JP2024029494A - Conductive composition for molded film, molded film and method for producing the same, molded body and method for producing the same - Google Patents

Abstract

An object of the present invention is to provide a conductive composition for a molded film, which can produce a molded film in which a decrease in conductivity due to a high-speed tensile force is suppressed under high-temperature conditions. [Solution] The resin (A) contains a resin (A), conductive fine particles (B), and a solvent (C), and the resin (A) is a polyester resin, a polyurethane resin, a polyamide resin, and a polycarbonate resin. The above problem is solved by a conductive composition for a molded film containing a resin (A1) which is any one of the structural units derived from a trifunctional monomer or a tetrafunctional monomer. [Selection diagram] Figure 1

Description

The present invention relates to a conductive composition for a molded film, a molded film and a method for manufacturing the same, a molded article and a method for manufacturing the same.

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

A printing method using conductive ink is being considered as a method for forming conductive circuits in place of the etching method. According to the method of printing conductive ink, compared to the etching method, there are no complicated steps, a conductive circuit can be easily formed, productivity can be improved, and costs can be reduced.
For example, Patent Document 2 describes a specific conductive ink containing specific conductive fine particles and a specific epoxy resin as a low-temperature processing type conductive ink that can form a high-definition conductive pattern by screen printing. A sex ink is disclosed. It is said that screen printing allows the conductive pattern to be made thicker and to reduce the resistance of the conductive pattern.

Furthermore, Patent Document 3 describes a method for manufacturing a decorative sheet capable of expressing a three-dimensional three-dimensional effect, which includes a laminate having a printed layer printed in a pattern on a transparent resin layer, and a base film. A method is disclosed in which the decorative layer is formed into an uneven shape along the pattern of the printed layer by thermocompression bonding a laminated sheet having a decorative layer thereon.

Japanese Patent Application Publication No. 2012-11691 Japanese Patent Application Publication No. 2011-252140 JP2007-296848A

According to the method of Patent Document 1, a conductor can be easily provided on the surface of a molded body. On the other hand, there is an increasing desire to form conductive circuits on the surfaces of base materials of various shapes, such as base materials having uneven surfaces or curved surfaces. When forming a conductive circuit by laminating a film having a conductive layer on the surface of such a base material, the film needs to be deformed to match the surface shape of the base material. When the film is deformed, a large tensile force may be partially generated in the conductive layer. The tensile force caused breakage of the conductive layer, resulting in a decrease in conductivity. Furthermore, when forming a conductive circuit on a base material having such an uneven or curved surface, the film and the base material are integrated after or at the same time as deforming the film having the conductive layer. However, during this integration step, stress is applied to the conductive circuit due to friction with the plastic base material at high temperatures. The high-temperature stress also caused breakage of the conductive layer, resulting in a decrease in conductivity.

The present invention has been made in view of the above circumstances, and provides a conductive composition for a molded film that can produce a molded film in which a decrease in conductivity due to tensile force and high-temperature stress is suppressed, It is an object of the present invention to provide a molded film whose conductivity is suppressed from decreasing due to high-temperature stress, a molded body with excellent conductivity, and a method for manufacturing the same.

The conductive composition for molded film according to this implementation is:
A conductive composition for producing a molded film for forming a conductive layer on the surface of a base material having an uneven surface or a three-dimensional curved surface,
Contains a resin (A), conductive fine particles (B), and a solvent (C),
The resin (A) is any one of the group consisting of a polyester resin, a polyurethane resin, a polyamide resin, and a polycarbonate resin, and includes a resin (A1) containing a structural unit derived from a trifunctional monomer or a tetrafunctional monomer.

In one embodiment of the conductive composition for molded film of this embodiment, the total content of structural units derived from trifunctional monomers and tetrafunctional monomers is 0.1% by mass to 15% by mass in resin (A1). .

In one embodiment of the conductive composition for molded film of this embodiment, the resin (A1) is a resin having a hydroxyl group or an amino group.

In one embodiment of the conductive composition for a molded film, the conductive fine particles (B) are selected from silver powder, copper powder, silver coated powder, copper alloy powder, conductive oxide powder, and carbon fine particles. Contains one or more types of conductive fine particles.

In one embodiment of the conductive composition for molded film of the present invention, the ratio of the resin (A) in the solid content of the conductive composition is 8 to 40% by weight.

One embodiment of the conductive composition for molded film of this embodiment further contains a crosslinking agent (D).

In one embodiment of the conductive composition for molded film of this embodiment, the crosslinking agent (D) is a trifunctional block isocyanate crosslinking agent.

The molded film according to this embodiment is a molded film comprising a conductive layer on a base film,
The conductive layer is a cured product of the conductive composition for molded film of the present embodiment.

One embodiment of the molded film of this embodiment is a molded film having a decorative layer and a conductive layer on a base film,
The conductive layer is a cured product of the conductive composition for molded film of the present embodiment.

In one embodiment of the molded film of this embodiment, the base film is a film selected from polycarbonate, polymethyl methacrylate, polypropylene, and polyethylene terephthalate, or a laminated film of these.

The molded body according to this embodiment is a molded body in which a conductive layer is laminated on a base material,
The conductive layer is a cured product of the conductive composition for molded film of the present embodiment.

A first method for producing a molded body according to the present embodiment includes a step of manufacturing a molded film by printing the conductive composition for a molded film according to the present embodiment on a base film and drying it;
arranging the molded film on a substrate;
The method includes a step of integrating the molded film and the base material by an overlay molding method.

A second method for producing a molded article according to the present embodiment includes a step of manufacturing a molded film by printing the conductive composition for a molded film according to the present embodiment on a base film and drying it;
a step of molding the molded film into a predetermined shape;
arranging the molded film after molding in a mold for injection molding;
The method includes the steps of molding a base material by injection molding and integrating the molded film and the base material.

A third method for producing a molded article according to the present embodiment includes a step of manufacturing a molded film by printing the conductive composition for a molded film according to the present embodiment on a base film and drying it;
placing the molded film in an injection mold;
The method includes the steps of molding a base material by injection molding and transferring the conductive layer in the molded film onto the base material side.

According to the present invention, a conductive composition for a molded film that can produce a molded film in which a decrease in conductivity due to tensile force and high temperature stress is suppressed, and a conductive composition that suppresses a decrease in conductivity due to tensile force and high temperature stress. It is possible to provide a molded film, a molded body with excellent conductivity, and a method for manufacturing the same.

It is a typical sectional view showing an example of a molded film of this embodiment. It is a typical sectional view showing another example of a molded film of this embodiment. It is a typical process diagram showing an example of the 1st manufacturing method of a molded object. It is a typical process diagram which shows another example of the 2nd manufacturing method of a molded object. It is a typical process diagram which shows another example of the 3rd manufacturing method of a molded object.

Hereinafter, a conductive composition for a molded film, a molded film, a molded article, and a method for producing the same according to the present embodiment will be explained in detail in order.
In this embodiment, the term "cured product" includes not only one that is cured by a chemical reaction, but also one that is hardened not by a chemical reaction, such as one that becomes hard due to volatilization of a solvent.

[Conductive composition for molded film]
Contains a resin (A), conductive fine particles (B), and a solvent (C),
The resin (A) includes any one of the group consisting of polyester resin, polyurethane resin, polyamide resin, and polycarbonate resin,
The resin (A) contains a structural unit derived from a trifunctional monomer or a tetrafunctional monomer.

The present inventors investigated screen-printable conductive compositions to produce formed films that are applicable to uneven substrate surfaces and have process suitability for integration with plastic substrates. I did it. In order to apply it to the production of molded films, various adjustments and studies were made to the resin structure, conductive fine particles, and solvent. The frequency of cracks that occur when the resulting molded film is tensile deformed at high moldable temperatures differs depending on the type of film being printed at high speed. It was found that the frequency of occurrence of printing defects such as chipping and blurring, and the magnitude of change in resistance value during tensile deformation under the above-mentioned high temperature, especially when the degree of deformation is large, were found to be different. The present inventors conducted studies based on these findings, and found that when a conductive composition containing no solvent having a specific aromatic alcohol structure was printed on a resin film and dried by heating, the formed film was When the conductive layer pattern is deformed by pulling at a high temperature that corresponds to its softening point, significant conductivity deterioration and cracking occur in the conductive layer, and furthermore, when the printing speed is increased when printing the above-mentioned conductive composition, It has become clear that the frequency of occurrence of printing defects such as chipping and blurring has increased significantly. The same applies to the case where a conductive layer is provided on the decorative layer.

Even if a molded film has a conductive layer that causes cracks in the conductive layer or large changes in resistance when it is deformed by tension at such high temperatures, it cannot be used alone as a flat film circuit board, etc. Problems occurred when the device was used in a state where it was bent onto a two-dimensional curved surface. However, when used as a molded film that follows and integrates the shape of an uneven base material surface, such as an uneven shape or a three-dimensional curved surface shape, the molded film will be deformed. Therefore, it is predicted that the conductive layer is unable to follow the deformation of the resin film, resulting in peeling or disconnection from the base film, resulting in a decrease in the conductivity of the conductive layer.
Note that the uneven surface or three-dimensional curved surface in the present invention refers not only to a surface having a gently curved cross section, but also to any three-dimensional surface having an acute corner or a rectangular shape. In other words, it refers to a three-dimensional shape that cannot be created simply by deforming a plane without expanding or contracting it, such as a hemispherical shape, a conical shape, a cylindrical shape, a quadrangular prism shape, etc. In addition, if a certain three-dimensional shape has elements of both the above-mentioned plane or two-dimensional curved surface and three-dimensional curved surface in a continuous three-dimensional surface, for example, if a planar shape has one or more partial hemispherical shapes in combination. Regarding the three-dimensional shape, this is also assumed to be a three-dimensional curved surface because it is a three-dimensional shape that cannot be created by deforming the plane as a whole without expanding or contracting it. That is, the uneven surface or three-dimensional curved surface in the present invention cannot be realized by bending a flexible substrate or the like, but can be realized by, for example, shaping a moldable film by three-dimensional molding under heating.

