Resin composition

Abstract

To provide a resin composition exhibiting superior dispersibility of an additive.SOLUTION: A resin composition contains copper chromium oxide particles and a resin. In a volume-based particle size distribution determined by laser diffraction / scattering for the copper chromium oxide particles, when particle sizes corresponding to cumulative frequencies of 10%, 50%, and 90% from the small particle side are defined as D10, D50, and D90, the spread of the particle size distribution, SPAN=(D90-D10) / D50, is 2.00 or less.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin composition.

Background Art

[0002] In recent years, in the fields of electronics and mechatronics, miniaturization, weight reduction, and multifunctionalization of devices have been progressing. Particularly in the automotive field, connection, service, and automation are advancing, sensors and modules are increasing, while weight reduction of vehicles is required for electrification, and strong demands are placed on the lightweight miniaturization of mechanical parts and electric circuit parts. As a technology capable of meeting this demand, technologies related to Molded Interconnect Devices (MID) have attracted attention. MID is a technology for forming circuits, electrodes, etc. on resin molded products, and by integrating the circuits, electrodes, etc. with the resin molded products, miniaturization and weight reduction of parts can be achieved.

[0003] For MID, there are a one-shot molding method in which the surface of a resin molded product is roughened and then plated, a two-shot molding method in which a resin for circuit formation and a resin for insulating part formation are separately molded twice and then integrated, a hot stamping method in which a circuit or the like is directly formed on a resin molded product using a stamping die, and the like.

[0004] Among these, the Laser Direct Structuring (LDS) technology, which is one of the one-shot molding methods, has attracted particular attention from the viewpoints of reducing manufacturing costs and being able to fabricate ultra-fine circuits in a short period. The LDS technology is a technology in which a predetermined additive is kneaded into a resin, and when a laser is irradiated on the injection-molded resin molded product, the irradiated part of the laser is surface-roughened, and further, the additive is activated, so that a strong plating layer is formed on the laser-irradiated part.

[0005] Currently, research on additives applicable to the LDS technology is underway. As additives, for example, spinel-type metal oxides are used (Patent Documents 1 and 2). In particular, spinel-type metal oxides containing copper are utilized from the viewpoint of adhesion to copper plating patterns.

[0006] Patent Document 1 discloses a conductor track structure containing a high oxide that is thermally highly stable, durable in an acidic or alkaline aqueous metallization bath, and has a spinel structure or is a simple d-metal oxide or a mixture thereof, or a mixed metal oxide similar to the spinel structure.

[0007] Patent Document 2 discloses a thermosetting resin composition for LDS containing a non-conductive metal compound that forms metal nuclei upon irradiation with active energy rays, wherein the non-conductive metal compound is selected from the group consisting of a spinel-type metal oxide, a metal oxide having two or more adjacent transition metal elements selected from Groups 3 to 12 of the periodic table, and a tin-containing oxide.

[0008] Patent Document 3 discloses a thermoplastic composition with improved plating performance, wherein the composition contains a metal compound in an amount of 1 wt% based on the weight of the crude composition, and the metal compound is represented by AB 2 O 4 as shown.

Prior Art Documents

Patent Documents

[0009]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0010] However, in the technologies described in Patent Documents 1 to 3 above, although commercially available metal oxides are used as additives, sufficient studies have not been conducted on the metal oxides. For example, when a resin composition in which metal oxides are not uniformly dispersed is subjected to LDS, there are problems such as poor adhesion of plating and unevenness in the plating treatment. Therefore, the development of additives with excellent dispersibility is required.

[0011] Therefore, an object of the present invention is to provide a resin composition having excellent dispersibility of additives.

Means for Solving the Problems

[0012] The present inventors have found that by using copper chromite particles as an additive and controlling the particle size distribution of the copper chromite particles, the dispersibility of the copper chromite particles in the resin composition can be enhanced, and thus the present invention has been completed.

[0013] That is, the present invention relates to the following. [1] A resin composition containing copper chromite particles and a resin, In the volume-converted particle size distribution of the copper chromite particles obtained by the laser diffraction scattering method, when the particle diameters at which the cumulative frequencies from the small particle size side are 10%, 50%, and 90% are D10, D50, and D90, respectively, the spread of the particle size distribution SPAN = (D90 - D10) / D50 is 2.00 or less.

Effects of the Invention

[0014] According to the present invention, a resin composition having excellent dispersibility of copper chromite particles can be provided.

Brief Description of the Drawings

[0015]

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Mode for Carrying Out the Invention

[0016] Hereinafter, embodiments of the present invention will be described in detail. In this specification, "mass" is synonymous with "weight". Also, in this specification, the symbol "~" indicating a numerical range is used to mean including the numerical values described before and after it as the lower limit value and the upper limit value, unless otherwise specified.

[0017] <Resin composition> The resin composition of this embodiment is characterized by containing copper chromite particles and a resin.

[0018] (Copper chromite particles) The copper chromite particles constituting the resin composition of this embodiment are characterized in that the spread of the particle size distribution calculated by the laser diffraction / scattering method is 2.00 or less. Since the spread of the particle size distribution of the copper chromite particles is 2.00 or less, the dispersibility of the copper chromite particles in the resin composition is excellent, so the plating adsorption characteristics when formed into a molded circuit component are improved. The spread of the particle size distribution is more preferably 1.90 or less, further preferably 1.70 or less, and particularly preferably 1.50 or less.

