WO2021241473A1

WO2021241473A1 - Composition, method for producing three-dimensionally molded circuit component, three-dimensionally molded circuit component and antenna

Info

Publication number: WO2021241473A1
Application number: PCT/JP2021/019518
Authority: WO
Inventors: 敦美山邊; 崇佐藤; 渉笠井
Original assignee: Ａｇｃ株式会社
Priority date: 2020-05-27
Filing date: 2021-05-24
Publication date: 2021-12-02
Also published as: TW202204508A; JPWO2021241473A1

Abstract

[Problem] To provide: a composition which is capable of forming a base material that exhibits high adhesion to a circuit; a three-dimensionally molded circuit component which has high adhesion between a base material and a circuit; a method for producing this three-dimensionally molded circuit component; and an antenna which is provided with this three-dimensionally molded circuit component. [Solution] A composition according to the present invention is used for the purpose of forming a base material of a three-dimensionally molded circuit component; this composition contains a thermofusible tetrafluoroethylene polymer and an inorganic filler that has an average particle diameter of more than 0.1 μm; and the content of the tetrafluoroethylene polymer is more than 50% by mass.

Description

Composition, manufacturing method of three-dimensional molded circuit parts, three-dimensional molded circuit parts and antennas

The present invention relates to a three-dimensional molded circuit component having high adhesion between a substrate and a circuit, a method for manufacturing the same, an antenna provided with the three-dimensional molded circuit component, and a composition capable of forming the substrate.

A three-dimensional molded circuit component having a three-dimensional resin molded product (base) called MID (Mold Interconnect Device) and a circuit formed on the surface thereof is for high frequency from the viewpoint of space saving and reduction of the number of components. It is useful for applications such as boards and in-vehicle sensors. In the method for producing MID, after roughening the surface of a resin molded product (original molded product), a catalyst is applied to the surface and electroless plating treatment is performed.

As a resin composition that can be used to form a resin molded product, a combination of a fluororesin having a polar functional group and a thermoplastic resin or a thermosetting resin has been proposed (see Patent Document 1). However, the adhesion of the catalyst and the plating layer to the surface of the resin molded product formed from the resin composition is not yet sufficient, and there is room for further improvement.

Japanese Unexamined Patent Publication No. 2019-054034

As a result of diligent studies in view of the above problems, the present inventors have found that if a composition in which a heat-meltable tetrafluoroethylene polymer and a predetermined inorganic filler are used in combination is used, the adhesion between the substrate and the circuit is high. It was found that a three-dimensional molded circuit component can be obtained.
An object of the present invention is to provide a composition capable of forming a substrate having high adhesion to a circuit, a three-dimensional molded circuit component having high adhesion between a substrate and a circuit, a method for manufacturing the same, and an antenna provided with the same.

The present invention has the following aspects.
<1> A composition used for forming a substrate for a three-dimensional molded circuit component, which comprises a heat-meltable tetrafluoroethylene polymer and an inorganic filler having an average particle size of more than 0.1 μm, and is tetra. A composition in which the content of the fluoroethylene-based polymer is more than 50% by mass.
<2> The composition of <1>, wherein the tetrafluoroethylene-based polymer is a tetrafluoroethylene-based polymer having a polar functional group.
<3> The composition of <1> or <2>, wherein the inorganic filler is an inorganic filler surface-treated with a silane coupling agent.
<4> The composition according to any one of <1> to <3>, wherein the average particle size of the inorganic filler is 0.5 to 20 μm.
<5> The composition according to any one of <1> to <4>, wherein the content of the inorganic filler is 5% by mass or more and less than 50% by mass.
<6> The inorganic filler is an inorganic filler containing at least one selected from the group consisting of silica, talc, titania, alumina, tin oxide, an organic palladium complex, copper oxide and boron nitride, <1> to <. 5> Any of the compositions.
<7> The composition according to any one of <1> to <6> further containing non-heat-meltable polytetrafluoroethylene.
<8> A substrate is formed using any of the compositions <1> to <7>, the surface of the substrate is roughened, a catalyst is applied, and the surface of the substrate is plated. A method for manufacturing a three-dimensional molded circuit component, wherein a circuit is formed to obtain a three-dimensional molded circuit component having the substrate and the circuit.
<9> The method for producing <8>, wherein a part of the inorganic filler is exposed from the surface of the substrate after the roughening treatment, and a part of the catalyst is supported on the exposed inorganic filler. ..
<10> The method for producing <8> or <9>, wherein the roughening treatment is performed by irradiating the surface of the substrate with ultraviolet rays or applying a solvent to the surface of the substrate.
<11> A substrate is formed using any of the compositions of <1> to <7>, the surface of the substrate is irradiated with a laser, and then a circuit is formed on the surface of the substrate by a plating treatment to form the substrate. A method for manufacturing a three-dimensional molded circuit component, which obtains a three-dimensional molded circuit component having the above-mentioned circuit.
<12> The method for producing <11>, wherein the inorganic filler is an inorganic filler containing copper oxide or tin oxide.
<13> A substrate containing a heat-meltable tetrafluoroethylene polymer and an inorganic filler having an average particle size of more than 0.1 μm and having a tetrafluoroethylene polymer content of more than 50% by mass, and the substrate. A three-dimensional molded circuit component having a circuit provided on the surface of the above.
<14> The three-dimensional molded circuit component of <13>, wherein a part of the inorganic filler is exposed from the surface of the substrate and the circuit is in contact with the exposed inorganic filler.
<15> An antenna provided with the three-dimensional molded circuit component of <13> or <14>.

According to the present invention, a three-dimensional molded circuit component having high adhesion between the substrate and the circuit can be obtained.

