JP2022065264A - Molded film, molded body, and method for manufacturing the same - Google Patents

Abstract

To provide a molded film which suppresses reduction in tensile force in a molding process and conductivity due to stress under high temperature, and is excellent in ion migration resistance between conductive patterns after molding, and a molded body which is excellent in conductivity and can maintain circuit characteristics even in use under a severe condition for a long period, and a method for manufacturing the same.SOLUTION: A molding film for forming a printing conductive circuit coated with an insulating layer on a base material surface having an uneven surface or a three-dimensional curved surface, in which the molded film has a conductive layer and an insulating layer on a base film, the conductive layer is a cured product of a conductive resin composition containing a resin (A1), a solvent (B1) and conductive particles (D), the insulating layer is a cured product of an insulating resin composition containing a resin (A2), a solvent (B2) and a modifier (E) having at least either one of an ester bond and an aromatic structure, and the modifier (E) satisfies a specific condition.SELECTED DRAWING: Figure 1

Description

The present invention relates to a molded film, 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 a conductive ink containing specific conductive fine particles and a specific epoxy resin as a low-temperature treatment type conductive ink capable of forming a high-definition conductive pattern by screen printing. Is disclosed. According to screen printing, it is possible to increase the thickness of the conductive pattern, and it is said that the resistance of the conductive pattern can be reduced.

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

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

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

According to the method of Patent Document 1, a 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 under severe conditions for a long period of time as a practical crisis, a short circuit between circuits due to ion migration has become a problem with the passage of time.

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

The molded film of 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, and the molded film has a conductive layer on a base film. A molded film with an insulating layer,
The conductive layer is a cured product of a conductive resin composition containing a resin (A1), a solvent (B1), and conductive particles (D).
The insulating layer is a cured product of an insulating resin composition containing a resin (A2), a solvent (B2), and a modifier (E) having at least one of an ester bond and an aromatic structure.
The volume resistivity of the insulating layer is 1 × 10 ¹⁰ Ω · cm or more and less than 1 × 10 ¹⁷ Ω · cm.
The modifier (E) satisfies all of the following conditions (1) to (3).
Conditions (1) Conditions that the number average molecular weight is 100 to 2000 (2) Conditions that have one or more hydroxyl groups in one molecule (3) The heating residue after heating at 105 ° C for 180 minutes is 60% or more and 100% or less.

In one embodiment of the present molded film, the resin (A1) has an aromatic structure in the main chain.

In one embodiment of the molded film, the resin (A1) has one or more linking groups selected from ester and amide bonds in the main chain.

One embodiment of the present molded film has a cross-linking agent (C2) which is an isocyanate-based compound in the insulating resin composition.

In one embodiment of the present molded film, the modifier (E) contains an aromatic hydrocarbon resin.

One embodiment of the molded film comprises a compound in which the modifier (E) has a polyester polyol structure.

One embodiment of the molded film comprises a compound in which the modifier (E) has a benzotriazole structure.

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

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

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

In one embodiment of the present molded film, 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. A molded body in which a printed conductive circuit coated with an insulating layer is formed on the surface of a base material having an uneven surface or a three-dimensional curved surface.

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

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

In one embodiment of the present molded film, the molding film described in the previous term is placed in a mold for injection molding, the base material is molded by injection molding, and the conductive layer in the molded film is placed on the base material side. Includes transfer steps.

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

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

Hereinafter, the molded film, the molded body, and the manufacturing method thereof according to the present 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 composition, and the insulating layer is a cured product of the insulating 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 three-dimensional 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 resin composition was examined. In order to apply it to the production of molded films, various adjustments were made to the volume resistivity of the insulating composition and the modifier component, and the molding was obtained with the insulating composition containing a specific modifier component. The presence or absence of disconnection and the magnitude of change in resistivity value that occur when the film is pulled at a high temperature that can be molded, and the ion migration characteristics over time when the conductive circuit integrated product is energized and used under harsh conditions for a long period of time are different. I found. Furthermore, it has been found that the conductive resin composition using the resin containing a specific structure and the molded film obtained by the above-mentioned insulating composition exhibit more remarkable characteristics.
As a result of studies based on such findings, the present inventors, when an insulating layer having a low volume eigenvalue is laminated on a conductive layer, are compared with a flat film circuit board or the like in a conductive circuit integrated product. It was confirmed that a significantly large ion migration occurred. Further, when the insulating layer formed on the conductive layer does not have a modifier, or when a modifier having no ester bond or aromatic structure is used, or whether the insulating layer has an ester bond or an aromatic structure. Even if it has one, the modifier whose number average molecular weight does not satisfy a specific range, does not have a hydroxyl group in one molecule, and has a heating residue of 60% or less at 105 ° C. for 180 minutes. When is used, when the molded film is deformed by pulling at a high temperature corresponding to its softening point, more cracks and local deformation of the conductive layer occur, and the insulating layer infiltrates into the conductive layer, so that the conductive layer is deformed. It was found that the conductivity was greatly deteriorated. Furthermore, due to the occurrence of cracks, the generation of black silver oxide increases due to ion migration when continuous conduction near the conductive layer under high temperature and high humidity, the insulation resistance value between the conductive patterns decreases, and leakage touch (dielectric breakdown) occurs. It became clear that the probability of occurrence is high. 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 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 of a formable film under heating.

As a result of diligent studies based on these findings, the present inventors have used a molded film having a volume resistivity of 1 × 10 ¹⁰ Ω · cm or more and less than 1 × 10 ¹⁷ Ω · cm. It was found that the occurrence of ion migration is suppressed in the conductive circuit integrally formed product. Further, the insulating resin composition forming the insulating layer has at least one of an ester bond and an aromatic structure, has a number average molecular weight of 100 to 2000, and has one or more hydroxyl groups in one molecule. When a molded film having a modifier, which has a residual heating content of 60% or more and 100% or less after heating at 105 ° C. for 180 minutes, is used, the occurrence of ion migration is suppressed in the conductive circuit integrally formed product. I found that. Further, by using the film, it is possible to obtain a formed 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. ..

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 this 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 opposite surface of 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. Above all, 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 composition, and the conductive composition may be printed on the anchor coat layer. The anchor coat layer is not particularly limited as long as it has good adhesion to the base film and further adheres to the conductive composition and follows the film at the time of molding, and is not particularly limited, and is an organic filler such as resin beads or a metal. Inorganic fillers such as 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 composition and, if necessary, a decorative layer may be printed on the opposite surface. The hard coat layer is not particularly limited as long as it has good adhesion to the base film and has good surface hardness and follows the film during molding, and is not particularly limited as long as it is an organic filler such as resin beads or an inorganic filler such as a metal oxide. May be added as needed. The method of providing the hard coat layer is not particularly limited, and it can be obtained by coating, drying and curing by a conventionally known coating method.