[0019] In this specification, the spread of the particle size distribution calculated by the laser diffraction / scattering method is calculated using the following conversion formula. Spread of particle size distribution: SPAN = (D90 - D10) / D50 In the above formula, D10, D50, and D90 respectively mean the particle diameters at which the cumulative frequency from the small particle size side is 10%, 50%, and 90% in the volume-converted particle size distribution obtained by the laser diffraction / scattering method.

[0020] In this embodiment, the median diameter (D50) of the copper chromite particles calculated by the laser diffraction / scattering method is preferably 2.0 μm or less, more preferably 0.2 to 2.0 μm, and further preferably 1.0 to 2.0 μm. When the D50 of the copper chromite particles is within the above range, the plating adsorption performance is improved.

[0021] In this embodiment, the volume-based cumulative 90% particle size (D90) of the copper chromite particles calculated by the laser diffraction / scattering method is preferably 10 μm or less, more preferably 1.0 to 9.0 μm, still more preferably 2.0 to 8.0 μm, and particularly preferably 2.5 to 4.0 μm. When the D90 of the copper chromite particles is within the above range, when the resin composition of this embodiment is cured to obtain a molded product, the unevenness on the surface of the molded product due to coarse particles is reduced, and the plating adsorption performance is improved.

[0022] In this embodiment, the average particle size of the copper chromite particles is preferably in the range of 0.1 to 10 μm, more preferably 0.1 to 2 μm, and still more preferably 0.1 to 1 μm. When the average particle size of the copper chromite particles is within the above range, the plating adsorption performance when the resin composition of this embodiment is subjected to LDS is improved.

[0023] In this specification, the "particle size" of the copper chromite particles is the shortest diameter (the shortest diameter: the shortest distance when each particle is sandwiched between two parallel line segments on the observation field of view or its image) and the longest diameter (the longest diameter: the longest distance when each particle is sandwiched between two parallel line segments on the observation field of view or its image) discriminated from the particle image of the primary particles of the copper chromite particles in the two-dimensional image taken by a scanning electron microscope (SEM), and is obtained by calculating the ratio (shortest diameter / longest diameter) respectively. The value of the "average particle size" of the copper chromite particles is the average value obtained from 50 or more copper chromite particles randomly selected from the particles having the above-mentioned self-shaped measurement objects.

[0024] In this embodiment, the specific surface area of the copper chromite particles is preferably 0.01 to 10 m 2 / g, more preferably 1 to 10 m 2 / g, and still more preferably 3.5 to 10 m 2 / g. When the specific surface area of the copper chromite particles is within the above range, the number of active sites increases, and the catalytic performance and plating adsorption performance are improved.

[0025] The specific surface area is measured using a specific surface area analyzer (for example, BELSORP-mini manufactured by MicrotracBEL Corp.), and the surface area per 1 g of the sample measured from the nitrogen gas adsorption amount by the BET method (Brunauer-Emmett-Teller method) is defined as the specific surface area (m 2 / g).

[0026] The particle diameter of the copper chromite particles can be adjusted, for example, by controlling the amount and type of raw materials, the firing temperature, etc. during the production of the copper chromite particles.

[0027] In the present embodiment, the particle shape of the copper chromite particles is not particularly limited, but preferably has a polygonal shape. In particular, a rectangular parallelepiped shape, a cubic shape, a polyhedral shape, a triangular pyramid shape, or a quadrangular pyramid shape is more preferable, a rectangular parallelepiped shape, a cubic shape, or a polyhedral shape is even more preferable, a polyhedral shape is even more preferable, and an octahedral shape is particularly preferable. When the shape of the copper chromite particles is the above shape, it has a high crystallinity with a single crystal structure. Since the copper chromite particles have high crystallinity, the absorption rate of the laser used when roughening the surface of the cured product of the resin composition is improved, and the surface roughening easily progresses, so that a resin composition excellent in plating deposition properties and plating adhesion can be obtained.

[0028] When the copper chromite particles include copper chromite particles having an octahedral shape, preferably 50% or more of the particles have an octahedral shape based on mass or number, more preferably 80% or more of the particles have an octahedral shape, and even more preferably 90% or more of the particles have an octahedral shape. The upper limit of the ratio of the copper chromite particles having an octahedral shape is not particularly limited, and is, for example, 100%. The shape of the copper chromite particles can be confirmed by SEM observation. Also, the proportion of the copper chromite particles having an octahedral shape can be specified by performing SEM observation and visually counting them.

[0029] Whether the copper chromite particles are highly crystalline can be determined by measurement using SmartLab (manufactured by Rigaku Corporation), an X-ray diffractometer, with a high-intensity and high-resolution crystal analyzer (CALSA) as the detector and PDXL as the analysis software. The 2θ / θ method is used for the measurement method, and a calculation method using the Scherrer equation from the half-value width of the peak can be applied for the analysis.

[0030] The particle shape of the copper chromite particles can be controlled, for example, by adjusting the firing conditions such as the firing temperature and the heating rate during the production of the copper chromite particles, or by adding a sodium compound or a potassium compound as a raw material.

