragrances, antioxidants, organic pigments, inorganic pigments, defoamers, and the like. Examples thereof include a silane coupling agent, a plasticizer, a flame retardant, and a moisturizing agent.

<Crosslinking agent (C1)>
In this embodiment, a cross-linking agent (C1) may be additionally used as an optional component for cross-linking the resin (A1). The cross-linking agent (C1) can be appropriately selected from those having two or more reactive functional groups in one molecule that can form cross-links with the reactive functional groups of the resin (A1). 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, a β-hydroxyalkylamide group and the like.

<Manufacturing method of conductive resin composition>
In the method for producing a conductive resin composition of this embodiment, the resin (A1), the conductive fine particles (D), a solvent (B1) used as necessary, a cross-linking agent (C1) and other components are dissolved. Any method may be used, and it can be produced by mixing with a known mixing means.

[Insulation layer]
In the molded film of this embodiment, the insulating layer is a cured product of an insulating resin composition containing a resin (A2) and a cross-linking agent (C2), and if necessary, a solvent (B2) and other components. Yes, the volume resistance value is 1 × 10 ¹⁰ Ω · cm or more ^{and less than 1 × 10 17} Ω · cm.
By covering the conductive layer with the insulating layer, it is possible to prevent frictional damage to the conductive layer during the manufacturing process of the molded film. It also serves as a heat-resistant stress protection layer that prevents frictional stress stress from the substrate under high temperature from being directly applied to the conductive layer. Furthermore, it is possible to secure the insulating property during long-term continuous energization between the conductive layer patterns, which means that the insulating resin composition surely permeates and seals the conductive layer having fine irregularities to every corner and also insulates. This is because the layer also acts as an adhesive layer with the resin molded body, so that it is possible to more reliably block moisture, sulfur compounds and other corrosive gases from the outside. In addition, it is possible to suppress the physical peeling of the molded film from the resin molded body base material against an impact from the outside.
The method for forming the insulating 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 printing method, a reverse offset printing method, and a microcontact printing method are used. It is preferably formed by a method, and more preferably formed by a screen printing method.
In the screen printing method, it is preferable to use a screen having a specific range of mesh, particularly preferably about 120 to 400 mesh, so that the conductive circuit pattern can be reliably insulated from the outside and a certain degree of patterning accuracy can be ensured. .. The open area of the screen at this time is preferably about 20 to 50%. The screen wire diameter is preferably about 10 to 70 μm.
Examples of the screen version include polyester screens, combination screens, metal screens, nylon screens and the like. Further, when printing a high-viscosity paste state, a high-tensile stainless steel screen can be used.
The screen-printed squeegee may have a round, rectangular or square shape, and a polished squeegee can also be used to reduce the attack angle (the angle between the plate and the squeegee at the time of printing). For other printing conditions and the like, conventionally known conditions may be appropriately designed.

The insulating layer used in the molded film of this embodiment is cured by printing an insulating resin composition, heating it, drying it, and performing a cross-linking reaction.
For sufficient volatilization and cross-linking reaction of the solvent, the heating temperature is preferably 80 to 230 ° C. and the heating time is preferably 10 to 120 minutes. Thereby, a patterned insulating layer can be obtained. The patterned insulating layer may cover the entire surface of the conductive pattern, but is a part of the conductive pattern while leaving an exposed conductive pattern surface so that it can be connected to an external device when the conductive pattern is used as a circuit. An insulating layer may be provided so as to cover the above.

The film thickness of the insulating layer may be appropriately adjusted according to the required insulating property and the like, and is not particularly limited, but may be, for example, 5 μm or more and 50 μm or less, and preferably 8 μm or more and 30 μm or less.

[Insulating resin composition]
The insulating resin composition used in the molded film of this embodiment contains a resin (A2) and a cross-linking agent (C2), and further contains a solvent (B2) and other components as necessary. It may be.
Hereinafter, each component of such an insulating resin composition for a molded film will be described.

<Resin (A2)>
The insulating resin composition of the present embodiment contains a binder resin (A2) in order to ensure film forming property and insulating property, and to impart adhesion to the conductive layer and the base film or the decorative layer.
Further, in this embodiment, by containing the resin (A2), it is possible to impart mechanical cushioning performance based on flexibility and toughness to the insulating layer when the insulating layer covers the conductive layer. Therefore, by containing the resin (A2), not only the breakage of the insulating layer due to stretching but also the breakage of the conductive layer is suppressed.

The resin (A2) can be appropriately selected and used from the resins used for the use of the insulating resin composition.
Examples of the resin (A2) include acrylic resin, vinyl ether resin, polyether resin, polyester resin, polyurethane resin, epoxy resin, phenoxy resin, polycarbonate resin, polyolefin resin, and styrene block copolymer resin. Examples thereof include polyamide-based resins and polyimide-based resins, and one type can be used alone or two or more types can be used in combination.

In this embodiment, the resin (A2) is also a group consisting of an ester bond, a carbonate bond and an amide bond when the above-mentioned resin (A1) contains a bond selected from the group consisting of an ester bond, a carbonate bond and an amide bond in the main chain. It is preferable that the main chain contains a more selected bond. By simultaneously including the above bond in the main chain of the resin (A1) and the resin (A2), the affinity between the conductive layer and the insulating layer is improved, and voids are generated at the interface between the conductive layer and the insulating layer and cracks during elongation are accompanied. -It is preferable in that the generation of defects and the subsequent ion migration are suppressed. Further, when the resin (A2) contains the same bond selected from the group consisting of an ester bond, a carbonate bond and an amide bond, which is the same as the above-mentioned resin (A1), the affinity between the conductive layer and the insulating layer is further improved. It is particularly preferable in that it is improved and the generation of voids at the interface between the conductive layer and the insulating layer and the accompanying cracks / defects during elongation and the subsequent ion migration are more strongly suppressed.

In this embodiment, the resin (A2) preferably has no halogen element in its structure or has an extremely low content. Since the halogen element is not present in the structure, it is preferable in that the ion migration resistance under harsh conditions is further excellent when used in a laminated manner with the conductive layer. Further, in this embodiment, the resin (A2) is particularly preferably a resin having a weight average molecular weight of 5,000 to 200,000, which contains an ester bond in the repeating structure. The resin having a weight average molecular weight of 5,000 to 200,000 containing an ester bond in the repeating structure allows the insulating layer to efficiently wet and spread on both the molded film and the surface of the conductive fine particles of the conductive layer and adhere strongly. At the same time, by exhibiting appropriate elasticity under high temperature conditions, it is possible to achieve both the protection property of the conductive layer from elongation during thermal molding and the ion migration resistance between the conductive patterns after forming the molded body at a high level. Will be.

