JP2021192960A - Molded film and its manufacturing method, and molded body and its manufacturing method - Google Patents

Abstract

To provide a molded film that suppresses a decrease in conductivity due to tensile force and stress at high temperatures in a molding process, and has excellent ion migration resistance between conductive patterns even after molding.SOLUTION: There is provided a molded film having a conductive layer and an insulating layer on a base film, in which the conductive layer is a cured product of a conductive resin composition containing a resin (A1), a solvent (B1), and a conductive granule (C), the insulating layer is a cured product of an insulating resin composition containing a resin (A2) and a solvent (B2), the resin (A1) is a resin having a glass transition point of 10°C or higher and 110°C or lower and a weight average molecular weight of 10,000 or higher and 100,000 or lower, the resin (A2) is a resin having a glass transition point of 30°C or higher and 140°C or lower and a weight average molecular weight of 20,000 or higher and 200,000 or lower, and a volume resistivity of the insulating layer is 1×1010 Ω.cm or more and less than 1×1017 Ω.cm.SELECTED DRAWING: Figure 1

Description

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

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, as a low-temperature treatment type conductive ink capable of forming a high-definition conductive pattern by screen printing, a specific conductive ink containing specific conductive fine particles and a specific epoxy resin. Sex inks are 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 resin molded body are described by the thermal molding of the molded film in which the conductive pattern is formed on the base film by the printing method using the conductive ink and the integration process with the resin molded body. A method of forming a conductive circuit integrated molded product having a conductive circuit arranged between the base film and the base film is disclosed.

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 conductor 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 according to this embodiment is 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), a solvent (B1), and conductive fine particles (C).
The insulating layer is a cured product of an insulating resin composition containing a resin (A2) and a solvent (B2).
The resin (A1) is a resin having a glass transition point of 10 ° C. or higher and 110 ° C. or lower and a weight average molecular weight of 10,000 or higher and 100,000 or lower.
The resin (A2) is a resin having a glass transition point of 30 ° C. or higher and 140 ° C. or lower and a weight average molecular weight of 20,000 or higher and 200,000 or lower.
The volume resistivity of the insulating layer is 1 × 10 ¹⁰ Ω · cm or more ^{and less than 1 × 10 17} Ω · cm.

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

The glass transition point of the resin (A1) is less than the glass transition point of the resin (A2).

In one embodiment of the molded film of the present embodiment, the weight average molecular weight of the resin (A1) is less than the weight average molecular weight of the resin (A2).

In one embodiment of the molded film of the present embodiment, the glass transition point of the resin (A1) and the glass transition point of the resin (A2) are both glass transition points of the base film (provided that they are made of two or more kinds of materials. In the case of a laminated film, it is less than the higher glass transition point).

In one embodiment of the molded film of the present embodiment, a conductive layer and an insulating layer are provided on both surfaces of the base film in this order.

In one embodiment of the molded film according to the present embodiment, a second conductive layer and a second insulating layer are further provided on the insulating layer in this order.

In one embodiment of the molded film of the present embodiment, the molded film molded into a predetermined shape is placed 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 product 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.

The first method for producing a molded product according to the present embodiment includes a step of arranging the molded film described above on a base material 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 second manufacturing method of the molded body according to the present embodiment includes a step of molding the molded film into a predetermined shape and a step of molding the molded film into a predetermined shape.
The step of arranging the molded film after molding in the injection molding mold, and
A step of molding a base material by injection molding and integrating the molding film and the base material is included.

The third manufacturing method of the molded body according to the present embodiment includes a step of arranging the described molding film in an injection molding mold and a step of arranging the molded film.
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.