[0031] In the present embodiment, the copper chromite particles refer to those containing copper chromite (CuCr 2 O 4 ).

[0032] In the present embodiment, the copper chromite particles preferably contain 90 to 99.9% by mass of CuCr 2 O 4 with respect to 100% by mass of the copper chromite particles, more preferably contain 95 to 99.9% by mass, and even more preferably contain 98 to 99.9% by mass. With respect to 100% by mass of the copper chromite particles, the content of CuCr 2 O 4 can be measured by a fluorescent X-ray analyzer.

[0033] Also, in the present embodiment, the content of copper contained in the copper chromite particles is the content ratio (Cu 1 ) in terms of CuO conversion with respect to 100% by mass of the copper chromite particles, preferably 25.0% by mass or more, more preferably 30.0 to 40.0% by mass, and even more preferably 32.0 to 35.0% by mass.

[0034] In the present embodiment, the "content ratio (Cu 1The term ")" refers to a value obtained by converting the copper content determined by XRF analysis of copper chromite particles using a calibration curve in terms of CuO to the amount of CuO. For the above XRF analysis, a fluorescent X-ray analyzer (for example, Primus IV manufactured by Rigaku Corporation) can be used.

[0035] In addition, in the present embodiment, it is preferable that the copper contained in the copper chromite particles is unevenly distributed on the surface layer of the copper chromite particles. In the present embodiment, when copper or a copper compound is unevenly distributed on the surface layer of the copper chromite particles, compared with the case where copper or a copper compound is uniformly present not only in the surface layer but also outside the surface layer (inner layer), by laser irradiation, more copper of the activated copper chromite particles is exposed on the surface, and as a result, the bonding points with plating increase and the adhesion of the plating is improved.

[0036] Here, in this specification, the "surface layer" refers to within 10 nm from the surface of the copper chromite particles of the embodiment. The distance from the surface corresponds to the detection depth of XPS. In addition, the phrase "copper is unevenly distributed in the surface layer" means a state where the mass of copper or a copper compound per unit volume in the surface layer is larger than the mass of copper or a copper compound per unit volume outside the surface layer.

[0037] The copper content contained in the surface layer of the copper chromite particles can be measured by XPS surface analysis. For the above XPS analysis, a scanning X-ray photoelectron spectroscopy analyzer (for example, QUANTERA SXM manufactured by ULVAC-PHI, Inc.) can be used.

[0038] The copper content in the surface layer of the copper chromite particles of the present embodiment is the content rate (Cu 2 ) in terms of CuO conversion with respect to 100% by mass of the surface layer of the copper chromite particles, which is determined by XPS surface analysis of the copper chromite particles, and is preferably 50.0% by mass or more, preferably 50.0 to 80.0% by mass, preferably 55.0 to 80.0% by mass, and more preferably 60.0 to 75.0% by mass. When the copper content contained in the surface layer of the copper chromium oxide particles is within the above range, since a large amount of copper exists in the copper chromium oxide particles activated by laser irradiation, plating is likely to bond.

[0039] The above "content rate in terms of CuO with respect to 100% by mass of the surface layer of the copper chromium oxide particles (Cu 2 )" is a value obtained by performing XPS surface analysis on the copper chromium oxide particles to obtain the abundance ratio (atom%) for each element, and converting the copper content into oxide form, and calculating the content rate of CuO with respect to 100% by mass of the surface layer of the copper chromium oxide particles.

[0040] In the present embodiment, the fact that copper contained in the copper chromium oxide particles is unevenly distributed on the surface layer of the copper chromium oxide particles can be determined by performing XPS surface analysis on the copper chromium oxide particles as shown in the examples described later. The content rate of copper in terms of CuO with respect to 100% by mass of the surface layer of the copper chromium oxide particles (Cu 2 ) is higher than the content rate of copper in terms of CuO with respect to 100% by mass of the copper chromium oxide particles obtained by performing XRF analysis on the copper chromium oxide particles (Cu 1 ).

[0041] In the present embodiment, as an index of the fact that copper contained in the copper chromium oxide particles is unevenly distributed on the surface layer of the copper chromium oxide particles, the content rate of copper in terms of CuO with respect to 100% by mass of the copper chromium oxide particles obtained by performing XRF analysis on the copper chromium oxide particles (Cu 2 ) with respect to the content rate of copper in terms of CuO with respect to 100% by mass of the surface layer of the copper chromium oxide particles obtained by performing XPS surface analysis on the copper chromium oxide particles (Cu 2 ), the surface layer uneven distribution ratio of copper (Cu 2 / Cu 1 ) is preferably greater than 1, more preferably 1.2 or more, still more preferably 1.5 or more, particularly preferably 1.7 or more, and preferably 3 or less, more preferably 2.5 or less.

[0042] In this embodiment, the copper chromite particles preferably further contain molybdenum. When the copper chromite particles contain molybdenum, copper chromite particles having a desired particle size distribution can be easily obtained. Further, characteristics derived from molybdenum can be obtained.

[0043] In this embodiment, when the copper chromite particles contain molybdenum, the state of existence and the amount thereof are not particularly limited, and in addition to molybdenum metal, molybdenum oxide or a molybdenum compound partially reduced may be present. When the copper chromite particles contain molybdenum, molybdenum is considered to exist in the copper chromite particles as MoO 3 However, in addition to MoO 3 it may also exist in the copper chromite particles as MoO 2 or MoO, or a molybdate or the like.