In this embodiment, the resin (A2) has a crosslinkable functional group capable of reacting with the crosslinking agent (C2) described later. In particular, it is preferable to have two or more functional groups selected from a hydroxy group, an amino group, a carboxyl group and an acid anhydride group in one molecule. Among these, a hydroxy group and an amino group are preferable from the viewpoint of reactivity with the cross-linking agent (C2). By using the crosslinkable functional group, the solvent can be sufficiently volatilized, and the crosslink can be carried out at a low temperature while suppressing the generation of voids due to the leaving group. Further, the resin (A2) can be three-dimensionally crosslinked by combining with the cross-linking agent (C2), and can be suitably used for applications requiring hardness. Furthermore, when the insulating layer covers the conductive layer by cross-linking, the insulating layer is enhanced with mechanical cushioning performance based on flexibility and toughness, and the extensibility of the insulating layer itself during thermoforming is also balanced at a high level. Since it is possible to achieve both, it can be used more preferably.

In this embodiment, the resin (A2) may be synthesized and used by the following examples or other known methods, or a commercially available product having desired physical properties may be used. In this embodiment, the resin (A2) can be used alone or in combination of two or more.

The content ratio of the resin (A2) in the insulating resin composition of the present embodiment may be appropriately adjusted according to the intended use and is not particularly limited, but is 50 mass by mass with respect to the total amount of solid content contained in the conductive resin composition. It is preferably% or more and 100% by mass or less, and more preferably 70% by mass or more and 100% by mass or less. When the content ratio of the resin (A2) is at least the above lower limit value, the film forming property and the adhesion to the base film and the like can be improved, and the conductive layer can be imparted with flexibility.

<Solvent (B2)>
The solvent (B2) is not particularly limited, but the boiling point is preferably 180 ° C. or higher and 270 ° C. or lower from the viewpoint of printability. Examples of the solvent include, but are not limited to, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, gamma butyrolactone, isophorone, and tetralin. In this embodiment, the solvent (B2) can be used alone or in combination of two or more.

<Crosslinking agent (C2)>
In this embodiment, the cross-linking agent (C2) contains two or more reactive functional groups capable of cross-linking with the cross-linking functional groups of the resin (A1) and the resin (A2) in one molecule. When the cross-linking agent (C2) is cross-linked with the resin (A1) and the resin (A2), the affinity between the conductive layer and the insulating layer is improved, the stress between the interfaces is relaxed, and cracks in the wiring are generated. It can be suppressed. Further, when the resin (A1) and the resin (A2) have the same reactive functional group, as described above, the affinity between the conductive layer and the insulating layer is further improved, and the three-dimensional crosslinking is effectively promoted. It can be suitably used for applications requiring hardness.

Examples of the reactive functional group of the cross-linking agent (C2) 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. Among these, in this embodiment, an epoxy group, an isocyanate group, and a blocked isocyanate group can be preferably used.

Examples of the blocked isocyanate include bifunctional isocyanates such as hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, and isophorone diisocyanate, or allophanates thereof, biurets, adducts, prepolymers, isocyanurates, and the like. The isocyanate group of the bifunctional or higher functional isocyanate comprising the above is not particularly limited as long as it is an isocyanate compound protected (blocked) with ε-caprolactum, MEK oxime, or the like. Specifically, the isocyanate group of the above isocyanate compound is blocked with ε-caprolactam, MEK oxime, cyclohexanone oxime, pyrazole, 3,5-dimethylpyrazole, diisopropylamine, diethyl malonate, ethyl acetoacetate, phenol, etc. Can be mentioned. Further, an alcohol-blocked aromatic isocyanate such as N-alkoxycarbonylmelamine obtained by treating an aromatic nitrogen element such as melamine or benzoguanamine with an alcohol such as methanol or butanol and a carbonic acid ester compound can also be used.

Further, the blocked isocyanate used in this embodiment includes a blocked isocyanate having a number average molecular weight of 700 to 1300 having an isocyanurate structure, a blocked isocyanate having a biuret structure and a number average molecular weight of 700 to 1300, and a trimethyl propane ester structure. , It is preferable to use a number average molecular weight of 1000 to 3000. By using the blocked isocyanate, the cross-linking reaction can proceed at a low temperature with hydroxy groups and amino groups as the reactive functional groups of the resin (A1) and the resin (A2), and the conductive layer due to the tensile force can be promoted. In addition to suppressing the decrease in conductivity, it is possible to achieve a well-balanced balance of extensibility during thermal formation of the insulating layer itself at a high level.

<Manufacturing method of insulating resin composition>
The method for producing the insulating resin composition of the present embodiment may be any known method as long as it dissolves or disperses the resin (A2), the solvent (B2), the cross-linking agent (C2) and other components. It can be produced by mixing by a mixing means.

[Decoration layer]
The molded film of this embodiment may have a decorative layer from the viewpoint of the design of the obtained molded product.
The decorative layer may be a layer having a monochromatic tint, or may have an arbitrary pattern.
As an example, the decorative layer can be formed by preparing a decorative ink containing a coloring material, a resin, and a solvent, and then applying the decorative ink to the base film by a known printing means. ..
As the coloring material, a known pigment or dye can be appropriately selected and used. Further, as the resin, it is preferable to appropriately select and use the same resin (A2) as the resin (A2) in the insulating resin composition of the present embodiment.
The thickness of the decorative layer is not particularly limited, but can be, for example, 0.5 μm or more and 10 μm or less, and preferably 1 μm or more and 5 μm or less.

[Molded product]
In the molded body of this embodiment, the molded film formed into a predetermined shape is laminated on the base material so that the insulating layer surface and the base material surface are in contact with each other, or the base film surface and the base material surface are in contact with each other. It is a molded body in which a printed conductive circuit coated with an insulating layer is formed on the surface of a base material having an uneven surface or a three-dimensional curved surface.
Hereinafter, three embodiments will be described with respect to the method for manufacturing the molded product of the present embodiment. The molded product of the present embodiment may be any as long as it is manufactured by using the conductive resin composition and the insulating resin composition of the present embodiment, and is not limited to these methods.

<First manufacturing method>
The process of arranging the molded film on the substrate and
A step of integrating the molded film and the base material by an overlay molding method is included.
Hereinafter, the description will be made with reference to FIG. 3, but since the method for manufacturing the molded film is as described above, the description thereof will be omitted here.

FIG. 5 is a schematic process diagram showing an example of a first manufacturing method of a molded product. 5 (A) to 5 (C) show the molding film 10 and the base material 20 arranged in the chamber box of the TOM (Three dimension Overlay Method) molding machine, respectively, and FIGS. 5 (B) and 5 (C) show. ) Omits the chamber box.
In the first manufacturing method, first, the base material 20 is placed on the 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 arranged so that the conductive layer faces either the base material 20 side or the side opposite to the base material 20, and is selected depending on the final use of the molded product. Next, after the upper and lower chamber boxes are evacuated, the molded film is heated. Then, 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. 5 (B)). At this time, the molded film is pressurized 16 to the base material side, and the molded film 10 and the base material 20 are bonded and integrated (FIG. 5 (C)). In this way, 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. Examples of the material of the base material 20 in the first production method include polycarbonate, polymethylmethacrylate, polyethylene terephthalate, polybutylene terephthalate, polystyrene, polyamide, polyether sulfone, polyphenylene sulfide, polyvinyl chloride, polyethylene, polypropylene, and cyclo. Thermoplastic resins such as olefin polymers, ABS (acrylonitrile-butadiene-styrene copolymer resin), modified polypropylene ethers, and polymers alloys consisting of two or more of these resins, metals such as stainless steel, copper, and aluminum, and other glasses and ceramics. Etc. can also be used.