As a result of intensive studies based on these findings, the present inventors found that when containing a resin having a structure made of specific constituent monomers, a molded film with conductive wiring formed thereon exhibits a large degree of deformation at a particularly high deformation rate. We have discovered that the change in wiring resistance value that occurs when the conductive wiring is pulled is reduced, and that the occurrence of wiring breakage is highly suppressed even when a strong impact is applied to the molded body that is integrally molded with the conductive wiring. As a result, the present invention was completed.
That is, the conductive composition for molded films of the present invention uses a resin having a structure made of specific constituent monomers, conductive fine particles, and a solvent in combination, so that a thick conductive film with excellent conductivity can be formed by screen printing or the like. Formed films with layers can be easily produced. Further, in a molded film manufactured using the conductive composition for molded film, a decrease in conductivity is suppressed even when used on an uneven base material surface. Furthermore, by using the molded film, conductive circuits can be formed on any surface such as steeply uneven surfaces or curved surfaces on a base material made of three-dimensional plastic with practical strength, resulting in high impact resistance. A molded body can be obtained.

The conductive composition for molded film of this embodiment contains at least a resin (A), conductive fine particles (B), and a solvent (C), and may further contain other components as necessary. It may be contained. Each component of such a conductive composition for a molded film will be explained below.

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

The resin (A) used in the conductive composition of this embodiment is any one of the group consisting of polyester resin, polyurethane resin, polyamide resin, and polycarbonate resin, and is a structural unit derived from a trifunctional monomer or a tetrafunctional monomer. It contains resin (A1) containing as an essential component.
The resin (A1) contains a structural unit derived from a trifunctional monomer or a tetrafunctional monomer, so that ester bonds, urethane bonds, amide bonds, and carbonate bonds are present in a high density and in the vicinity of the branched structure derived from the trifunctional monomer or tetrafunctional monomer. Since it is arranged in a planar shape and exhibits strong adsorption to the conductive fine particles (B) described later, it is possible to suppress the generation of voids, which become disconnections between the particles and the particles even during tensioning during molding. Further, when a crosslinking agent (D) to be described later is used in combination, a stronger resin crosslinked network is formed, thereby exhibiting even stronger resistance to wire breakage during molding.

The polyester resin used as the resin (A1) in this embodiment contains, as monomers, a diol monomer having two hydroxyl groups in one molecule, a dicarboxylic acid monomer having two carboxyl groups in one molecule, and a dicarboxylic acid monomer having two carboxyl groups in one molecule. It is a resin obtained by copolymerizing a trifunctional monomer or a tetrafunctional monomer having a total of 3 to 4 of either hydroxyl group or carboxyl group.
Examples of the diol monomer having two hydroxy groups in one molecule include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, neopentyl glycol, and 3-methyl-1,5-pentane. Diols, aliphatic diols such as 1,6-hexanediol and nonanediol, cycloaliphatic diols such as 1,4-cyclohexanedimethanol, and aromatic diols such as O,O'-bis-(2-hydroxyethyl)bisphenol A. Examples include, but are not limited to, diols. In addition, prepolymer diols are synthesized in advance by copolymerizing these diol monomers with dicarboxylic acid monomers described below, or alkylene oxides such as ethylene oxide and propylene oxide, and cyclic monomers such as ε-caprolactone and ε-caprolactam. It may be subjected to multi-step copolymerization, such as polymerization with dicarboxylic acid.
Examples of the dicarboxylic acids having two carboxyl groups in one molecule include aliphatic dicarboxylic acids such as succinic acid, adipic acid, and sebacic acid; alicyclic dicarboxylic acids such as hexahydroterephthalic acid and dimer acid; and phthalic acid. Aromatic dicarboxylic acids such as , isophthalic acid, and terephthalic acid can be used, and dicarboxylic acid esters such as methyl ester and ethyl ester can also be suitably used, but are not limited thereto. Alternatively, a prepolymer dicarboxylic acid obtained by copolymerizing these dicarboxylic acid monomers with a cyclic monomer such as ε-caprolactone or ε-caprolactam may be synthesized in advance and subjected to multi-step copolymerization.
Examples of the trifunctional monomer or tetrafunctional monomer having a total of 3 to 4 of either one or both of a hydroxy group and a carboxyl group in one molecule include trimethylolpropane, glycerin, pentaerythritol, trimellitic acid, and hexahydro Examples include trimellitic acid, pyromellitic acid, hexahydropyromellitic acid, trimeric acid, 1,2,3-tricarboxylpropane, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, and citric acid. It is not limited to this.

The polyester resin used as the resin (A1) in this embodiment includes monofunctional monomers having only one type of hydroxyl group or carboxyl group in one molecule, and oils and fats (coconut oil, linseed oil, etc.). Those containing a total of 20% by mass or more of triglyceride consisting of glycerin and fatty acids as constituent monomers (so-called alkyd resins) do not fall under this category because they do not exhibit properties suitable for the resin (A1) of this embodiment.

The urethane resin used as the resin (A1) in this embodiment contains, as monomers, a diol monomer having two hydroxy groups in one molecule, a diisocyanate monomer having two isocyanate groups in one molecule, and It is a resin obtained by copolymerizing trifunctional or tetrafunctional monomers having 3 to 4 of either hydroxy groups or isocyanate groups.
Examples of the diol monomer having two hydroxyl groups in one molecule include, but are not limited to, the various diols listed as examples of raw materials for polyester synthesis.
Examples of the diisocyanate having two isocyanate groups in one molecule include aliphatic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, alicyclic diisocyanates such as hexahydro-1,3-xylylene diisocyanate, and 1,3-tolylene diisocyanate. Isocyanate, 1,4-tolylene diisocyanate, diphenylmethane diisocyanate, 1,3-xylylene diisocyanate, C,C,C',C',-tetramethyl-1,3-xylylene diisocyanate, 1,6-naphthyl diisocyanate, etc. aromatic diisocyanates, but are not limited thereto. Alternatively, a prepolymer diisocyanate obtained by copolymerizing these diisocyanate monomers and the diol monomer may be synthesized in advance and subjected to multi-stage copolymerization.
Examples of the trifunctional monomer or tetrafunctional monomer having 3 to 4 of either hydroxy group or isocyanate group in one molecule include trimethylolpropane, glycerin, pentaerythritol, and 3 to 4 amounts of each of the above diisocyanates. Examples thereof include, but are not limited to, isocyanurates, allophanates, biurets, and the like, which are obtained by incorporation into a compound.

The polyamide resin used as the resin (A1) in this embodiment contains, as monomers, a diamine monomer having two amino groups in one molecule, a dicarboxylic acid monomer having two carboxyl groups in one molecule, and It is a resin obtained by copolymerizing a trifunctional monomer or a tetrafunctional monomer having a total of 3 to 4 of either one or both of an amino group and a carboxyl group.
Examples of the diamine monomer having two amino groups in one molecule include 1,3-propanediamine, 1,4-butanediamine, 1,4-piperazine, dimer diamine, and 1,3-xylylenediamine. However, it is not limited to this. Alternatively, alkylene oxide such as ethylene oxide or propylene oxide may be subjected to ring-opening polymerization in advance, and then subjected to multi-stage copolymerization via polyalkylene oxide diamine in which the terminal hydroxy group is converted to an amino group.
Examples of the dicarboxylic acid having two carboxyl groups in one molecule include, but are not limited to, the various dicarboxylic acids listed as examples of raw materials for polyester synthesis.
Examples of the trifunctional monomer or tetrafunctional monomer having a total of 3 to 4 of either one or two of amino groups and carboxyl groups in one molecule include the various trifunctional monomers listed as raw materials for polyester synthesis. Alternatively, examples include, but are not limited to, tetrafunctional monomers.

The polycarbonate resin used as the resin (A1) in this embodiment contains, as monomers, a diol monomer having two hydroxy groups in one molecule, a carbonate monomer having one carbonate group in one molecule, and It is a resin obtained by copolymerizing a trifunctional or tetrafunctional monomer having 3 to 4 hydroxy groups.
Examples of the diol monomer having two hydroxyl groups in one molecule include, but are not limited to, the various diols listed as examples of raw materials for polyester synthesis.
Examples of the carbonate monomer having one carbonate group in one molecule include, but are not limited to, dimethyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate.
Examples of the trifunctional monomer or tetrafunctional monomer having 3 to 4 hydroxy groups in one molecule include, but are not limited to, trimethylolpropane, glycerin, and pentaerythritol.

The total content of structural units derived from trifunctional monomers and tetrafunctional monomers in the resin (A) is preferably 0.1% by mass to 15% by mass, more preferably 0.5% to 10% by mass. Among them, the total content of structural units derived from trifunctional monomers and tetrafunctional monomers in the resin (A1) is preferably 0.2% by mass to 15.5% by mass, and 0.5% to 10% by mass. More preferred.
If the total content of structural units derived from trifunctional monomers and tetrafunctional monomers is equal to or higher than the above lower limit, ester bonds, urethane bonds, amide bonds, and carbonate bonds are highly concentrated near the branched structures derived from trifunctional monomers or tetrafunctional monomers. The density of the molecular structure arranged in a planar manner increases, and this exhibits strong adsorption to the conductive fine particles (B) described later, resulting in disconnection notches between the particles and the particles during tension during molding. This is preferable because void generation can be suppressed. Further, when used in combination with a crosslinking agent (D) to be described later, it is possible to form a resin crosslinked network with excellent heat-resistant elongation, and it is preferable because it has excellent resistance to molding processes with a high deformation rate.
If the total content of structural units derived from trifunctional monomers and tetrafunctional monomers is below the above upper limit, an excellent molding process can be achieved while maintaining good solubility and toughness of the resin (A) in the solvent (C). This is preferable because it provides resistance to Further, when used in combination with the crosslinking agent (D), it is possible to achieve both heat-resistant elongation, toughness, and high limit elongation, which is preferable.