[0044] When the copper chromite particles contain molybdenum, the form of inclusion of molybdenum is not particularly limited, and it may be included in a form adhering to the surface of the copper chromite particles, may be included in a form substituted for a part of the crystal structure of the copper chromite particles, may be included in an amorphous state, or may be a combination of these.

[0045] When the copper chromite particles contain molybdenum, the molybdenum content contained in the copper chromite particles can be measured by XRF analysis.

[0046] When the copper chromite particles contain molybdenum, the content (Mo 3 ) in terms of MoO 1 relative to 100% by mass of the copper chromite particles is preferably 0.03% by mass or more, more preferably 0.03 to 5.0% by mass, still more preferably 0.05 to 5.0% by mass, and particularly preferably 0.1 to 2.5% by mass.

[0047] Here, the above-mentioned "content in terms of MoO 3 relative to 100% by mass of the copper chromite particles (Mo 1)" refers to the molybdenum content determined by XRF analysis of copper chromium oxide particles, expressed as MoO 3 MoO converted using a calibration curve 3 This refers to a value calculated from the quantity.

[0048] In the present embodiment, when the copper oxide chromium particles contain molybdenum, the molybdenum is preferably distributed unevenly in the surface layer of the copper oxide chromium particles. By dispersing molybdenum or a molybdenum compound in the surface layer of the copper oxide chromium particles, excellent properties such as catalytic activity can be efficiently imparted compared to the case where molybdenum or a molybdenum compound is uniformly present not only in the surface layer but also in the other part (inner layer) of the copper oxide chromium particles.

[0049] In this specification, the phrase "molybdenum is unevenly distributed in the surface layer of the copper chromium oxide particle" refers to a state in which the mass of molybdenum or molybdenum compounds per unit volume in the surface layer is greater than the mass of molybdenum or molybdenum compounds per unit volume in areas other than the surface layer.

[0050] The molybdenum content in the surface layer of the copper chromium oxide particles can be measured by XPS (X-ray photoelectron spectroscopy) surface analysis.

[0051] In this embodiment, the molybdenum content in the surface layer of the copper oxide chromium particle is MoO 3 Conversion rate (Mo 2 ), preferably 0.03 mass% or more, more preferably 0.03 to 15.0 mass%, further preferably 0.05 to 15.0 mass%, particularly preferably 1.0 to 10.0 mass%, and extremely preferably 1.0 to 7.0 mass%. When the molybdenum content in the surface layer of the copper oxide chromium particles is within the above range, the copper in the copper oxide chromium particles exposed by laser irradiation is more activated, and plating is more easily bonded.

[0052] The above "MoO 3 Conversion rate (Mo 2The "***" refers to the value obtained by acquiring the abundance ratio (atom%) for each element through XPS surface analysis of copper chromite particles and converting the molybdenum content into an oxide, which is the content rate of MoO*** with respect to 100% by mass of the surface layer of the copper chromite particles. 3 Here, the molybdenum in the copper chromite particles is unevenly distributed in the surface layer of the copper chromite particles. As shown in the examples described later, the content rate of molybdenum in terms of MoO*** with respect to 100% by mass of the surface layer of the copper chromite particles, which is obtained by XPS surface analysis of the copper chromite particles, is higher than the content rate of molybdenum in terms of MoO*** with respect to 100% by mass of the copper chromite particles, which is obtained by XRF (X-ray fluorescence) analysis of the copper chromite particles. This can be confirmed.

[0053] In this embodiment, as an index indicating that molybdenum is unevenly distributed in the surface layer of the copper chromite particles, the surface layer uneven distribution ratio of molybdenum (Mo*** / Mo***), which is the content rate of molybdenum in terms of MoO*** with respect to 100% by mass of the surface layer of the copper chromite particles obtained by XPS surface analysis of the copper chromite particles, with respect to the content rate of molybdenum in terms of MoO*** with respect to 100% by mass of the copper chromite particles, is preferably greater than 1.0, more preferably 2.0 or more, particularly preferably 10 or more, and preferably 300 or less, more preferably 50 or less, and even more preferably 30 or less. 3 Here, the copper chromite particles can be provided as an aggregate of copper chromite particles, and the values of the above copper content and molybdenum content can adopt the values obtained using the aggregate as a sample. 2 The "***" refers to the value obtained by acquiring the abundance ratio (atom%) for each element through XPS surface analysis of copper chromite particles and converting the molybdenum content into an oxide, which is the content rate of MoO*** with respect to 100% by mass of the surface layer of the copper chromite particles. 3 Here, the molybdenum in the copper chromite particles is unevenly distributed in the surface layer of the copper chromite particles. As shown in the examples described later, the content rate of molybdenum in terms of MoO*** with respect to 100% by mass of the surface layer of the copper chromite particles, which is obtained by XPS surface analysis of the copper chromite particles, is higher than the content rate of molybdenum in terms of MoO*** with respect to 100% by mass of the copper chromite particles, which is obtained by XRF (X-ray fluorescence) analysis of the copper chromite particles. This can be confirmed. 1 Here, the copper chromite particles can be provided as an aggregate of copper chromite particles, and the values of the above copper content and molybdenum content can adopt the values obtained using the aggregate as a sample.