The frictional stress stress with the base material plastic at high temperature in the above-mentioned integration step with the base material in the first manufacturing method is that the molded film in FIG. 5 (C) is applied to the base material side. This is due to the frictional stress between the conductive circuit of the molded film and the base material under high temperature when the pressure 16 is applied and the molded film 10 and the base material 20 are bonded and integrated. That is, in the first manufacturing method, the conductive layer is simultaneously subjected to a load due to tensile stress during molding and a frictional stress stress with the base plastic at a high temperature.

<Second manufacturing method>
The second manufacturing method of the molded product according to this implementation is
The process of molding the molded film into a predetermined shape and
The step of arranging the molded film after molding in a mold for injection molding, and
It includes a step of molding a base material by injection molding and integrating the molding film and the base material. Hereinafter, it will be described with reference to FIG. The second manufacturing method may be referred to as a film insert method.

FIG. 6 is a schematic process diagram showing an example of a second manufacturing method of a molded product. In the second manufacturing method, the molded film 10 is preliminarily molded into a predetermined shape by the mold 11 (FIG. 6 (A)). The molding film 10 is formed by the mold 11 after being softened by heating or while being softened by suction to the mold by vacuum, pressing against the mold by pressure air, or both in combination (FIG. 6). (B)). At this time, the molded film 10 may be molded so that the conductive layer faces either the base material 20 side described later or the side opposite to the base material 20, and is selected depending on the final use of the molded body. .. Next, the molded film 10 after molding is placed in the mold 12 for injection molding (FIGS. 6 (C) to 6 (D)). 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. 6 (E)). ..

In the second manufacturing method, the base material 20 does not need to be prepared in advance, and the base material can be molded and integrated with the molded film at the same time. The material of the base material 20 can be appropriately selected and used from known resins used for injection molding. As an example of the material of the base material 20 in the second manufacturing method, the same thermoplastic resin as mentioned in the example of the material of the base material 20 in the first manufacturing method can be used.

The frictional stress stress with the base material under high temperature in the above-mentioned step of integrating with the base material in the second manufacturing method is that the resin is injected 14 from the opening 13 in FIG. 6 (E). This is due to the frictional stress that the conductive layer on the molded film receives due to the injection of the high-temperature molten resin into the mold when the base material 20 is formed and the molded film 10 and the base material 20 are integrated. It is a thing. That is, in the second manufacturing method, the conductive layer is subjected to a load due to tensile stress during molding, and then is subjected to frictional stress stress with the base plastic under high temperature in another step.

<Third manufacturing method>
The third manufacturing method of the molded product according to this implementation is
The step of arranging the molding film in the mold for injection molding and
It includes a step of molding a base material by injection molding and transferring the conductive layer in the molding film to the base material side.
Hereinafter, description will be made with reference to FIG. 7. The third manufacturing method may be referred to as an in-mold transfer method.

FIG. 7 is a schematic process diagram showing an example of a third manufacturing method of a molded product. In the third production method, the molded film 10 is selected and used as a base film having peelability. The molded film 10 is placed in a mold 12 for injection molding so that the conductive layer faces the base material 20 side described later (FIG. 7 (A)). 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 in close contact with each other, and at least the conductive layer is transferred to the base material 20 side (FIG. 7 (FIG. 7). B)), the molded body 30 is obtained (FIG. 7 (C)). When the molded film 10 has a decorative layer, the decorative layer and the conductive layer are 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. 7. The material of the base material 20 can be appropriately selected and used from known resins used for injection molding. As an example of the material of the base material 20 in the third manufacturing method, the same thermoplastic resin as mentioned in the example of the material of the base material 20 in the first manufacturing method can be used.

In the third manufacturing method, the frictional stress stress with the base material at a high temperature in the above-mentioned integration step with the base material is as follows: In FIG. 7C, the resin is injected 14 from the opening 13 and the resin is injected. This is due to the frictional stress that the conductive layer on the molded film receives due to the injection of the high-temperature molten resin into the mold when the base material 20 is formed and the molded film 10 and the base material 20 are in close contact with each other. .. That is, in the third manufacturing method, the conductive layer is simultaneously subjected to the load due to the tensile stress at the time of molding and the frictional stress stress with the base material at a high temperature.

The molded body thus obtained makes it possible to mount circuits, touch sensors, and various electronic parts on plastic housings such as home appliances, automobile parts, robots, and drones. In addition, it is extremely useful for making electronic devices lighter, thinner, shorter, smaller, improving the degree of freedom in design, and increasing the number of functions.

Hereinafter, the present invention will be described in more detail by way of examples, but the following examples do not limit the present invention in any way. In the examples, "part" represents "parts by mass" and "%" represents "% by mass".
The weight average molecular weight and the number average molecular weight in the examples are polystyrene-equivalent molecular weights in the measurement using GPC (gel permeation chromatography) "HLC-8320" manufactured by Tosoh Corporation.
The blocked effective NCO group content was calculated from "JIS K 1603-1: 2007 Plastic-Polyurethane Raw Material Aromatic Isocyanate Test Method-Part 1: How to Obtain Isocyanate Group Content".

<Resin (A1): (A-1) to (A-6)>
The following resins (A-1) to (A-6) were used as the resin (A1).
-Resin (A-1): Acrylic resin manufactured by Toa Synthetic Co., Ltd., "Alfon UC3000", weight average molecular weight 10,000, contains a carboxyl group as a crosslinkable functional group, and has an ester bond, an amide bond, or a carbonate bond in the main chain. I don't have it.
Resin (A-2): Phenoxy resin manufactured by Mitsubishi Chemical Corporation, "jER4250", weight average molecular weight 60000, containing a hydroxyl group as a crosslinkable functional group, and having no ester bond, amide bond, or carbonate bond in the main chain. ..
Resin (A-3): Polyester resin manufactured by Toyo Boseki Co., Ltd., "Byron 290", weight average molecular weight 22000, containing a hydroxyl group as a crosslinkable functional group, and having an ester bond in the main chain.
-Resin (A-4): Thermoplastic polyamide resin manufactured by Tsukino Foods Industry Co., Ltd., "Veggiem Green V550", containing an amino group as a crosslinkable functional group, and having an amide bond in the main chain.
-Resin (A-5): Polycarbonate resin manufactured by Mitsubishi Engineering Plastics Co., Ltd. "Iupilon FPC2136", which contains a hydroxyl group as a crosslinkable functional group and has a carbonate bond in the main chain.
-Resin (A-6): Acrylic resin manufactured by Mitsubishi Chemical Co., Ltd., "Dianal BR115", weight average molecular weight 55000, does not contain crosslinkable functional groups, and has ester bond, amide bond, and carbonate bond in the main chain. Do not.