According to the present invention, a molding film in which a decrease in conductivity due to tensile force and stress stress under high temperature in a molding process is suppressed, and ion migration resistance between conductive patterns is excellent even after molding, and excellent conductivity are obtained. 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 producing 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 implementation will be described in detail in order.
In this embodiment, 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 this embodiment is a molded film having a conductive layer and an insulating layer on the base film.
The conductive layer is a cured product of the conductive resin composition, and the insulating layer is a cured product of the insulating resin composition.
According to the molded film of this embodiment, 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 screen-printable conductive resin compositions and screen-printable conductive resin compositions for producing molded films that are applicable to uneven substrate surfaces and have process suitability for integration steps with plastic substrates. The insulating surgical composition was examined. In order to apply it to the production of molded films, various adjustments were made to the volume specific resistance and resin structure of the conductive resin composition and the insulating surgical composition, and the glass of the conductive resin composition and the insulating surgical composition was examined. The obtained molded film is molded by the transition temperature, the weight average molecular weight relationship, the glass transition temperature relationship between the conductive / insulating resin composition and the base film, the volume specific resistance of the insulating surgical composition, and the repeating structure in the resin. The presence or absence of disconnection and the magnitude of change in resistance value that occur when pulled under possible high temperatures, and the difference in ion migration characteristics over time when the conductive circuit integrated molded 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 have compared with a flat film circuit board or the like in a conductive circuit integrated molded product when an insulating layer having a low volume resistivity is laminated on the conductive layer. It was confirmed that a significantly large ion migration occurred. Further, when the resin (B1) of the insulating layer having a glass transition point lower than the glass transition point of the resin (A1) of the conductive layer is heated and dried and laminated, the molded film is deformed by pulling at a high temperature corresponding to the softening point. At that time, it was clarified that more cracks and local deformation of the conductive layer occurred. Further, when the weight average molecular weight of the resin is lower in the resin (B1) of the insulating layer than in the resin (A1) of the conductive layer, the insulating resin component is moistened to the conductive layer, so that the resin is stretched during thermoforming. It has become clear that sometimes cracks and local deformation occur in the conductive layer. Furthermore, there is a probability that the generation of black silver oxide will increase due to ion migration when the area around the conductive layer is continuously energized under high temperature and high humidity conditions, the insulation resistance value between the conductive patterns will decrease, and leakage touch (dielectric breakdown) will occur. It became clear that it would be higher. The same applies to the case where the conductive layer and the insulating layer are provided on the decorative layer.

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 resin film, the deformation stress generated on 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 formable film.

As a result of diligent studies based on these findings, the present inventors have a glass transition point of the resin (A1) of the conductive layer of 10 ° C. or higher and 110 ° C. or lower, and a weight average molecular weight of 10,000 or higher and 100,000 or lower. It is a resin, the glass transition point of the resin (A2) of the insulating layer is 30 ° C. or higher and 140 ° C. or lower, the weight average molecular weight is 20,000 or more and 200,000 or less, and the volume resistivity of the insulating layer is 1 × 10. It has been found that the occurrence of ion migration is suppressed in the conductive circuit integrated molded product when a molded film having a ^{size of 10} Ω · cm or more ^{and less than 1 × 10 17 Ω · cm is used.} In addition to this, when the glass transition point of the resin (A1) of the conductive layer is less than the glass transition point of the resin (BI) of the insulating layer, the conductive layer when the molded film is pulled under high temperature conditions. When cracking and local deformation are suppressed and the weight average molecular weight of the resin (A1) of the conductive layer is less than the weight average molecular weight of the resin (BI) of the insulating layer, the high-viscosity heat melted on the molded film. We have found that it is possible to suppress a decrease in the insulation resistance value between conductive patterns and the occurrence of leak touch due to ion migration in a conductive circuit integrated molded product in which a plastic resin is pressure-welded at high pressure, and have completed the present invention.
That is, in the molded film of the present invention, the molded film having the volume resistivity of the insulating layer of 1 × 10 ¹⁰ Ω · cm or more ^{and less than 1 × 10 17} Ω · cm is used on an uneven substrate surface. However, circuit deterioration due to ion migration is suppressed. Further, this characteristic is that the glass transition point of the resin (A1) of the conductive layer is less than the glass transition point of the resin (BI) of the insulating layer, and the weight average molecular weight of the resin (A1) of the conductive layer is that of the insulating layer. This is even more remarkable when a molded film satisfying the relationship of less than the weight average molecular weight of the resin (BI) is used. Further, by using the molded 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 base material made of a three-dimensional plastic having practical strength. can.

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 3 on the base film 1, a conductive layer 2 on the decorative layer 3, 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 3, in addition to the example of FIG. 2, the decorative layer 3 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 forming 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 a resin bead 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 by screen printing, it is heated to dry and, if a cross-linking agent is contained, a cross-linking reaction is carried out to cure.
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 at least a resin (A1), a solvent (B1), and conductive particles (C), and if necessary, another It may contain an ingredient.
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.

