Conductive composition for forming film, formed body and manufacturing method thereof
阅读说明：本技术 成形膜用导电性组合物、成形膜、成形体及其制造方法 (Conductive composition for forming film, formed body and manufacturing method thereof ) 是由 戸崎広一 中里睦 于 2019-04-12 设计创作，主要内容包括：本发明提供一种可制造由拉伸力引起的导电性的降低得到抑制的成形膜的成形膜用导电性组合物。一种成形膜用导电性组合物,含有树脂(A)、导电性微粒子(B)、以及溶剂(C),所述溶剂(C)在所述溶剂(C)100质量份中包含40质量份以上的满足下述条件(1)及条件(2)的溶剂(C’)。(1)沸点为180℃以上且270℃以下。(2)满足汉森溶解性参数(HSP)的极性参数δp为0≦δp≦5.0,以及汉森溶解性参数(HSP)的氢键参数δh为9.8≦δh≦24.0中的至少一者。(The invention provides a conductive composition for a forming film, which can produce a forming film with suppressed reduction of conductivity caused by stretching force. A conductive composition for a formed film, comprising a resin (A), conductive fine particles (B), and a solvent (C), wherein the solvent (C) comprises 40 parts by mass or more of a solvent (C') satisfying the following conditions (1) and (2) per 100 parts by mass of the solvent (C). (1) The boiling point is 180 ℃ or higher and 270 ℃ or lower. (2) At least one of a polarity parameter p satisfying a Hansen Solubility Parameter (HSP) of 0 ≦ p ≦ 5.0, and a hydrogen bonding parameter h of the Hansen Solubility Parameter (HSP) of 9.8 ≦ h ≦ 24.0.)
1. A conductive composition for a formed film, comprising a resin (A), conductive fine particles (B), and a solvent (C),
the solvent (C) comprises 40 parts by mass or more of a solvent (C') satisfying the following condition (1) and at least one of the conditions (2-1) and (2-2) in 100 parts by mass of the solvent (C),
(1) A boiling point of 180 ℃ or higher and 270 ℃ or lower
(2-1) a polarity parameter p of Hansen Solubility Parameter (HSP) is 0 ≦ p ≦ 5.0
(2-2) a hydrogen bonding parameter h of the Hansen Solubility Parameter (HSP) is 9.8 h 24.0.
2. The electroconductive composition for a formed film according to claim 1, wherein the solvent (C') further satisfies the following condition (2-3),
(2-3) dispersion parameter d of Hansen Solubility Parameter (HSP) is 14.0 ≦ d ≦ 20.0.
3. The conductive composition for a formed film according to claim 1 or 2, wherein the conductive fine particles (B) include at least one conductive fine particle selected from the group consisting of silver powder, copper powder, silver coating powder, copper alloy powder, conductive oxide powder, and carbon fine particles.
4. The electroconductive composition for a formed film according to any one of claims 1 to 3, wherein the resin (A) has one or more substituents selected from a hydroxyl group, an amino group, a carboxyl group, and an acid anhydride group.
5. The conductive composition for a formed film according to any one of claims 1 to 4, wherein the resin (A) has two or more reactive functional groups selected from one or more of a hydroxyl group, an amino group, a carboxyl group, and an acid anhydride group in a molecule, and the conductive composition for a formed film further contains a crosslinking agent (D) having two or more reactive functional groups in a molecule that can be crosslinked with the reactive functional groups of the resin (A).
6. The electroconductive composition for a formed film according to claim 5, wherein the weight average molecular weight of the resin (A) is 20,000 or more and 600,000 or less,
the total amount F of the substances of the second reactive functional groups of the crosslinking agent (D)D(mol) mass M of the resin (A)A(g) The ratio of (A) to (B) satisfies the following formula (1),
5.0X 10 of the formula (1)-5≦FD/MA≦6.0×10-4。
7. A formed film is a formed film comprising a conductive layer on a base film, wherein
The conductive layer is a cured product of the conductive composition for a formed film according to any one of claims 1 to 6.
8. The formed film according to claim 7, wherein the relationship of the elongation at break of the layers at the softening point temperature of the base film satisfies the following formula:
elongation at break of the base film > elongation at break of the conductive layer.
9. A formed film is a formed film with a decorative layer and a conductive layer on a substrate film, wherein
The conductive layer is a cured product of the conductive composition for a formed film according to any one of claims 1 to 6.
10. The formed film according to claim 9, wherein the relationship of the elongation at break of the layers at the softening point temperature of the base film satisfies the following formula:
the elongation at break of the base film is larger than the elongation at break of the decoration layer and larger than the elongation at break of the conductive layer.
11. The shaped film according to any one of claims 7 to 10, wherein the base film is a film selected from polycarbonate, polymethyl methacrylate, and polyethylene terephthalate, or a laminated film of these.
12. A molded article comprising a substrate and a conductive layer laminated thereon, wherein
The conductive layer is a cured product of the conductive composition for a formed film according to any one of claims 1 to 6.
13. A method of manufacturing a shaped body comprising:
a step of producing a formed film by printing the conductive composition for a formed film according to any one of claims 1 to 6 onto a base film and drying;
disposing the formed film on a substrate; and
and integrating the molded film with the base material by a cover molding method.