<Resin (A2): (A-7) to (A-12)>
The following resins (A-7) to (A-12) were used as the resin (A2).
-Resin (A-7): Acrylic resin manufactured by Toa Synthetic Co., Ltd., "Alfon UC3080", weight average molecular weight 14000, containing a carboxyl group as a crosslinkable functional group, and any of an ester bond, an amide bond, and a carbonate bond in the main chain. I don't have it.
Resin (A-8): Polyester resin manufactured by Toyo Boseki Co., Ltd., "Byron GK880", weight average molecular weight 18000, containing carboxyl group and hydroxyl group as crosslinkable functional groups, and having an ester bond in the main chain.
Resin (A-9): Cellulose ester resin manufactured by Tomoe Kogyo Co., Ltd., "CAB-583-0.4", weight average molecular weight 20000, containing hydroxyl group as a crosslinkable functional group, ester bond, amide bond in the main chain, It does not have any of the carbonate bonds.
-Resin (A-10): Thermoplastic polyamide resin manufactured by Tsukino Foods Industry Co., Ltd., "Veggiem Green V59D", containing an amino group as a crosslinkable functional group, and having an amide bond in the main chain.

-<Synthesis Example 1: Synthesis of resin (A-11)>
328.2 parts of 1,4-butanediol, 903.5 parts of diphenyl carbonate, 2.6 parts of magnesium acetate tetrahydrate aqueous solution in a separable flask equipped with a stirrer, distillate trap, and pressure regulator (concentration: 8.4 g / L) was added and replaced with nitrogen gas. Under stirring, the internal temperature was raised to 160 ° C. to heat and dissolve the contents. Then, the pressure was lowered to 24 kPa, and the reaction was carried out for 90 minutes while removing the residual phenol from the system. Subsequently, the pressure was further reduced to 9.3 kPa, and then gradually reduced to 0.7 kPa to continue the reaction. Then, the temperature was raised to 170 ° C., and the reaction was carried out for 60 minutes while removing the residual phenol and the unreacted dihydroxy compound to the outside of the system to obtain a polycarbonate diol-containing composition. Subsequently, 30.5 parts of the above polycarbonate diol was placed in a separable flask equipped with a thermocouple and a cooling tube, and the flask was immersed in an oil bath at 60 ° C., and then 8.8 parts of isophorone diisocyanate and reaction suppression. 0.1 part of triisooctylphosphite was added as an agent, and the temperature was raised to 80 ° C. over 1 hour while stirring the inside of the flask under a nitrogen atmosphere. After raising the temperature, 0.03 part of Neostan U-830 was added as a urethanization catalyst, and after the heat generation had subsided, the temperature of the oil bath was raised again to 100 ° C., and the mixture was further stirred for 2 hours. Subsequently, the reaction product was diluted with 3.3 parts of dehydrated toluene. Subsequently, 80.5 parts of dehydrated N, N-dimethylformamide was added, and the flask was immersed in an oil bath at 55 ° C. and stirred to dissolve it. After stirring for another 1 hour, 0.215 parts of morpholine was added, and the mixture was further stirred for 1 hour to obtain a polyurethane solution having a weight average molecular weight of 51,000. Polyurethane was used by drying the polyurethane solution at 45 ° C. under reduced pressure overnight and diluting it with an ethylene glycol monoethyl ether acetate solution so as to have a solid content concentration of 40%. The polyurethane has a hydroxyl group and an amino group as a crosslinkable functional group.

-Resin (A-12): Acrylic resin manufactured by Mitsubishi Chemical Co., Ltd., "Dianal BR113", weight average molecular weight 30,000, does not contain crosslinkable functional groups, and has an ester bond, an amide bond, or a carbonate bond in the main chain. Do not.

The following substances were used as solvents, cross-linking agents, conductive fine particles and other components.
<Solvent (B-1) to (B-3)>
Solvent (B-1): 1,2,3,4-tetrahydronaphthalene, boiling point 209 ° C.
Solvent (B-2): diethylene glycol monoethyl ether acetate, boiling point 217 ° C.
-Solvent (B-3): Propylene glycol monomethyl ether, boiling point 121 ° C.

<Crosslinking agents (C-1) to (C-6)>
-Crosslinking agent (C-1)
Isocyanuric acid derivative manufactured by Shikoku Kasei Co., Ltd., "MA-DGIC", contains two epoxy groups as cross-linking sites in one molecule. 100% non-volatile content.
-Crosslinking agent (C-2)
Baxeneden Chemicals blocked isocyanate solution, Trixene BI7982, isocyanurate modified product containing 3 isocyanate groups blocked with dimethylpyrazole in one molecule, effective NCO group content 10.2%, number average molecular weight 792, Non-volatile content 70% (solvent (B-3): propylene glycol monomethyl ether)
-Crosslinking agent (C-3)
Made by Asahi Kasei Corporation, Duranate TPA-100, isocyanurate modified hexamethylene diisocyanate, contains 3 isocyanate groups in 1 molecule, NCO group content 23.1%, number average molecular weight 504, non-volatile content 100%.

-<Synthesis Example 2: Synthesis of Crosslinking Agent (C-4)>
Mitsui Chemicals, Inc., Takenate D-165N (biuret modified hexamethylene diisocyanate, containing 3 isocyanate groups in 1 molecule, NCO group content 23.5%) 15.0 parts into a flask with a stirring rod It was charged and the temperature was raised to 80 ° C. Subsequently, 2.0 parts of methyl ethyl ketooxime was gradually added, and after all was added, the mixture was stirred for 2 hours. After confirming the disappearance of the absorption peak derived from isocyanate by FT-IR, the reaction was stopped to obtain 17.4 parts of blocked isocyanate having a biuret structure and blocked with methyl ethyl ketooxime. The blocked isocyanate group had an effective NCO group content of 7.5% and a number average molecular weight of 1050. The obtained blocked isocyanate was diluted with propylene glycol monomethyl ether so as to have a non-volatile content of 70%.

-<Synthesis Example 3: Synthesis of Crosslinking Agent (C-5)>
Adduct type polyisocyanate manufactured by Asahi Kasei Co., Ltd., Duranate (registered trademark) P-301-75E (Adduct type of trimethylolpropane ester of hexamethylene diisocyanate, containing 3 isocyanate groups in 1 molecule, NCO group content 12.5 %, Non-volatile content 75% ethyl acetate solution) 25.0 parts, diethyl malonate 8.0 parts, ethyl acetoacetate 2.0 parts, 28% sodium methylate solution 0.1 parts added at room temperature, 60 The reaction was carried out at ° C. for 6 hours. Then, 0.25 part of 1-butanol was added, and the mixture was continuously stirred for 1 hour. After stirring, 0.02 part of butyl phosphate was added to obtain 19.3 parts of an adduct-type blocked isocyanate composition having a trimethylolpropane ester structure and blocked with diethyl malonate. The blocked isocyanate group had an effective NCO group content of 5.5% and a number average molecular weight of 1430. The obtained blocked isocyanate was diluted with propylene glycol monomethyl ether so as to have a non-volatile content of 70%.