Here, a method for measuring the glass transition point is defined. In this specification, the glass transition point is determined by DSC (Differential Scanning Calimorimetry). For the arbitrary component for which the glass transition point is to be obtained, first the first heating operation, then the cooling operation, and then the second heating operation are measured. The heating rate in the first heating operation and the second heating operation is 10 ° C./min, and the cooling rate in the cooling operation is also 10 ° C./min. In the DSC diagram, a step is obtained in the region of the glass transition of the arbitrary component during the second heating operation. The glass transition temperature of the optional component corresponds to the temperature at half the height of the step in the DSC diagram.

The glass transition point of the resin (A1) is 10 ° C. or higher and 110 ° C. or lower, more preferably 15 ° C. or higher to 105 ° C., and even more preferably 30 ° C. or higher to 100 ° C. Within the above range, the resistance value of the conductive layer pattern does not significantly increase with respect to the stretching of the molded film during molding, and excellent ions are based on the insulating performance of the insulating layer itself and high adhesion to the base film and the injection molding resin. Has a migration resistance effect.

The weight average molecular weight of the resin (A1) is 10,000 or more and 100,000 or less, more preferably 15,000 or more and 90,000 or less, and further preferably 20,000 or more and 85,000 or less. Within the above range, there is an excellent ion migration resistance effect.

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 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 continuous screen 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 (C)>
The conductive fine particles (C) 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 (C), 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 (C) 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 (C) is calculated as follows. Based on the laser diffraction / scattering method described in JIS M8511 (2014), a commercially available surfactant polyoxyethylene octylphenyl is used as a dispersant using a laser diffraction / scattering type particle size distribution measuring device (Microtrac 9220FRA manufactured by Nikkiso Co., Ltd.). An appropriate amount of conductive fine particles (C) 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 (C).

In this embodiment, the conductive fine particles (C) can be used alone or in combination of two or more.
The content ratio of the conductive fine particles (C) 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 based on the total solid content contained in the conductive resin composition. 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 (C) 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 (C) is equal to or less 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 cross-linking agents, such other components include dispersants, friction improvers, infrared absorbers, ultraviolet absorbers, fragrances, antioxidants, organic pigments, inorganic pigments, defoamers, and silane couplings. Examples include agents, plasticizers, flame retardants, moisturizers and the like.

<Manufacturing method of conductive resin composition>
The method for producing the conductive resin composition of the present embodiment is a method of dissolving or dispersing the resin (A1), the solvent (B1), the conductive fine particles (C), and other components used as necessary. Anything is sufficient, and it can be produced by mixing by a known mixing means.

<Insulation layer>
In the molded film of this embodiment, the insulating layer has a volume resistance value of 1 × 10 ¹⁰ Ω · cm or more ^{and less than 1 × 10 17} Ω · cm, and is a cured product of the insulating resin composition described later.
By covering the conductive layer with the insulating layer, it is possible to prevent frictional damage to the conductive layer during the manufacturing process. It also serves as a heat-resistant stress protection layer that prevents frictional stress stress from the base plastic at high temperatures 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.

After printing the insulating resin composition by screen printing, it is heated to dry and, if it contains a cross-linking agent, undergoes a cross-linking reaction to cure.
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 at least a resin (A2) and a solvent (B2), and may further contain other components if necessary.
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 glass transition point of the resin (A2) is 30 ° C. or higher and 140 ° C. or lower, more preferably 45 ° C. or higher and 135 ° C. or lower, and further preferably 50 ° C. or higher and 130 ° C. or lower. Within the above range, the resistance value of the conductive layer pattern does not significantly increase with respect to the stretching of the molded film during molding, and excellent ions are based on the insulating performance of the insulating layer itself and high adhesion to the base film and the injection molding resin. Has a migration resistance effect.

The weight average molecular weight of the resin (A2) is 20,000 or more and 200,000 or less, more preferably 25,000 or more and 195,000, and further preferably 40,000 or more and 180,000. Within the above range, there is an excellent ion migration resistance effect.

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) 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.

In this embodiment, the resin (A2) preferably contains an ester bond derived from a reaction product of a dicarboxylic acid and a diol. By including the ester bond derived from the reaction product of the dicarboxylic acid and the diol, the insulating layer efficiently wets and spreads on both the surface of the conductive fine particles of the molded film and the conductive layer and adheres strongly, and is moderately adhered under high temperature conditions. By exhibiting elasticity, it is possible to achieve both the protective 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.

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.

In this embodiment, the glass transition point of the resin (A1) is preferably less than the glass transition point of the resin (A2). Since the glass transition point of the resin (A1) is less than the glass transition point of the resin (A2), stress concentration on the conductive layer during stretching can be suppressed, which is preferable.