14. A method of manufacturing a shaped body comprising:
a step of producing a formed film by printing the conductive composition for a formed film according to any one of claims 1 to 6 onto a base film and drying;
forming the formed film into a predetermined shape;
disposing the molded film after molding in an injection molding die; and
And a step of molding the base material by injection molding and integrating the molded film with the base material.
15. A method of manufacturing a shaped body comprising:
a step of producing a formed film by printing the conductive composition for a formed film according to any one of claims 1 to 6 onto a base film and drying;
disposing the molded film in an injection molding die; and
and a step of molding the base material by injection molding, and transferring the conductive layer in the molded film to the base material side.
Technical Field
The present invention relates to a conductive composition for a molded film, a molded body, and a method for producing the same.
Background
Patent document 1 discloses a specific conductive circuit integrated molded article including: a resin molded body; a base film embedded in the same plane as one surface of the resin molded body; and a conductive circuit disposed between the resin molded body and the base film.
Patent document 1 describes, as a method for producing the conductive circuit integrated molded article, a method in which a base film on which a specific conductive circuit is formed is disposed on a cavity surface of an injection molding die, and then a molten resin is injected to perform injection molding on a resin molded article.
In patent document 1, a conductive circuit is formed by etching a specific transparent metal thin film.
As a method of forming a conductive circuit instead of the etching method, a printing method using a conductive ink is being studied. According to the method of printing the conductive ink, compared with the etching method, the method has the advantages of no complicated steps, easy formation of a conductive circuit, improvement of productivity and realization of low cost.
For example,
Further, patent document 3 discloses, as a method for producing a decorative sheet capable of expressing a three-dimensional stereoscopic effect, a method comprising: the laminate having a print layer printed in a pattern on a transparent resin layer and the laminate having a decorative layer on a base film are thermally bonded to each other, whereby the decorative layer is formed into an uneven shape along the pattern of the print layer.
Disclosure of Invention
Problems to be solved by the invention
According to the method of patent document 1, a conductor can be easily provided on the surface of the molded body. On the other hand, there is an increasing demand for forming conductive circuits on the surface of a substrate having various shapes such as a substrate having an uneven surface or a curved surface. When a film having a conductive layer is attached to the surface of such a substrate to form a conductive circuit, the film needs to be deformed in accordance with the surface shape of the substrate. When the film is deformed, a large tensile force may be locally generated in the conductive layer. The tensile force causes breakage of the conductive layer, which causes a problem of decrease in conductivity.
The present invention has been made in view of such circumstances, and an object thereof 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 tensile force is suppressed, a molded article having excellent conductivity, and a method for producing the same.
Means for solving the problems
The conductive composition for a formed film in the present embodiment is a conductive composition for a formed film as follows:
which comprises a resin (A), conductive fine particles (B) and a solvent (C),
the solvent (C) contains 40 parts by mass or more of a solvent (C') that satisfies the following condition (1) and at least one of the conditions (2-1) and (2-2) in 100 parts by mass of the solvent (C).
(1) A boiling point of 180 ℃ or higher and 270 ℃ or lower
(2-1) the polar parameter p of Hansen Solubility Parameters (HSPs) is 0. ltoreq. p.ltoreq.5.0
(2-2) the hydrogen bond parameter h of the Hansen Solubility Parameter (HSP) is not less than 9.8 and not more than 24.0
In one embodiment of the conductive composition for a formed film of the present embodiment, the solvent (C') further satisfies the following condition (2-3).
(2-3) dispersion parameter d of Hansen Solubility Parameter (HSP) is 14.0-20.0
In one embodiment of the conductive composition for a formed film of the present embodiment, the conductive fine particles (B) include at least one conductive fine particle selected from the group consisting of silver powder, copper powder, silver coating powder, copper alloy powder, conductive oxide powder, and carbon fine particles.
In one embodiment of the conductive composition for a molded film of the present embodiment, the resin (a) has at least one substituent selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, and an acid anhydride group.
In one embodiment of the conductive composition for a formed film of the present embodiment, the resin (a) has two or more reactive functional groups selected from one or more of a hydroxyl group, an amino group, a carboxyl group, and an acid anhydride group in a molecule, and the conductive composition for a formed film further contains a crosslinking agent (D) having two or more reactive functional groups in a molecule that can crosslink with the reactive functional groups of the resin (a).
In one embodiment of the conductive composition for a formed film of the present embodiment,
the weight average molecular weight of the resin (A) is 20,000-600,000,
the total amount F of the substances of the second reactive functional groups of the crosslinking agent (D)D(mol) mass M of the resin (A) A(g) The ratio (A) satisfies the following formula (1).
5.0
The formed film in this embodiment is a formed film including a conductive layer on a base film, wherein
The conductive layer is a cured product of the conductive composition for a formed film of the present embodiment.
In one embodiment of the formed film of the present embodiment, the relationship between the elongation at break of each layer at the softening point temperature of the base film satisfies
Elongation at break of the base film > elongation at break of the conductive layer.
One embodiment of the formed film of the present embodiment is a formed 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 a formed film of the present embodiment.
In one embodiment of the formed film of the present embodiment, the relationship between the elongation at break of each layer at the softening point temperature of the base film satisfies
The elongation at break of the base film is larger than the elongation at break of the decoration layer and larger than the elongation at break of the conductive layer.
In one embodiment of the formed film of the present embodiment, the base film is a film selected from the group consisting of polycarbonate, polymethyl methacrylate, and polyethylene terephthalate, or a laminated film thereof.