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

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

<Conductive layer>
In the molded film of this embodiment, the conductive layer is a cured product of the conductive resin composition described later.
The method for forming the conductive layer is not particularly limited, but in this embodiment, a screen printing method, a pad printing method, a stencil printing method, a screen offset printing method, a dispenser printing method, a gravure offset printing method, a reverse offset printing method, and a microcontact printing method are used. It is preferably formed by a method, and more preferably formed by a screen printing method.
In the screen printing method, it is preferable to use a fine mesh, particularly preferably a screen having a fine mesh of about 300 to 650 mesh, in order to cope with high definition of the conductive circuit pattern. The open area of the screen at this time is preferably about 20 to 50%. The screen wire diameter is preferably about 10 to 70 μm.
Examples of the screen version include polyester screens, combination screens, metal screens, nylon screens and the like. Further, when printing a high-viscosity paste state, a high-strength 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 composition by screen printing, it is heated to dry and crosslink to be cured.
For sufficient volatilization and cross-linking reaction of the solvent, the heating temperature is preferably 80 to 230 ° C. and the heating time is preferably 10 to 120 minutes. Thereby, a patterned conductive layer can be obtained.

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

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

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

The resin (A1) can be appropriately selected and used from the resins used for the conductive 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) is preferably a resin containing an aromatic structure in the main chain. Having an aromatic structure not only suppresses excessive solvent infiltration from the insulating composition, but also improves the affinity at the interface with the insulating layer containing the modifier, thereby heat under higher temperature conditions. It is preferable because it can suppress the generation of cracks during stretching formation and suppress the decrease in conductivity.

Further, in this embodiment, the resin (A1) is more preferably a resin having a bond selected from the group consisting of an ester bond and an amide bond in the main chain. In this case, in addition to preventing solvent infiltration into the above-mentioned conductive layer, the affinity with the insulating layer containing a modifier is more excellent, so that crack generation during thermal stretching formation under high temperature conditions is suppressed, and the conductivity is high. It is more preferable because the decrease can be further suppressed and the produced molded product has excellent ion migration resistance.

In this embodiment, the resin (A1) may have a crosslinkable functional group. The crosslinkable functional group is a substituent selected from a hydroxy group, an amino group, a carboxyl group and an acid anhydride group, and may contain one or two or more in one molecule. These crosslinkable functional groups can crosslink the resin (A1) three-dimensionally by combining with a crosslinking agent (C1) described later, if necessary, and can be suitably used in applications where hardness is required for the conductive layer. .. Further, by combining with a cross-linking agent (C2) and a modifier (E) described later, the interface between the conductive layer containing the resin (A1) and the insulating layer is three-dimensionally cross-linked to reduce the interfacial stress of the conductive layer. It can be reduced, and stress relaxation during thermal stretching and generation of cracks and voids can be suppressed.

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 composition of this embodiment may be appropriately adjusted according to the intended use and is not particularly limited, but is 5% by mass or more with respect to the total amount of solid content contained in the conductive composition. It is preferably 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, butyl acetate, gamma butyrolactone, isophorone, and tetralin. Can be done. In this embodiment, the solvent (B1) can be used alone or in combination of two or more.

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

In this embodiment, it is preferable to include one or more conductive fine particles selected from silver powder, copper powder, silver-coated powder, copper alloy powder, conductive oxide powder, and carbon fine particles. By using these conductive fine particles (D), it is possible to form a conductive layer having excellent conductivity without sintering, and further, stretchability and conductivity when molded into a three-dimensional shape as a molding film described later. It is possible to form a conductive layer having excellent property retention performance.

The shape of the conductive fine particles (D) is not particularly limited, but is preferably flake-shaped or chain-aggregated. In the case of a flake shape, the shape is not particularly limited as long as it is a flat shape having a two-dimensional plane shape. The "flake-like" in the present invention refers to a general flat shape of a two-dimensional plane called a scale-like, a scale-like, a plate-like, a flat-like, a sheet-like, or the like. Above all, the aspect ratio is 3 or more and 500 or less from the viewpoint of maintaining printability, maintaining conductivity during molding tension, and friction stress stress resistance with the base plastic at high temperature in the process of integrating with the plastic base material. Those are particularly preferable. Further, in the case of chain aggregation, 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 indefinite shapes formed by the settlement of spherical particles called bound spheres, chained spheres, agglomerated 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 composition are maintained, the conductivity is maintained during molding, and the injection molding process resistance by the molten resin or the high temperature to the molded resin is obtained. From the viewpoint of tensile resistance, 0.5 μm or more and 30 μm or less are preferable, and 1 μm or more and 15 μm or less are more preferable.
In this implementation, the average particle size of the conductive fine particles (D) is calculated as follows. Based on the laser diffraction / scattering method described in JISM8511 (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 (D) was added to an aqueous solution containing 0.5% by volume of ether (manufactured by Roche Diffractives Co., Ltd .: Triton X-100), and 40 W ultrasonic waves were irradiated for 180 seconds while stirring. After that, the measurement was performed. The value of the obtained median diameter (D50) was taken as the average particle size of the conductive fine particles (D).

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

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

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

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

[Insulation layer]
In the molded film of this embodiment, the insulating layer is a cured product of the insulating resin composition described later, and the volume resistance value is 1 × 10 ¹⁰ Ω · cm or more and less than 1 × 10 ¹⁷ Ω · cm.
By covering the conductive layer with the insulating layer, it is possible to prevent frictional damage to the conductive layer during the manufacturing process. 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. Further, it is possible to secure the insulating property during long-term continuous energization between the conductive layer patterns, which means that the insulating composition surely permeates and seals the conductive layer having fine irregularities to every corner and seals the insulating layer. This is because, by acting as an adhesive layer with the resin molded body, 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-strength stainless steel screen can be used.
The screen-printed squeegee may have a round, rectangular or square shape, and a polished squeegee can also be used to reduce the attack angle (the angle between the plate and the squeegee at the time of printing). For other printing conditions and the like, conventionally known conditions may be appropriately designed.

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

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

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

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

The resin (A2) can be appropriately selected and used from the resins used for the use of the insulating 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. Further, in this embodiment, the resin (A2) is particularly preferably a resin having a weight average molecular weight of 5,000 to 200,000, which contains an ester bond in the repeating structure. The resin having a weight average molecular weight of 5,000 to 200,000 containing an ester bond in the repeating structure allows the insulating layer to efficiently wet and spread on both the molded film and the surface of the conductive fine particles of the conductive layer and adhere strongly. At the same time, by exhibiting appropriate elasticity under high temperature conditions, it is possible to achieve both the protection property of the conductive layer from elongation during thermal molding and the ion migration resistance between the conductive patterns after forming the molded body at a high level. Will be.