In this embodiment, the weight average molecular weight of the resin (A1) is preferably less than the weight average molecular weight of the resin (A2). When the weight average molecular weight of the resin (A1) is less than the weight average molecular weight of the resin (A2), the adverse effect of wetting the insulating resin component on the conductive layer is suppressed. This is suitable in that the generation of fine cracks in the conductive layer during stretching during thermoforming is prevented, and the generation of ion migration due to the generation of fine cracks is suppressed, thereby improving the long-term insulation reliability between the molded body wirings. be.

In this embodiment, it is preferable that the glass transition point of the resin (A1) and the glass transition point of the resin (A2) are both less than the glass transition point of the base film. Since the glass transition point of the resin (A1) and the glass transition point of the resin (A2) are both less than the glass transition point of the base film, it is preferable in that stress concentration on the conductive layer during stretching can be suppressed. be.

<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 continuous screen 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.

<Manufacturing method of insulating resin composition>
The method for producing the insulating resin composition of the present embodiment may be any method as long as it is a method of dissolving or dispersing the resin (A2), the solvent (B2) and, if necessary, other components, and is a known mixing means. It can be manufactured by mixing with.

<Decorative 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]
The molded product of the present embodiment is a molded product in which at least a conductive layer is laminated on a base material, and the conductive layer is a cured product of the conductive resin composition for a molding film. Since the molded body of this embodiment is formed by a molding film using the conductive resin composition for molding film of this embodiment, it is a molded body in which a conductive circuit is formed on an arbitrary surface such as an uneven surface or a 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 manufactured by using the conductive resin composition of the present embodiment, and is not limited to these methods.

<First manufacturing method>
The first method for producing a molded product according to the present embodiment is one of the conductive layers formed after the conductive resin composition for a molded film is printed on a base film and dried to form a conductive layer. A step of manufacturing a molded film by forming an insulating composition by printing and drying the insulating resin composition so as to cover a part or the whole.
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, it will be described with reference to FIG.

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 polyphenylene 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 method for producing a molded product according to the present embodiment is one of the conductive layers formed after the conductive resin composition for a molded film is printed on a base film and dried to form a conductive layer. A step of manufacturing a molded film by forming an insulating composition by printing and drying the insulating resin composition so as to cover a part or the whole.
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.

In the second manufacturing method, the frictional stress stress with the base material plastic under high temperature in the above-mentioned integration step with the base material is as shown in FIG. 6 (E) by injecting the resin 14 from the opening 13. 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 forming the base material 20 and integrating the molded film 10 and the base material 20. It is something to do. 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 at a high temperature in another step.

<Third manufacturing method>
A third method for producing a molded product according to the present embodiment is one of the conductive layers formed after the conductive resin composition for a molded film is printed on a base film and dried to form a conductive layer. A step of manufacturing a molded film by forming an insulating composition by printing and drying the insulating resin composition so as to cover a part or the whole.
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 plastic under high temperature in the above-mentioned integration step with the base material is as shown in FIG. 7 (C) by injecting the resin 14 from the opening 13. 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 molded film 10 and the base material 20 are in close contact with each other while forming the base material 20. be. That is, in the third 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.

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 in the examples is the polystyrene-equivalent molecular weight in the measurement using GPC (gel permeation chromatography) “HLC-8320” manufactured by Tosoh Corporation.

<Resin (A-1) to (A-6)>
The following resins were used as the resins (A-1) to (A-6).
-Resin (A-1): Acrylic resin manufactured by Mitsubishi Chemical Corporation, Dianal MB7922, glass transition point 45 ° C., weight average molecular weight 70,000.
-Resin (A-2): Acrylic resin manufactured by Mitsubishi Chemical Corporation, Dianal BR52, glass transition point 106 ° C., weight average molecular weight 75,000.
-Resin (A-3): Polyester resin manufactured by Unitika Ltd., Elitel UE-3500, glass transition point 15 ° C., weight average molecular weight 30,000.
-Resin (A-4): Polyester resin manufactured by Unitika Ltd., Elitel UE-9200, glass transition point 65 ° C., weight average molecular weight 15,000.
-Resin (A-5): Cellulose ester resin manufactured by Eastman Chemical Company, CAB551-0.01, glass transition point 85 ° C., weight average molecular weight 16,000.
-Resin (A-6): Acrylic resin manufactured by Negami Kogyo Co., Ltd., DT-3, glass transition point -42 ° C., weight average molecular weight 200,000.