The molded article in this embodiment is a molded article in which 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.
The first manufacturing method of the molded body in the present embodiment includes:
a step of producing a formed film by printing the conductive composition for a formed film on a base film and drying the printed conductive composition;
disposing the formed film on a substrate; and
and integrating the molded film with the base material by a cover molding method.
The second manufacturing method of the molded body in the present embodiment includes:
a step of producing a formed film by printing the conductive composition for a formed film on a base film and drying the printed conductive composition;
forming the formed film into a predetermined shape;
disposing the molded film after molding in an injection molding die; and
and a step of molding the base material by injection molding and integrating the molded film with the base material.
The third manufacturing method of the molded body in the present embodiment includes:
a step of producing a formed film by printing the conductive composition for a formed film on a base film and drying the printed conductive composition;
disposing the molded film in an injection molding die; and
And a step of molding the base material by injection molding, and transferring the conductive layer in the molded film to the base material side.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there can be provided a conductive composition for a molded film which can produce a molded film in which a decrease in conductivity due to a tensile force is suppressed, a molded article having excellent conductivity, and a method for producing the same.
Drawings
FIG. 1 is a schematic cross-sectional view showing an example of a formed film of the present embodiment.
Fig. 2 is a schematic cross-sectional view showing another example of the formed film of the present embodiment.
Fig. 3A is a schematic step diagram showing an example of the first method for producing a molded body, and is a cross-sectional view showing the arrangement of the molded film and the base material in the chamber box.
Fig. 3B is a schematic step diagram showing an example of the first method for producing a molded body, and is a cross-sectional view showing a state where a molded film is in contact with a substrate.
Fig. 3C is a schematic step diagram showing an example of the first method for producing a molded body, and is a cross-sectional view showing a state in which a molded film is bonded and integrated with a base material.
Fig. 4A is a schematic step diagram showing another example of the second method for producing a molded body, and is a cross-sectional view showing a state in which a molded film is disposed on a mold.
Fig. 4B is a schematic step diagram showing another example of the second method for producing a molded body, and is a cross-sectional view showing a state in which a molded film is molded by a mold.
Fig. 4C is a schematic step diagram showing another example of the second method for producing a molded body, and is a cross-sectional view showing a state in which a molded film is disposed on an injection molding die.
Fig. 4D is a schematic step diagram showing another example of the second method for producing a molded body, and is a cross-sectional view showing a state in which a molded film is disposed on an injection molding die.
Fig. 4E is a schematic step diagram showing another example of the second method for producing a molded body, and is a cross-sectional view showing a state in which a molded film is bonded to and integrated with a base material.
Fig. 5A is a schematic step diagram showing another example of the third method for producing a molded body, and is a cross-sectional view showing a state in which a molded film is disposed on an injection molding die.
Fig. 5B is a schematic step diagram showing another example of the third method for producing a molded article, and is a cross-sectional view showing a state in which a resin for injection molding is injected.
Fig. 5C is a schematic step diagram showing another example of the third method for producing a molded body, and is a cross-sectional view showing a state in which a molded film is bonded and integrated with a base material.
Detailed Description
The following are detailed descriptions of the conductive composition for a molded film, the molded body, and the method for producing the same.
In the present embodiment, the cured product includes not only a cured product that is cured by a chemical reaction but also a cured product that is not cured by a chemical reaction, such as a cured product that is cured by volatilization of a solvent.
[ conductive composition for Forming film ]
The conductive composition for a formed film of the present embodiment contains a resin (A), conductive fine particles (B), and a solvent (C),
the solvent (C) contains 40 parts by mass or more of a solvent (C') that satisfies the following condition (1) and at least one of the conditions (2-1) and (2-2) in 100 parts by mass of the solvent (C).
(1) A boiling point of 180 ℃ or higher and 270 ℃ or lower
(2-1) the polar parameter p of the Hansen Solubility Parameter (HSP) is 0. ltoreq. p.ltoreq.5.0
(2-2) the hydrogen bond parameter h of the Hansen Solubility Parameter (HSP) is not less than 9.8 and not more than 24.0
According to the conductive composition for a formed film of the present embodiment, a formed film in which a decrease in conductivity due to a tensile force is suppressed can be produced.
The present inventors have studied a conductive composition that can be screen-printed in order to produce a formed film that can be applied to a substrate surface that is not flat. In order to be applied to screen printing, a solvent having a boiling point of 180 ℃ or higher and 270 ℃ or lower was selected and studied, and as a result, the following findings were obtained: the magnitude of the change in resistance value generated when the obtained formed film is stretched varies depending on the type of the solvent contained in the conductive composition. As a result of studies based on such findings, the inventors have found that when a conductive composition containing a specific solvent is printed and dried by heating on a resin film, the solvent penetrates into the resin film at the contact surface between the conductive composition and the resin film, and the resin film slightly dissolves or shrinks. It is presumed that such solvent penetration, dissolution or shrinkage occurs over the entire contact surface between the resin film and the conductive layer. In addition, the same applies to the case where the conductive layer is provided on the decorative layer. Therefore, it is expected that the adhesion between the resin film and the conductive layer is slightly lowered, and the solvent impregnated into the resin film migrates to the conductive layer during or after drying, so that the cohesive force of the conductive layer is also lowered.