In addition, by copolymerizing a trifunctional monomer and/or a tetrafunctional monomer with a bifunctional monomer, an alkylene oxide such as ethylene oxide or propylene oxide, or a cyclic monomer such as ε-caprolactone or ε-caprolactam, the trifunctional monomer or the tetrafunctional monomer can be prepared. A prepolymer containing a structural unit derived from a functional monomer is synthesized in advance, and the resin (A1) is synthesized through multi-step copolymerization, such as polymerizing this with a trifunctional monomer, a tetrafunctional monomer, or a difunctional monomer. However, in this case, the total content of structural units derived from trifunctional monomers and tetrafunctional monomers in the resin (A1) should not exceed the repeating structure derived from difunctional monomers, regardless of whether the synthesis is in one step or in multiple steps. It is not the entire prepolymer contained therein, but the mass ratio in the resin (A1) of the constituent units derived from the smallest trifunctional monomer and tetrafunctional monomer in the prepolymer.

In addition, in calculating the mass fraction of the structural units derived from the trifunctional monomer and tetrafunctional monomer, for polyester resin, the carbonyl group (-C(=O)-) in the ester bond is on the carboxy group monomer side, Regarding the bonded oxygen atom (-O-), its mass shall be assigned to the hydroxy group monomer side. Similarly, for urethane resins, the imino group (-NH-) and carbonyl group (-C(=O)-) in the urethane bond are placed on the isocyanate group monomer side, and the single-bonded oxygen atom (-O-) is placed on the hydroxy group monomer side. For polyamide resins, the carbonyl group (-C(=O)-) in the amide bond is assigned to the carboxy group monomer side, and the imino group (-NH-) is assigned to the amino group monomer side. The mass shall be attributed to each. Regarding polycarbonate resin, the mass of the carbonyl group (-C(=O)-) in the carbonate bond is assigned to the carbonate group monomer side, and the mass of the single-bonded oxygen atom (-O-) is assigned to the hydroxy group monomer side. do.

In this embodiment, the resin (A1) preferably has two or more substituents selected from a hydroxy group, an amino group, a carboxyl group, and an acid anhydride group in one molecule; It is particularly preferable to have two or more of them. In this case, the resin (A1) can be three-dimensionally crosslinked by combining with the crosslinking agent (D) described below, and particularly high high-speed elongation resistance can be obtained under the high temperature conditions of forming the conductive layer into a film.

When the resin (A1) has a functional group selected from a hydroxy group, an amino group, a carboxyl group, and an acid anhydride group, the functional group value thereof is preferably 1 mgKOH/g or more and 400 mgKOH/g or less, It is preferably 2 mgKOH/g or more and 350 mgKOH/g or less. Note that the details of the method for calculating the functional group value will be explained in Examples described later.
In addition, when resin (A1) has multiple types of functional groups, let the functional group value be the sum total. For example, when the resin (A1) has a hydroxyl group and a carboxyl group, the functional group value represents the sum of the hydroxyl value and the acid value of the resin (A1).

The glass transition temperature (Tg) of the resin (A) is determined from the viewpoints of maintaining conductivity during molding and tensioning and resistance to frictional stress with the base plastic at high temperatures during the integration process with the plastic base material. The glass transition temperature (Tg) of (A) is preferably 0°C or more and 130°C or less, more preferably 5°C or more and 120°C or less. From the same viewpoint, when the resin (A) has a plurality of glass transition points, it is preferable that none of the glass transition points is lower than 0°C.

In this embodiment, the resin (A1) may be synthesized and used according to the Examples described below or other known methods, or a commercially available product that satisfies the above conditions may be used. Resin (A1) can be used alone or in combination of two or more, and as resin (A), resin (A1) and other resins (A2) that do not correspond to resin (A1) can be used in combination. It can also be used. When resin (A1) and other resin (A2) are used in combination, resin (A1) preferably accounts for 20 to 100% by mass of the total amount of resin (A1) and other resin (A2). It is more preferable that the resin (A1) accounts for 30 to 100% by mass.

The content ratio of the resin (A) in the conductive composition of this embodiment is not particularly limited as long as it can be adjusted as appropriate depending on the application, but it is 8% by mass or more based on the total solid content contained in the conductive composition. It is preferably 40% by mass or less, and more preferably 10% by mass or more and 30% by mass or less. When the content rate of the resin (A) is at least the above lower limit, film formability and adhesion to a base film etc. can be improved, and flexibility can be imparted to the conductive layer. Moreover, if the content rate of resin (A) is below the said upper limit, the content rate of electroconductive fine particles (B) can be relatively increased, and a conductive layer excellent in electroconductivity can be formed.

<Conductive fine particles (B)>
The conductive fine particles (B) are particles that exhibit conductivity when a plurality of conductive fine particles come into contact within the conductive layer. Used selectively.
Examples of the conductive fine particles used in this embodiment include metal fine particles, carbon fine particles, and conductive oxide fine particles.
Examples of metal fine particles include elemental metal powders such as gold, silver, copper, nickel, chromium, palladium, rhodium, ruthenium, indium, aluminum, tungsten, molybuten, and platinum, as well as copper-nickel alloys, silver-palladium alloys, Examples include alloy powders such as copper-tin alloys, silver-copper alloys, and copper-manganese alloys, and metal coated powders in which the surface of the above-mentioned single metal powders or alloy powders is coated with silver or the like. Further, examples of carbon fine particles include carbon black, graphite, carbon nanotubes, and the like. Further, examples of the conductive oxide fine particles include silver oxide, indium oxide, tin oxide, zinc oxide, and ruthenium oxide.

In this implementation, it is particularly preferable to include one or more types of conductive fine particles selected from silver powder, copper powder, silver coated powder, copper alloy powder, conductive oxide powder, and carbon fine particles. By using these conductive fine particles (B), it is possible to form a conductive layer with excellent conductivity without sintering, and it also improves stretchability and conductivity when molded into a three-dimensional shape as a molded film, which will be described later. It is possible to form a conductive layer with excellent property of retaining properties.

The shape of the conductive fine particles (B) is not particularly limited, and shapes such as spherical, flake, and chain agglomerate shapes can be used as appropriate, but from the viewpoint of maintaining printability and maintaining conductivity during molding and tensioning, Preferably, it is in the form of flakes or chain aggregates.
In the present invention, "spherical" refers to all particles having a low aspect ratio, such as true spheres, oval shapes, crushed spheres, gravel shapes, and polyhedral shapes, specifically, particles having an aspect ratio of about 1 or more and about 2 or less. Furthermore, the term "flake shape" in the present invention refers to two-dimensional flat shapes in general, such as scales, scales, plates, flat shapes, sheet shapes, etc., and among them, those having an aspect ratio of 3 or more and 500 or less. Particularly preferred. Further, in the present invention, the term "chain aggregate" refers to any irregular shape in which a plurality of the above-mentioned spherical conductive fine particles are directly fused and bonded.

The D50 particle diameter of the conductive fine particles (B) is not particularly limited, but it is important to maintain dispersibility and printability in the conductive composition, maintain conductivity during molding, and resistance to injection molding process using molten resin or molded resin. From the viewpoint of high-temperature friction resistance, the thickness is preferably 0.2 μm or more and less than 30 μm, and particularly preferably 0.7 μm or more and less than 15 μm. In addition, in this implementation, the average particle diameter of the conductive fine particles (B) is calculated as follows. In accordance with the laser diffraction/scattering method described in JISM8511 (2014), a commercially available surfactant polyoxyethylene octylphenyl was used as a dispersant using a laser diffraction/scattering particle size distribution analyzer (Microtrac 9220FRA, manufactured by Nikkiso Co., Ltd.). An appropriate amount of conductive fine particles (B) was added to an aqueous solution containing 0.5% by volume of ether (manufactured by Roche Diagnostics Co., Ltd.: Triton After that, measurements were taken. The value of the determined median diameter (D50) was taken as the average particle diameter of the conductive fine particles (B).

In this embodiment, the conductive fine particles (B) can be used alone or in combination of two or more.
The content ratio of the conductive fine particles (B) in the conductive composition of this embodiment is not particularly limited as long as it can be adjusted as appropriate depending on the application, etc. % or more and 90% by mass or less, and preferably 55% by mass or more and 85% by mass or less. When the content of the conductive fine particles (B) is equal to or higher than the above lower limit, a conductive layer with excellent conductivity can be formed. In addition, if the content rate of the conductive fine particles (B) is below the above upper limit, the content rate of the resin (A) can be increased, film formability and adhesion to the base film etc. are improved, and , flexibility can be imparted to the conductive layer.

<Solvent (C)>
In this implementation, a solvent (C ). In addition, in this implementation, by containing the solvent (C), the spread of the molecular chains is adjusted and the patterning accuracy during printing is improved by imparting wettability to the base film during printing. I can do it.