<Resin (A-7) to (A-15)>
The following resins were used as the resins (A-7) to (A-15).
Resin (A-7): Contains a cellulose ester resin manufactured by Eastman Chemical Company, CAB381-2, a glass transition point of 133 ° C., a weight average molecular weight of 40,000, and an ester structure derived from a reaction product of a dicarboxylic acid and a diol. No.
Resin (A-8): phenoxy resin manufactured by Mitsubishi Chemical Corporation, jER-4250, glass transition point 78 ° C., weight average molecular weight 55,000, and does not contain an ester structure derived from a reaction product of a dicarboxylic acid and a diol.
Resin (A-9): Contains a polyester resin manufactured by Toyobo Co., Ltd., Byron 103, a glass transition point of 47 ° C., a weight average molecular weight of 23,000, and an ester structure derived from a reaction product of a dicarboxylic acid and a diol.
Resin (A-10): Contains a polyester resin manufactured by Unitica, Elitel UE-3600, a glass transition point of 75 ° C., a weight average molecular weight of 20,000, and an ester structure derived from a reaction product of a dicarboxylic acid and a diol.
Resin (A-11): Acrylic resin manufactured by Evonik Industries, DEGALANP675, glass transition point 48 ° C., weight average molecular weight 180,000, and does not contain an ester structure derived from a reaction product of a dicarboxylic acid and a diol.

<Manufacturing Example A: Adjustment of Resin (A-12)>
Resin (A-12): Polyethylene urethane resin manufactured by Toyo Boseki Co., Ltd., Byron UR-1400 (glass transition point 83 ° C., weight average molecular weight 40,000, including ester structure derived from reaction product of dicarboxylic acid and diol). Place it on a stainless steel bat coated with Teflon (registered trademark), dry it in a hot air drying oven at 120 ° C. for 5 hours to completely remove the solvent, and then remove the obtained resin from 1,2,3,4-tetrahydronaphthalene. : Diethylene glycol monoethyl ether acetate = 1: 1 dissolved in a mixed solvent, glass transition point 83 ° C., weight average molecular weight 40,000, 40% polyester urethane resin containing an ester structure derived from the reaction product of dicarboxylic acid and diol. , 1, 2, 3, 4-Tetrahydronaphthalene solvent 30%, diethylene glycol monoethyl ether acetate solvent 30%, and a non-volatile content 40% polyester urethane solution was obtained.

<Manufacturing Example B: Adjustment of Resin (A-13)>
Resin (A-13): Polyethylene urethane resin manufactured by Toyo Boseki Co., Ltd., Byron UR-4800 (glass transition point 106 ° C., weight average molecular weight 25,000, including ester structure derived from reaction product of dicarboxylic acid and diol). Place it on a bat coated with Teflon (registered trademark), dry it in a hot air drying oven at 120 ° C. for 5 hours to completely remove the solvent, and then remove the obtained resin from 1,2,3,4-tetrahydronaphthalene. : Diethylene glycol monoethyl ether acetate = 1: 1 dissolved in a mixed solvent, glass transition point 106 ° C., weight average molecular weight 25,000, 40% polyester urethane resin containing an ester structure derived from the reaction product of dicarboxylic acid and diol. , 1, 2, 3, 4-Tetrahydronaphthalene solvent 30%, diethylene glycol monoethyl ether acetate solvent 30%, and a non-volatile content 40% polyester urethane solution was obtained.

Resin (A-14): Acrylic resin manufactured by Negami Kogyo Co., Ltd., ME-2000, glass transition point -35 ° C., weight average molecular weight 600,000, and does not contain an ester structure derived from a reaction product of a dicarboxylic acid and a diol.

<Synthesis Example 3: Synthesis of Resin (A-15)>
74.8 parts of polyester polyol ("Kurare polyol P-3010" manufactured by Kurare Co., Ltd.), 11.4 parts of hexamethylene diisocyanate, and diethylene glycol mono in a reaction device equipped with a stirrer, thermometer, reflux cooling tube, and nitrogen gas introduction tube. 31.9 parts of ethyl ether acetate was charged and reacted at 90 ° C. for 3 hours under a nitrogen stream, then 2.0 parts of isophorondiamine was added and further reacted at 90 ° C. for 2 hours, and then diluted with diethylene glycol monoethyl ether acetate. As a result, the glass transition point is 2 ° C., the weight average molecular weight is 12,000, the urethane resin (A-15) containing an ester structure derived from the reaction product of dicarboxylic acid and diol is 40%, and the diethylene glycol monoethyl ether acetate solvent is 60%. A urethane resin solution having a non-volatile content of 40% was obtained.