Even if the formed film for forming the conductive layer is a resin film having such a solvent-permeable, soluble or shrinkable resin film, the film is problematic when the film is used alone as a flat film circuit board or the like. However, when the film is used as a molded film that conforms to and is integrated with a shape of a non-flat substrate surface, the molded film is deformed. During the deformation, friction with the molding die, tensile force, or the like is applied to the molded film. In the case of a formed film having a resin film impregnated with, dissolved in, or shrunk by a solvent, it is presumed that detachment of the conductive layer due to the reduction of the friction or cohesive force, disconnection of the conductive layer with respect to extension, or the like occurs at the time of the deformation, and the conductivity is reduced.
The present inventors have made extensive studies based on these findings and found that a solvent having a Hansen Solubility Parameter (HSP) with a polarity parameter p of more than 5.0 and a hansen solubility parameter with a hydrogen bond parameter h of less than 9.8 easily permeates into the substrate film. That is, it was found that the permeation into the base material film can be suppressed by using a solvent in which the polar parameter p of the Hansen Solubility Parameter (HSP) is 0. ltoreq. p.ltoreq.5.0 or a solvent in which the hydrogen bond parameter h of the Hansen Solubility Parameter (HSP) is 9.8. ltoreq. h.ltoreq.24.0, and the present invention was completed.
By using the specific solvent (C'), the conductive composition for a formed film of the present invention can easily produce a formed film having a conductive layer with a thick film excellent in conductivity by screen printing or the like. Further, a formed film produced using the conductive composition for a formed film can suppress a decrease in conductivity even when used on a substrate surface which is not flat. Further, by using the molded film, a molded body having a conductive circuit formed on an arbitrary surface such as a concave-convex surface or a curved surface can be obtained.
The conductive composition for a molded film of the present embodiment contains at least a resin (a), conductive fine particles (B), and a solvent (C), and may further contain other components as needed. The respective components of the conductive composition for a formed film will be described below.
< resin (A) >
The conductive composition of the present embodiment contains a binder resin (a) to impart film formability or adhesiveness to a base film or a decorative layer. In addition, in the present embodiment, by containing the resin (a), flexibility can be imparted to the conductive layer. Therefore, by containing the resin (a), disconnection of the conductive layer with respect to the extension can be suppressed.
The resin (a) may be suitably selected from resins used for conductive composition applications.
Examples of the resin (a) include: one kind of acrylic resin, vinyl ether resin, polyether resin, polyester resin, polyurethane resin, epoxy resin, phenoxy resin, polycarbonate resin, polyvinyl chloride resin, polyolefin resin, styrene block copolymer resin, polyamide resin, polyimide resin, or the like may be used alone, or two or more kinds may be used in combination.
In the present embodiment, the resin (a) preferably has a substituent selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, and an acid anhydride group. Having such a substituent improves the affinity with the conductive fine particles (B) described later, and improves the adhesion to a base film or the like.
Further, in the present embodiment, the resin (a) preferably has two or more substituents selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, and an acid anhydride group in one molecule. In this case, the resin (a) can be three-dimensionally crosslinked by combining with a crosslinking agent (D) described later, and can be preferably used for applications requiring hardness for the conductive layer.
When the resin (A) has a functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group and an acid anhydride group, the valence of the functional group is preferably 1mgKOH/g or more and 400mgKOH/g or less, more preferably 2mgKOH/g or more and 350mgKOH/g or less. The details of the method for calculating the functional group valence will be described in the examples described later.
When the resin (a) has a plurality of functional groups, the valences of the functional groups are the total of the functional groups. For example, when the resin (a) has a hydroxyl group and a carboxyl group, the functional group valence represents the total of the hydroxyl group valence and the acid valence of the resin (a).
The weight average molecular weight of the resin (a) is not particularly limited, but is preferably 5,000 or more and 1,000,000 or less, more preferably 10,000 or more and 800,000 or less, and further preferably 20,000 or more and 600,000 or less, from the viewpoint of workability in forming a coating film.
In the present example, the weight average molecular weight was determined using polystyrene equivalent molecular weight in the measurement of Gel Permeation Chromatography (GPC) "HLC-8320" manufactured by Tosoh corporation.
The glass transition temperature (Tg) of the resin (a) is not particularly limited, but in terms of ease of handling of the conductive layer, the glass transition temperature (Tg) of the resin (a) is preferably 0 ℃ or higher and 150 ℃ or lower, and more preferably 5 ℃ or higher and 120 ℃ or lower.
In this embodiment, the resin (a) can be synthesized and used by the following examples and other conventional methods, and commercially available products having desired physical properties can also be used. In this embodiment, the resin (a) may be used alone or in combination of two or more.
The content of the resin (a) in the conductive composition of the present embodiment is not particularly limited as long as it is appropriately adjusted according to the application and the like, but is preferably 5 mass% or more and 50 mass% or less, and more preferably 8 mass% or more and 40 mass% or less, relative to the total amount of solid components contained in the conductive composition. When the content ratio of the resin (a) is not less than the lower limit, the film forming property or the adhesiveness to a base film or the like can be improved, and flexibility can be imparted to the conductive layer. When the content of the resin (a) is not more than the upper limit, the content of the conductive fine particles (B) can be relatively increased, and a conductive layer having excellent conductivity can be formed.
< conductive Fine particles (B) >
The conductive fine particles (B) are conductive fine particles exhibiting conductivity by contacting a plurality of conductive fine particles in a conductive layer, and in this embodiment, can be suitably selected from fine particles that can obtain conductivity without being heated at a high temperature.