[0054] In this embodiment, as an index indicating that molybdenum is unevenly distributed in the surface layer of the copper chromite particles, the surface layer uneven distribution ratio of molybdenum (Mo*** / Mo***), which is the content rate of molybdenum in terms of MoO*** with respect to 100% by mass of the surface layer of the copper chromite particles obtained by XPS surface analysis of the copper chromite particles, with respect to the content rate of molybdenum in terms of MoO*** with respect to 100% by mass of the copper chromite particles, is preferably greater than 1.0, more preferably 2.0 or more, particularly preferably 10 or more, and preferably 300 or less, more preferably 50 or less, and even more preferably 30 or less. 3 Here, the molybdenum in the copper chromite particles is unevenly distributed in the surface layer of the copper chromite particles. As shown in the examples described later, the content rate of molybdenum in terms of MoO*** with respect to 100% by mass of the surface layer of the copper chromite particles, which is obtained by XPS surface analysis of the copper chromite particles, is higher than the content rate of molybdenum in terms of MoO*** with respect to 100% by mass of the copper chromite particles, which is obtained by XRF (X-ray fluorescence) analysis of the copper chromite particles. This can be confirmed. 1 In this embodiment, as an index indicating that molybdenum is unevenly distributed in the surface layer of the copper chromite particles, the surface layer uneven distribution ratio of molybdenum (Mo*** / Mo***), which is the content rate of molybdenum in terms of MoO*** with respect to 100% by mass of the surface layer of the copper chromite particles obtained by XPS surface analysis of the copper chromite particles, with respect to the content rate of molybdenum in terms of MoO*** with respect to 100% by mass of the copper chromite particles, is preferably greater than 1.0, more preferably 2.0 or more, particularly preferably 10 or more, and preferably 300 or less, more preferably 50 or less, and even more preferably 30 or less. 3 Here, the molybdenum in the copper chromite particles is unevenly distributed in the surface layer of the copper chromite particles. As shown in the examples described later, the content rate of molybdenum in terms of MoO*** with respect to 100% by mass of the surface layer of the copper chromite particles, which is obtained by XPS surface analysis of the copper chromite particles, is higher than the content rate of molybdenum in terms of MoO*** with respect to 100% by mass of the copper chromite particles, which is obtained by XRF (X-ray fluorescence) analysis of the copper chromite particles. This can be confirmed. 2 In this embodiment, as an index indicating that molybdenum is unevenly distributed in the surface layer of the copper chromite particles, the surface layer uneven distribution ratio of molybdenum (Mo*** / Mo***), which is the content rate of molybdenum in terms of MoO*** with respect to 100% by mass of the surface layer of the copper chromite particles obtained by XPS surface analysis of the copper chromite particles, with respect to the content rate of molybdenum in terms of MoO*** with respect to 100% by mass of the copper chromite particles, is preferably greater than 1.0, more preferably 2.0 or more, particularly preferably 10 or more, and preferably 300 or less, more preferably 50 or less, and even more preferably 30 or less. 2 Here, the molybdenum in the copper chromite particles is unevenly distributed in the surface layer of the copper chromite particles. As shown in the examples described later, the content rate of molybdenum in terms of MoO*** with respect to 100% by mass of the surface layer of the copper chromite particles, which is obtained by XPS surface analysis of the copper chromite particles, is higher than the content rate of molybdenum in terms of MoO*** with respect to 100% by mass of the copper chromite particles, which is obtained by XRF (X-ray fluorescence) analysis of the copper chromite particles. This can be confirmed. 1 In this embodiment, as an index indicating that molybdenum is unevenly distributed in the surface layer of the copper chromite particles, the surface layer uneven distribution ratio of molybdenum (Mo*** / Mo***), which is the content rate of molybdenum in terms of MoO*** with respect to 100% by mass of the surface layer of the copper chromite particles obtained by XPS surface analysis of the copper chromite particles, with respect to the content rate of molybdenum in terms of MoO*** with respect to 100% by mass of the copper chromite particles, is preferably greater than 1.0, more preferably 2.0 or more, particularly preferably 10 or more, and preferably 300 or less, more preferably 50 or less, and even more preferably 30 or less.

[0055] Here, the copper chromite particles can be provided as an aggregate of copper chromite particles, and the values of the above copper content and molybdenum content can adopt the values obtained using the aggregate as a sample.

[0056] In this embodiment, the copper chromite particles may further contain sodium or potassium.

[0057] The crystal structure of the copper chromite particles is preferably a spinel-type crystal structure. By using copper chromite particles with a spinel-type crystal structure, they exhibit black color and can improve the absorption rate of the laser used when roughening the surface of the cured product of the resin composition. The crystal structure of the copper chromite particles can be controlled, for example, by adjusting the firing temperature during the synthesis of the copper chromite particles. The structure of the copper chromite particles can be confirmed by identifying the crystal phase using an X-ray diffractometer (XRD).