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

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

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

<Solvent (B2)>
The solvent (B2) is not particularly limited, but the boiling point is preferably 180 ° C. or higher and 270 ° C. or lower from the viewpoint of 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, butyl acetate, gamma butyrolactone, isophorone, and tetralin. Can be done. In this embodiment, the solvent (B2) can be used alone or in combination of two or more.

<Crosslinking agent (C2)>
In this embodiment, a cross-linking agent (C2) may be additionally used as an optional component for cross-linking the resin (A2). The cross-linking agent (C2) can be appropriately selected from those having two or more reactive functional groups in one molecule that can form cross-links with the reactive functional groups of the resin (A2). Examples of such a reactive functional group include an epoxy group, an isocyanate group, a blocked isocyanate group, an alkyloxyamino group, an aziridinyl group, an oxetanyl group, a carbodiimide group, a β-hydroxyalkylamide group and the like. It is preferable to use an isocyanate-based compound having an isocyanate group and a blocked isocyanate group, and blocked isocyanate having a blocked isocyanate group can be particularly preferably used.

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

By using the cross-linking agent (C2) in combination with the resin (A2), not only the insulating layer is three-dimensionally cross-linked, but also by forming a cross-link with the resin (A1), the affinity between the conductive layer and the insulating layer is improved. However, the stress between the interfaces is relaxed, and cracks in the wiring can be suppressed.

<Modifier (E)>
In this embodiment, the insulating resin composition forming the insulating layer contains the modifier (E) in order to suppress the generation of cracks during thermal stretching. The modifier (E) has at least one of an ester bond and an aromatic structure, and contains a modifier (E) that satisfies the following conditions (1) to (3).
Conditions (1) Conditions where the number average molecular weight is 100 to 2000 (2) Conditions where one molecule has one or more hydroxyl groups (3) The heating residue after heating at 105 ° C for 180 minutes is 60% or more and 100% or less. By containing the modifier (E), it is possible to relieve the stress between the interface between the conductive layer and the insulating layer when the laminate obtained by printing the insulating composition on the conductive layer is thermally stretched and molded at a high temperature. can. As a result, it becomes possible to manufacture a molded film in which cracking of the conductive layer is suppressed, deterioration of the conductive layer is prevented, and deterioration of conductivity is suppressed.

The modifier (E) is not particularly limited as long as the above conditions are satisfied, but for example, a copolymer such as polyester, polyurethane, polyamide, phenoxy, or epoxy, an aromatic hydrocarbon resin, or a low molecular weight hetero. A ring compound or the like can be used, and among them, an aromatic hydrocarbon resin, a polyester polyol compound, or a benzotriazole compound is particularly preferable.

The above-mentioned aromatic hydrocarbon resin is an aromatic hydrocarbon formaldehyde resin obtained from aromatic hydrocarbons and formaldehyde. The above-mentioned aromatic hydrocarbon The aromatic hydrocarbon used as a raw material for the formaldehyde resin is an aromatic ring such as a benzene ring or a naphthalene ring, or an alkylated aromatic compound in which any hydrogen atom thereof is substituted with an alkyl group. If there is, the present invention is not particularly limited, and specific examples thereof include toluene, orthoxylene, metaxylene, paraxylene, mesitylene, pseudocumene, monocyclic aromatic hydrocarbon compounds having 10 or more carbon atoms, and polycycles such as naphthalene and methylnaphthalene. Aromatic hydrocarbons and the like can be mentioned. The aromatic hydrocarbons used in these reactions may be used alone or in combination of two or more. Further, a modified aromatic hydrocarbon formaldehyde resin obtained by copolymerizing the above-mentioned aromatic hydrocarbon with a phenol compound such as phenol, alkylphenol, and cresol as an essential component may be used.

Commercially available products of the above-mentioned aromatic hydrocarbon formaldehyde resin include xylene resins such as Nicanol Y-50, Y-100, Y-300, Y-1000, LLL, LL, L, H and G manufactured by Fudow Co., Ltd., and Nicanol. Alkylphenol-modified xylene resins such as GHP-150, HP120, HP-100 and HP-210, novolak-modified xylene resins such as Nikanol P-100 and GP-200, resol-modified xylene resins Nikanol PR-1440 and ethylene oxide-modified xylene resins. Nicanol L5 and the like.

The polyester polyol described above is not particularly limited as long as it is a polyester polymer composed of a polycondensation of a polyhydric alcohol and a polyvalent carboxylic acid. Examples of the above-mentioned polyhydric alcohol include ethylene glycol, aliphatic diols such as 1,4-butanediol and 1,6-hexanediol, branched diols such as propylene glycol, neopentyl glycol and 1,3-butanediol, and 1, Alicyclic diols such as 4-bis (hydroxymethyl) cyclohexane, 2,2-bis (4-hydroxycyclohexyl) propane, m-xylylene glycol, p-xylylene glycol, bisphenol A, bisphenol S, bisphenol F, etc. Aromatic diols can be mentioned. Examples of the above-mentioned polyvalent carboxylic acid include aromatic carboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid, aliphatic dicarboxylic acids such as succinic acid, adipic acid and maleic acid, 1,2-cyclohexanedicarboxylic acid and 1,4. -Alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid can be mentioned.

Specific examples of the above-mentioned polyester polyol include Kuraray polyols P510 and P1010 manufactured by Kuraray Co., Ltd., FLEXOREZ188 manufactured by King Industries, Inc., A308, 148, A307 and the like.

一般式（２）

The above-mentioned benzotriazole compound may have a benzotriazole structure, and examples thereof include the structure of the following general formula (1) or (2).
General formula (1)

General formula (2)

In the general formulas (1) and (2), R ¹ and R ⁶ have a hydrogen atom, a hydroxy group, an amino group, an alkyl group having 1 to 6 carbon atoms which may have a substituent, and a substituent. It may be a phenyl group, an organic group having a sulfonyl group, or -A ¹ -A ² . A ¹ is a carbonyl group, an arylene group which may have a substituent, an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group having ³ to 12 carbon atoms or ^—A3 −O—, and A3 is It is an alkylene group having 1 to 12 carbon atoms. A ² has a hydrogen atom, a halogen atom, a cyano group, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, a carboxy group, an aryl group which may have a substituent, or each alkyl group having 1 to 6 carbon atoms. It is a dialkylamino group of 6.

In the general formulas ( ¹ ) and ( ² ), ^R2 to R5 and ^R7 to R10 may independently have a hydrogen atom, a halogen atom, a hydroxy group, and a substituent, and may have 1 to 6 carbon atoms. An organic group having an alkyl group, an alkoxy group having 1 to 6 carbon atoms, a sulfonyl group, or an organic group represented by the following formula (general formula (3)).

General formula (3)

In the general formula (3), R ¹¹ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms which may be substituted. n is 0 or 1.