Examples of the conductive fine particles used in this embodiment include metal fine particles, carbon fine particles, conductive oxide fine particles, and the like.
Examples of the metal fine particles include metal monomer powders such as gold, silver, copper, nickel, chromium, palladium, rhodium, ruthenium, indium, aluminum, tungsten, molybdenum, and platinum, and in addition to the following: alloy powders such as copper-nickel alloy, silver-palladium alloy, copper-tin alloy, silver-copper alloy, and copper-manganese alloy, and metal coating powders obtained by coating the surface of the metal powder or alloy powder with silver or the like. Examples of the 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, ruthenium oxide, and the like.
In the present embodiment, among them, conductive fine particles containing at least one selected from silver powder, copper powder, silver coating powder, copper alloy powder, conductive oxide powder, and carbon fine particles are preferable. By using these conductive fine particles (B), a conductive layer having excellent conductivity can be formed without sintering.
The shape of the conductive fine particles (B) is not particularly limited, and amorphous, agglomerated, scaly, microcrystalline, spherical, flaky, and linear particles can be suitably used. From the viewpoint of maintaining the conductivity during molding or from the viewpoint of the adhesion of the conductor pattern to the base material, the conductive pattern is preferably in the form of aggregates, scales, flakes, or lines.
The average particle diameter of the conductive fine particles is not particularly limited, and is preferably 0.1 μm or more and 50 μm or less, and more preferably 0.5 μm or more and 30 μm or less, in terms of dispersibility in the conductive composition or conductivity when the conductive layer is formed.
In the present embodiment, the average particle diameter of the conductive fine particles (B) is calculated as follows. An appropriate amount of conductive fine particles (B) was added to an aqueous solution containing 0.5 vol% of a commercially available surfactant polyoxyethylene octylphenyl ether (manufactured by Roche diagnostics GmbH: Triton X-100) as a dispersant by a laser diffraction/scattering type particle size distribution measuring apparatus (manufactured by Nikkiso Co., Ltd.: Microtrac 9220FRA) according to a laser diffraction/scattering method described in Japanese Industrial Standards (JIS) M8511(2014), and the measurement was carried out after irradiation with 40W ultrasonic waves for 180 seconds while stirring. The value of the obtained intermediate particle diameter (D50) is set as the average particle diameter of the conductive fine particles (B).
In this embodiment, the conductive fine particles (B) may be used singly or in combination of two or more.
The content of the conductive fine particles (B) in the conductive composition of the present embodiment is not particularly limited as long as it is appropriately adjusted according to the application and the like, but is preferably 50 mass% to 95 mass%, more preferably 60 mass% to 90 mass%, relative to the total amount of solid components contained in the conductive composition. When the content ratio of the conductive fine particles (B) is not less than the lower limit, a conductive layer having excellent conductivity can be formed. When the content of the conductive fine particles (B) is not more than the upper limit, the content of the resin (a) can be increased, the film-forming property or the adhesion to a base film or the like can be improved, and the conductive layer can be provided with flexibility.
< solvent (C) >
The conductive composition of the present embodiment is characterized in that: the solvent (C) contains 40 parts by mass or more of a solvent (C') satisfying the following condition (1) and at least one of the conditions (2-1) and (2-2) in 100 parts by mass of the solvent (C).
(1) A boiling point of 180 ℃ or higher and 270 ℃ or lower
(2-1) the polar parameter p of the Hansen Solubility Parameter (HSP) is 0. ltoreq. p.ltoreq.5.0
(2-2) the hydrogen bond parameter h of the Hansen Solubility Parameter (HSP) is not less than 9.8 and not more than 24.0
By containing the specific solvent (C') in an amount of 40 mass% or more based on the whole solvent, solvent permeation, dissolution, or shrinkage of the resin film to be a base film can be suppressed, and a formed film in which a decrease in conductivity due to a stretching force is suppressed can be produced. The proportion of the solvent (C') may be 40 mass% or more and 100 mass% or less with respect to the whole solvent, and is preferably 60 mass% or more, and more preferably 80 mass% or more.
The solvent (C') satisfying the condition (2-1) preferably has a hydrogen bond parameter h of 2.9. ltoreq. h.ltoreq.9.1 for the Hansen Solubility Parameter (HSP).
Further, the solvent (C') satisfying the condition (2-2) is preferably such that the polar parameter p of the Hansen Solubility Parameter (HSP) is 5.5. ltoreq. p.ltoreq.15.3.
The solvent (C') is preferably further one satisfying the following condition (2-3).