The following substances were used as the solvent, 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): Methyl ethyl ketone, boiling point 79 ° C.

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

<Other components (E-1) to (E-2)>
-Other ingredients (E-1): Made by Big Chemie, antifoaming agent, BYK-1790 100% solid content
-Other components (E-2): Tosoh Corporation, blocked isocyanate, coronate 2507, non-volatile content 80% (solvent (B-3): methyl ethyl ketone).

<Production Example 1: Preparation of Conductive Resin Composition (F-1) for Molded Film>
Dissolve 20.0 parts of the resin (A-1) in 30.0 parts of the solvent (B-1), stir and mix 80.0 parts of the conductive fine particles (C-1), and use 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 11 and Comparative Production Example 1: Preparation of Conductive Resin Compositions (F-2) to (F-12) for Molded Film>
In Production Example 1, the type of resin, solvent, conductive fine particles, (when the other component (E-2) is used, the other component (E-2) was added immediately before the uniform stirring and mixing by the planetary mixer). Conductive resin compositions for molded films (F-2) to (F-12) were obtained in the same manner as in Production Example 1, except that the blending amounts were changed as shown in Table 1.

<Production Example 12: Preparation of Insulating Resin Composition (G-1) for Molded Film>
Dissolve 20.0 parts of the resin (A-7) in 15.0 parts of the solvent (B-1) and 15.0 parts of (B-2), and add 0.2 parts by weight of the defoaming agent (E-1). Then, the insulating resin composition for a molded film (G-1) was obtained by uniformly stirring and mixing with a planetary mixer.

<Production Examples 13 to 20, Comparative Production Examples 2 to 3: Preparation of Insulating Resin Compositions (G-2) to (G-11) for Molded Film>
Insulating resin compositions for molded films (G-2) to the same as in Production Example 17, except that the types and blending amounts of the resin, solvent and other components were changed as shown in Table 2 in Production Example 12. (G-11) was obtained.
The numerical values of each material in Tables 1 to 7 are parts by mass.

<Examples 1-33, 41-52, and Comparative Examples 1-4>
The conductive resin compositions (F-1) to (F-12) for a molded film are screen-printed on a polycarbonate (PC) base film (manufactured by Teijin Co., Ltd., Panlite 2151, thickness 300 μm, glass transition temperature 150 ° C.). Printing was performed by a machine (Minomat SR5575 semi-automatic screen printing machine manufactured by Minoscreen). Then, by heating in a hot air drying oven at 120 ° C. for 30 minutes, (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 linear pattern having a line width of 2 mm, a length of 60 mm and a thickness of 10 μm. (3) A molded film having a conductive layer having a comb-shaped wiring pattern of (3) facing portion 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-11) 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, 4 and 6, respectively. (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 34, 35, and Comparative Examples 5 to 8>
In Examples 1 and 3 and Comparative Examples 1 to 4, an acrylic resin base film (Technoloy S001G manufactured by Sumitomo Chemical Co., Ltd., thickness 250 μm, glass transition temperature 103 ° C.) (300 mm × 210 mm) was used instead of the polycarbonate base film. Molded films were obtained in the same manner as in Examples 1 and 3 and Comparative Examples 1 to 4 except that they were used and the drying conditions in the hot air drying oven were set to 80 ° C. for 30 minutes.

<Examples 36 and 37>
In Examples 1 and 3, instead of the polycarbonate base film, a polycarbonate resin / acrylic resin 2 type 2-layer coextruded base film (Technoloy C001 manufactured by Sumitomo Chemical Co., Ltd., thickness 125 μm, glass transition temperature 150 ° C.) was used, and polycarbonate was used. A molded film was obtained in the same manner as in Examples 1 and 3 except that the conductive resin composition for a molded film and the insulating resin composition were printed on the resin side.

<Example 38>
In Example 1, a polypropylene film (Pure Thermo AG-306 manufactured by Idemitsu Unitech, thickness 200 μm, glass transition temperature 0 ° C.) was used instead of the polycarbonate base film, and drying conditions in a hot air drying oven. A molded film was obtained in the same manner as in Example 1 except that the temperature was set to 80 ° C. for 30 minutes.