As the solvent (C) of the present invention, any known and publicly available solvent can be used without particular limitation as long as it can dissolve the resin (A). The solvent (C) can be used alone or in combination of two or more. Further, even if it is solid at room temperature when used alone, it can be used without problems if it becomes liquid as a mixed solvent with a solvent of another structure. Furthermore, it is particularly preferable that the solvent (C) has a boiling point of 180°C or higher and 270°C or lower, such as glycol esters such as 2-ethoxy(2-ethoxy)ethyl acetate and 2-ethoxy(2-ethoxy)butyl acetate; Examples include glycol ethers such as -ethoxy(2-ethoxy)ethanol, 2-butoxy(2-ethoxy)ethanol, and diethylene glycol diethyl ether, but are not particularly limited.

<Optional ingredients>
The conductive composition of the present invention may further contain other components as necessary. Such other components include, in addition to the crosslinking agent (D) described below, dispersants, antifriction improvers, infrared absorbers, ultraviolet absorbers, fragrances, antioxidants, organic pigments, inorganic pigments, and antifoaming agents. agents, silane coupling agents, plasticizers, flame retardants, humectants, etc.

<Crosslinking agent (D)>

In this embodiment, a crosslinking agent (D) may be additionally used to crosslink the resin (A). The crosslinking agent (D) can be appropriately selected from those having two or more reactive functional groups in one molecule that can form a crosslink with the reactive functional groups of the resin (A). Examples of such reactive functional groups include epoxy groups, isocyanate groups, blocked isocyanate groups, alkyloxyamino groups, aziridinyl groups, oxetanyl groups, carbodiimide groups, and β-hydroxyalkylamide groups.
The crosslinking agent (D) is preferably used in a range of 0.05 parts by mass to 30 parts by mass, and more preferably in a range of 0.3 parts by mass to 25 parts by mass, based on 100 parts by mass of the resin (A).

Furthermore, in this embodiment, it is preferable that the resin (A) has two or more first reactive functional groups selected from hydroxy groups or amino groups in one molecule, and further, as the crosslinking agent (D), Particular preference is given to selecting and combining blocked isocyanates.
Blocked isocyanates include bifunctional isocyanates such as hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, and isophorone diisocyanate, or their allophanates, biurets, adducts, prepolymers, and isocyanurates. There are no particular limitations, as long as the isocyanate group of the bifunctional or higher-functional isocyanate consisting of, etc., is protected (blocked) with ε-caprolactam, MEK oxime, etc. Specifically, those in which 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.
It is also preferable to use a reaction catalyst having the effect of promoting the reaction between the crosslinking agent (D) and the resin (A). As the reaction catalyst, any known catalyst can be used without particular limitation.
When used in such a combination, the unique crosslinking point structure generated by crosslinking with the resin (A) and the multi-point adsorption point structure with the conductive particles increase, resulting in particularly excellent toughness and ability to withstand high temperatures. Because it has excellent ability to suppress the generation of voids that can become notches for disconnection, which can occur between the conductive fine particles (B) in the coating film, it is possible to obtain a conductive layer in which the decrease in conductivity due to tensile force is particularly suppressed. .

<Method for manufacturing conductive composition>
The method for producing the conductive composition of this embodiment is a method of dissolving or dispersing the resin (A), conductive fine particles (B), wire-like fine particles (C), and other components used as necessary. It can be produced by mixing using a known mixing means.

[Forming film]
The molded film of this embodiment is a molded film comprising a conductive layer on a base film,
The conductive layer is characterized in that it is a cured product of the conductive composition for molded film.
According to the molded film of this embodiment, it is possible to obtain a molded article in which a conductive circuit is formed on any base material surface such as an uneven surface or a curved surface.
According to the molded film of this embodiment, it is possible to obtain a molded article in which a conductive circuit is formed on any base material surface such as an uneven surface or a curved surface.
The layer structure of the molded film of this embodiment will be explained with reference to FIGS. 1 and 2. FIGS. 1 and 2 are schematic cross-sectional views showing an example of the molded film of this embodiment.
A molded film 10 shown in the example of FIG. 1 includes a conductive layer 2 on a base film 1 . The conductive layer 2 may be formed on the entire surface of the base film 1, or may be formed in a desired pattern as in the example of FIG.
The molded film 10 shown in the example of FIG. 2 has a decorative layer 3 on a base film 1, and a conductive layer 2 on the decorative layer 3. Further, as shown in the example of FIG. 2, the molded film 10 may include, on the conductive layer 2, pins 5 for connecting to an electronic component 4 or a take-out circuit.
Although not shown, a resin layer may be provided on the conductive layer 2 or on the electronic component 4 to protect the conductive layer or the electronic component, and the resin layer may be connected to the base material described below. It may serve as an adhesive layer or adhesive layer to improve the adhesion of the material.
Although not shown, in the case where the molded film 10 of this embodiment is provided with a decorative layer 3, in addition to the example shown in FIG. A layered structure including layer 2 may also be used.
The molded film of this embodiment includes at least a base film and a conductive layer, and may have other layers as necessary. Each layer of such a molded film will be explained below.

<Base film>
In this implementation, the base film can be appropriately selected from those that have flexibility and stretchability to the extent that it can follow the shape of the base material surface under the molding temperature conditions during base material formation. , it is preferable to select according to the manufacturing method of the molded body, etc.
For example, when using the overlay molding method or film insert method, which will be described later, as a manufacturing method for the molded product, consideration should be given to the fact that the base film remains in the molded product and functions as a protective layer for the conductive layer. You can then choose the base film.
On the other hand, when employing an in-mold transfer method, which will be described later, as a method for producing a molded article, it is preferable to select a base film that has releasability.

The base film can be selected as appropriate from the above point of view, and examples include polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polystyrene, polyimide, polyamide, polyether sulfone, polyethylene naphthalate, polybutylene terephthalate, polyvinyl chloride, polyethylene, polypropylene. , cycloolefin polymer, ABS (acrylonitrile-butadiene-styrene copolymer resin), AES (acrylonitrile-ethylene-styrene copolymer resin), Kydac (acrylic modified PVC resin), modified polyphenylene ether, and two or more of these resins. A film such as a polymer alloy or a laminated film of these may be used. Among these, preferred is a film selected from polycarbonate, polymethyl methacrylate, polypropylene, polyethylene terephthalate, or a laminated film of these. Among the laminated films, a laminated film of polycarbonate and polymethyl methacrylate is preferred.
The method for producing a laminated film of polycarbonate and polymethyl methacrylate is not particularly limited, and a polycarbonate film and a polymethyl methacrylate film may be bonded together and laminated, or a laminated film may be produced by coextruding polycarbonate and polymethyl methacrylate. good.
It is also preferable that the surface of these base films is subjected to a modification treatment such as corona treatment.

Moreover, if necessary, for the purpose of improving the printability of the conductive composition, an anchor coat layer may be provided on the base film, 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 adhesion to the conductive composition and follows the film during molding, and may also be made of organic fillers such as resin beads or metals. Inorganic fillers such as oxides may also be added as necessary. The method for providing the anchor coat layer is not particularly limited, and it can be obtained by coating, drying, and curing using a conventionally known coating method.
Furthermore, if necessary, a hard coat layer may be provided on the base film in order to prevent damage to the surface of the molded body, and a conductive composition and, if necessary, a decorative layer may be printed on the opposite surface of the hard coat layer. The hard coat layer is not particularly limited as long as it has good adhesion to the base film and surface hardness and follows the film during molding, and may also include organic fillers such as resin beads or inorganic fillers such as metal oxides. may also be added if necessary. The method for providing the hard coat layer is not particularly limited, and it can be obtained by coating, drying, and curing using a conventionally known coating method.

Further, when the molded film of this 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 formed film of this embodiment, the conductive layer is a cured product of the conductive composition. The conductive layer may be a patterned conductive layer or a solid conductive layer.
The method of forming the conductive layer is not particularly limited, but in this implementation, screen printing method, pad printing method, stencil printing method, screen offset printing method, dispenser printing method, gravure offset printing method, reverse offset printing method, micro contact printing method is used. It is preferable to form by a method, and it is more preferable to form by a screen printing method.
In the screen printing method, it is preferable to use a screen with a fine mesh, particularly preferably a fine mesh of about 300 to 650 mesh, in order to correspond to the 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.
Types of screen plates include polyester screens, combination screens, metal screens, nylon screens, and the like. Furthermore, when printing a highly viscous paste, a high-tensile stainless steel screen can be used.
A screen printing squeegee may be round, rectangular, or square in shape, and a polished squeegee may also be used to reduce the attack angle (the angle between the plate and the squeegee during printing). Other printing conditions may be appropriately designed using conventionally known conditions.

After printing the conductive composition by screen printing, it is heated to dry and undergo a crosslinking reaction to be cured.
For sufficient volatilization of the solvent and crosslinking reaction, 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 pattern of the conductive layer is not particularly limited, but includes, for example, straight lines, curves, meshes, solid patterns such as partial squares, circles, diamond shapes, solid patterns, and any combination thereof, or the entire conductive layer is solid on one side. It may be a pattern, and is not limited as long as the conductive layer functions as a conductive circuit or a part of a conductive circuit.
The patterned conductive layer may be provided with an insulating layer to cover the conductive pattern, if necessary. The insulating layer is not particularly limited, and any known insulating layer can be used.

The thickness of the conductive layer may be adjusted as appropriate depending on the required conductivity, etc., 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.

<Decoration layer>
The molded film of this embodiment may have a decorative layer from the viewpoint of the design of the resulting molded product.
The decorative layer may be a layer having a monochromatic color, or may be provided with an arbitrary pattern.
For 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 a base film using a known printing method. .
The coloring material can be appropriately selected from known pigments and dyes. Further, as the resin, it is preferable to appropriately select and use resins similar to the resin (A) in the conductive 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, preferably 1 μm or more and 5 μm or less.