Specific examples of the above-mentioned benzotriazole compound (general formula (1) or (2)) include JF-77, 80, 83, JUST-500 manufactured by Johoku Chemical Co., Ltd., eversorb74, eversorb81, eversorb89, eversorb109 manufactured by Everlight Chemical Co., Ltd. And so on.

The content ratio of the modifier (E) in the insulating composition of this embodiment may be appropriately adjusted according to the intended use and is not particularly limited, but is 0. It is preferably 01% by mass or more and 25% by mass or less, and more preferably 0.1% by mass or more and 15% by mass or less. When the content ratio of the modifier (E) is within the above range, it is possible to suppress the generation of cracks and local deformation of the conductive layer when the molded film is deformed by pulling at a high temperature corresponding to the softening point, and the insulating layer. It is possible to suppress deterioration of the conductivity of the conductive layer due to infiltration into the conductive layer.

<Manufacturing method of insulating resin composition>
In the method for producing an insulating composition of this embodiment, the resin (A2), the solvent (B2), the cross-linking agent (C2), the modifier (E) and the other component (F) are dissolved or dissolved. Any method may be used as long as it is a dispersion method, and it can be produced by mixing by a known mixing means.

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

[Molded product]
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 composition for a molding film described above. Since the molded body of this embodiment is formed by a molding film using the conductive 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 composition of the present embodiment, and is not limited to these methods.

<First manufacturing method>
The first method for producing a molded body according to the present embodiment includes a step of printing the conductive composition for a molded film of the present embodiment on a base film and drying the molded film to produce the molded film.
The process of arranging the molded film on the substrate and
A step of integrating the molded film and the base material by an overlay molding method is included.
Hereinafter, the description will be made with reference to FIG. 3, but since the method for manufacturing the molded film is as described above, the description thereof will be omitted here.

FIG. 5 is a schematic process diagram showing an example of a first manufacturing method of a molded product. 5 (A) to 5 (C) show the molding film 10 and the base material 20 arranged in the chamber box of the TOM (Three dimension Overlay Method) molding machine, respectively, and FIGS. 5 (B) and 5 (C) show. ) Omits the chamber box.
In the first manufacturing method, first, the base material 20 is placed on the table of the lower chamber box 22. Next, the molded film 10 of the present embodiment is passed between the upper chamber box 21 and the lower chamber box 22 and placed on the base material 20. At this time, the molded film 10 may be arranged so that the conductive layer faces either the base material 20 side or the base material 20 side, and is selected depending on the final use of the molded body. Next, after the upper and lower chamber boxes are evacuated, the molded film is heated. Then, the base material 20 is raised 15 by raising the table. Next, only the inside of the upper chamber box 21 is opened to the atmosphere (FIG. 5 (B)). At this time, the molded film is pressurized 16 to the base material side, and the molded film 10 and the base material 20 are bonded and integrated (FIG. 5 (C)). In this way, the molded body 30 can be obtained.

In the first manufacturing method, the base material 20 can be prepared in advance by any method. In the first manufacturing method, the material of the base material 20 is not particularly limited, and may be made of resin or metal. Examples of the material of the base material 20 in the first production method include polycarbonate, polymethylmethacrylate, polyethylene terephthalate, polybutylene terephthalate, polystyrene, polyamide, polyether sulfone, polyphenylene sulfide, polyvinyl chloride, polyethylene, polypropylene, and cyclo. Thermoplastic resins such as olefin polymers, ABS (acrylonitrile-butadiene-styrene copolymer resin), modified polypropylene ethers, and polymers alloys consisting of two or more of these resins, metals such as stainless steel, copper, and aluminum, and other glasses and ceramics. Etc. can also be used.

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

<Second manufacturing method>
The second method for producing a molded body according to the present embodiment includes a step of printing the conductive composition for a molded film of the present embodiment on a base film and drying it to produce a molded film.
The process of molding the molded film into a predetermined shape and
A 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 under high temperature in another step.

<Third manufacturing method>
The third method for producing a molded body according to the present embodiment includes a step of printing the conductive composition for a molded film of the present embodiment on a base film by screen printing and drying to produce a molded film.
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 and the number average molecular weight in the examples are polystyrene-equivalent molecular weights in the measurement using GPC (gel permeation chromatography) "HLC-8320" manufactured by Tosoh Corporation.
The blocked effective NCO group content was calculated from "JIS K 1603-1: 2007 Plastic-Polyurethane Raw Material Aromatic Isocyanate Test Method-Part 1: How to Obtain Isocyanate Group Content".
As for the heating residue of the modifier (E), 1.0 g of the modifier (E) was placed in a mentum can having a diameter of 4.5 cm and a depth of 1.2 cm, spread evenly, and dried with hot air at 105 ° C. The amount of the residual modifier (E) after baking in the oven for 180 minutes is described.

<Resin (A1): (A-1) to (A-5)>
The following resins (A-1) to (A-5) were used as the resin (A1).
-Resin (A-1): Acrylic resin manufactured by Mitsubishi Chemical Corporation, "BR83", weight average molecular weight 40,000, has no aromatic structure, ester bond, or amide bond in the main chain.
-Resin (A-2): Bisphenol A type phenoxy resin manufactured by Nittetsu Chemical Materials Co., Ltd., "Fetonate YP-50S", weight average molecular weight 60,000, containing hydroxyl group as a crosslinkable functional group, aromatic structure in the main chain. Has no ester bond or amide bond.
Resin (A-3): Polyester resin manufactured by Unitika Ltd., "Elitel UE3400", having a weight average molecular weight of 25,000, and having an aromatic structure and an ester bond in the main chain.

<Synthesis Example 1: Synthesis of resin (A-4)>
In a separable flask equipped with a stirrer, thermometer, distillate trap, nitrogen gas introduction tube, and decompression regulator, 25.0 parts of resin (A-3) (“Elitel UE3400”), 75.0 parts of isophorone diisocyanate, And 95.6 parts of toluene were charged, and the mixture was stirred at 90 ° C. for 4 hours under a nitrogen stream, then 6.7 parts of isophorone diisocyanate was added and reacted at 90 ° C. for 2 hours, and then cooled to stop the reaction. After taking it out, it was transferred to a pallet whose surface was treated with fluorine, dried in a hot air drying oven at 120 ° C. for 4 hours, and vacuum dried for another 24 hours. A solid urethane resin (A-4) having an aromatic structure and an ester bond in a main chain having an amino group (functional group value 5 mgKOH / g) was obtained.