<Examples 39 and 40>
In Examples 1 and 3, a PET film (A-PET film manufactured by RP TEPCO, NOACRYSTAL-V, thickness 300 μm, glass transition temperature 70 ° C.) was used instead of the polycarbonate base film, and hot air drying was used. A molded film was obtained in the same manner as in Examples 1 and 3 except that the drying condition in the oven was set to 80 ° C. for 30 minutes.

<Example 53>
The conductive resin composition for film and the insulating resin composition so as to overlap the conductive pattern and the insulating pattern of Example 1 on the back surface of the molded film obtained in Example 1 on the front and back sides. A second conductive layer and a second insulating layer laminated so as to cover a part of the second conductive layer are formed on both sides of the base film in the same manner as in the first embodiment, except that the material is printed. 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 54>
On the insulating pattern of the molded film obtained in Example 1, 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 the first embodiment, 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 Example 9>
A molded film was obtained in the same manner as in Example 1 except that the insulating layer was not formed in Example 1.

<Comparative Example 10>
Similar to Comparative Example 9 except that the acrylic resin base film was used instead of the polycarbonate base film and the drying conditions in the hot air drying oven were set to 80 ° C. for 30 minutes. To obtain a molded film.

[(1) Wiring resistance evaluation]
A 2 mm × 60 mm linear conductive layer pattern formed on the molded films of Examples 1 to 54 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 at 4 cm intervals with an oil-based magic using a line perpendicular to the conductive layer as a mark from the longitudinal end. According to this mark, the resistance value was measured using a tester at the positions at intervals of 4 cm, and this was defined as the wiring resistance (Ω). The results are shown in Tables 3-7.

[(2) Thermal stretching evaluation 1]
The measurement coupons of Examples 1 to 33, 36, 37, 41 to 54 and Comparative Examples 1 to 4 and 9 are placed in a heating oven at 160 ° C. in a longitudinal direction with a pulling speed of 10 mm / min and an elongation rate of up to 50%. I stretched it. 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 at the time of thermal stretching. The fluctuation rate was set to (double), and each was evaluated according to the following criteria. The results are shown in Tables 3-7.
(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 3-7.
(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 34 to 40 and Comparative Examples 5 to 8 and 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 at the time of thermal stretching. The fluctuation rate was set to (double), and each was evaluated according to the following criteria. The results are shown in Tables 4 and 6.
(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 4 and 6.
(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 so as to overlap the position of the 2 mm × 60 mm linear pattern of the molded films of Examples 1 to 33, 36, 37, 41 to 54 and Comparative Examples 1 to 4, 9. The molding film formed into a hemispherical shape and the ABS resin molded product are formed by overlay molding at a set temperature of 160 ° C. using a TOM molding machine (manufactured by Fuse Vacuum Co., Ltd.). An integrated molded product was obtained. 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. It was evaluated according to the criteria of. The results are shown in Tables 3-7.
(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]
Molded product by 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 34, 35, 38 to 40 and Comparative Examples 5 to 8 and 10. A molded body was obtained in the same manner as in the process resistance evaluation 1 at the time of manufacturing, and the scraping of the linear pattern wiring and the resistance fluctuation rate at the time of overlay molding were evaluated. The results are shown in Tables 4 and 6.

[(8) Process resistance evaluation at the time of manufacturing a molded product by film insert molding 1]
It has a hemispherical recess with a radius of 4 cm in the center so as to overlap the positions of the 2 mm × 60 mm linear patterns of the molded films of Examples 1 to 33, 36, 37, 41 to 54 and Comparative Examples 1 to 4, 9. The block-shaped metal mold was aligned so as to face the surface on the conductive layer and the insulating layer side, and overlay molding was performed at a set temperature of 160 ° C. using a TOM molding machine (manufactured by Fuse Vacuum Co., Ltd.) to form a hemispherical shape. A molding film having a patterned conductor inside 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. It was evaluated according to the criteria of. The results are shown in Tables 3-7.
(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]
Molding 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 34, 35, 38 to 40 and Comparative Examples 5 to 8 and 10. A molded product was obtained in the same manner as in the process resistance evaluation 1 at the time of body manufacturing, and the degree of washout and the resistance fluctuation rate due to the injection of the molten resin of the linear pattern at the time of film insert molding were evaluated. The results are shown in Tables 4 and 6.