[0058] In the resin composition of this embodiment, the content of the copper chromite particles, with respect to 100 parts by mass of the resin composition, may exceed 0 part by mass as the lower limit, preferably 1 part by mass or more, more preferably 5 parts by mass or more, and preferably less than 30 parts by mass, more preferably less than 20 parts by mass as the upper limit. By the content of the copper chromite particles being within the above range, the plating property of the obtained molded product can be improved.

[0059] (Method for producing copper chromite particles) The method for producing the copper chromite particles includes, for example, firing a copper compound and a chromium compound. More specifically, it may include mixing a copper compound and a chromium compound to obtain a mixture and firing the mixture, but it is not particularly limited.

[0060] A preferred method for producing copper chromite particles includes a step of mixing a copper compound and a chromium compound to obtain a mixture (mixing step) and a step of firing the mixture (firing step).

[0061] [Mixing step] The mixing step is a step of mixing a copper compound and a chromium compound to obtain a mixture.

[0062] The mixing method is not particularly limited, and simple mixing of a powder of a copper compound and a powder of a chromium compound, mechanical mixing using a pulverizer or the like, mixing using a mortar or the like, mixing in a dry state or a wet state, etc. can be used.

[0063] As an example of mixing in a wet state, a method of adding a powder of a copper compound and a powder of a chromium compound to a liquid medium and mixing them with a stirring mill can be mentioned.

[0064] As the above liquid medium, an organic solvent, an oil or fat, water, etc. can be used, but water is preferably used because the post-treatment is easy.

[0065] The above stirring mill is not particularly limited as long as it is a medium stirring mill using media (beads, balls, sand), and examples include a bead mill, a ball mill, a sand mill, a paint shaker, etc. Among these, a paint shaker using balls as the medium is preferably used because it is easy to handle.

[0066] From the viewpoint of sufficiently mixing the raw materials, the stirring time is preferably 5 to 240 minutes, more preferably 30 to 180 minutes, and even more preferably 60 to 180 minutes.

[0067] Also, as an example of mixing in a dry state, for example, a powder of a copper compound and a powder of a chromium compound may be put into a bag and mixed by manual methods such as shaking or kneading and loosening, and a ball mill, a tube mill, a vibration mill, a planetary mill, etc. using media (beads, balls, sand) can be mentioned. Among these, a planetary mill using balls as the medium is preferably used because it is easy to handle.

[0068] (Copper compound) The type of the copper compound is not particularly limited. As the copper compound, specifically, it may be monovalent or divalent, and examples include copper chloride, copper sulfate, copper sulfide, copper carbonate, copper oxide, etc. From the viewpoint of easy availability, copper carbonate and copper oxide are preferred.

[0069] Since the shape of the copper chromite particles after firing hardly reflects the shape of the raw material copper compound, as the copper compound, for example, spherical, amorphous, structured bodies with an aspect (wire, fiber, ribbon, tube, etc.), sheets, etc. can also be suitably used.

[0070] (Chromium compound) The type of chromium compound is not particularly limited. Examples of chromium compounds include chromium chloride, chromium sulfate, chromium sulfide, chromium carbonate, chromium oxide, etc. From the viewpoint of easy availability, chromium carbonate and chromium oxide are preferred.

[0071] Since the shape of the copper chromite particles after firing hardly reflects the shape of the raw material chromium compound, as the chromium compound, for example, spherical, amorphous, structured bodies with an aspect (wire, fiber, ribbon, tube, etc.), sheets, etc. can also be suitably used.

[0072] In the method for producing copper chromite particles, the molar ratio of chromium to copper (Cr / Cu) in the raw material, for example, in the above mixture, may be 1.5 to 2.5, or may be 2. However, since excess products or raw materials can be easily removed, for example, by washing with an aqueous sodium hydroxide solution, the molar ratio is not limited to the above range.

[0073] In the method for producing copper chromite particles, a molybdenum compound may be further added. When adding a molybdenum compound, the production method can include a step of mixing a copper compound, a chromium compound, and a molybdenum compound to obtain a mixture (mixing step), and can include a step of firing the mixture (firing step).

[0074] By firing a copper compound and a chromium compound in the presence of a molybdenum compound, compared with the case where no molybdenum compound is used, polyhedral particles with high crystallinity can be obtained, and copper chromite particles with a desired particle size and particle size distribution can be obtained without going through the subsequent pulverization and / or classification steps, which is preferable in terms of simplifying the manufacturing process.

[0075] (Molybdenum compound) Examples of the molybdenum compound include molybdenum oxide, molybdic acid, molybdenum sulfide, molybdenum silicide, silicomolybdic acid, magnesium molybdate, molybdate compounds, etc., and molybdenum oxide is preferred.

[0076] Examples of the above molybdenum oxide include molybdenum dioxide (MoO 2 ), molybdenum trioxide (MoO 3 ), etc., and molybdenum trioxide is preferred.

[0077] The above molybdate compound is not limited as long as it is a salt compound of a molybdenum oxoanion such as MoO 4 2- , Mo 2 O 7 2- , Mo 3 O 10 2- , Mo 4 O 13 2- , Mo 5 O 16 2- , Mo 6 O 19 2- , Mo 7 O 24 6- , Mo 8 O 26 4- . It may be an alkali metal salt, an alkaline earth metal salt, or an ammonium salt of a molybdenum oxoanion.