The following terms have the following meanings.
The "heat-meltable polymer" means a polymer showing melt fluidity, and the melt flow rate is 0.1 to 1000 g / 10 at a temperature 20 ° C. or higher higher than the melt temperature of the polymer under the condition of a load of 49 N. It means a polymer in which a temperature of minutes is present.
"Melting flow rate (MFR)" means the melt mass flow rate of a polymer as defined in JIS K 7210: 1999 (ISO 1133: 1997).
The “polymer melting temperature (melting point)” is the temperature corresponding to the maximum value of the melting peak measured by the differential scanning calorimetry (DSC) method.
The "glass transition point (Tg) of the polymer" is a value measured by analyzing the polymer by the dynamic viscoelasticity measurement (DMA) method.
The "average particle size (D50)" is a volume-based cumulative 50% diameter of an object (grain or filler) determined by a laser diffraction / scattering method. That is, the particle size distribution of the object is measured by the laser diffraction / scattering method, the cumulative curve is obtained with the total volume of the group of particles of the object as 100%, and the particles at the point where the cumulative volume is 50% on the cumulative curve. The diameter.
“D10” and “D90” are volume-based cumulative 10% and 90% diameters of the object, respectively, measured in the same manner.
The "unit" in the polymer may be an atomic group formed directly from the monomer, or may be an atomic group in which a part of the structure is converted by treating the obtained polymer by a predetermined method. The unit based on the monomer A contained in the polymer is also simply referred to as "monomer A unit".

The composition of the present invention (hereinafter, also referred to as "the present composition") is used for forming a substrate of a three-dimensional molded circuit component. The present composition contains a heat-meltable tetrafluoroethylene polymer (hereinafter, also referred to as “F polymer”) and an inorganic filler having an average particle size of more than 0.1 μm, and is a tetrafluoroethylene polymer. Content is over 50% by mass. That is, when the tetrafluoroethylene-based polymer in the present composition consists only of the F polymer, the content of the F polymer in the present composition is more than 50% by mass, and the tetrafluoroethylene-based polymer in the present composition is the F polymer and F. When composed of a tetrafluoroethylene-based polymer other than the polymer (non-heat-meltable polytetrafluoroethylene, etc. described later), the total content of the F polymer and the tetrafluoroethylene-based polymer other than the F polymer in this composition is 50. It is over% by mass.

Further, in the method for manufacturing a three-dimensional molded circuit component of the present invention (hereinafter, also referred to as "this method"), a substrate is formed using the present composition, the surface of the substrate is roughened, and then a catalyst is used. A method of forming a circuit on the surface of the substrate by a plating treatment to obtain a three-dimensional molded circuit component having the substrate and the circuit (hereinafter, also referred to as “this method 1”) or a substrate using the present composition. A method of forming, irradiating the surface of the substrate with a laser, and then forming a circuit on the surface of the substrate by a plating treatment to obtain a three-dimensional molded circuit component having the substrate and the circuit (hereinafter, also referred to as "this method 2"). Is.

According to this composition, since the inorganic filler having a relatively large size is contained, it is difficult for the inorganic filler to be separated from the substrate when the surface of the formed substrate is roughened, laser-irradiated or plated. In addition, when the catalyst is supported on the surface of the substrate after the roughening treatment to form plating, the inorganic filler existing near the surface of the substrate is appropriately etched during the roughening treatment, and the surface is uneven. Is formed, so that the catalyst is easily supported on the unevenness. When the inorganic filler is used as the starting point for forming the plating, the plating is directly formed on the inorganic filler existing on the surface of the substrate. It is considered that these factors cause the circuit (plating layer) formed by the plating process to be firmly fixed to the surface of the substrate via the inorganic filler.
Further, since the addition of the inorganic filler can impart low linear expansion property to the substrate, the difference in the linear expansion coefficient between the plating layer and the substrate becomes small, and from this viewpoint, high adhesion between the substrate and the circuit is also obtained. Is considered to have been obtained.
Further, since the substrate containing the F polymer and the inorganic filler is excellent in electrical characteristics, the transmission loss of the obtained three-dimensional molded circuit component can be sufficiently reduced. Further, an antenna having a high gain can be formed from such a three-dimensional molded circuit component.

The F polymer in the present invention is a heat-meltable polymer containing a unit (TFE unit) based on tetrafluoroethylene (TFE).
The melting temperature of the F polymer is preferably 260 to 320 ° C, more preferably 290 to 310 ° C.
The glass transition point of the F polymer is preferably 75 to 125 ° C, more preferably 80 to 100 ° C.

The F polymer is preferably a polymer containing a TFE unit and a unit based on perfluoro (alkyl vinyl ether) (PAVE) (PAVE unit) or a unit based on hexafluoropropylene (HFP) (HFP unit). In this case, since the F polymer forms spherulites having a small size, the surface smoothness of the substrate is improved and the adhesion to the circuit is likely to be improved. In addition, it is easy to suppress the modification of the F polymer in the heat treatment to a higher degree.
The F polymer may contain both PAVE units and HFP units, or may contain only one of them.
The PAVE is preferably CF ₂ = CFOCF ₃ , CF ₂ = CFOCF ₂ CF ₃ , CF ₂ = CFOCF ₂ CF ₂ CF ₃ (PPVE) or CF ₂ = CFOCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ CF _3. Is more preferable.

The F polymer preferably has a polar functional group. In this case, the adhesion between the obtained substrate and the circuit tends to be further enhanced while suppressing the modification of the F polymer in the heat treatment to a higher degree.
The polar functional group may be contained in a unit in the F polymer, or may be contained in the terminal group of the main chain of the polymer. Examples of the latter embodiment include an F polymer having a polar functional group as a terminal group derived from a polymerization initiator, a chain transfer agent, etc., and an F polymer having a polar functional group obtained by subjecting the F polymer to plasma treatment or ionization line treatment. Be done.

The polar functional group is preferably a hydroxyl group-containing group or a carbonyl group-containing group, and a carbonyl group-containing group is more preferable from the viewpoint of excellent adhesion to the circuit (metal layer).
The hydroxyl group-containing group is preferably a group containing an alcoholic hydroxyl group, and preferably -CF ₂ CH ₂ OH or -C (CF ₃ ) ₂ OH.
The carbonyl group-containing group is a group containing a carbonyl group (> C (O)), and is a carboxyl group, an alkoxycarbonyl group, an amide group, an isocyanate group, a carbamate group (-OC (O) NH ₂ ), and an acid anhydride residue. A group (-C (O) OC (O)-), an imide residue (-C (O) NHC (O)-etc.) or a carbonate group (-OC (O) O-) is preferred.
When the F polymer has a carbonyl group-containing group, the number of carbonyl group-containing groups in the F polymer is preferably 10 to 5000, more preferably 100 to 3000, and more preferably 800 per ^{1 × 10 6 carbon atoms in the main chain.} ~ 1500 pieces are more preferable. The number of carbonyl group-containing groups in the F polymer can be quantified by the composition of the polymer or the method described in International Publication No. 2020/145133.