[(10) Evaluation of ion migration resistance of molded product by film insert molding]
Using the molding film having the comb-shaped wiring pattern and the insulating layer of the molding films of Examples 1 to 90 and Comparative Examples 1 to 8, 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 Tables 3-7.
(Presence / absence of short circuit due to ion migration and insulation resistivity)
A: Insulation resistance volatility is less than ± 25% at the initial stage 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 to 8, although the insulating layer is formed on the conductive layer, the glass transition temperature and the weight average molecular weight of the resins (A1) and (A2) are below or above the preferable ranges, so that the comb of the molded body is formed. It was found that the ion migration resistance between the mold electrodes was inferior, short circuits were likely to occur over time, and the molded body was not suitable for use as a three-dimensional wiring circuit. Although the insulating layer is formed in Comparative Examples 4 and 8, the volume resistivity of the insulating layer ^{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 not practical. It was a level.
In Comparative Examples 9 and 10 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. ..

On the other hand, from the results of Examples 1 to 54, 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, Examples 1 to 8, 13 to 19, 21, 23, 28 to 31, 33 satisfy the relationship that the glass transition temperature of the resin (A1) of the conductive layer is less than the glass transition point of the resin (B1) of the insulating layer. In the molded films of ~ 41, 43, 44, 46, 47, 49 to 54, the insulation performance of the insulating layer itself and the base film and the base film without significantly increasing the resistance value of the conductive layer pattern with respect to the stretching of the molded film during molding. Excellent ion migration resistance based on high adhesion to the injection molding resin was achieved at the same time. Further, the above-mentioned characteristic balance is compatible when the relationship that the weight average molecular weight of the resin (A1) of the conductive layer is less than the weight average molecular weight of the resin (B1) of the insulating layer is satisfied, or the glass transition of the resin (A1) of the conductive layer is satisfied. When both the temperature and the glass transition point of the resin (B1) of the insulating layer satisfy less than the glass transition point of the base film, these characteristics are further excellent, and the insulating resin (A2) becomes a reaction product of dicarboxylic acid and diol. It was even better when it had the derived ester structure. Although there are some unclear points in the mechanism for exhibiting such characteristics, regarding the improvement of the conductive characteristics of the conductive layer pattern with respect to the stretching of the molded film during molding, the molecular skeleton of the insulating layer of the molded film of the present invention is hard and the conductive layer. It is considered that the deterioration of the wiring was suppressed because the stress and local deformation were not concentrated on the conductive layer during the thermal molding of the molded film under high temperature conditions by suppressing the wetting of the insulating resin component inward.

Further, due to the above characteristics, according to the molded film provided with the conductive layer of the conductive resin composition of the present invention, an excellent molded body with integrated wiring was obtained even if the base material surface was not flat and had a three-dimensional shape. .. Regarding the ion migration resistance of this molded body, the generation of microcracks in the conductive layer pattern during molding of 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. I think it has 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), a solvent (B1), and conductive fine particles (C).
The insulating layer is a cured product of an insulating resin composition containing a resin (A2) and a solvent (B2).
The resin (A1) is a resin having a glass transition point of 10 ° C. or higher and 110 ° C. or lower and a weight average molecular weight of 10,000 or higher and 100,000 or lower.
The resin (A2) is a resin having a glass transition point of 30 ° C. or higher and 140 ° C. or lower and a weight average molecular weight of 20,000 or higher and 200,000 or lower.
A molded film having a volume resistivity of 1 × 10 ¹⁰ Ω · cm or more ^{and less than 1 × 10 17} Ω · cm of the insulating layer. The molded film according to claim 1, wherein the base film is a film selected from polycarbonate, polymethylmethacrylate, polypropylene, and polyethylene terephthalate, or a laminated film thereof. The glass transition point of the resin (A1) is less than the glass transition point of the resin (A2).
The molding film according to claim 1 or 2. The weight average molecular weight of the resin (A1) is less than the weight average molecular weight of the resin (A2).
The molding film according to any one of claims 1 to 3. The glass transition point of the resin (A1) and the glass transition point of the resin (A2) are both the highest when the base film is a laminated film made of two or more kinds of materials. The molding film according to any one of claims 1 to 4, which is less than the glass transition point). The molding film according to any one of claims 1 to 5, wherein the resin (A2) has an ester structure derived from a reaction product of a dicarboxylic acid and a diol. 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. The 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, to form an uneven surface or a three-dimensional curved surface. 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 base material.
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 a 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 molded 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 the injection molding mold, 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 an injection molding mold, 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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