-<Synthesis Example 4: Synthesis of Crosslinking Agent (C-6)>
Takenate D-120N manufactured by Mitsui Kagaku Co., Ltd. (Adduct type of trimethylolpropane ester of xylene diisocyanate, containing 3 isocyanate groups in 1 molecule, NCO group content 12.0%, non-volatile content 75% ethyl acetate solution) 25.0 parts were placed in a flask equipped with a stirring rod, and the temperature was raised to 80 ° C. Subsequently, 11.1 parts of 3,5-dimethylpyrazole was gradually added, and after all was added, the mixture was stirred for 2 hours. After confirming the disappearance of the absorption peak derived from isocyanate by FT-IR, the reaction was stopped, and 14.4 parts of adduct-type blocked isocyanate having a trimethylolpropane structure and blocked with 3,5-dimethylpyrazole was added. Obtained. The effective NCO group content of the blocked isocyanate group was 7.4%, and the number average molecular weight was 1015. The obtained blocked isocyanate was diluted with propylene glycol monomethyl ether so as to have a non-volatile content of 70%.

<Conductive fine particles (D-1) to (D-4)>
-Conductive fine particles (D-1): Fukuda Metal Foil Powder Co., Ltd., flake-shaped silver powder, average particle diameter 5.2 μm
-Conductive fine particles (D-2): manufactured by Fukuda Metal Foil Powder Co., Ltd., chain-aggregated silver powder, average particle diameter 1.5 μm
-Conductive fine particles (D-3): manufactured by DOWA Electronics, flake-shaped silver-coated copper powder, silver coating amount 10%, average particle diameter 4.0 μm
-Conductive fine particles (D-4): manufactured by Ito Graphite Co., Ltd., scaly graphite, average particle diameter 15 μm

<Other components (E-1), (E-2)>
-Other ingredients (E-1): Made by Big Chemie, antifoaming agent, BYK-1790 100% solid content
-Other ingredients (E-2): Manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., anionic lubricant, Calisekken HY solid content 100%

<Production Example 1: Preparation of Conductive Resin Composition (F-1) for Molded Film>
20.0 parts of the resin (A-1) is dissolved in 30.0 parts of the solvent (B-1), 80.0 parts of the conductive fine particles (D-1) are stirred and mixed, and a 3-roll mill (manufactured by Kodaira Seisakusho). After kneading with the above, the conductive resin composition for a molded film (F-1) was obtained by uniformly stirring and mixing with a planetary mixer.

<Production Examples 2 to 16: Preparation of Conductive Resin Compositions (F-2) to (F-16) for Molded Film>
In Production Example 1, a resin, a solvent, conductive fine particles, and a cross-linking agent (when a cross-linking agent or other component (E-1) is used, the cross-linking agent and the other component (E-1) are uniformly stirred and mixed by a planetary mixer. Conductive resin compositions for molded film (F-2) to (F-16) in the same manner as in Production Example 1 except that the type and blending amount of (added immediately before) were changed as shown in Table 1. Got

<Production Example 17: Preparation of Insulating Resin Composition (G-1) for Molded Film>
20.0 parts of the resin (A-7) is dissolved in 30.0 parts of the solvent (B-1), 6.0 parts by weight of the cross-linking agent (C-5) and 0.2 parts by weight of the defoaming agent (E-1). After adding the parts, the insulating resin composition for a molded film (G-1) was obtained by uniformly stirring and mixing with a planetary mixer.

<Production Examples 18 to 39: Preparation of Insulating Resin Compositions (G-2) to (G-23) for Molded Film>
Insulating resin composition for molded film (G-2) in the same manner as in Production Example 17, except that the types and blending amounts of the resin, solvent and cross-linking agent were changed as shown in Tables 2 and 3 in Production Example 17. ) ~ (G-23) were obtained.

<Manufacturing example 1: Creation of decorative ink (H-1)>
Prepare 175 parts of resin solution (A-8) (70 parts for resin (A-8) only), and add 20 parts of phthalocyanine blue pigment (Toyo Color Co., Ltd., Lionol Blue FG7351) and titanium oxide pigment (Ishihara Sangyo). TIPAQUE CR-93) 10 parts by mass is stirred and mixed, kneaded with a 3-roll mill (manufactured by Kodaira Seisakusho), and then 5 parts of an isocyanate cross-linking agent (Death Module N3300 manufactured by Sumika Cobestro Urethane, 100% non-volatile content). And 90 parts of the solvent (B-2) were added and mixed uniformly with stirring to obtain a decorative ink (H-1).

The numerical values of each material in Tables 1 to 3 are all parts by mass.

<Examples 1 to 93 and Comparative Examples 2 to 5>
On a polycarbonate (PC) base film (manufactured by Teijin Co., Ltd., Panlite 2151, thickness 300 μm), the conductive resin compositions (F-1) to (F-16) for a molding film are applied to a screen printing machine (Minoscreen Co., Ltd.). Manufactured by Minomat SR5575 semi-automatic screen printing machine). Then, by heating at 120 ° C. for 30 minutes in a hot air drying oven, (1) a square solid pattern having a width of 70 mm, a length of 120 mm and a thickness of 10 μm, and (2) a straight line having a line width of 2 mm, a length of 60 mm and a thickness of 10 μm. A molded film having a similar pattern and (3) a conductive layer having a comb-shaped wiring pattern having a line length of 50 mm and L / S = 100 μm / 100 μm of 10 positive and negative lines was obtained, respectively. For the (1) quadrangular solid pattern at this stage, the volume resistivity of the conductive layer was measured using a resistivity meter (Roresta GX MCP-T700 manufactured by Mitsubishi Chemical Analytical Corporation).
Further, the insulating resin compositions for molding films (G-1) to (G-23) are formed on the surface on which the conductive pattern of the molded film provided with the conductive layer is formed, and (1) the square solid conductive pattern is formed. On the other hand, the width is 90 mm, the length is 140 mm, and the thickness is 15 μm so as to cover the entire conductive pattern. The width is 10 mm, the length is 40 mm, and the thickness is 15 μm so as to cover the portion of (3). , Each of which was overprinted by the screen printing machine so as to have a thickness of 15 μm. Then, by heating in a hot air drying oven at 120 ° C. for 30 minutes, a molded film provided with the patterned conductive layer and an insulating layer laminated so as to cover a part or all of the patterned conductive layer was obtained. At this time, molded films were prepared so that the combinations of the conductive resin composition and the insulating resin composition were as shown in Tables 3 to 6. (1) Regarding the insulating layer portion at the end that does not overlap with the conductive layer in the (1) square solid pattern, the resistivity meter (HIRESTA UX MCP-HT800, manufactured by Mitsubishi Chemical Analytical Co., Ltd.) measures the volume intrinsic resistance of the insulating layer. Was measured using.