As the F polymer, a tetrafluoroethylene polymer containing PAVE units and containing 1.5 to 5.0 mol% of PAVE units with respect to all units is preferable, and a polymer containing PAVE units and having a polar functional group (1). Or, a polymer (2) having no polar functional group, which contains PAVE units and contains 2.0 to 5.0 mol% of PAVE units with respect to all units, is more preferable. Not only are these F polymers excellent in handleability and blendability in their granules (pellets or powders), but they also tend to form microspherulites in the substrate formed from them, thereby enhancing the adhesion of the substrate to the circuit. ..

The polymer (1) has 90 to 98 mol% of TFE units, 1.5 to 9.97 mol% of PAVE units and 0.01 to 3 mol of units based on a monomer having a polar functional group with respect to all the units. %, It is preferable to contain each.
Further, the monomer having a polar functional group is maleic anhydride, itaconic anhydride, citraconic anhydride or 5-norbornen-2,3-dicarboxylic acid anhydride (also known as hymic anhydride; hereinafter, also referred to as “NAH”). Is preferable.
Specific examples of the polymer (1) include the polymers described in International Publication No. 2018/16644.

The polymer (2) consists of only TFE units and PAVE units, and contains 95.0 to 98.0 mol% of TFE units and 2.0 to 5.0 mol% of PAVE units with respect to all the units. preferable.
The content of PAVE units in the polymer (2) is preferably 2.1 mol% or more, more preferably 2.2 mol% or more, based on all the units.
The fact that the polymer (2) does not have polar functional groups means that the number of polar functional groups possessed by the polymer is less than 500 per ^{1 × 10 6 carbon atoms constituting the polymer main chain.} Means. The number of the polar functional groups is preferably 100 or less, more preferably less than 50. The lower limit of the number of polar functional groups is usually 0.

The polymer (2) may be produced by using a polymerization initiator, a chain transfer agent, or the like that does not generate a polar functional group as the terminal group of the polymer chain, and is derived from an F polymer having a polar functional group (derived from the polymerization initiator). An F polymer or the like having a polar functional group at the terminal group of the main chain of the polymer) may be fluorinated to produce the polymer. Examples of the fluorination treatment method include a method using fluorine gas (see JP-A-2019-194314, etc.).

The substrate in the present invention may be formed by either injection molding or press molding, and is preferably formed by injection molding. Since the F polymer in the present invention exhibits good thermal meltability and its melt viscosity converges within a predetermined range, it is likely to be filled and molded at high density in injection molding or press molding. As a result, bubbles (air layer) are less likely to be formed in the formed substrate, and deterioration of the physical properties (water resistance, etc.) of the substrate due to the presence of the bubbles is suppressed. In particular, injection molding is preferable in that a substrate having a finer and more complicated shape can be formed. Further, according to press molding, it is easy to form a sheet-shaped substrate.
The injection molding method includes a general injection molding method, a high-speed injection molding method, a multicolor molding method, a coin injection molding method, an injection compression molding method, a gas-assisted injection molding method, a foam injection molding method (MUCELL), and rapid molding. Examples thereof include a heat-and-cool molding method using a heating mold, an insert molding method, and an in-mold decoration molding method.

The melt viscosity of the F ^{polymer, 1 × 10 2 ~ 1 ×} 10 6 Pa · s is preferably at 380 ° C., and more preferably ^{^{1 × 10 2 ~ 1 × 10}} 6 Pa · s at 300 ° C.. In this case, it becomes easier to form a substrate by injection at a lower temperature.
The MFR of the F polymer is preferably 20 g / 10 minutes or less, and more preferably 10 g / 10 minutes or less. In this case, it becomes easy to form a substrate having a more complicated shape.
The melt viscosity of the present composition is preferably 50 to 1000 Pa · s, more preferably 75 to 750 Pa · s at a shear rate of 1000 / sec. In this case as well, it becomes easy to form a substrate having a more complicated shape.

The shape of the F polymer in the present composition is preferably granular, more preferably pelletized.
When used to form a substrate by injection molding, the shape of the F polymer in the present composition is preferably in the form of pellets having a maximum length of 3 to 5 mm. In this case, the injection moldability of the present composition is further improved, and it is easy to form a substrate highly filled with the F polymer.
When used for forming a substrate by press molding, the F polymer in the present composition is preferably granular, more preferably 0.1 to 10 μm for D10 and 0.3 to 50 μm for D50. preferable.

Examples of the inorganic filler in this composition include silica, titania, alumina, magnesia, zinc oxide, calcium oxide, iron oxide, tin oxide, antimony oxide, calcium carbonate, mica, diatomaceous earth, calcium hydroxide, magnesium hydroxide, and aluminum hydroxide. , Basic magnesium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, calcium sulfate, barium sulfate, calcium silicate, clay, talc, dosonite, hydrotalcite, montmorillonite, bentonite, active white clay, sepiolite, imogolite, sericite, glass fiber , Glass beads, silica balloons, carbon black, carbon nanotubes, carbon nanohorns, graphite, carbon fibers, glass balloons, carbon burns, zinc borate, boron nitride, inorganic fillers including copper oxide. As the inorganic filler, one kind may be used alone, or two or more kinds may be used in combination.