[0078] Examples of the above molybdate compound include alkali metal salts of molybdenum oxoanions, such as lithium molybdate, potassium molybdate, or sodium molybdate.

[0079] The above molybdate compound may be a hydrate.

[0080] The molybdenum compound is preferably at least one compound selected from the group consisting of molybdenum trioxide, lithium molybdate, potassium molybdate, and sodium molybdate, more preferably at least one compound selected from the group consisting of molybdenum trioxide, potassium molybdate, and sodium molybdate, and particularly preferably molybdenum trioxide.

[0081] When using a molybdate compound, a mixture of molybdenum oxide and a metal chloride (e.g., metal carbonate, halogen salt, sulfate, etc.) may be pre-fired and the formed molybdate compound may be used. For example, in the case of sodium molybdate, a mixture of molybdenum oxide and sodium carbonate can be fired and the formed sodium molybdate can be used.

[0082] In the present embodiment, a preferable combination of raw materials includes using copper(II) oxide, chromium(III) oxide, and molybdenum trioxide.

[0083] In the method for producing copper chromium oxide particles, the molybdenum compound is used as a fluxing agent. In this specification, hereinafter, this production method using a molybdenum compound as a fluxing agent may be simply referred to as the "flux method". By such firing, the copper compound, the chromium compound, and the molybdenum compound react at a high temperature, and a part of them forms copper molybdate and chromium molybdate. Then, the copper molybdate and chromium molybdate further decompose at a higher temperature along with the formation of copper chromium oxide particles. At this time, it is considered that a part of the molybdenum oxide is incorporated into the copper chromium oxide particles. Although a part of the molybdenum oxide evaporates and is removed from the system, when using sodium molybdate or the like as the molybdenum compound, the alkali metal compound and molybdenum oxide easily combine to form a molybdate again and remain in the system with almost no discharge to the outside of the system.

[0084] In the above flux method, for example, when using sodium molybdate, sodium molybdate reacts with a copper compound and a chromium compound to form copper molybdate and chromium molybdate. It is considered that after further high-temperature firing, these copper molybdate and chromium molybdate decompose to form copper chromium oxide. And, for example, in the presence of liquid-phase sodium molybdate, after copper molybdate and chromium molybdate decompose to form copper chromium oxide and then crystal growth is carried out, evaporation of the above flux (sublimation of MoO 3 is suppressed, and it is considered that copper chromium oxide particles with a low degree of aggregation or no aggregation can be easily obtained.

[0085] It is assumed that the above effects can also be obtained by substituting sodium molybdate with a molybdenum compound and a sodium compound. When a molybdenum compound and a sodium compound are used in combination, first, it is considered that the molybdenum compound and the sodium compound react to form sodium molybdate. Then, in the same manner as above, the molybdenum compound reacts with the copper compound and the chromium compound to form copper molybdate and chromium molybdate. It is considered that after further high-temperature firing, these copper molybdate and chromium molybdate decompose to form copper chromium oxide. And, for example, in the presence of liquid-phase sodium molybdate, after copper molybdate and chromium molybdate decompose to form copper chromium oxide and then crystal growth is carried out, evaporation of the above flux (sublimation of MoO 3 is suppressed, and it is assumed that copper chromium oxide particles with a low degree of aggregation or no aggregation can be easily obtained.

[0086] In the method for producing the above copper chromium oxide particles, when using a molybdenum compound, the blending amount is not particularly limited. However, in the raw materials, for example, in the above mixture, it is preferably blended in an amount of 1 to 1000 parts by mass, more preferably 5 to 100 parts by mass, based on 100 parts by mass of the total blending amount of the copper compound and the chromium compound.

[0087] In the method for producing copper chromite particles, the mass part ratio (molybdenum / (copper + chromium)) of molybdenum atoms in the raw material, for example, in the molybdenum compound in the mixture, to copper and chromium atoms in the copper compound and the chromium compound is preferably 0.001 or more, more preferably 0.005 or more, even more preferably 0.01 or more, and particularly preferably 0.02 or more. Also, the upper limit of the above mass part ratio (molybdenum / (copper + chromium)) is not particularly limited, but from the viewpoints of reducing the molybdenum compound to be used and improving the production efficiency, 1 is preferable, 0.5 is more preferable, 0.2 is even more preferable, and 0.1 is particularly preferable.

[0088] As an example of the numerical range of the above mass part ratio (molybdenum / (copper + chromium)) in the raw material, for example, in the mixture, the value of molybdenum / (copper + chromium) is preferably from 0.001 to 1, more preferably from 0.005 to 0.5, even more preferably from 0.01 to 0.2, and particularly preferably from 0.02 to 0.1.

[0089] By using various compounds within the above range, the obtained copper chromite particles can have a desired particle diameter and particle size distribution without going through the subsequent pulverization and / or classification steps.

[0090] (Other additives) In the method for producing the above copper chromite particles, a sodium compound and / or a potassium compound may be further used.

[0091] In the production method of this embodiment, by using a sodium compound and / or a potassium compound, it is easy to adjust the particle diameter of the produced copper chromite particles, and it is possible to easily produce copper chromite particles with little or no aggregation.