[Molded object]
The molded product of this embodiment is a molded product in which at least a conductive layer is laminated on a base material, wherein the conductive layer is a cured product of the conductive composition for a molded film according to any one of claims 1 to 5. It is characterized by Since the molded article of this embodiment is formed from a molded film using the conductive composition for molded films of this embodiment, the molded article has a conductive circuit formed on any surface such as an uneven surface or a curved surface.
Hereinafter, three embodiments will be described regarding the method for manufacturing a molded body according to the present embodiment. Note that the molded article of this embodiment may be produced using the conductive composition of this embodiment, and is not limited to these methods.

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

FIG. 3 is a schematic process diagram showing an example of the first method for producing a molded body. 3(A) to 3(C) respectively illustrate the molding film 10 and the base material 20 arranged in the chamber box of a TOM (Three Dimension Overlay Method) molding machine, and FIGS. 3(B) and 3(C) ), the chamber box is omitted.
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 this embodiment is passed between the upper chamber box 21 and the lower chamber box 22 and placed on the base material 20. At this time, the molded film 10 may be arranged so that the conductive layer faces either the base material 20 side or the side opposite to the base material 20, which is selected depending on the final use of the molded product. Next, after evacuating the upper and lower chamber boxes, the formed film is heated. Next, the base material 20 is raised 15 by raising the table. Next, only the inside of the upper chamber box 21 is opened to the atmosphere (FIG. 3(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 together and integrated (FIG. 3(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.

In addition, in the first manufacturing method, the friction stress with the base plastic under high temperature in the above-mentioned integration step with the base material refers to the stress caused by the molded film being applied to the base material side in FIG. 3(C) above. This is caused by frictional stress between the conductive circuit of the molded film and the base material under high temperature when the molded film 10 and the base material 20 are bonded together and integrated under pressure 16. 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 due to the base plastic under high temperature.

<Second manufacturing method>
A second method for producing a molded article according to the present embodiment includes a step of manufacturing a molded film by printing the conductive composition for a molded film according to the present embodiment on a base film and drying it;
a step of molding the molded film into a predetermined shape;
arranging the molded film after molding in a mold for injection molding;
The method includes the steps of molding a base material by injection molding and integrating the molded film and the base material. This will be explained below with reference to FIG. Note that the second manufacturing method is sometimes referred to as a film insert method.

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

In the second manufacturing method, there is no need to prepare the base material 20 in advance, and the molding of the base material and the integration with the molded film can be performed simultaneously. The material of the base material 20 can be appropriately selected from known resins used for injection molding.

In addition, in the second manufacturing method, the frictional stress with the base plastic under high temperature in the above-mentioned integration step with the base material refers to the stress caused by injecting the resin from the opening 13 14 in FIG. 4(E). , when forming the base material 20 and integrating the molded film 10 and the base material 20, the conductive layer on the molded film is caused by the frictional stress that is received by the injection of high temperature molten resin into the mold. 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 with the base plastic at a high temperature in a separate process.

<Third manufacturing method>
A third method for producing a molded article according to the present embodiment includes a step of manufacturing a molded film by printing the conductive composition for a molded film according to the present embodiment on a base film by screen printing, and drying the conductive composition for a molded film.
placing the molded film in an injection mold;
The method includes the steps of molding a base material by injection molding and transferring the conductive layer in the molded film onto the base material side.
This will be explained below with reference to FIG. Note that the third manufacturing method is sometimes referred to as an in-mold transfer method.

FIG. 5 is a schematic process diagram showing an example of the third method for producing a molded body. In the third manufacturing method, a base film having peelability is selected and used for the molded film 10. The molded film 10 is placed in a mold 12 for injection molding so that the conductive layer faces the base material 20, which will be described later (FIG. 5(A)). Next, resin is injected 14 from the opening 13 to form a base material 20, and the molded film 10 and the base material 20 are brought into close contact with each other, and at least the conductive layer is transferred to the base material 20 side (see FIG. 5). B)), a molded body 30 is obtained (FIG. 5(C)). Note that when the molded film 10 has a decorative layer, the decorative layer and the conductive layer are transferred.

In the third manufacturing method, since there is no need to cut the base film, a long base film can be arranged as shown in the example of FIG. The material of the base material 20 can be appropriately selected from known resins used for injection molding.

In addition, in the third manufacturing method, the frictional stress with the base plastic under high temperature in the above-mentioned step of integrating with the base material is the stress caused by injecting the resin from the opening 13 14 in FIG. 5(C). This is due to the frictional stress that the conductive layer on the molded film receives due to the injection of high temperature molten resin into the mold when the base material 20 is formed and the molded film 10 and the base material 20 are brought into close contact. 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 with the base plastic under high temperature.

The molded bodies obtained in this way make it possible to mount circuits, touch sensors, and various electronic components into plastic casings for home appliances, automobile parts, robots, drones, and other devices. In addition, it is extremely useful for making electronic devices lighter, thinner, shorter, and more compact, increasing the degree of freedom in design, and making them multifunctional.

EXAMPLES Below, the present invention will be explained in more detail with reference to Examples, but the following Examples are not intended to limit the present invention in any way. In addition, "part" in the examples represents "part by mass", and "%" represents "% by mass".
In addition, the weight average molecular weight in the examples is the polystyrene equivalent molecular weight measured using Tosoh GPC (gel permeation chromatography) "HLC-8320", polystyrene divinylbenzene gel as the stationary phase, and tetrahydrofuran as the mobile phase. It is.

In addition, the "functional group value" in the examples is based on the molecular weight per functional group of each raw material (this is taken as the functional group equivalent), and the amount of functional groups per 1 g of raw material is calculated by the following formula. It is expressed as the mass (mg) of potassium hydroxide.
(Functional group value) [mgKOH/g] = (56.1×1000)/(Functional group equivalent)
The above functional group value is a general term for quantities expressed as, for example, acid value when the functional group is a carboxyl group, hydroxyl value when the functional group is a hydroxy group, amine value when the functional group is an amino group, etc. When comparing the functional group ratios of substances having different functional groups, it may be considered that substances having the same functional group value have the same molar amount of functional groups.

When titration of potassium hydroxide is used to quantify functional groups such as carboxyl groups and hydroxyl groups, the above functional group value can be determined by measuring the water used for neutralization using a publicly known measuring method specified in JIS K 0070, for example. Measured values (acid value and hydroxyl value) can also be directly determined from the appropriate amount of potassium oxide, and can be handled in the same way as the calculated values using the above formula.
In addition, even when the above titration with potassium hydroxide is not used to quantify the value of functional groups such as isocyanate groups, the above functional group equivalents derived from the respective measured values representing the amount of functional groups and the above calculation formula can be used. For convenience, it can be calculated as potassium hydroxide equivalent. A specific calculation example is shown below.

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

In addition, in the examples, the weight ratio of the trifunctional monomer and the tetrafunctional monomer in the constituent monomers of the resin was determined by ¹³ C-NMR quantitative measurement (measurement solvent: chloroform-d , pulse interval 20 seconds, gated decoupling: non-NOE mode (NNE), number of integrations 4000 times), and attribution by comparing the chemical shift of the peak obtained with the value obtained for the carbon nucleus in the known structure. It was determined by identifying all constituent monomer structures and their molar ratios, and calculating the mass ratio of each constituent monomer in the resin based on the identified structures.

<Resin (A1) to (A3)>

<Synthesis Example 1: Synthesis of resin (A1-1)>
25.0 parts of isophthalic acid, 25.0 parts of terephthalic acid, 14.0 parts of ethylene glycol, and 10.0 parts of neopentyl glycol were added to a reaction apparatus equipped with a stirrer, a thermometer, a rectification tube, a nitrogen gas introduction tube, and a pressure reducing device. 1 part, trimellitic acid 3.0 parts and tetrabutyl titanate 0.03 parts as a catalyst were charged, and the mixture was gradually heated to 180°C with stirring under a nitrogen stream, and excess glycol components were distilled off at 180°C for 3 hours. The transesterification reaction is carried out, the acid value is measured, and when it becomes 15 or less, the pressure inside the reactor is gradually reduced to 1 to 2 Torr, and when the specified viscosity is reached, the reaction is stopped and the surface is treated with fluorine after being taken out. By transferring it to a prepared pallet and cooling it, it has a number average molecular weight of 24,000, a hydroxyl group (functional group value 6 mgKOH/g), and a ratio of trifunctional monomer and tetrafunctional monomer in the constituent monomers of 3.6 weight. % and had an aromatic ring structure in its main chain (A1-1).

<Synthesis Examples 2 to 12: Synthesis of resins (A1-2) to (A1-11) and other resins (A2-1)>
The polyester resins (A1-2) to (A1-11) and (A2- A solid product of 1) was obtained.