<Synthesis Example 2: Synthesis of resin (A-5)>
Polyetheramine ("JEFFAMINE D-2000" manufactured by Huntsman, weight average molecular weight 2,000) 200 in a separable flask equipped with a stirrer, a thermometer, a reflux condenser equipped with a water content metering receiver, and a nitrogen gas introduction tube. .0 parts, 175.0 parts of isophthalic acid, and 95.6 parts of toluene were charged, and while stirring the mixture, the outflow of water was confirmed, and the temperature was raised to 220 ° C. to continue the dehydration reaction. Sampling was performed every hour, and it was confirmed that the weight average molecular weight reached 30,000, and the reaction was stopped by sufficiently cooling. Then, after taking it out, it is transferred to a pallet whose surface is treated with fluorine, dried in a hot air drying oven at 120 ° C. for 4 hours, and further vacuum dried for 24 hours to have a weight average molecular weight of 30,000 and an aromatic content in the main chain. A solid polyamide resin (A-5) having a group structure and an amide bond was obtained.

<Resin (A2): (A-6) to (A-9)>
The following resins (A-6) to (A-9) were used as the resin (A2).
-Resin (A-6): The resin (A-1) was used as it was.
-Resin (A-7): Polyester resin manufactured by Toyobo Co., Ltd., "Byron 245", weight average molecular weight 19,000, having an aromatic structure and an ester bond in the main chain.

<Synthesis Example 3: Synthesis of Resin (A-8)>
225.0 parts of polyester resin ("Byron 200" manufactured by Toyobo Co., Ltd.), 32.3 parts of isophorone diisocyanate, in a separable flask equipped with a stirrer, thermometer, distillate trap, nitrogen gas introduction tube, and decompression regulator. And 63.6 parts of toluene were charged, stirred at 90 ° C. for 4 hours under a nitrogen stream, then 3.6 parts of isophorone diisocyanate was added, and the mixture was further reacted at 90 ° C. for 2 hours, then cooled to stop the reaction. .. Then, after taking it out, it is transferred to a pallet whose surface is treated with fluorine, dried in a hot air drying oven at 120 ° C. for 4 hours, and further vacuum dried for 24 hours to have a weight average molecular weight of 25,000, a glass transition point of 20 ° C., and an amino. A solid urethane resin (A-8) having an aromatic structure and an ester bond in a main chain having a group (functional group value 7 mgKOH / g) was obtained.

Resin (A-9): Phenoxy resin manufactured by Mitsubishi Chemical Corporation, "jER4250", weight average molecular weight 60000, having an aromatic structure in the main chain, and having no ester bond or amide bond.

The following substances were used as solvents, cross-linking agents, conductive fine particles, modifiers 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): Butyl acetate, boiling point 126 ° C.

<Crosslinking agents (C-1) to (C-2)>
-Crosslinking agent (C-1)
Asahi Kasei Corporation, Duranate MFA-75B, isocyanurate modified hexamethylene diisocyanate, contains 3 isocyanate groups in 1 molecule, NCO group content 13.7%, number average molecular weight 504, non-volatile content 75% butyl Isocyanate solution.

-<Synthesis Example 4: Synthesis of Crosslinking Agent (C-2)>
Cross-linking agent (C-1) (manufactured by Asahi Kasei Co., Ltd., Duranate MFA-75B (isocyanurate modified form of hexamethylene diisocyanate, containing 3 isocyanate groups in 1 molecule, NCO group content, non-volatile content 75% butyl acetate) 25.0 parts of solution), 8.0 parts of diethyl malonate, and 2.0 parts of ethyl acetate were added, 0.1 part of 28% sodium methylate solution was added at room temperature, and the mixture was reacted at 60 ° C. for 6 hours. Then, 0.25 part of 1-butanol was added and stirred continuously for 1 hour. After stirring, 0.02 part of butyl phosphate was added to obtain 19.3 blocked isocyanate composition blocked with diethyl malonate. The effective NCO group content of the blocked isocyanate group was 5.5%, and the number average molecular weight was 670. The obtained blocked isocyanate was diluted with butyl acetate so as to have a non-volatile content of 75%. Using.

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

<Modifiers (E-1) to (E-13)>
-Modifier (E-1): Manufactured by Fudow Co., Ltd., aromatic hydrocarbon resin "Nicanor LLL", having an aromatic structure. The number average molecular weight is 258, and one molecule has one or more hydroxyl groups, and the residual heat after 180 minutes at 105 ° C. is 98%.
-Modifier (E-2): Manufactured by Fudow Co., Ltd., aromatic hydrocarbon resin "Nicanor Y-300", which has an aromatic structure. Number average molecular weight 213, having one or more hydroxyl groups in one molecule, the residual heating after 180 minutes at 105 ° C is 98%.
-Modifier (E-3): Manufactured by Fudow Co., Ltd., aromatic hydrocarbon resin "Nicanor H", having a fragrant aromatic structure. Number average molecular weight 411, having one or more hydroxyl groups in one molecule, the residual heating after 180 minutes at 105 ° C is 96%.
Modifier (E-4): Polyester polyol "FLEXOREZA307" manufactured by King Industries, Inc., having an ester bond. Number average molecular weight 1203, having one or more hydroxyl groups in one molecule, the residual heating after 180 minutes at 105 ° C. is 91%.
Modifier (E-5): Polyester polyol "FLEXOREZ188" manufactured by King Industries, Inc., having an ester bond. Number average molecular weight 612, having one or more hydroxyl groups in one molecule, the residual heating after 180 minutes at 105 ° C. is 91%.
-Modifier (E-6): Manufactured by Yasuhara Chemical Co., Ltd., aromatic-modified terpene phenol resin, "YS Polystar U130", having an aromatic structure. The number average molecular weight is 800, and one molecule has one or more hydroxyl groups, and the residual heat after 180 minutes at 105 ° C. is 98%.
-Modifier (E-7): Manufactured by Johoku Chemical Co., Ltd., benzotriazole-based compound "JF-83", having an aromatic structure. Number average molecular weight 561, one molecule contains one hydroxyl group, and the heating residue after 180 minutes at 105 ° C is 99%.
-Modifier (E-8): A benzotriazole-based compound "eversorb74" manufactured by Everlite Chemical Co., Ltd., which has an aromatic structure. The number average molecular weight 351 contains one hydroxyl group in one molecule, and the residual heating residue after 180 minutes at 105 ° C. is 99%.
-Modifier (E-9): A benzotriazole compound "eversorb81" manufactured by Everlite Chemical Co., Ltd., which has an aromatic structure. The number average molecular weight 351 contains one hydroxyl group in one molecule, and the residual heating residue after 180 minutes at 105 ° C. is 94%.
Modifier (E-10): Kuraray Co., Ltd., polyester polyol, "Kuraray polyol P6010", having an ester bond. The number average molecular weight is 6,000, and one molecule has one or more hydroxyl groups, and the residual heat after 180 minutes at 105 ° C. is 96%.
-Modifier (E-11): Manufactured by Yasuhara Chemical Co., Ltd., aromatic-modified terpene resin, "YS resin TO85", having an aromatic structure. Number average molecular weight 820, the number of hydroxyl groups in one molecule is not included, and the heating residue after 180 minutes at 105 ° C is 98%.
-Modifier (E-12): 2-phenoxyethanol manufactured by FUJIFILM Wako Chemical Co., Ltd. It has an aromatic structure. The number average molecular weight 136, one hydroxyl group contained in one molecule, and the residual heating residue after 180 minutes at 105 ° C. was 0.1%.
Modifier (E-13): Polyterpene resin "YS resin PX800" manufactured by Yasuhara Chemical Co., Ltd., which has neither aromatic structure nor ester bond. The number average molecular weight 841, which does not contain the hydroxyl group contained in one molecule, is 98% after heating at 105 ° C. for 180 minutes.