Among them, the inorganic filler is preferably an inorganic filler containing at least one selected from the group consisting of silica, talc, titania, alumina, tin oxide, organic palladium complex, copper oxide and boron nitride, preferably silica, copper oxide and tin oxide. And an inorganic filler containing boron nitride is more preferred. These inorganic fillers, particularly inorganic fillers containing silica or boron nitride, are preferable because they are easily etched by themselves by the roughening treatment and have a high ability to carry a catalyst.
In addition, it has a relatively wide bandgap (for example, 5.5 to 9 eV) because it promotes carbonization of the F polymer existing around the inorganic filler due to heat generation due to absorption of ultraviolet rays and easily forms irregularities on the surface of the substrate. Inorganic fillers are preferred. Preferable specific examples of such an inorganic filler include an inorganic filler containing silica or boron nitride.
When the inorganic filler is an inorganic filler containing silica or boron nitride, the content of silica or boron nitride in the inorganic filler is preferably 80% by mass or more, more preferably 90% by mass or more. The upper limit of the content is 100% by mass.

When the inorganic filler is an inorganic filler containing silica, the inorganic filler may be hollow silica having a cavity (air) inside. The three-dimensional molded circuit component formed from the composition containing such an inorganic filler tends to have a lower dielectric constant.
When the inorganic filler is an inorganic filler having a laser activating action (laser direct structuring additive; hereinafter, also referred to as "LDS additive"), the substrate formed from the present composition containing such an inorganic filler may be used. It is more suitable for manufacturing three-dimensional molded circuit parts by the LDS (laser direct structuring) method (hereinafter, also referred to as "LDS method").

The LDS method starts with an activated LDS additive by irradiating the substrate with a laser to roughen the substrate and activate an inorganic filler which is an LDS additive contained in the substrate. This is a method of forming a plating on a substrate to form a three-dimensional molded circuit component.
The LDS additive is preferably an inorganic filler containing copper oxide or tin oxide. The copper oxide is preferably copper spinel, and the tin oxide is preferably doped tin dioxide.
Since the substrate in the present invention contains a high proportion of F polymer having excellent electrical properties (dielectric constant, dielectric loss tangent, etc.) and heat resistance, the electrical properties are unlikely to deteriorate even when irradiated with a laser. Therefore, it is easy to form a three-dimensional molded circuit component having a low transmission loss from the substrate in the present invention.

The D50 of the inorganic filler is more than 0.1 μm, more preferably 0.2 μm or more, and further preferably 0.5 μm or more. The D50 of the inorganic filler is preferably 10 μm or less. In this case, the inorganic filler is dispersed densely and uniformly, and it is easy to obtain a substrate having excellent electrical characteristics and low linear expansion. Further, when the roughening treatment and the plating treatment are performed, the inorganic filler is less likely to be separated from the substrate.
The inorganic filler may be surface-treated with a surface-treating agent from the viewpoint of enhancing the dispersibility in the F polymer.
Examples of the surface treatment agent used for such surface treatment include polyhydric alcohols (trimethylolethane, pentaeristol, propylene glycol, etc.), saturated fatty acids (stearic acid, lauric acid, etc.), esters thereof, alkanolamines, amines (trimethylamine, etc.). Triethylamine etc.), paraffin wax, silane coupling agent, silicone, polysiloxane, aluminum, silicon, zirconium, tin, titanium, antimony and other oxides, their hydroxides, their hydrated oxides, their phosphoric acid Salt is mentioned.

Further, a silane coupling agent can also be used as the surface treatment agent.
Examples of the silane coupling agent include 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-. Examples thereof include isocyanate propyltriethoxysilane.
When the inorganic filler is surface-treated with a silane coupling agent (particularly, a silane coupling agent having a functional group), it is preferable because it is easy to mix uniformly with the F polymer and it is difficult for powder to fall off from the formed substrate.
Therefore, as the inorganic filler, silica surface-treated with a silane coupling agent is more suitable.

Examples of the shape of the inorganic filler include granular, needle-like (fibrous), and plate-like, and specifically, spherical, scaly, layered, leaf-like, apricot kernel-like, columnar, chicken crown-like, equiaxed, and leaf-like. , Mica-like, block-like, flat plate-like, wedge-like, rosette-like, mesh-like, and prismatic. Of these, spherical and scaly are preferable, and spherical is more preferable.
Specific examples of the inorganic filler include silica filler ("Admafine (registered trademark)" series manufactured by Admatex Co., Ltd.) and zinc oxide surface-treated with an ester such as propylene glycol dicaprate (manufactured by Sakai Chemical Industry Co., Ltd.). "FINEX (registered trademark)" series, etc.), spherical fused silica ("SFP (registered trademark)" series manufactured by Denka Co., Ltd., etc.), rutile-type titanium oxide coated with polyhydric alcohol and inorganic substances (manufactured by Ishihara Sangyo Co., Ltd.) "Typake (registered trademark)" series, etc.), rutile-type titanium oxide surface-treated with alkylsilane ("JMT (registered trademark)" series manufactured by Teika, etc.), hollow silica filler ("E" manufactured by Pacific Cement Co., Ltd.) -SPHERES "series, Nittetsu Mining Co., Ltd." Sirinax "series, Emerson & Cumming Co., Ltd." Ecocos Fire "series, Nippon Aerosil Co., Ltd. hydrophobic AEROSIL series" RX200 ", Tarkufiller (manufactured by Nippon Tarku Co., Ltd.) Examples include "SG" series) and steatite filler ("BST" series manufactured by Nippon Tarku Co., Ltd.).

The content of the tetrafluoroethylene polymer in the present composition is preferably more than 50% by mass, preferably more than 50% by mass and 95% by mass or less, and more preferably 55% by mass or more and 90% by mass or less. .. In this case, the moldability (particularly, injection moldability) of the present composition becomes better.
Further, the content of the inorganic filler in the present composition is preferably 5% by mass or more and less than 50% by mass. In this case, the above effect due to the inclusion of the inorganic filler is further improved. When the inorganic filler is silica, the content thereof is preferably 30% by mass or more and less than 50% by mass. When the inorganic filler is a compound other than silica (particularly boron nitride), the content thereof is preferably 5% by mass or more and 30% by mass or less. In this case, in addition to the above effects, the surface of the obtained substrate is less likely to be roughened (missing filler, cracks, etc.).