<Synthesis Example 13: Synthesis of other resin (A2-2)>
150.0 parts of coconut oil and 48.0 parts of pentaerythritol were charged into a reaction apparatus equipped with a stirrer, a thermometer, a rectification tube, a nitrogen gas introduction tube, and a pressure reducing device, and heated using a mantle heater under a nitrogen gas atmosphere. When the temperature reached 200°C, 1.0 part of 5% lithium hydroxide (alcohol/water mixture) was added as a catalyst, and the temperature was gradually raised to 240°C and maintained. It was confirmed that the transesterification reaction progressed and the cloudy reaction liquid turned clear, and the mixture was stirred for an additional 1 hour and maintained for a total of 2 hours to complete the transesterification reaction. After cooling to a temperature of 100°C or lower, 3.6 parts of ethylene glycol, 93.0 parts of phthalic anhydride, and 15.0 parts of paratertiary butylphenol, a monofunctional monomer, were added. Next, 30 ml of xylene was added to the decounter to remove condensation reaction water produced by the esterification reaction, and the temperature was raised and maintained at 225° C. over about 2 hours. . The reaction was terminated when the condensation reaction water reached the expected production amount (12.9 g), and the water was transferred to a pallet with a fluorine-treated surface and cooled. /g), the ratio of trifunctional monomers and tetrafunctional monomers in the constituent monomers was 16.6% by weight, and a solid alkyd resin (A'2) having an aromatic ring structure in the main chain was obtained. . As mentioned above, the alkyd resin (A2-2) contains 5.3% by mass of monofunctional monomer (paratertiary butylphenol), 52.9% by mass of oil (coconut oil), 58.2% by mass in total (20% by mass or more). ), so it is not included in the polyester resin in the present invention.

<Synthesis Example 14: Synthesis of resin (A1-12)>
In a reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser tube, and a nitrogen gas inlet tube, a polyester polyol obtained from the alternating copolymerization of isophthalic acid and 3-methyl-1,5-pentanediol (Kuraray Polyol P manufactured by Kuraray Co., Ltd.) was placed. -2030''), 5 parts of trimethylolpropane, 22.0 parts of isophorone diisocyanate, and 36.5 parts of toluene were charged and reacted at 90°C for 3 hours under a nitrogen stream, then cooled and reacted. After stopping and finally taking it out, it was transferred to a pallet with a fluorine-treated surface and vacuum-dried in a hot air drying oven at 120°C for 5 hours, and then for a further 24 hours. 5mgKOH/g), the ratio of trifunctional monomers and tetrafunctional monomers in the constituent monomers was 3.9% by weight, and a solid of urethane resin (A1-12) having an aromatic ring structure in the main chain was obtained. Ta.

<Synthesis Examples 15 to 21: Synthesis of resins (A1-13) to (A1-18) and other resins (A2-3)>
The urethane resins (A1-13) to (A1-18) and (A2-3) shown in Table 2 were prepared in the same manner as in Synthesis Example 13, except that the raw materials and the amounts used were changed as shown in Table 2. A solid was obtained. The contents of raw materials not indicated by compound names are as follows.

・P-2010: Polyester polyol obtained from alternating copolymerization of adipic acid and 3-methyl-1,5-pentanediol (“Kuraray Polyol P-2010” manufactured by Kuraray Co., Ltd.)
・PTG-1000: Polyether polyol obtained from ring-opening polymerization of tetrahydrofuran (“PTG-1000” manufactured by Hodogaya Chemical Co., Ltd.)
・F-1010: Polyester polyol obtained from alternating copolymerization of adipic acid, 3-methyl-1,5-pentanediol, and trimethylolpropane (“Kuraray Polyol F-1010” manufactured by Kuraray Co., Ltd.)

<Synthesis Example 22: Synthesis of resin (A1-19)>
In a reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas introduction tube, 4.0 parts of isophthalic acid, 2.0 parts of trimellitic acid, and molecular chain ends obtained by ring-opening polymerization of propylene oxide were added. 70 parts of polyether diamine converted to an amino group ("Jeffamine D-2000" manufactured by Huntsman) and 36.5 parts of toluene were charged, and after refluxing at 110°C for 2 hours under a nitrogen stream, the temperature was lowered. was gradually heated to 180°C and reacted for 3 hours while distilling off the solvent and condensed water to stop the reaction, and then transferred to a pallet with a fluorine-treated surface and cooled. polyamide resin (A1-19) which has a group (functional group value 7 mgKOH/g), the ratio of trifunctional monomers and tetrafunctional monomers in the constituent monomers is 2.1% by weight, and has an aromatic ring structure in the main chain. A solid substance was obtained.

<Synthesis Examples 23 to 27: Synthesis of resins (A1-20) to (A1-23) and other resins (A2-4)>
The polyamide resins (A1-20) to (A1-23) and (A2-4) shown in Table 3 were prepared in the same manner as in Synthesis Example 21, except that the raw materials and the amounts used were changed as shown in Table 3. A solid was obtained. Note that the polyamide resins (A1-34) and (A1-35) do not have an amino group but have a carboxyl group as a functional group. Further, the contents of raw materials not indicated by compound names are as follows.

・Pripol 1009: Hydrogenated and generated dimer acid monomer (“Pripol 1009” manufactured by Croda)

<Synthesis Example 28: Synthesis of resin (A1-24)>
30.0 parts of neopentyl glycol, 30.0 parts of 1,6-hexanediol, 2.0 parts of trimethylolpropane, and 45 parts of ethylene carbonate were placed in a reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas introduction tube. 0 parts and 40.0 parts of toluene were charged, and the mixture was refluxed at 110°C for 2 hours under a nitrogen stream, and then the temperature was gradually heated to 180°C to distill off the solvent and ethylene glycol produced by condensation. The reaction was stopped for 3 hours, and then transferred to a pallet with a fluorine-treated surface and cooled. A solid polycarbonate resin (A1-24) having a ratio of trifunctional monomer and tetrafunctional monomer of 2.6% by weight and having no aromatic ring structure in the main chain was obtained.

The following were used as the conductive fine particles, solvent, and crosslinking agent.
<Conductive fine particles (B1) to (B5)>
- Conductive fine particles (B1): manufactured by Fukuda Metal Foil and Powder Co., Ltd., flaky silver powder, average particle size 5.2 μm
・Conductive fine particles (B2): Manufactured by Fukuda Metal Foil and Powder Co., Ltd., chain agglomerated silver powder, average particle size 1.7 μm
- Conductive fine particles (B3): manufactured by Mitsui Kinzoku Mining Co., Ltd., silver coated copper powder, silver coating amount 10%, average particle size 2.0 μm
- Conductive fine particles (B4): manufactured by Ishihara Sangyo Co., Ltd., acicular conductive Sb-doped tin oxide powder, average particle size 2.9 μm
- Conductive fine particles (B5): manufactured by Ito Graphite Co., Ltd., expanded graphite, average particle diameter 15 μm

<Solvent (C1) to (C4)>
The following was used as the solvent (C).
・Solvent (C1): Benzyl alcohol ・Solvent (C2): Dipropylene glycol monomethyl ether ・Solvent (C3): Diethylene glycol monobutyl ether acetate ・Solvent (C4): 2-methoxypropanol

<Crosslinking agents (D1) to (D3)>
・Crosslinking agent (D1):
Blocked isocyanate solution manufactured by Baxeneden Chemicals, Trixene BI7982, contains three blocked isocyanate groups in one molecule (functional group value 195 mgKOH/g), non-volatile content 70% (solvent (C4): 2-methoxypropanol)
・Crosslinking agent (D2): Blocked isocyanate solution manufactured by Baxeneden Chemicals, Trixene BI7960, contains 3 blocked isocyanate groups per molecule (functional group value 195mgKOH/g), non-volatile content 70% (solvent (C4) ):2-methoxypropanol)
・Crosslinking agent (D3):
Epoxy resin manufactured by Mitsubishi Gas Chemical Co., Ltd., TETRAD-X, contains 4 epoxy groups in one molecule (functional group value 623 mgKOH/g), non-volatile content 100%

<Manufacture example 1: Creation of decorative ink (E1)>
Prepare 200 parts of a resin solution consisting of 80 parts of resin (A1-12) and 120 parts of solvent (C3), and add 20 parts of phthalocyanine blue pigment (LIONOL BLUE FG7351 manufactured by Toyo Color Co., Ltd.) and titanium oxide pigment (manufactured by Ishihara Sangyo Co., Ltd.) to this. After stirring and mixing 10 parts by mass of TIPAQUE CR-93) and kneading with a three-roll mill (manufactured by Kodaira Seisakusho), 5 parts of an isocyanate crosslinking agent (Desmodur N3300, manufactured by Sumika Covestro Urethane Co., Ltd., non-volatile content 100%) and a solvent were mixed. Decorative ink (E1) was obtained by adding 90 parts of (C3) and uniformly stirring and mixing.

<Example 1: Creation of conductive composition for molded film (F1)>
20.0 parts of resin (A1-1) was dissolved in 30.0 parts of solvent (C1), stirred and mixed with 80.0 parts of conductive fine particles (B1), and kneaded with a three-roll mill (manufactured by Kodaira Seisakusho). , 1.0 part of a crosslinking agent (D1) was added, and the mixture was uniformly stirred and mixed using a planetary mixer to obtain a conductive composition for a molded film (F1).

<Examples 2 to 57: Creation of conductive compositions (F2) to (F57) for molded films>
In Example 1, the types and amounts of the resin, solvent, conductive particles, and crosslinking agent (if used, the crosslinking agent was added just before uniform stirring and mixing with a planetary mixer as in Example 1) Conductive compositions (F2) to (F57) for molded films were obtained in the same manner as in Example 1, except that they were changed as shown in Tables 5 to 8.
Note that all numerical values for each material in Tables 5 to 8 are parts by mass.

<Comparative Examples 1 to 4: Creation of conductive compositions (F58) to (F61) for molded films>
A conductive composition for molded film (F58) was prepared in the same manner as in Example 1, except that the types and blending amounts of the resin, solvent, conductive particles, and crosslinking agent were changed as shown in Table 8. ～(F61) was obtained.