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

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

<Production Examples 2 to 18: Preparation of Conductive Compositions (G-2) to (G-18) for Molded Film>
In Production Example 1, the resin (A1), the solvent (B1), the conductive fine particles (D), the cross-linking agent (C1), or the other component (F-1), (the other component (E-1) is a planetary mixer. Conductive compositions for molded films (G-2) to (G-) in the same manner as in Production Example 1 except that the type and blending amount of (added immediately before uniform stirring and mixing) were changed as shown in Table 1. 18) was obtained.

<Production Example 19: Preparation of Insulating Composition (H-1) for Molded Film>
Dissolve 20.0 parts of the resin (A-6) in 30.0 parts of the solvent (B-1), 2.0 parts by weight of the modifier (E-1) and 0.2 parts of the defoaming agent (F-1). After adding parts by weight, the insulating composition for a molded film (H-1) was obtained by uniformly stirring and mixing with a planetary mixer.

<Production Examples 19 to 46: Preparation of Insulating Compositions (H-2) to (H-28) for Molded Film>
In Production Example 19, the type of resin (A2), solvent (B2), cross-linking agent (C2), modifier (E) or other component (F-1) (other component (F-1) is determined by a planetary mixer. Insulating compositions for molded films (H-2) to (H-), respectively, in the same manner as in Production Example 19 except that (added immediately before uniform stirring and mixing) and the blending amount were changed as shown in Tables 2 and 3, respectively. 28) was obtained.

<Manufacturing example 47: Preparation of decorative ink (I-1)>
Prepare 175 parts of resin solution (A-7) (70 parts for resin (A-7) only), and add 20 parts of phthalocyanine blue pigment (Toyo Color Co., Ltd., Lionol Blue FG7351) and titanium oxide pigment (Ishihara Sangyo). TIPAQUE CR-93) 10 parts by mass is stirred and mixed, kneaded with a 3-roll mill (manufactured by Kodaira Seisakusho), and then 5 parts of an isocyanate cross-linking agent (Death Module N3300 manufactured by Sumika Cobestro Urethane, 100% non-volatile content). And 90 parts of the solvent (B-2) were added and mixed uniformly with stirring to obtain a decorative ink (I-1).

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

<Examples 1 to 84 and comparisons 2 to 7>
Conductive compositions for molding films (G-1) to (G-18) are printed on a polycarbonate (PC) base film (Teijin, Panlite 2151, thickness 300 μm), respectively, on a screen printing machine (Minoscreen). , Minomat SR5575 semi-automatic screen printing machine). Then, by heating at 120 ° C. for 30 minutes in a hot air drying oven, (1) a square solid pattern having a width of 70 mm, a length of 120 mm and a thickness of 10 μm, and (2) a straight line having a line width of 2 mm, a length of 60 mm and a thickness of 10 μm. A molded film having a similar pattern and (3) a conductive layer having a comb-shaped wiring pattern 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 intrinsic resistance of the conductive layer was measured using a resistivity meter (Roresta GX MCP-T700 manufactured by Mitsubishi Chemical Analytical Corporation).
Further, the insulating compositions for molded film (H-1) to (H-28) are applied onto the surface on which the conductive pattern of the molded film provided with the conductive layer is formed, (1) with respect to the square solid conductive pattern. The width is 90 mm, the length is 140 mm, and the thickness is 15 μm so as to cover the entire conductive pattern. (2) For the linear conductive pattern, 10 mm at both ends are exposed in the length direction of the conductive pattern. The width is 10 mm, the length is 40 mm, and the thickness is 15 μm so as to cover the portion. Overprinting was performed 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 composition and the insulating composition were as shown in Tables 3 to 6. (1) Regarding the insulating layer portion at the end that does not overlap with the conductive layer in the (1) square solid pattern, the resistivity meter (HIRESTA UX MCP-HT800, manufactured by Mitsubishi Chemical Analytical Co., Ltd.) measures the volume intrinsic resistance of the insulating layer. Was measured using.

<Examples 85 to 88>
In Examples 1, 27, 47 and 70, an acrylic resin base film (Technoloy S001G, manufactured by Sumitomo Chemical Co., Ltd., thickness 250 μm) (300 mm × 210 mm) was used instead of the polycarbonate base film, and a hot air drying oven. A molded film was obtained in the same manner as in Examples 1, 27, 47 and 70, except that the drying conditions were set at 80 ° C. for 30 minutes.

<Examples 89 to 92>
In Examples 1, 27, 47 and 70, instead of the polycarbonate base film, a polycarbonate resin / acrylic resin type 2 two-layer coextruded base film (Technoloy C001 manufactured by Sumitomo Chemical Co., Ltd., thickness 125 μm) was used, and the polycarbonate resin side was used. A molded film was obtained in the same manner as in Examples 1, 27, 47 and 70, except that the conductive composition for the molded film and the insulating composition were printed on the film.

<Examples 93 and 94>
In Examples 1 and 27, a polypropylene resin base film (Pure Thermo AG-306 manufactured by Idemitsu Unitech Co., Ltd., thickness 200 μm) was used instead of the polycarbonate base film, and the drying conditions in a hot air drying oven were 80. Molded films were obtained in the same manner as in Examples 1 and 27 except that the temperature was set to 30 minutes.

<Examples 95 and 96>
In Examples 47 and 70, a polyethylene terephthalate resin base film (A-PET film manufactured by RP Topra Co., Ltd., NOACRYSTAL-V, thickness 300 μm) was used instead of the polycarbonate base film, and the film was dried in a hot air drying oven. Molded films were obtained in the same manner as in Examples 47 and 70 except that the conditions were set to 80 ° C. for 30 minutes.

<Examples 97 to 100>
A decorative ink (I-1) is applied onto a polycarbonate base film (Teijin Co., Ltd., Panlite 2151, thickness 300 μm) using a blade coater so that the dry film thickness is 2 μm, and the temperature is 120 ° C. It was heated for 30 minutes to form a decorative layer.
Next, in Examples 1, 27, 47, and 70, the base film with a decorative layer was used instead of the polycarbonate base film, and the conductive layer and the insulating layer were formed on the decorative layer. , 27, 47 and 70, a molded film in which a polycarbonate base film, a decorative ink layer, a conductive layer and an insulating layer were laminated in this order was obtained.