(2-3) dispersion parameter d of Hansen Solubility Parameter (HSP) is 14.0-20.0
Specific examples of such a solvent (C') include: diethylene glycol monomethyl ether (boiling point 194 ℃, d ═ 16.2, p ═ 7.8, h ═ 12.6), diethylene glycol monoethyl ether (boiling point 202 ℃, d ═ 16.1, p ═ 9.2, h ═ 12.2), diethylene glycol monobutyl ether (boiling point 231 ℃, d ═ 16.0, p ═ 7.0, h ═ 10.6), diethylene glycol dibutyl ether (boiling point 256 ℃, d ═ 15.8, p ═ 4.4, h ═ 4.7), triethylene glycol monomethyl ether (boiling point 249 ℃, d ═ 16.2, p ═ 7.6, h ═ 12.5), triethylene glycol dimethyl ether (boiling point 220 ℃, d ═ 15.8, p ═ 2.3, h ═ 8.2), dipropylene glycol monomethyl ether acetate (boiling point 213 ℃, d ═ 16.3, p ═ 4.9, h ═ 8, benzyl alcohol (boiling point h ═ 8, p ═ 2.3, h ═ 8, h ═ 8.2), naphthalene acetate (boiling point 239, h ═ 4.8, h ═ 4.4, h ═ 4, 7, 7.6, h ═ 4.7, h ═ 4.6, 7, 7.6, 7.4, 7, 7.6, 7, 7.5), naphthalene ═ 4.9, 7, 7.9, 7.4.4, Terpineol (boiling point 217 ℃, d ═ 13.9, p ═ 8.0, h ═ 10.3), glycerol triacetate (boiling point 258 ℃, d ═ 16.5, p ═ 4.5, h ═ 9.1), propylene glycol (boiling point 187 ℃, d ═ 16.8, p ═ 9.3, h ═ 23.3), 1, 3-butanediol (boiling point 208 ℃, d ═ 16.6, p ═ 10.0, h ═ 21.5), 1, 4-butanediol (boiling point 228 ℃, d ═ 16.6, p ═ 15.3, h ═ 21.7), dipropylene glycol monopropyl ether (boiling point 212 ℃, d ═ 15.5, p ═ 5.7, h ═ 11.2), dipropylene glycol monopropyl ether (boiling point 214 ℃, d ═ 16.0, p ═ 7.2, h ═ 11.3, h ═ 5, h ═ 5.7, h ═ 11.2), dipropylene glycol monopropyl ether (boiling point 15, h ═ 15.5, h ═ 15, h ═ 15.5, h ℃.
The solvent (C) may contain a solvent other than the above-mentioned solvent (C') in an amount of less than 60% by mass. Examples of such a solvent include a solvent (C-1) which satisfies the above condition (1) and does not satisfy the above condition (2), and a solvent (C-2) which does not satisfy the above condition (1) and has a boiling point of less than 180 ℃.
In the present embodiment, the solvent (C-1) is a solvent that penetrates into the base film, dissolves or shrinks. Therefore, the solvent (C-1) is preferably 40% by mass or less, more preferably 20% by mass or less, and even more preferably 0% by mass, based on the total amount of the solvent (C), i.e., substantially not contained, although the dissolution or shrinkage can be greatly reduced by using the solvent (C') in combination.
Examples of the solvent corresponding to the solvent (C-1) include: diethylene glycol monoethyl ether acetate, gamma-butyrolactone, isophorone, etc.
Even when the condition (2) is not satisfied, the solvent (C-2) having a boiling point of less than 180 ℃ evaporates relatively quickly by the drying heat after screen printing, and therefore the contact time with the base film is short. Therefore, although the effect of penetrating into the base film and dissolving or shrinking is small, when used in a large amount, the volatility at the time of printing is too high, and therefore it becomes significantly difficult to stably continue printing, and therefore, it is preferably 30 mass% or less with respect to the total amount of the solvent (C).
Examples of the solvent (C-2) having a boiling point of less than 180 ℃ include: 1-methoxypropanol, 2-methoxypropanol, 1-methoxypropyl acetate, 2-methoxypropyl acetate, mineral spirits, butyl acetate, ethyl acetate, 1-butanol, acetone, cyclohexanone, and the like.
The proportion of the solvent (C) to the entire conductive composition of the present embodiment is not particularly limited, but is preferably 5% by mass or more and 60% by mass or less, and more preferably 10% by mass or more and 50% by mass or less, in terms of workability at the time of screen printing.
< optional Components >
The conductive composition of the present invention may further contain other components as necessary. Examples of such other components include, in addition to the crosslinking agent (D): a dispersant, a friction-improving agent, an infrared absorber, an ultraviolet absorber, an aromatic agent, an antioxidant, an organic pigment, an inorganic pigment, an antifoaming agent, a silane coupling agent, a plasticizer, a flame retardant, a humectant, and the like.
The crosslinking agent (D) is used for crosslinking the resin (a). The crosslinking agent (D) may be suitably selected from those having two or more reactive functional groups in one molecule which can be crosslinked with the reactive functional groups of the resin (a) and used. Examples of such reactive functional groups include: epoxy groups, isocyanate groups, blocked isocyanate groups, alkoxyamino groups, aziridinyl groups, oxetanyl groups, carbodiimide groups, β -hydroxyalkylamide groups, and the like.
When the crosslinking agent (D) is used, the amount thereof is preferably 0.05 to 30 parts by mass, more preferably 1 to 25 parts by mass, per 100 parts by mass of the resin (a).
Further, in the present embodiment, it is particularly preferable that the resin (A) is one having two or more first reactive functional groups selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group and an acid anhydride group in one molecule and having a weight average molecular weight of 20,000 or more and 600,000 or less, and the crosslinking agent (D) is one having two or more second reactive functional groups crosslinkable with the first reactive functional groups in one molecule,
in total amount F of the substance of the second reactive functional group of the crosslinking agent (D)D(mol) mass M of the resin (A)A(g) The ratio (c) satisfies the following formula (1).