The composition may further contain a polymer different from the F polymer. Examples of the different polymers include aromatic polyesters, polyamideimides, polyimides, polyphenylene ethers, polyphenylene oxides and maleimides, with thermoplastic aromatic polyimides being preferred.
Further, as the polymer different from the F polymer, a non-heat-meltable tetrafluoroethylene-based polymer is preferable, and a non-heat-meltable polytetrafluoroethylene (PTFE) is more preferable. When such PTFE is contained, the inorganic filler is entangled with the PTFE due to its fibril property, so that it is more difficult for the inorganic filler to fall off from the formed substrate, which is preferable. In this case, the content of the non-heat-meltable PTFE in the present composition is preferably 1 to 60% by mass, more preferably 10 to 40% by mass. When the present composition contains non-heat-meltable PTFE, the total content of F polymer and non-heat-meltable PTFE in the present composition is more than 50% by mass, which is non-heat-meltable with respect to the content of F polymer. The mass ratio of the PTFE content is preferably 0.1 to 2.0, more preferably 0.5 to 1.5.
In addition, this composition contains a dehydrating agent, a plasticizer, a weather resistant agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, a whitening agent, a coloring agent, and a conductive agent, as long as the effects of the present invention are not impaired. It may contain a mold release agent and a flame retardant.

The present composition may be produced by dry blending each component, or may be melt-kneaded to produce pellets.
Specifically, the pellets are prepared by mixing each component in advance using various mixers such as a tumbler and a Henschel mixer, and then using a Banbury mixer, a roll, a brabender, a single-screw kneading extruder, a twin-screw kneading extruder, and a kneader. It can be manufactured by melt-kneading using or the like.
In addition, pellets can be produced without premixing each component or by premixing only some of the components and supplying the pellets to an extruder using a feeder for melt-kneading.
Further, in the pellet, even if some components are mixed in advance and supplied to an extruder to be melt-kneaded, the kneaded product is used as a masterbatch, and the masterbatch and the remaining components are mixed and melt-kneaded. Can be manufactured.

In this method, it is preferable to process the composition into a substrate by injection molding or press molding. The shape of the substrate may be a sheet shape or a three-dimensional shape having a complicated shape. By the above-mentioned mechanism of action, it is possible to form a substrate from the present composition in which the inorganic filler is less likely to be removed even if the shape is complicated.
In this method 1, it is preferable to perform a roughening treatment on the surface of the formed substrate. As a result, the surface of the substrate is etched to form minute irregularities. As a result, the catalyst is easily supported on the surface of the substrate, and the adhesion of the formed circuit to the substrate is improved.
In particular, it is advisable to perform the roughening treatment to the extent that a part of the inorganic filler is exposed from the surface of the substrate. In this case, the surface of the inorganic filler is also etched, and minute irregularities are formed on the surface as well. As a result, a larger amount of catalyst is supported on the surface of the inorganic filler. Since the circuit comes into contact with the exposed inorganic filler, the anchor effect of the inorganic filler is exhibited, and the circuit is more reliably prevented from peeling from the substrate.

The roughening treatment may be carried out by any treatment such as physical treatment or chemical treatment. Above all, the roughening treatment is preferably carried out by irradiating the surface of the substrate with ultraviolet rays or by applying a solvent to the surface of the substrate. According to these methods, it is relatively easy to form irregularities on the surface of the substrate.
It is preferable to form a mask having an opening corresponding to the region to be roughened on the surface of the substrate and roughen the surface through the mask. In this case, a circuit with a clear outline can be formed.

When irradiating with ultraviolet rays, a low-pressure mercury lamp, a high-pressure mercury lamp, and an excimer lamp can be used as the light source. The illuminance of ultraviolet rays is preferably 5 to 150 mW / cm ^{2 at a wavelength of 254 nm.} The irradiation time of ultraviolet rays is preferably 0.1 to 50 minutes, more preferably 0.2 to 40 minutes, and even more preferably 0.3 to 30 minutes. Irradiation with ultraviolet rays under such conditions further improves the adhesion between the circuit and the substrate.
On the other hand, ozone water and an acid solution (chromic acid anhydride solution, hydrofluoric acid solution, etc.) can be used as the solvent.
Prior to the roughening treatment, the surface of the substrate may be degreased by treatment with a surfactant.

After the roughening treatment, the first surface adjustment may be performed by immersing the substrate in the first treatment liquid for the purpose of cleaning the surface of the substrate and / or imparting wettability to the surface.
As the first treatment liquid, a CP conditioner (manufactured by Kizai Co., Ltd.) can be mentioned. When this CP conditioner is used, the treatment conditions are preferably a temperature of 30 to 60 ° C. and a soaking time of 1 to 5 minutes. If the treatment is carried out under such conditions, the plating layer is evenly deposited, and the adhesion of the circuit to the substrate is further improved.

After the roughening treatment, the second surface adjustment may be performed by immersing the substrate in the second treatment liquid for the purpose of facilitating the precipitation of the catalyst on the surface of the substrate. When the first surface adjustment is performed, it is preferable that the second roughening treatment is performed after the first surface preparation.
As the treatment agent contained in the second treatment liquid, a compound capable of adsorbing (binding) to both a functional group exposed on the surface of the substrate etched by irradiation with ultraviolet rays and a catalyst is preferable. As such a compound, polyvalent amine is preferable, specifically, ethyleneamine, polyethyleneimine, polyethyleneamine or polyallylamine is more preferable, and polyethyleneimine or polyallylamine is further preferable. In this case, it is easy to improve the adhesion between the circuit and the substrate.

When polyallylamine is used as the treatment agent, the concentration in the second treatment liquid is preferably 0.01 to 10 g / L, more preferably 0.1 to 1 g / L.
The temperature of the second treatment liquid is preferably 30 to 60 ° C, more preferably 35 to 50 ° C.
The treatment time is preferably 1 to 10 minutes, more preferably 1 to 5 minutes.
If the surface of the substrate is treated under these conditions, a plating layer having less unevenness and higher adhesion can be realized.

Then, in the present method 1, a catalyst is applied to the surface of the substrate. As a result, a circuit (plating layer) can be formed on the surface of the substrate, starting from the catalyst applied (supported) on the surface of the substrate.
Examples of the catalyst include metal fine particles such as palladium (Pd), nickel (Ni), platinum (Pt), and copper (Cu), metal complexes, and metal alkoxides, and compounds containing palladium having high catalytic activity are preferable.
Examples of the method of applying the catalyst to the surface of the substrate include a method of applying a catalyst solution in which the catalyst is dissolved or dispersed in a solvent to the surface of the substrate, and a method of immersing the substrate in the catalyst solution. From the viewpoint of productivity, a method of immersing the substrate in the catalyst solution is preferable.