<Examples 94 to 97 and Comparative Examples 7 to 10>
In Examples 7, 28, 42, 69 and Comparative Examples 2 to 5, an acrylic resin base film (Technoloy S001G, manufactured by Sumitomo Chemical Co., Ltd., thickness 250 μm) (300 mm × 210 mm) was used instead of the polycarbonate base film. A molded film was obtained in the same manner as in Examples 7, 28, 42, 69 and Comparative Examples 2 to 5 except that the drying conditions in the hot air drying oven were set to 80 ° C. for 30 minutes.

<Examples 98 to 101>
In Examples 7, 28, 42, and 69, instead of the polycarbonate base film, a polycarbonate resin / acrylic resin type 2 two-layer coextruded base film (Technoloy C001 manufactured by Sumitomo Chemical Co., Ltd., thickness 125 μm) was used, and the polycarbonate resin side was used. A molded film was obtained in the same manner as in Examples 7, 28, 42, and 69, except that the conductive resin composition for a molded film and the insulating resin composition were printed.

<Examples 102 to 105>
A decorative ink (H-1) is applied onto a polycarbonate base film (Teijin Co., Ltd., Panlite 2151, thickness 300 μm) using a blade coater so that the dry film thickness is 2 μm, and the temperature is 120 ° C. It was heated for 30 minutes to form a decorative layer.
Next, in Examples 7, 28, 42, and 69, the base film with a decorative layer was used instead of the polycarbonate base film, and the conductive layer and the insulating layer were formed on the decorative layer. , 28, 42, 69, and a molded film in which a polycarbonate base film, a decorative ink layer, a conductive layer, and an insulating layer were laminated in this order was obtained.

<Example 106>
The conductive resin composition for film and the insulating resin composition so as to overlap the conductive pattern and the insulating pattern of Example 7 on the front and back surfaces of the molded film obtained in Example 7 without printing. A second conductive layer and a second insulating layer laminated so as to cover a part of the second conductive layer were formed by printing an object, and the same as in Example 7 above, on both sides of the base film. A molded film having a conductive layer and an insulating layer laminated so as to cover a part or all of the conductive layer was obtained.

<Example 107>
On the insulating pattern of the molded film obtained in Example 7, the conductive pattern of Example 1 was further printed and dried at a position where the edge spacing was 5 mm in the width direction from the conductive pattern of Example 1. By performing the same procedure as in the process and further printing the second insulating layer pattern at a position overlapping the insulating pattern of Example 7, the first conductive layer and a part thereof are covered on one side of the base film. A molded film having a first insulating layer laminated on the surface, a second conductive layer, and a second insulating layer laminated so as to cover a part thereof was obtained in this order.

<Comparative Examples 1 and 6>
Molded films were obtained in the same manner as in Examples 7 and 94 except that the insulating layer was not formed in Examples 7 and 94.

[(1) Wiring resistance evaluation]
A 2 mm × 60 mm linear conductive layer pattern formed on the molded films of Examples 1 to 107 and Comparative Examples 1 to 10 is cut into 70 mm in the longitudinal direction and 10 mm in the width direction so as to be in the center, and is used for measurement. I made it a coupon. On the surface of the coupon for measurement opposite to the conductive layer, two lines were added from the longitudinal end so as to be 4 cm apart with an oil-based magic using a line perpendicular to the conductive layer as a mark. According to this mark, both measuring portions of the tester were brought into contact with the conductive layer, and the resistance value of the conductive layer having a width of 4 cm was measured, and this was defined as the wiring resistance (Ω). The results are shown in Tables 4-11.

[(2) Thermal stretching evaluation 1]
The measurement coupons of Examples 1 to 93, 98 to 107, and Comparative Examples 1 to 5 were stretched in a heating oven at 160 ° C. in the longitudinal direction at a pulling speed of 10 mm / min to an elongation rate of 50%. It was taken out of the oven, cooled, and then evaluated for disconnection using an optical microscope. In addition, the wiring resistance (Ω) at the position corresponding to the interval of 4 cm is measured by the same method as the measurement of the wiring resistance above, and the wiring resistance after expansion / contraction / the wiring resistance before expansion / contraction is the resistance during thermal stretching. The volatility was set to (double) and evaluated according to the following criteria. The results are shown in Tables 4-11.
(Presence / absence of disconnection)
A: No disconnection was seen.
B: 1 to 2 minor cracks were confirmed C: Severe disconnection or peeling of the conductive coating film was confirmed (resistance fluctuation rate during thermal stretching)
A: 5 times or more and less than 10 times B: 10 times or more and less than 50 times C: 50 times or more

The elongation rate is a value calculated as follows.
(Elongation rate) [%] = {(Length after stretching-Length before stretching) / (Length before stretching)} x 100

[(3) Thermal stretching evaluation 2]
In the heat stretching evaluation 1, the evaluation was performed according to the following criteria in the same manner as in the heat stretching evaluation 1 except that the elongation rate was changed to 100%. The results are shown in Tables 4-11.
(Presence / absence of disconnection)
A: No disconnection was seen.
B: 1 to 2 minor cracks were confirmed C: Severe disconnection or peeling of the conductive coating film was confirmed (resistance fluctuation rate during thermal stretching)
A: 10 times or more and less than 50 times B: 50 times or more and less than 200 times C: 200 times or more

[(4) Thermal stretching evaluation 3]
The measurement coupons of Examples 94 to 97 and Comparative Examples 6 to 10 were stretched in a heating oven at 120 ° C. in the longitudinal direction at a pulling speed of 10 mm / min to an elongation rate of 50%. It was taken out of the oven, cooled, and then evaluated for disconnection using an optical microscope. In addition, the wiring resistance (Ω) at the position corresponding to the interval of 4 mm is measured by the same method as the measurement of the wiring resistance above, and the wiring resistance after expansion / contraction / the wiring resistance before expansion / contraction is the resistance during thermal stretching. The volatility was set to (double) and evaluated according to the following criteria. The results are shown in Tables 9 and 10.
(Presence / absence of disconnection)
A: No disconnection was seen.
B: 1 to 2 minor cracks were confirmed C: Severe disconnection or peeling of the conductive coating film was confirmed (resistance fluctuation rate during thermal stretching)
A: 5 times or more and less than 10 times B: 10 times or more and less than 50 times C: 50 times or more

[(5) Thermal stretching evaluation 4]
In the heat stretching evaluation 3, the evaluation was performed according to the following criteria in the same manner as in the heat stretching evaluation 3 except that the elongation rate was changed to 100%. The results are shown in Tables 9 and 10.
(Presence / absence of disconnection)
A: No disconnection was seen.
B: 1 to 2 minor cracks were confirmed C: Severe disconnection or peeling of the conductive coating film was confirmed (resistance fluctuation rate during thermal stretching)
A: 10 times or more and less than 50 times B: 50 times or more and less than 200 times C: 200 times or more