5.0X 10 of the formula (1)-5≤FD/MA≤6.0×10-4
Here, the total amount F of substances of the second reactive functional groups of the crosslinking agent (D) is illustratedDExample of calculation of (mol). 10g of a crosslinking agent having three second reactive functional groups in one molecule and a molecular weight of 600 was used as an exampleIn the case of (ii), it is FD(3/600) × 10 ═ 0.05 (mol). At this time, when the mass of the resin (a) to be combined is 500(g), F is defined as D/MA＝0.05(mol)/500(g)＝1.0×10-4(mol/g), and is therefore a combination satisfying formula (1).
By using these combinations, a conductive layer having both flexibility and hardness and in which a decrease in conductivity due to tensile force is suppressed can be obtained.
< method for producing conductive composition >
The method for producing the conductive composition of the present embodiment may be a method of dissolving or dispersing the resin (a), the conductive fine particles (B), and other components used as necessary in the solvent (C), and may be produced by mixing them by a conventional mixing means.
[ formed film ]
The formed film of the present embodiment is a formed film including a conductive layer on a base film, and is characterized in that:
the conductive layer is a cured product of the conductive composition for a molded film.
According to the molded film of the present embodiment, a molded body in which a conductive circuit is formed on an arbitrary substrate surface such as a concave-convex surface or a curved surface can be obtained.
According to the molded film of the present embodiment, a molded body in which a conductive circuit is formed on an arbitrary substrate surface such as a concave-convex surface or a curved surface can be obtained.
The layer structure of the formed film of the present embodiment will be described with reference to fig. 1 and 2. Fig. 1 and 2 are schematic cross-sectional views showing an example of a formed film according to the present embodiment.
The formed
The formed
Further, although not shown, the
In addition, although not shown, when the formed
The formed film of this embodiment includes at least a base film and a conductive layer, and may have other layers as necessary. The layers of such a formed film will be described below.
< basement membrane >
In the present embodiment, the base film can be suitably selected from those having flexibility and stretchability to such an extent that the base film can follow the shape of the surface of the base material under the molding temperature conditions at the time of forming the molded article, and is preferably selected according to the use of the molded article, the method for producing the molded article, and the like.
For example, when a cover molding method or a film embedding method, which will be described later, is employed as a method for producing a molded body, the base film may be selected in consideration of having a function as a protective layer of the conductive layer or the like since the base film remains on the molded body.
On the other hand, when the in-mold transfer method described later or the like is employed as a method for producing a molded article, it is preferable to select a base film having peelability.
The base film may be suitably selected from the above-described viewpoints, and for example, may be a film of polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polystyrene, polyimide, polyamide, polyether sulfone, polyethylene naphthalate, polybutylene terephthalate, polyvinyl chloride, polyethylene, polypropylene, a cyclic olefin polymer, acrylonitrile-butadiene-styrene copolymer resin (ABS), acrylonitrile-ethylene-styrene copolymer resin (AES), acrylic-modified vinyl chloride resin (kydac), modified polyphenylene ether, a polymer blend containing two or more of these resins, or a laminated film of these resins. Among them, a film selected from polycarbonate, polymethyl methacrylate, polyethylene terephthalate, or a laminated film of these is preferable. Among these, a laminated film of polycarbonate and polymethyl methacrylate is preferable.
The method for producing the multilayer film of polycarbonate and polymethyl methacrylate is not particularly limited, and a polycarbonate film and a polymethyl methacrylate film may be laminated, or a polycarbonate and polymethyl methacrylate film may be formed into a multilayer film by coextrusion.
In addition, an anchor coat layer (anchor coat layer) may be provided on the base film and the conductive composition may be printed on the anchor coat layer, if necessary, for the purpose of improving printability of the conductive composition, or the like. The anchor coat layer is not particularly limited as long as it has good adhesion to the base film and further to the conductive composition and follows the film during molding, and an organic filler such as resin beads or an inorganic filler such as a metal oxide may be added as necessary. The method for providing the anchor coat layer is not particularly limited, and the anchor coat layer can be obtained by coating, drying, and curing by a conventional coating method.
Further, in order to prevent the surface of the molded article from being damaged, a hard coat layer may be provided on the base film, and the conductive composition and, if necessary, a decorative layer may be printed on the opposite surface. The hard coat layer is not particularly limited as long as it has good adhesion to the base film and further has good surface hardness and follows the film during molding, and an organic filler such as resin beads or an inorganic filler such as a metal oxide may be added as necessary. The method of providing the hard coat layer is not particularly limited, and the hard coat layer can be obtained by coating, drying, and hardening by a conventional coating method.
When the formed film of the present embodiment has a decorative layer, it is preferable to select a base film having transparency.
The thickness of the base film is not particularly limited, and may be, for example, 10 μm or more and 500 μm or less, and preferably 20 μm or more and 450 μm or less.
< conductive layer >
In the formed film of the present embodiment, the conductive layer is a cured product of the conductive composition.
The method for forming the conductive layer is not particularly limited, but in the present embodiment, the conductive layer is preferably formed by a screen printing method, a pad printing method, a stencil (stencil) printing method, a screen offset printing method, a dispenser printing method, a gravure offset printing method, a reverse offset printing method, or a micro-contact printing method, and more preferably, by a screen printing method.
In order to cope with the high definition of the conductive circuit pattern in the screen printing method, it is preferable to use a screen having a fine mesh (mesh), particularly, a fine mesh having about 300 to 650 meshes. The open area of the screen at this time is preferably about 20% to 50%. The screen line diameter is preferably about 10 to 70 μm.