Examples of the solvent used for the catalyst solution include water, alcohol (methanol, ethanol, propyl alcohol, isopropyl alcohol, butanol, etc.) and hydrocarbons (hexane, heptane, etc.).
The catalyst used in the catalyst solution is preferably a palladium complex because of its high catalytic activity. Specific examples of the palladium complex include sodium tetrachloropalladium acid, potassium tetrachloropalladium acid, palladium acetate, palladium chloride, acetylacetonatopalladium (II), and hexafluoroacetylacetonatopalladium (II).
The content of the catalyst in the catalyst solution is preferably 0.01 to 5% by mass.
The treatment temperature is preferably 30 to 60 ° C., and the treatment (immersion) time is preferably 1 to 5 minutes.

Other methods of applying the catalyst to the surface of the substrate include a sensitizer-activator method or a catalyzer-accelerator method.
In the sensitizer-activator method, for example, the surface of the substrate is treated with a solution containing ^{Sn 2+} (sensitizer treatment) so that the catalyst can be easily supported, and the substrate is immersed in a solution containing the ^{catalyst (for example, Pd 2+).} (Activator processing).
In the catalyzer-accelerator method, a substrate is immersed in a solution containing a catalyst (for example, ^{a palladium colloidal solution obtained by mixing Sn 2+} and Pd ²⁺ ) (catalyzer treatment), and the substrate is immersed in a hydrochloric acid solution or the like to provide a catalyst (catalyst). Metal) is deposited on the surface of the substrate (accelerator treatment).

Then, if necessary, the catalyst supported on the surface of the substrate is activated.
When activating the catalyst, the substrate is treated with a solution containing a reducing agent. As the reducing agent, hydrogen, sodium hypophosphite, sodium borohydride are preferable, and sodium hypophosphite is more preferable. The content of the reducing agent in the solution is preferably 0.01 to 10% by mass.
The solution is preferably an aqueous solution.
The treatment temperature is preferably 30 to 60 ° C., and the treatment (immersion) time is preferably 1 to 5 minutes.

After that, in the present method 1, a plating layer (metal layer) is deposited on the surface of the substrate by a plating treatment to form a circuit.
As the plating treatment, it is preferable to perform an electroless plating treatment. For the electroless plating treatment, copper plating, nickel plating, palladium plating, silver plating, gold plating, or alloy plating thereof can be used, which are selected according to the purpose.
In the plating treatment, an electrolytic plating treatment may be further performed. The electrolytic plating treatment is performed using the electroless plating layer formed by the electroless plating treatment as an electrode. The electrolytic plating process is performed for the purpose of adjusting the thickness (electrical resistance value) of the circuit, imparting corrosion resistance to the circuit, and the like.
Further, a plating layer of tin, gold, silver or the like may be formed on the outermost surface of the circuit in order to improve the solder wettability of the circuit so as to cope with the solder reflow.
Through the above steps, a three-dimensional molded circuit component having a substrate and a circuit can be obtained.

In the present method 2, a three-dimensional molded circuit component is obtained from a substrate formed by using the present composition by the LDS method. In this case, the LDS additive may be contained as an inorganic filler in the present composition, or may be contained as a component different from the inorganic filler. Further, it may be an inorganic filler coated with an LDS additive.
When the LDS additive is contained in the inorganic filler, the plating is formed starting from the inorganic filler, so that the plating is easily firmly fixed to the substrate.
Examples of the LDS additive include an organopalladium complex, copper spinel, and antimony-doped tin dioxide.
The content of the LDS additive in the present composition is preferably 0.1 to 30% by mass, more preferably 0.5 to 15% by mass, still more preferably 1 to 10% by mass, based on the F polymer.
As the plating treatment in the LDS method, an electroless plating treatment is preferable.

The three-dimensional molded circuit component of the present invention (hereinafter, also referred to as “the present component”) contains an F polymer and an inorganic filler having an average particle diameter of more than 0.1 μm, and the content of the F polymer is more than 50% by mass. It has a substrate which is, and a circuit provided on the surface of the substrate.
The thickness of the circuit (wiring constituting the circuit) is preferably 0.5 to 30 μm, more preferably 2 to 10 μm. In this case, the electric resistance value of the circuit can be sufficiently reduced.

Further, it is preferable that a part of the inorganic filler is exposed from the surface of the substrate and the circuit is in contact with the exposed inorganic filler. In this case, the anchor effect of the inorganic filler more reliably prevents the circuit from peeling from the substrate.
The definitions and scope of F-polymers and inorganic fillers in this component are similar to those in this composition, including preferred embodiments. In addition, the configuration and scope of the circuit in this component are the same as those in this method, including preferred embodiments.
The parts are preferably parts manufactured by this method.
An antenna with high gain can be formed from this component.

Applications of this component include electrical equipment and electronic equipment (personal computers, wearable terminals, medical devices, various sensors, displays, OA equipment, mobile phones, mobile information terminals, facsimiles, video cameras, digital cameras, optical equipment, audio, etc. Air conditioners, lighting equipment, entertainment products, toy products, other home appliances, etc.), circuit parts such as automobiles, aircraft, railways, drones, antennas, sensors, connectors, semiconductor packages, etc.
According to this component, space saving and weight reduction can be realized by reducing the amount of circuit boards and wire harnesses used in electrical equipment, electronic equipment, automobiles, aircraft, railways, drones and the like.

Although the composition of the present invention, the method for manufacturing the three-dimensional molded circuit component, the three-dimensional molded circuit component, and the antenna have been described above, the present invention is not limited to the configuration of the above-described embodiment.
For example, the composition, the three-dimensional molded circuit component, and the antenna of the present invention may be added to any other configuration in the configuration of the above embodiment, or may be replaced with any configuration that exhibits the same function. You may be.
Further, the method for manufacturing a three-dimensional molded circuit component of the present invention may additionally have any other step in the configuration of the above embodiment, or may be replaced with any step that produces the same action. ..