<Example 101>
The conductive composition for film and the insulating composition so as to overlap the conductive pattern and the insulating pattern of Example 70 on the front and back surfaces of the molded film obtained in Example 70 without printing. In the same manner as in the 70th embodiment, the conductive layers are formed on both sides of the base film, except that the second conductive layer and the second insulating layer laminated so as to cover a part of the second conductive layer are formed by printing. And a molded film having an insulating layer laminated so as to cover a part or the whole thereof was obtained.

<Example 102>
On the insulating pattern of the molded film obtained in Example 70, the conductive pattern of Example 70 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 70. By performing the same procedure as in the process and further printing the second insulating layer pattern at a position overlapping the insulating pattern of Example 70, 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 1>
A molded film was obtained in the same manner as in Example 1 except that the insulating layer was not formed in Example 1.

[(1) Wiring resistance evaluation]
A 2 mm × 60 mm linear conductive layer pattern formed on the molded films of Examples 1 to 102 and Comparative Examples 1 to 7 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 with an oil-based marker at intervals of 4 cm from the end in the longitudinal direction using a line perpendicular to the conductive layer as a mark. According to this mark, both measuring portions of the tester were brought into contact with the conductive layer, and the resistance value of the conductive layer having a width of 4 cm was measured, and this was defined as successful wiring (Ω). The results are shown in Tables 4-11.

[(2) Thermal stretching evaluation 1]
The measurement coupons of Examples 1 to 84, 89 to 92, 97 to 102 and Comparative Examples 1 to 7 were stretched in a heating oven at 170 ° C. in the longitudinal direction at a pulling speed of 10 mm / min to an elongation rate of 50%. .. It was taken out of the oven, cooled, and then evaluated for disconnection using an optical microscope. In addition, the wiring resistance (Ω) at the position corresponding to the interval of 4 cm is measured by the same method as the measurement of the wiring resistance above, and the wiring resistance after expansion / contraction / the wiring resistance before expansion / contraction is the resistance 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 4-11.
(Presence / absence of disconnection)
A: No disconnection was observed 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 Examples 1 to 84, 89 to 92, 97 to 102 and Comparative Examples 1 to 7, the same as in the heat stretching evaluation 1 except that the elongation rate was changed to 100% in the heat stretching evaluation 1. It was evaluated according to the following criteria. The results are shown in Tables 4-11.
(Presence / absence of disconnection)
A: No disconnection was observed 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 85 to 88 and 93 to 96 were stretched in a heating oven at 130 ° 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 Table 9.
(Presence / absence of disconnection)
A: No disconnection was observed 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 Examples 85 to 88 and 93 to 96, the evaluation was performed according to the following criteria in the same manner as in the thermal stretching evaluation 3 except that the elongation rate was changed to 100% in the thermal stretching evaluation 3. The results are shown in Table 9.
(Presence / absence of disconnection)
A: No disconnection was observed B: 1 to 2 minor cracks were confirmed C: Severe disconnection or peeling of the conductive coating film was confirmed (resistance fluctuation rate during thermal stretching)
A: 10 times or more and less than 50 times B: 50 times or more and less than 200 times C: 200 times or more

[(6) Process resistance evaluation 1 when manufacturing a molded product by overlay molding]
A hemispherical ABS resin molded product having a radius of 4 cm is conductive so as to overlap the positions of the 2 mm × 60 mm linear patterns of the molded films of Examples 1 to 84, 89 to 92, 97 to 102 and Comparative Examples 1 to 7. By aligning them so that they face the surface on the body side and performing overlay molding at a set temperature of 170 ° C using a TOM molding machine (manufactured by Fuse Vacuum Co., Ltd.), the molded film molded into a hemispherical shape and the ABS resin molded product are integrated. A 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. Evaluated according to the criteria of. The results are shown in Tables 4-11.
(Presence / absence of disconnection and resistance volatility)
A: No wiring scraping is seen, and the resistance fluctuation rate is 5 times or more and less than 30 times. 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]
Except for the fact that the linear patterns of 2 mm × 60 mm of the molded films of Examples 85 to 88 and 93 to 96 were used and overlay molding was performed at 130 ° C. Similarly, a molded product was obtained, and the scraping and resistance fluctuation rate of the linear pattern wiring during overlay molding were evaluated. The results are shown in Table 9.

[(8) Process resistance evaluation at the time of manufacturing a molded product by film insert molding 1]
A block shape having 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 84, 89 to 92, 97 to 102 and Comparative Examples 1 to 7. By aligning the metal mold so that it faces the surface on the conductive layer and the insulating layer side, and performing overlay molding at a set temperature of 170 ° C using a TOM molding machine (manufactured by Fuse Vacuum Co., Ltd.), the inside of the hemispherical shape is formed. A molding film having a patterned conductor was obtained.
Next, the molding film molded into the hemispherical shape was set in an injection molding machine (IS170 (i5), manufactured by Toshiba Machinery Co., Ltd.) equipped with a valve gate type in-mold molding test mold, and a PC / ABS resin was used. (LUPOYPC / ABSHI5002, manufactured by LG Chemical Co., Ltd.) was injection-molded to obtain a molded body integrated with a molding film with a patterned conductor (injection conditions: screw diameter 40 mm, cylinder temperature 260 ° C, mold). Temperature (fixed side, movable side) 80 ° C., injection pressure 180 MPa, holding pressure 120 MPa, injection speed 60 mm / sec (28%), injection time 4 seconds, cooling time 20 seconds). The washout (deformation and disconnection of the wiring pattern due to the temperature and injection pressure of the molten thermoplastic resin) and the resistance fluctuation rate due to the injection of the molten resin of the linear pattern of this molded product were confirmed. For the resistance fluctuation rate, measure the wiring resistance (Ω) at the position corresponding to the 6 cm interval based on the original mark, and set the wiring resistance after expansion and contraction / the wiring resistance before expansion and contraction as the resistance fluctuation rate during thermal stretching (double), and each is as follows. Evaluated according to the criteria of. The results are shown in Tables 4-11.
(Presence / absence of disconnection and resistance volatility)
A: No wiring washout is seen, and the resistance fluctuation rate is 10 times or more and less than 50 times. B: Wiring distortion due to slight washout is confirmed, or the resistance fluctuation rate is 50 times or more and less than 500 times C : One or more disconnections due to wiring washout are confirmed

[(9) Process resistance evaluation at the time of manufacturing a molded product by film insert molding 2]
Process resistance evaluation 1 at the time of manufacturing a molded product by the film insert molding, except that the linear pattern of 2 mm × 60 mm of the molded films of Examples 85 to 88 and 93 to 96 was used and overlay molding was performed at 130 ° C. A molded product was obtained in the same manner as in the above, and the degree of washout and the resistance fluctuation rate due to the injection of the molten resin into the linear pattern during film insert molding were evaluated. The results are shown in Table 9.