The types of screen printing plates include: polyester screen, combination screen, metal screen, nylon screen, etc. In the case of printing a paste of high viscosity, a high-tension stainless steel screen plate can be used.
The screen printing squeegee can be any shape of circle, rectangle, square, and can also be a ground squeegee to reduce the attack angle (angle of plate to squeegee during printing). Other printing conditions may be used as long as the existing conditions are appropriately designed.
The conductive composition is printed by screen printing, and then heated and dried to be cured. When the conductive composition contains the crosslinking agent (D), the crosslinking reaction is further carried out by heating to cure the composition.
In the case where the crosslinking agent is not contained, the heating temperature is preferably 80 to 230 ℃ and the heating time is preferably 10 to 120 minutes for sufficient volatilization of the solvent and sufficient crosslinking reaction in the case where the crosslinking agent is contained. Thus, a patterned conductive layer can be obtained. The patterned conductive layer may be provided with an insulating layer so as to cover the conductive pattern as necessary. The insulating layer is not particularly limited, and a conventional insulating layer can be applied.
The thickness of the conductive layer is not particularly limited as long as it is appropriately adjusted in accordance with the required conductivity and the like, and 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.
< decorative layer >
In terms of the design of the molded article obtained, the molded film of the present embodiment may have a decorative layer.
The decorative layer may be a layer having a single color tone, or a layer with an arbitrary pattern attached thereto.
For example, the decorative layer may be formed by preparing a decorative ink containing a coloring material, a resin, and a solvent, and then coating the decorative ink on the base film by a conventional printing method.
The coloring material may be suitably selected from conventional pigments and dyes. The resin is preferably suitably selected from the same resins as the resin (a) in the conductive composition of the present embodiment.
The thickness of the decorative layer is not particularly limited, and may be, for example, 0.5 μm or more and 10 μm or less, and preferably 1 μm or more and 5 μm or less.
In the case where the molded film of the present embodiment has a base film and a conductive layer, it is preferable that the relationship between the elongation at break of each layer at the softening point temperature of the base film satisfies
Elongation at break of the base film > elongation at break of the conductive layer.
In addition, when the formed film to be applied includes a base film, a decorative layer, and a conductive layer in this order, it is preferable that the relation of the elongation at break of each layer at the softening point temperature of the base film satisfies the relationship
The elongation at break of the base film is larger than the elongation at break of the decoration layer and larger than the elongation at break of the conductive layer.
By satisfying such a relationship, it is possible to prevent a tensile force from concentrating on the conductive layer and applying a large mechanical load, and further suppress a decrease in conductivity due to the tensile force.
[ formed article ]
The molded article of the present embodiment is a molded article in which at least a conductive layer is laminated on a base material, and is characterized in that: the conductive layer is a cured product of the conductive composition for a formed film according to any one of claims 1 to 5. Since the molded article of the present embodiment is formed of the molded film using the conductive composition for a molded film of the present embodiment, the molded article has a conductive circuit formed on an arbitrary surface such as a concave-convex surface or a curved surface.
Three embodiments of the method for producing a molded body according to the present embodiment will be described below. The molded article of the present embodiment is not limited to these methods as long as it is produced using the conductive composition of the present embodiment.
< first production method >
The first manufacturing method of the molded body of the present embodiment includes:
a step of producing a formed film by printing the conductive composition for a formed film on a base film and drying the printed conductive composition;
Disposing the formed film on a substrate; and
and integrating the molded film with the base material by a cover molding method.
Hereinafter, the description will be made with reference to fig. 3A to 3C, but since the method of producing the formed film is as described above, the description thereof will be omitted.
Fig. 3A to 3C are schematic step diagrams showing an example of a first method for producing a molded body. Fig. 3A to 3C respectively show the formed
In the first manufacturing method, the
In the first manufacturing method, the
< second production method >
The second manufacturing method of the molded body of the present embodiment includes:
a step of producing a formed film by printing the conductive composition for a formed film on a base film and drying the printed conductive composition;
forming the formed film into a predetermined shape;
disposing the molded film after molding in an injection molding die; and
and a step of molding the base material by injection molding and integrating the molded film with the base material. The following description will be made with reference to fig. 4A to 4E. The second manufacturing method is sometimes referred to as a film embedding method.
Fig. 4A to 4E are schematic step diagrams showing an example of a second method for producing a molded body. In the second manufacturing method, the molded
In the second production method, the
< third production method >
The third manufacturing method of the molded body of the present embodiment includes:
a step of producing a formed film by printing the conductive composition for a formed film of the present embodiment on a base film by screen printing and drying;
disposing the molded film in an injection molding die; and
and a step of molding the base material by injection molding, and transferring the conductive layer in the molded film to the base material side.
The following description will be made with reference to fig. 5A to 5C. The third production method may be referred to as an in-mold transfer method.
Fig. 5A to 5C are schematic step diagrams showing an example of a third method for producing a molded body. In the third manufacturing method, the formed
In the third manufacturing method, since the base film does not need to be cut, a long base film can be arranged as shown in the examples of fig. 5A to 5C. The material of the
The molded body thus obtained can be used for mounting a circuit, a touch sensor, and various electronic components on a plastic housing of a home appliance, an automobile component, a robot, an unmanned aerial vehicle, or the like. Further, the present invention is extremely useful for making electronic devices light, thin, short, compact, and more versatile with an improved degree of freedom in design.
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