[(6) Process resistance evaluation 1 when manufacturing a molded product by overlay molding]
A hemispherical ABS resin molded product having a radius of 4 cm is placed on the surface on the conductor side so as to overlap the positions of the 2 mm × 60 mm linear patterns of the molded films of Examples 1 to 93, 98 to 107, and Comparative Examples 1 to 5. A molded product in which a hemispherical molded film and an ABS resin molded product are integrated by performing overlay molding at a set temperature of 160 ° C. using a TOM molding machine (manufactured by Fuse Vacuum Co., Ltd.). Got The scraping and resistance volatility of the linear pattern wiring of this molded product were confirmed. For the resistance fluctuation rate, measure the wiring resistance (Ω) at the position corresponding to the 6 cm interval based on the original mark, and set the wiring resistance after expansion and contraction / the wiring resistance before expansion and contraction as the resistance fluctuation rate during thermal stretching (double), and each is as follows. Evaluated according to the criteria of. The results are shown in Tables 4-11.
(Presence / absence of disconnection and resistance volatility)
A: No wiring scraping is seen and the resistance fluctuation rate is 5 times or more and less than 30 times. B: End chipping due to scraping of wiring in 1 or 2 places is confirmed, or the resistance fluctuation rate is 30 times or more and 500 times. Less than C: One or more disconnections due to scraping of wiring are confirmed.

[(7) Process resistance evaluation 2 during manufacturing of molded product by overlay molding]
Process resistance during manufacturing of a molded product by the overlay molding, except that overlay molding was performed at 120 ° C. using a 2 mm × 60 mm linear pattern of the molded films of Examples 94 to 97 and Comparative Examples 6 to 10. A molded product was obtained in the same manner as in Evaluation 1, and the scraping and resistance fluctuation rate of the linear pattern wiring during overlay molding were evaluated. The results are shown in Tables 4-11.

[(8) Process resistance evaluation at the time of manufacturing a molded product by film insert molding 1]
A block-shaped metal mold having a hemispherical recess with a radius of 4 cm in the center so as to overlap the position of a 2 mm × 60 mm linear pattern of the molded films of Examples 1 to 93, 98 to 107, and Comparative Examples 1 to 5. Is placed facing the surface of the conductive layer and the insulating layer, and overlay molding is performed at a set temperature of 160 ° C. using a TOM molding machine (manufactured by Fuse Vacuum Co., Ltd.) to form a hemispherical shape and pattern the inside. A molding film having a body was obtained.
Next, the molding film molded into the hemispherical shape was set in an injection molding machine (IS170 (i5), manufactured by Toshiba Machinery Co., Ltd.) equipped with a valve gate type in-mold molding test mold, and a PC / ABS resin was used. (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 260 ° C, mold). Temperature (fixed side, movable side) 80 ° C., injection pressure 180 MPa, holding pressure 120 MPa, injection speed 60 mm / sec (28%), injection time 4 seconds, cooling time 20 seconds). The washout (deformation and disconnection of the wiring pattern due to the temperature and injection pressure of the molten thermoplastic resin) and the resistance fluctuation rate due to the injection of the molten resin of the linear pattern of this molded product were confirmed. For the resistance fluctuation rate, measure the wiring resistance (Ω) at the position corresponding to the 6 cm interval based on the original mark, and set the wiring resistance after expansion and contraction / the wiring resistance before expansion and contraction as the resistance fluctuation rate during thermal stretching (double), and each is as follows. Evaluated according to the criteria of. The results are shown in Tables 4-11.
(Presence / absence of disconnection and resistance volatility)
A: No wiring washout is seen, and the resistance fluctuation rate is 10 times or more and less than 50 times. B: Wiring distortion due to slight washout is confirmed, or the resistance fluctuation rate is 50 times or more and less than 500 times C : One or more disconnections due to wiring washout are confirmed

[(9) Process resistance evaluation at the time of manufacturing a molded product by film insert molding 2]
Steps at the time of manufacturing a molded product by the film insert molding, except that overlay molding was performed at 120 ° C. using a 2 mm × 60 mm linear pattern of the molded films of Examples 94 to 97 and Comparative Examples 6 to 10. A molded product was obtained in the same manner as in the resistance evaluation 1, and the degree of washout and the resistance fluctuation rate due to the injection of the molten resin of the linear pattern during film insert molding were evaluated. The results are shown in Tables 4-11.

[(10) Evaluation of ion migration resistance of molded product by film insert molding]
Using the molded film having the comb-shaped wiring pattern and the insulating layer of the molded films of Examples 1 to 107 and Comparative Examples 1 to 10, the molds are overlapped and molded so that the position and the center position of the comb-shaped wiring pattern overlap. A molded product was obtained in the same manner as in the process resistance evaluation 1 at the time of manufacturing the molded product by the film insert molding.
The exposed parts of the positive and negative electrodes of the comb-shaped wiring of each of the above molded bodies are connected to the wiring with an alligator clip, and 5V is applied using the IMV migration tester insulation deterioration evaluation tester "MIG-8600B" at 85 ° C. 85. The insulation resistance values between the comb-shaped wiring terminals after 1000 hours under the% RH condition were confirmed and evaluated according to the following criteria. The results are shown in Table 14.
(Presence / absence of short circuit due to ion migration and insulation resistivity)
A: Insulation resistance volatility is less than the initial ± 25% B: Insulation resistance volatility is ± 25% or more and less than ± 100% at the initial stage C: Insulation resistance volatility is ± 100% or more at the initial stage or leak touch (short circuit between electrodes) History) Yes

[Summary of results]
In Comparative Examples 1 and 6 in which the insulating layer is not formed on the conductive layer, the ion migration resistance between the comb-shaped electrodes of the molded body is inferior, short circuits are likely to occur over time, and the molded body is suitable for use as a three-dimensional wiring circuit. It turned out not. It is considered that this is because the adhesion between the base film of the molded product and the injection molding resin is not sufficient, and therefore the mechanical deterioration of the conductive pattern due to the promotion of ionization due to the intrusion of moisture from this interface and the thermal expansion and contraction is large. .. Further, in Comparative Examples 2 and 7, although the insulating layer is formed, the volume resistivity is ^{as low as less than 10 10} Ω · cm, so that the ion migration resistance between the comb-shaped electrodes of the molded body is at a level that cannot withstand practical use. rice field. Further, in Comparative Examples 3 and 8, a resin having an ester bond portion is used in the conductive layer, but since the insulating layer contains a cross-linking agent and a cross-linking reactive group, resistance due to disconnection in the conductive layer during thermal stretching occurs. The magnitude of the value fluctuation rate and the ion migration resistance between the electrodes were at a level that could not be put to practical use. On the other hand, in Comparative Examples 4 and 9, a resin having an ester bond portion in the main chain is used for the conductive resin composition and the insulating resin composition, but since there is no cross-linking agent in the insulating layer, a comb-shaped molded product is used. The ion migration resistance between the electrodes did not withstand practical use. In addition, the same tendency is seen in the resin used for conductivity, and as shown in Comparative Examples 5 and 10, both the conductive layer and the insulating layer do not have a crosslinkable functional group, and further, there is no crosslinker. The ion migration resistance between the comb-shaped electrodes of the molded product was at a level that could not be put to practical use.