[(10) Evaluation of ion migration resistance of molded product by film insert molding]
Using the molded film having the comb-shaped wiring pattern and the insulating layer of the molded films of Examples 1 to 102 and Comparative Examples 1 to 7, 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.
Connect the exposed parts of the positive and negative electrodes of the comb-shaped wiring of each of the above moldings to the wiring with an alligator clip, and apply 5V at 85 ° C using the migration tester insulation deterioration evaluation tester "MIG-8600B" manufactured by IMV. The insulation resistance values between the comb-shaped wiring terminals after 1000 hours under the% RH condition were confirmed and evaluated according to the following criteria. The results are shown in Table 11.
(Presence / absence of short circuit due to ion migration and insulation resistivity)
A: Insulation resistance volatility is less than the initial ± 25% B: Insulation resistance volatility is ± 25% or more and less than ± 100% at the initial stage C: Insulation resistance volatility is ± 100% or more at the initial stage or leak touch (short circuit between electrodes) History) Yes

[Summary of results]
In Comparative Example 1 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 not suitable for use as a three-dimensional wiring circuit. I understood. 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 water from this interface and the thermal expansion and contraction is large. .. Further, in Comparative Example 2, although the insulating layer was formed, since it did not have the modifier (E), the ion migration resistance between the comb-shaped electrodes of the molded product could not withstand practical use. On the other hand, in Comparative Example 3, since the volume resistivity was as low as less than 10 ¹⁰ Ω · cm, the ion migration resistance between the comb-shaped electrodes of the molded product was at a level that could not withstand practical use. Hereinafter, the conditions of the modifier (E) will be described. In Comparative Example 4, the modifier (E) is used for the insulating layer, but since the number average molecular weight is larger than the specified range of the condition (1), the stress relaxation effect between the conductive layer and the insulating layer does not work, and during thermal stretching, the stress relaxing effect does not work. The magnitude of the resistance value fluctuation rate due to the disconnection in the conductive layer and the ion migration resistance between the electrodes were at a level that could not be put into practical use. Further, in Comparative Example 5, the number average molecular weight and the heating residue of the modifier (E) satisfy the predetermined ranges, but since they do not have the hydroxyl group of the condition (2), they are contained in the conductive layer and the insulating layer. No crosslinked body was formed, and the ion migration resistance between the comb-shaped electrodes of the molded body did not withstand practical use at all. Further, in Comparative Example 6, since the heating residue of the condition (3) was not satisfied, cracks were generated in the conductive layer, and the ion migration resistance could not withstand practical use. In addition, although the conditions (1) and (3) are satisfied in Comparative Example 7, since it does not have an aromatic structure or an ester bond, it has low conductivity and affinity with the resin used for the insulating layer, and wiring. The cracks could not be suppressed and the ion migration resistance was insufficient.

On the other hand, from the results of Examples 1 to 102, 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, when the resin (A1) used for the conductive composition has an aromatic structure in the main chain and has an ester bond or an amide bond, the modifier (E) is used in the insulating layer. In the molded films of Examples 3 to 13, 15 to 18, 40 to 81, 83, 84, 87, 88, 91, 92, 95, 96, 99, 100, the conductive layer is formed by the effect of the modifier in the insulating layer. As a result of stress relaxation between the interfaces during thermal molding and stretching, fine cracks could be prevented and the thermal stretching resistance fluctuation rate was as good as less than 10 times. In particular, in the molded films of Examples 53 to 84, 88, 92, 96, and 100 in which an isocyanate compound is used as the cross-linking agent, in addition to the high affinity between the conductive layer and the insulating layer, between the modifier and the resin. By cross-linking with, there are no fine cracks during thermal molding stretching, the thermal stretching resistance fluctuation rate is less than 10 times, no wiring washout is seen, and the insulation resistance fluctuation rate is the initial value. It showed very good results of less than ± 25%. It is considered that the migration between the molded body wirings was suppressed by the affinity between the conductive layer and the insulation correlation and the cross-linking with the cross-linking agent, and the insulation reliability between the molded body wirings was improved.

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

In this way, the molded film using the conductive composition and the wiring-integrated molded body of the present implementation have a degree of freedom in designing directly to plastic housings and three-dimensional shaped parts such as home appliances, automobile parts, robots, and drones. It is possible to build a lightweight and space-saving circuit without damaging it, build a touch sensor, antenna, heating element, electromagnetic wave shield, inductor (coil), resistor, and mount various electronic components. .. 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 (14)

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 particles (D), and the insulating layer is a resin (A2), a solvent (B2), and the like. A cured product of an insulating resin composition containing a modifier (E) having at least one of an ester bond and an aromatic structure.
Molding in which the volume resistivity of the insulating layer is 1 × 10 ¹⁰ Ω · cm or more and less than 1 × 10 ¹⁷ Ω · cm, and the modifier (E) satisfies all of the following conditions (1) to (3). the film.
Conditions (1) Conditions where the number average molecular weight is 100 to 2000 (2) Conditions where one molecule has one or more hydroxyl groups (3) The heating residue after heating at 105 ° C for 180 minutes is 60% by mass or more and 100% by mass or less. Is The molded film according to claim 1, wherein the resin (A1) has an aromatic structure in the main chain. The molded film according to claim 1 or 2, wherein the resin (A1) has one or more bonding groups selected from an ester bond and an amide bond in the main chain. The molded film according to any one of claims 1 to 3, wherein the insulating resin composition contains a cross-linking agent (C2) which is an isocyanate compound. The molded film according to any one of claims 1 to 4, wherein the modifier (E) contains an aromatic hydrocarbon resin. The molded film according to any one of claims 1 to 4, wherein the modifier (E) contains a compound having a polyester polyol structure. The molded film according to any one of claims 1 to 4, wherein the modifier (E) contains a compound having a benzotriazole structure. The molded film according to any one of claims 1 to 7, wherein the base film is a film selected from polycarbonate, polymethylmethacrylate, polypropylene, and polyethylene terephthalate, or a laminated film thereof. The molded film according to any one of claims 1 to 8, 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 9, 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, wherein the molded film is the molded film according to any one of claims 1 to 10. The step of arranging the molded film according to any one of claims 1 to 10 on a substrate, and
A method for producing a molded product, comprising 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 10 into a predetermined shape, and
A step of arranging the molded film after molding in a mold for injection molding, and
A method for manufacturing 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 10 in a mold for injection molding, and
A method for producing a molded product, comprising a step of molding a base material by injection molding and transferring a conductive layer in the molding film to the base material side.

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