<Examples 58 to 114 and Comparative Examples 5 to 8>
Conductive compositions (F1) to (F55) for forming films were applied onto a polycarbonate (PC) base film (Teijin Co., Ltd., Panlite 2151, thickness 300 μm, 300 mm x 210 mm) using a screen printing machine (Mino Screen Co., Ltd., Printing was performed using a Minomat SR5575 semi-automatic screen printing machine at a printing speed of 50 mm/sec. Next, by heating at 120°C for 30 minutes in a hot air drying oven, a square solid pattern with a width of 15 mm, a length of 30 mm, and a thickness of 10 μm, a linear pattern with a line width of 3 mm, a length of 60 mm, and a thickness of 10 μm, and a line width of 150 μm were obtained. A molded film having a conductive layer having a stripe pattern with a distance between lines of 150 μm and a length of 60 mm was obtained.

<Example 115>
Decorative ink (G1) was coated on a polycarbonate base film (manufactured by Teijin, Panlite 2151, thickness 300 μm, 300 mm x 210 mm) using a blade coater so that the dry film thickness was 2 μm. A decorative layer was formed by heating at ℃ for 30 minutes.
Next, in the same manner as in Example 58, except that the film with a decorative layer was used instead of the polycarbonate base film and a conductive layer was formed on the decorative layer, the polycarbonate film and the decorative layer were prepared in the same manner as in Example 58. A molded film was obtained in which an ink layer and a conductor were laminated in this order.

<Example 116>
In Example 58, instead of the polycarbonate base film, a two-layer coextruded film of polycarbonate resin/acrylic resin (manufactured by Sumitomo Chemical Co., Ltd., Technoloy C001, thickness 125 μm, 300 mm x 210 mm) was used, and the molded film was placed on the polycarbonate resin side. A molded film was obtained in the same manner as in Example 58, except that the conductive composition was printed.

<Example 117>
In Example 58, an acrylic resin film (manufactured by Sumitomo Chemical Co., Ltd., Technoloy S001G, thickness 250 μm, 300 mm x 210 mm) was used instead of the polycarbonate base film, and the drying conditions in the hot air drying oven were 80 ° C. A molded film was obtained in the same manner as in Example 58 except that the time was 30 minutes.

<Example 118>
In Example 58, an easily moldable PET resin film (manufactured by Morino Kako Co., Ltd., Emron PETG resin sheet, thickness 250 μm, 300 mm x 210 mm) was used instead of the polycarbonate base film, and the drying conditions in a hot air drying oven were A molded film was obtained in the same manner as in Example 58 except that the temperature was 30 minutes at 70°C.

<Example 119>
In Example 58, a polypropylene film (manufactured by Idemitsu Unitec, Pure Thermo AG-306, thickness 200 μm, 300 mm x 210 mm) was used instead of the polycarbonate film, and the drying conditions in the hot air drying oven were 80°C. A molded film was obtained in the same manner as in Example 58 except that the heating time was 30 minutes.

[(1) Volume resistivity measurement]
Regarding the 15 mm x 30 mm rectangular solid conductive layer formed on the molded films of Examples 58 to 119 and Comparative Examples 5 to 8, a resistivity meter (manufactured by Mitsubishi Chemical Analytech Co., Ltd., Loresta GP MCP-T610 type) was used. The volume resistivity (Ω·cm) was measured using a resistivity meter, compliant with JIS-K7194, 4-terminal 4-probe legal current application method (4-terminal probes spaced at 0.5 cm intervals). The results are shown in Tables 5-8.

[(2) Peel adhesion evaluation]
The 15 mm x 30 mm rectangular solid conductive layer formed on the molded films of Examples 58 to 119 and Comparative Examples 5 to 8 was cut with a cutter knife using a cross-cut guide with 1 mm intervals manufactured by Gardner. A 10 x 10 square grid-like cut was made to penetrate the conductive layer, and cellophane tape manufactured by Nichiban Co., Ltd. was pasted on it to remove any trapped air to ensure good adhesion, and then it was peeled off vertically. The degree of peeling of the coating film was evaluated as follows according to the ASTM D3359 standard. The results are shown in Tables 5-8.
(Peel adhesion evaluation criteria)
A: Evaluation is 5B to 4B, excellent adhesion B: Evaluation is 5B to 4B, but the coating film suffers cohesive failure and part of the coating film on the surface side comes off. C: Evaluation is 3B or less, adhesion. inferior to

[(3) Wiring resistance evaluation]
The molded films of Examples 58 to 119 and Comparative Examples 5 to 8 were cut out to 70 mm in the longitudinal direction and 10 mm in the width direction so that the 3 mm x 60 mm linear pattern of the conductive layer was in the middle, and measured. It was used as a coupon for On the surface of this measurement coupon opposite to the conductive layer, two lines were drawn at intervals of 4 cm from the longitudinal end using a permanent marker, using lines perpendicular to the conductive layer as marks. Following this mark, resistance values were measured using a tester at positions 4 cm apart, and this was defined as the wiring resistance (Ω). The results are shown in Tables 5-8.

[(4) Hot stretching evaluation 1]
The measurement coupons of Examples 58 to 116 and Comparative Examples 5 to 8 were stretched in the longitudinal direction at a stretching rate of 100 mm/min to an elongation rate of 100% in a heating oven at 160°C. After being taken out of the oven and cooled, the presence or absence of wire breakage was evaluated using an optical microscope. In addition, using the same method as the wiring resistance measurement above, measure the wiring resistance (Ω) at positions corresponding to 4 cm intervals based on the original landmark, and calculate the wiring resistance after stretching/wiring resistance before stretching to the resistance during hot stretching. The rate of change (times) was evaluated using the following criteria. The results are shown in Tables 5-8.
(Presence or absence of disconnection)
A: No wire breakage was observed.
B: 1 to 2 minor cracks were confirmed C: Severe disconnection or peeling of the conductive coating was confirmed (resistance fluctuation rate during hot stretching)
A: 5 times or more and less than 10 times B: 10 times or more and less than 100 times C: 100 times or more

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

[(5) Hot stretching evaluation 2]
In the hot stretching evaluation 1, the evaluation was performed in the same manner as in the hot stretching evaluation 1 except that the elongation rate was changed to 150%, using the following criteria. The results are shown in Tables 5-8.
(Presence or absence of disconnection)
A: No wire breakage was observed.
B: 1 to 2 minor cracks were confirmed C: Severe disconnection or peeling of the conductive coating was confirmed (resistance fluctuation rate during hot stretching)
A: 10 times or more and less than 100 times B: 100 times or more and less than 1000 times C: 1000 times or more

[(6) Hot stretching evaluation 3]
The measurement coupons of Examples 117 to 119 were stretched in the longitudinal direction at a stretching rate of 100 mm/min to an elongation rate of 100% in a heating oven at 120°C. After being taken out of the oven and cooled, the presence or absence of wire breakage was evaluated using an optical microscope. In addition, using the same method as the measurement of the wiring resistance above, measure the wiring resistance (Ω) at positions corresponding to 4 mm intervals based on the original landmark, and calculate the wiring resistance after stretching/wiring resistance before stretching to the resistance during hot stretching. The rate of change (times) was evaluated using the following criteria. The results are shown in Tables 7-8.
(Presence or absence of disconnection)
A: No wire breakage was observed.
B: 1 to 2 minor cracks were confirmed C: Severe disconnection or peeling of the conductive coating was confirmed (resistance fluctuation rate during hot stretching)
A: 5 times or more and less than 10 times B: 10 times or more and less than 100 times C: 100 times or more

[(7) Hot stretching evaluation 4]
In the hot stretching evaluation 3, evaluation was made in the same manner as in the hot stretching evaluation 3 except that the elongation rate was changed to 150%, using the following criteria. The results are shown in Tables 7-8.
(Presence or absence of disconnection)
A: No wire breakage was observed.
B: 1 to 2 minor cracks were confirmed C: Severe disconnection or peeling of the conductive coating was confirmed (resistance fluctuation rate during hot stretching)
A: 10 times or more and less than 100 times B: 100 times or more and less than 1000 times C: 1000 times or more

[(8) Evaluation of process resistance during molded body production by overlay molding 1]
A rectangular parallelepiped ABS resin molded product with a height of 10 mm and a length and width of 30 mm x 30 mm was placed on the conductor side surface so as to overlap the position of the 3 mm x 60 mm linear pattern of the molded films of Examples 58 to 116 and Comparative Examples 5 to 8. By overlay molding using a TOM molding machine (manufactured by Fuse Shinku Co., Ltd.) at a set temperature of 160°C, a molded body is created in which the rectangular parallelepiped-shaped molded film and ABS resin molded product are integrated. I got it. The scraping of the linear pattern wiring and the resistance fluctuation rate of this molded body were confirmed. The resistance variation rate is determined by measuring the wiring resistance (Ω) at positions corresponding to 6cm intervals using the original landmark standard, and calculating the wiring resistance after stretching/wiring resistance before stretching as the resistance fluctuation rate during hot stretching (times), and the following values are obtained: It was evaluated based on the following criteria. The results are shown in Tables 5-8.
(Presence or absence of wire breakage and resistance fluctuation rate)
A: No scraping of the wiring is observed, and the resistance fluctuation rate is 10 times or more and less than 50 times. B: Edge chipping is confirmed due to wiring scraping in one or two places, or the resistance fluctuation rate is 50 times or more and less than 500 times. Less than C: Disconnection due to scratched wiring is confirmed in one or more places.

[(9) Evaluation of process resistance during molded body production by overlay molding 2]
The molded product was carried out in the same manner as in Process resistance evaluation 1 when manufacturing a molded product by overlay molding, except that the linear pattern of 3 mm x 60 mm of the molded film of Examples 117 to 119 was used and overlay molding was performed at 120°C. The scraping of the linear pattern wiring and the resistance fluctuation rate during overlay molding were evaluated. The results are shown in Tables 7-8.