On the other hand, from the results of Examples 1 to 107, the molded film having the conductive layer and the insulating layer of this embodiment is not only less likely to be disconnected from the molten resin injection during overlay molding and film insert molding, but also the heat of the molded film. The disconnection of the conductive layer pattern was also suppressed during stretching. In particular, the main chain of the resin (A1) used in the conductive resin composition and the resin (A2) used in the insulating resin composition has any bonding group selected from an ester bond, an amide bond and a carbonate bond. In the molded films of Examples 7, 9 to 14, 18 to 24, 26, 28 to 37, 39, 41 to 52, 60 to 65, 68, 70 to 74, 76, 77, 80 to 105, the resin is insulated from the conductive layer. Since the affinity between the layers is high, stress relaxation between the interfaces during thermoforming and stretching works, and as a result, fine cracks can be prevented and the fluctuation rate of the thermoforming resistance is also good at less than 10 times. In particular, Examples 7, 12-14, 28, 31-34 which use blocked isocyanate as a cross-linking agent, have the same bond to the resin (A1) and the resin (A2), and have a hydroxyl group or an amino group as a reactive group. , 42, 47, 49-52, 60, 62-65, 68, 73, 74, 80, 81, 85-87, 89-105, in addition to the high affinity between the conductive layer and the insulating layer. By cross-linking between the interfaces, there are no fine cracks during thermal molding stretching, the thermal stretching resistance fluctuation rate is less than 10 times, no washout of the wiring is seen, and the insulation resistance fluctuation rate is high. Very good results were shown, which was less than ± 25% of the initial value. It is considered that the migration between the molded body wirings was suppressed by the affinity between the conductive layer and the insulation correlation and the cross-linking with the cross-linking agent, and the insulation reliability between the molded body wirings was improved.

Further, due to the above characteristics, the molded film provided with the conductive layer of the conductive resin composition of the present invention has an excellent wiring-integrated molded body even if the base material surface is not flat and has a three-dimensional shape. Regarding the ion migration resistance of this molded product, the generation of microcracks in the conductive layer pattern when molding the molded film of the present invention and the accompanying void generation near the surface layer of the conductive layer are suppressed, and as a result, the ion migration resistance is also improved. It is considered to have improved.

In this way, the molded film using the conductive resin composition and the wiring-integrated molded body of this embodiment can be directly designed freely for plastic housings and three-dimensional shaped parts such as home appliances, automobile parts, robots, and drones. It is possible to build lightweight and space-saving circuits without compromising the degree, build touch sensors, antennas, heating elements, electromagnetic wave shields, inductors (coils), resistors, and mount various electronic components. do. In addition, it is extremely useful for making electronic devices lighter, thinner, shorter, smaller, improving the degree of freedom in design, and increasing the number of functions.

1 Base film 2 Conductive layer 3 Insulation layer 4 Electronic parts 5 Pin 6 Decorative layer 7 Second conductive layer 8 Second insulation layer 10 Molding film 11 Mold 12 Mold 12 Injection molding mold 13 Opening 14 Injection 15 Rise 16 Pressurized 17 Resin 20 Base material 21 Upper chamber box 22 Lower chamber box 30 Mold

Claims (12)

A molded film for forming a printed conductive circuit coated with an insulating layer on the surface of a base material having an uneven surface or a three-dimensional curved surface.
The molded film is a molded film having a conductive layer and an insulating layer on the base film.
The conductive layer is a cured product of a conductive resin composition containing a resin (A1), conductive particles (D), and if necessary, a cross-linking agent (C1).
The insulating layer is a cured product of an insulating resin composition containing a resin (A2) and a cross-linking agent (C2).
The volume resistivity of the insulating layer is 1 × 10 ¹⁰ Ω · cm or more ^{and less than 1 × 10 17} Ω · cm.
A molded film having a crosslinkable functional group in which the resin (A1) and the resin (A2) can react with the crosslinker (C2). The first aspect of the present invention, wherein the resin (A1) and the resin (A2) each independently have one or more kinds of bonding portions selected from the group consisting of an ester bonding portion, a carbonate bonding portion, and an amide bonding portion in the main chain. The molded film described. 2. The second aspect of the present invention is characterized in that at least one kind of the joint portion of the resin (A1) and at least one kind of the joint portion of the resin (A2) are the same kind of joint portion. The molded film of the description. The molded film according to any one of claims 1 to 3, wherein the base film is a film selected from polycarbonate, polymethylmethacrylate, polypropylene, and polyethylene terephthalate, or a laminated film thereof. The molded film according to any one of claims 1 to 4, wherein the cross-linking agent (C2) is a blocked isocyanate according to any one of i) to iii) below.
i) Block isocyanate with a number average molecular weight of 700 to 1300 having an isocyanurate structure ii) Block isocyanate with a number average molecular weight of 700 to 1300 having a biuret structure iii) Trimethylolpropane ester structure with a number average molecular weight of 1000 to 3000 Block isocyanate The molded film according to any one of claims 1 to 5, wherein the crosslinkable functional group of the resin (A1) and the resin (A2) is a hydroxyl group or an amino group. The molded film according to any one of claims 1 to 6, wherein a conductive layer and an insulating layer are provided on both surfaces of the base film in this order. The molded film according to any one of claims 1 to 7, further comprising a second conductive layer and a second insulating layer on the insulating layer in this order. A molded film molded into a predetermined shape is laminated on the base material so that the insulating layer surface and the base material surface are in contact with each other, or the base film surface and the base material surface are in contact with each other, and the uneven surface or the three-dimensional surface is formed. A molded product in which a printed conductive circuit coated with an insulating layer is formed on the surface of a base material having a curved surface.
A molded product in which the molded film is for the molded film according to any one of claims 1 to 8. The step of arranging the molded film according to any one of claims 1 to 8 on the substrate, and
A method for manufacturing a molded product, which comprises a step of integrating the molded film and the base material by an overlay molding method. The step of molding the molding film according to any one of claims 1 to 8 into a predetermined shape, and
The step of arranging the molded film after molding in a mold for injection molding, and
A method for producing a molded product, which comprises a step of molding a base material by injection molding and integrating the molding film and the base material. A step of arranging the molding film according to any one of claims 1 to 8 in a mold for injection molding, and
A method for producing a molded product, comprising a step of molding a base material by injection molding and transferring a conductive layer in the molding film to the base material side.

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