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to the following description.
1. 1. Preparation of each component [F polymer]
F polymer 1: A PFA polymer containing 98.0 mol%, 0.1 mol% and 1.9 mol% of TFE units, NAH units and PPVE units in this order and having a polar functional group (melting temperature: 300 ° C., Content of polar functional group: 1000 per ^{6 carbon atoms in the main chain)}
F polymer 2: A PFA polymer containing 97.5 mol% and 2.5 mol% of TFE units and PPVE units in this order and having no polar functional group (melting temperature: 305 ° C.).
F Polymer 3: Non-heat-meltable PTFE

[pellet]
Pellet 1: Pellet made of F polymer 1 with a maximum length of 3.5 mm Pellet 2: Pellet made of F polymer 2 with a maximum length of 3.5 mm Pellet 3: Made of liquid crystal polyester 1 with a maximum length of 3 .5 mm pellet Pellet 4: Pellet with a maximum length of 3.5 mm made of F polymer 3 [Liquid crystal polyester]
Liquid crystal polyester 1: Units derived from p-hydroxybenzoic acid, units derived from 4,4'-dihydroxybiphenyl, ethylenedioxy units derived from polyethylene terephthalate, units derived from terephthalic acid, 66.7 mol%, 6. Liquid crystal polyester containing 3 mol%, 10.4 mol%, 16.7 mol% (melting temperature: 313 ° C)

[Inorganic filler]
Inorganic filler 1: Silane particles with D50 of 2 μm Inorganic filler 2: Boron nitride particles with D50 of 4 μm Inorganic filler 3: Boron nitride particles with D50 of 20 μm Inorganic filler 4: Silane particles with D50 of 0.1 μm Inorganic filler 5: D50 1 μm hollow silica particles Inorganic filler 6: Silica particles with D50 of 2 μm LDS additive 1: Copper spinel particles containing copper chromium oxide The inorganic filler 1 is a silane coupling agent (3-aminopropyltriethoxysilane). The surface is treated, and the inorganic filler 6 is not surface-treated with a silane coupling agent.

2. 2. Preparation of composition [Example 1]
60 parts by mass of pellet 1 and 40 parts by mass of inorganic filler 1 were dry-blended to obtain composition 1.
[Example 2]
90 parts by mass of pellet 1 and 10 parts by mass of inorganic filler 2 were dry-blended to obtain composition 2.

[Example 3]
90 parts by mass of the pellet 2 and 10 parts by mass of the inorganic filler 3 were dry-blended to obtain the composition 3.
[Example 4]
60 parts by mass of pellet 1 and 40 parts by mass of inorganic filler 4 were dry-blended to obtain composition 4.
[Example 5]
100 parts by mass of pellet 1 was used as the composition 5.

3. 3. Manufacture of three-dimensional molded circuit parts First, each composition 1 to 5 was press-molded with a melt heat press machine (manufactured by Tester Sangyo Co., Ltd.) to obtain sheets 1 to 5 (thickness: 2.8 mm) as a substrate.
Next, the surface of the sheet was roughened by irradiating the surface of the sheet with ultraviolet rays for 3 minutes at an irradiation distance of 50 cm using KOV1-30H (manufactured by Koto Electric Co., Ltd.).
Next, the mixture was immersed in an aqueous solution prepared by dissolving palladium chloride at 0.5 g / L, stannous chloride at 50 g / L and 35% hydrochloric acid at 500 mL / L at 30 ° C. for 6 minutes, and then immersed in 20% sulfuric acid for 30 minutes. After soaking at ° C. for 3 minutes, it was washed with water.

Then, the sheet to which the catalyst was applied was immersed in an electroless nickel plating solution at 85 ° C. (“TMP Chemical Nickel HR-T” manufactured by Okuno Pharmaceutical Co., Ltd.) for 15 minutes to precipitate an electroless nickel plating layer.
Further, an electrolytic copper plating layer was deposited on the surface of the electroless nickel plating layer by a general-purpose method to form a circuit.
Through the above steps, three-dimensional molded circuit parts 1 to 5 were obtained.

4. Evaluation 4-1. Plating adhesion A commercially available cellophane tape was attached to the circuits of the three-dimensional molded circuit parts 1 to 5 obtained, and the cells were rubbed well with a finger from above to bring them into close contact with the surfaces of the three-dimensional molded circuit parts 1 to 5.
Then, one end of the cellophane tape was picked up with a finger and peeled off from the sheet at once.
After that, the peeling condition of the circuit from the sheet was visually confirmed, and the plating adhesion was evaluated according to the following criteria.
[Evaluation criteria]
○: No peeling △: Partially peeled ×: Significant peeling

4-2. Heat cycle test Each of the obtained three-dimensional molded circuit parts 1 to 5 was held at −40 ° C. for 20 minutes, then heated to 200 ° C. over 60 minutes, held at 200 ° C. for 30 minutes, and then over 60 minutes. The temperature was lowered to −40 ° C. and kept at −40 ° C. for 20 minutes, and the temperature cycle was set as one cycle, and 10 cycles were repeated.
After 10 cycles, the peeling condition of the circuit from the sheet was visually confirmed, and the resistance to the heat cycle test was evaluated according to the following criteria.
[Evaluation criteria]
◯: No peeling Δ: Partially peeled ×: Significant peeling These results are also shown in Table 1 below.

Similarly, the three-dimensional molded circuit component obtained by subjecting the upper bottom surface and the hypotenuse surface of the trapezoidal substrate, which is the injection molded product of the composition 1, to the treatment of "3." Excellent resistance to testing.

5. Preparation of composition [Example 6]
58 parts by mass of pellet 1, 38 parts by mass of inorganic filler 1 and 4 parts by mass of LDS additive 1 were dry-blended to obtain composition 6.
[Example 7]
58 parts by mass of pellet 1, 38 parts by mass of inorganic filler 5 and 4 parts by mass of LDS additive 1 were dry-blended to obtain composition 7.
[Example 8]
58 parts by mass of pellet 3 and 38 parts by mass of inorganic filler 1 and 4 parts by mass of LDS additive 1 were dry-blended to obtain composition 8.