[(10) Evaluation of process resistance during molded body production by film insert molding 1]
A block-shaped metal mold having a rectangular parallelepiped projection with a 20 mm step and 30 mm x 30 mm in the center was placed so as to overlap the position of the 3 mm x 60 mm linear pattern of the molded films of Examples 58 to 116 and Comparative Examples 5 to 8. By aligning the conductor to face the opposite side and performing overlay molding at a temperature of 160°C using a TOM molding machine (manufactured by Fuse Shinku Co., Ltd.), the patterned conductor is formed on the inside of the rectangular parallelepiped shape. A molding film was obtained.
Next, the molded film formed into the rectangular parallelepiped shape was set in an injection molding machine (IS170 (i5), manufactured by Toshiba Machine Co., Ltd.) equipped with a valve gate type in-mold test mold, and the PC/ABS resin was By injection molding (LUPOYPC/ABSHI5002, manufactured by LG Chem.), a molded body integrated with a molding film with a patterned conductor was obtained (injection conditions: screw diameter 40 mm, cylinder temperature 260°C, mold Temperature (fixed side, movable side) 60°C, injection pressure 160 MPa (80%), holding pressure 100 MPa, injection speed 60 mm/sec (28%), injection time 4 seconds, cooling time 20 seconds). Washout (deformation or disconnection of the wiring pattern due to the temperature and injection pressure of the molten thermoplastic resin) and resistance fluctuation rate due to injection of the molten resin in the linear pattern of this molded body were confirmed. The resistance variation rate is determined by measuring the wiring resistance (Ω) at positions corresponding to 6cm intervals using the original landmark standard, and calculating the wiring resistance after stretching/wiring resistance before stretching as the resistance fluctuation rate during hot stretching (times), and the following values are obtained: It was evaluated based on the following criteria. The results are shown in Tables 5-8.
(Presence or absence of wire breakage and resistance fluctuation rate)
A: No wiring washout is observed, and the resistance fluctuation rate is 10 times or more and less than 50 times.B: Wiring distortion due to mild washout is confirmed, or the resistance fluctuation rate is 50 times or more and less than 500 timesC. : Disconnection due to wiring washout is confirmed in one or more places.

[(11) Evaluation of process resistance during molded body production by film insert molding 2]
The molded product was carried out in the same manner as in Process resistance evaluation 1 when manufacturing a molded product by overlay molding, except that the linear pattern of 3 mm x 60 mm of the molded film of Examples 117 to 119 was used and overlay molding was performed at 120°C. The degree of washout and resistance fluctuation rate due to linear pattern molten resin injection during film insert molding were evaluated. The results are shown in Tables 7-8.

[(12) Falling ball impact test of molded body]
Examples 58 to 116 and Comparative Examples 5 to 8 [(10) Process resistance evaluation 1 during production of molded object by film insert molding] and Examples 117 to 119 above [(11) Molded object by film insert molding A falling ball impact test was conducted on the molded product obtained in [Process resistance evaluation 2 during manufacturing] to evaluate impact resistance.
Using "JIS Falling Ball Impact Tester IM-4100" manufactured by Shimadzu Corporation, the obtained molded body was mounted in a predetermined position, and an iron ball weighing 500 g was dropped from a height of 80 cm into the center of the molded body. The presence or absence of cracks in the wiring and the presence or absence of continuity were visually observed from the film side. The presence or absence of continuity was confirmed by touching both measuring parts of the tester to the conductive layer of the linear pattern and measuring the resistance value of the conductive layer, and comprehensively evaluated based on the following criteria. The results are shown in Tables 5-8.
(Presence or absence of cracks)
A: Continuity was confirmed, and no cracks were found in the wiring.
B: Continuity was confirmed, but several minor cracks were observed in the wiring. C: Continuity could not be confirmed, and clear breaks were observed in the wiring.

[Summary of results]
The conductive layers formed using the conductive compositions of Comparative Examples 5 to 8, which do not contain resin (A1) as a resin component, are furthermore It has become clear that especially when the stretching elongation is large, breakage occurs and the resistance value increases. In addition, even when the final molded product was formed, it was clear that the three-dimensional wiring was likely to break due to strong impact from the outside.

On the other hand, from the results of Examples 58 to 119, it was found that the conductive composition of the present example did not cause wire breakage when stretched at high speed under high temperature conditions during the three-dimensional molding process of the formed film, especially when the stretching elongation was large. This did not occur, and the increase in resistance value was well suppressed. This is because the resin component of the conductive composition of this embodiment contains a resin (A1) with a specific molecular structure containing structural units derived from trifunctional monomers or tetrafunctional monomers. Due to the dense functional groups around the branched structure caused by the unit, it exhibits reversible yet strong adsorption behavior at multiple points on the surface of the conductive fine particles (B), making it difficult to cause wire breakage. It is estimated that there are. At the same time, this is particularly noticeable when a crosslinking agent (D) is used in combination, but the polymer chains of the resin (A1) component are often entangled with each other, forming a flexible resin connection network that spreads over a wide area, resulting in further improvement. It is inferred that this is due to the conductive layer's excellent cohesive strength and conductivity retention properties at high temperatures that can withstand stretching at high temperatures and large elongations during molding.

Furthermore, due to the above-mentioned characteristics, the formed film provided with the conductive layer of the conductive composition of the present invention has an uneven three-dimensional shape on the base material surface, particularly steep steps, etc., and requires higher speed and higher elongation during molding. Even if the wiring had a complex three-dimensional shape where the wiring would undergo elongation deformation, an excellent wiring-integrated molded body could be obtained. Moreover, the wiring as a molded body obtained after film insert molding also had excellent impact resistance properties. This is also due to the synergistic effect of the reversible yet stronger adsorption behavior of the resin (A1) component on the surface of the conductive fine particles (B) at multiple points and the formation of a flexible resin connection network that spreads over a wide area. This is thought to be due to the fact that by instantly relieving the impact without concentrating it on a specific location, voids that become notches for wiring breaks are less likely to form.

In this way, the molded film and wiring-integrated molded product using the conductive composition of this embodiment can be directly applied to plastic casings and three-dimensional shaped parts of home appliances, automobile parts, robots, drones, etc. with a high degree of design freedom. It is possible to create lightweight and space-saving circuits, create touch sensors, antennas, heating elements, electromagnetic shields, inductors (coils), resistors, and mount various electronic components without compromising the overall performance. enable. In addition, it is extremely useful for making electronic devices lighter, thinner, shorter, and more compact, increasing the degree of freedom in design, and making them multifunctional.

1 Base film 2 Conductive layer 3 Decoration layer 4 Electronic component 5 Pin 10 Molding film 11 Mold 12 Injection mold 13 Opening 14 Injection 15 Rise 16 Pressure 17 Resin 20 Base material 21 Upper chamber box 22 Lower chamber Box 30 Molded object

Claims (14)

A conductive composition for producing a molded film for forming a conductive layer on the surface of a base material having an uneven surface or a three-dimensional curved surface, the conductive composition comprising:
Contains a resin (A), conductive fine particles (B), and a solvent (C),
The resin (A) is at least one selected from the group consisting of polyester resin, polyurethane resin, polyamide resin, and polycarbonate resin, and contains a structural unit derived from a trifunctional monomer and/or a tetrafunctional monomer (A1 )including,
Conductive composition for forming films. The conductive composition for a molded film according to claim 1, wherein the total content of structural units derived from trifunctional monomers and tetrafunctional monomers is 0.1% by mass to 15% by mass in the resin (A). The conductive composition for a molded film according to claim 1, wherein the resin (A1) is a resin having a hydroxyl group and/or an amino group. 1. The conductive fine particles (B) include at least one kind of conductive fine particles selected from the group consisting of silver powder, copper powder, silver coated powder, copper alloy powder, conductive oxide powder, and carbon fine particles. A formed film conductive composition as described. The conductive composition for a molded film according to claim 1, wherein the proportion of the resin (A) in the solid content of the conductive composition is 8 to 40% by mass. The conductive composition for a molded film according to claim 1, further comprising a crosslinking agent (D). The conductive composition for a molded film according to claim 6, wherein the crosslinking agent (D) is a trifunctional block isocyanate crosslinking agent. A formed film comprising a conductive layer on a base film,
A molded film, wherein the conductive layer is a cured product of the conductive composition for molded films according to any one of claims 1 to 7. A molded film comprising a decorative layer and a conductive layer on a base film,
A molded film, wherein the conductive layer is a cured product of the conductive composition for molded films according to any one of claims 1 to 7. The molded film according to claim 8, wherein the base film is a film selected from polycarbonate, polymethyl methacrylate, polypropylene, and polyethylene terephthalate, or a laminated film thereof. A molded body in which a conductive layer is laminated on a base material,
A molded article, wherein the conductive layer is a cured product of the conductive composition for molded film according to any one of claims 1 to 7. A step of manufacturing a molded film by printing the conductive composition for a molded film according to any one of claims 1 to 7 on a base film and drying it;
arranging the molded film on a substrate;
A method for producing a molded body, comprising the step of integrating the molded film and the base material by an overlay molding method. A step of manufacturing a molded film by printing the conductive composition for a molded film according to any one of claims 1 to 7 on a base film and drying it;
a step of molding the molded film into a predetermined shape;
arranging the molded film after molding in a mold for injection molding;
A method for manufacturing a molded article, comprising the steps of molding a base material by injection molding and integrating the molded film and the base material. A step of manufacturing a molded film by printing the conductive composition for a molded film according to any one of claims 1 to 7 on a base film and drying it;
placing the molded film in an injection mold;
A method for manufacturing a molded body, comprising the steps of molding a base material by injection molding and transferring a conductive layer in the molded film to the base material side.