6. Manufacture of Three-dimensional Molded Circuit Parts First, each composition 6 to 8 was press-molded with a melt heat press machine (manufactured by Tester Sangyo Co., Ltd.) to obtain sheets 6 to 8 (thickness: 0.2 mm) as a substrate. The surface of the obtained molded product was irradiated with a laser using a Panasonic LP-V10U FAYb laser device under the conditions of a wavelength of 1064 nm, a frequency of 50 Hz, a laser output of 5.0 W, and a scanning speed of 3000 mm / s. The molded product was subjected to an electroless copper plating treatment having a thickness of 12 μm.
Through the above steps, three-dimensional molded circuit parts 6 to 8 were obtained.

7. Evaluation 7-1. Dielectric constant The dielectric constant (measurement frequency: 10 GHz) of the obtained sheets 6 to 8 was measured by the SPDR (split post dielectric resonance) method.
7-2. Plating Adhesion The plating adhesion of the circuits of the obtained three-dimensional molded circuit components 6 to 8 was evaluated in the same manner as in 4-1.

7-3. Antenna gain A patch antenna gain simulation was performed on the obtained three-dimensional molded circuit components 6 to 8. The substrate size was a 6.4 mm (= 0.6λ0) square, and the thickness was 0.2 mm. The size of the patch antenna was designed according to the dielectric constant, and the three-dimensional molded circuit components 6 to 8 were made into squares having a side of 3.0 mm, 3.3 mm, and 2.6 mm in this order, respectively. The gain of the antenna at a wavelength of 28 GHz was evaluated according to the following criteria.
[Evaluation criteria]
〇: 6.5 dBi or more ×: less than 6.5 dBi

8. Preparation of composition [Example 9]
60 parts by mass of pellet 1 and 40 parts by mass of inorganic filler 6 were dry-blended to obtain composition 9.
[Example 10]
30 parts by mass of pellet 1, 30 parts by mass of pellet 4 and 40 parts by mass of inorganic filler 1 were dry-blended to obtain a composition 10.

9. Manufacture of Three-dimensional Circuit Parts Three-dimensional molded circuit parts 9 and 10 were obtained in the same manner as the three-dimensional molded circuit parts 1 except that the composition 1 was changed to the composition 9 and the composition 10.
10. Evaluation As a result of evaluating the plating adhesion and resistance by the heat cycle test of the three-dimensional molded circuit parts 9 and 10 by the methods described in 4-1 and 4-2, the results of the three-dimensional molded circuit parts 9 are "○" in order. The results of "Δ" and the three-dimensional molded circuit component 10 were "○" and "○" in order. Compared to the three-dimensional molding circuit component 1, the three-dimensional molding circuit component 10 was further suppressed from powder dropping of the inorganic filler at its end portion and curved surface portion.

The composition and the three-dimensional molded circuit component of the present invention include electrical equipment and electronic equipment (personal computer, wearable terminal, medical device, various sensors, displays, OA equipment, mobile phone, mobile information terminal, facsimile, video camera, digital camera, etc. It is useful in applications such as optical equipment, audio, air conditioners, lighting equipment, entertainment equipment, toy equipment, and other home appliances), circuit parts such as automobiles, aircraft, railways, and drones, antennas, sensors, connectors, and semiconductor packages.

Claims

A composition used to form a substrate for a three-dimensional molded circuit component, which comprises a heat-meltable tetrafluoroethylene-based polymer and an inorganic filler having an average particle size of more than 0.1 μm, and is a tetrafluoroethylene-based polymer. A composition having a polymer content of more than 50% by weight.
The composition according to claim 1, wherein the tetrafluoroethylene-based polymer is a tetrafluoroethylene-based polymer having a polar functional group.
The composition according to claim 1 or 2, wherein the inorganic filler is an inorganic filler surface-treated with a silane coupling agent.
The composition according to any one of claims 1 to 3, wherein the average particle size of the inorganic filler is 0.5 to 20 μm.
The composition according to any one of claims 1 to 4, wherein the content of the inorganic filler is 5% by mass or more and less than 50% by mass.
Any of claims 1 to 5, wherein the inorganic filler is an inorganic filler containing at least one selected from the group consisting of silica, talc, titania, alumina, tin oxide, an organic palladium complex, copper oxide and boron nitride. The composition according to item 1.
The composition according to any one of claims 1 to 6, further comprising non-heat-meltable polytetrafluoroethylene.
A substrate is formed using the composition according to any one of claims 1 to 7, a roughening treatment is performed on the surface of the substrate, a catalyst is applied, and a circuit is applied to the surface of the substrate by a plating treatment. A method for manufacturing a three-dimensional molded circuit component, which comprises forming the substrate and the circuit to obtain a three-dimensional molded circuit component.
The production method according to claim 8, wherein a part of the inorganic filler is exposed from the surface of the substrate after the roughening treatment, and a part of the catalyst is supported on the exposed inorganic filler.
The production method according to claim 8 or 9, wherein the roughening treatment is performed by irradiating the surface of the substrate with ultraviolet rays or applying a solvent to the surface of the substrate.
A substrate is formed using the composition according to any one of claims 1 to 7, the surface of the substrate is irradiated with a laser, and then a circuit is formed on the surface of the substrate by a plating treatment to form a circuit with the substrate. A method for manufacturing a three-dimensional molded circuit component, which obtains a three-dimensional molded circuit component having the circuit.
The production method according to claim 11, wherein the inorganic filler is an inorganic filler containing copper oxide or tin oxide.
On a substrate containing a heat-meltable tetrafluoroethylene polymer and an inorganic filler having an average particle size of more than 0.1 μm and having a tetrafluoroethylene polymer content of more than 50% by mass, and on the surface of the substrate. A three-dimensional molded circuit component having a provided circuit.
The three-dimensional molded circuit component according to claim 13, wherein a part of the inorganic filler is exposed from the surface of the substrate and the circuit is in contact with the exposed inorganic filler.
An antenna provided with the three-dimensional molded circuit component according to claim 13 or 14.