[0092] Here, when using a molybdenum compound as a fluxing agent, instead of at least a part of the molybdenum compound and the sodium compound, a compound containing molybdenum and sodium, such as sodium molybdate, can also be used. Similarly, instead of at least a part of the molybdenum compound and the potassium compound, a compound containing molybdenum and potassium, such as potassium molybdate, can also be used.

[0093] In addition, a compound containing molybdenum and sodium that is suitable as a fluxing agent can be produced, for example, from a more inexpensive and easily available molybdenum compound and sodium compound during the firing process. Here, when using a molybdenum compound and a sodium compound as a fluxing agent and when using a compound containing molybdenum and sodium as a fluxing agent, both cases are considered as the case of using a molybdenum compound and a sodium compound as a fluxing agent, that is, in the presence of a molybdenum compound and a sodium compound.

[0094] A compound containing molybdenum and potassium that is suitable as a fluxing agent can be produced, for example, from a more inexpensive and easily available molybdenum compound and potassium compound during the firing process. Here, when using a molybdenum compound and a potassium compound as a fluxing agent and when using a compound containing molybdenum and potassium as a fluxing agent, both cases are considered as the case of using a molybdenum compound and a potassium compound as a fluxing agent, that is, in the presence of a molybdenum compound and a potassium compound.

[0095] (Sodium compound) The sodium compound is not particularly limited, and examples include sodium carbonate, sodium molybdate, sodium oxide, sodium sulfate, sodium hydroxide, sodium nitrate, sodium chloride, metallic sodium, etc. Among these, it is preferable to use sodium carbonate, sodium molybdate, and sodium sulfate from the viewpoints of being industrially easily available and being easier to handle.

[0096] In addition, the above-mentioned sodium compound may be used alone or in combination of two or more kinds.

[0097] Similarly, since sodium molybdate contains molybdenum, it may also have the function as the above-mentioned molybdenum compound.

[0098] (Potassium compound) The potassium compound is not particularly limited, and examples thereof include potassium chloride, potassium chlorite, potassium chlorate, potassium sulfate, potassium hydrogen sulfate, potassium sulfite, potassium hydrogen sulfite, potassium nitrate, potassium carbonate, potassium hydrogen carbonate, potassium acetate, potassium oxide, potassium bromide, potassium bromate, potassium hydroxide, potassium silicate, potassium phosphate, potassium hydrogen phosphate, potassium sulfide, potassium hydrogen sulfide, potassium molybdate, potassium tungstate and the like. At this time, the potassium compound contains isomers, similar to the case of the molybdenum compound. Among these, it is preferable to use potassium carbonate, potassium hydrogen carbonate, potassium oxide, potassium hydroxide, potassium chloride, potassium sulfate, potassium molybdate, and it is more preferable to use potassium carbonate, potassium hydrogen carbonate, potassium chloride, potassium sulfate, potassium molybdate. In addition, the above-mentioned potassium compound may be used alone or in combination of two or more kinds.

[0099] Similarly, since potassium molybdate contains molybdenum, it may also have the function as the above-mentioned molybdenum compound.

[0100] (Metal compound) In the method for producing copper chromite particles, a metal compound may be further used during firing if desired.

[0101] The metal compound is not particularly limited, but preferably contains at least one selected from the group consisting of Group II metal compounds and Group III metal compounds.

[0102] Examples of the Group II metal compound include calcium compounds, strontium compounds, barium compounds, and the like.

[0103] Examples of the Group III metal compound include scandium compounds, yttrium compounds, lanthanum compounds, cerium compounds, and the like.

[0104] Note that the above metal compounds mean oxides, hydroxides, carbonates, and chlorides of metal elements. For example, in the case of a yttrium compound, yttrium oxide (Y 2 O 3 ), yttrium hydroxide, and yttrium carbonate can be mentioned. Among these, the metal compound is preferably an oxide of a metal element. Note that these metal compounds include isomers.

[0105] Among these, it is preferably a metal compound of a third-period element, a fourth-period element, a fifth-period element, or a sixth-period element, more preferably a metal compound of a fourth-period element or a fifth-period element, and even more preferably a metal compound of a fifth-period element. Specifically, it is preferable to use a calcium compound, a yttrium compound, or a lanthanum compound, more preferably a calcium compound or a yttrium compound, and particularly preferably a yttrium compound.

[0106] The metal compound is preferably used in a proportion of, for example, 0 to 1.2% by mass (for example, 0 to 1 mol%) with respect to the total amount of the chromium compound used in the mixing step.

[0107] [Firing Step] The firing step is a step of firing the mixture. By firing the mixture, copper chromite particles constituting the resin composition of the present embodiment are obtained.

[0108] The states of the copper compound and the chromium compound during firing are not particularly limited as long as they are present in the same space.

[0109] The conditions of the firing temperature are not particularly limited and are appropriately determined in consideration of the particle diameter, particle size distribution, shape, etc. of the target copper chromite particles. The firing temperature may be 800 °C or higher, 900 °C or higher, or 1200 °C or higher. By setting the firing temperature within the above range, the shape of the copper chromite particles can be easily controlled.

[0110] From the viewpoint of production efficiency, the heating rate may be 20 to 600 °C / h, 40 to 500 °C / h, 100 to 400 °C / h, or 200 to 400 °C / h.

[0111] Regarding the firing time, it is preferable to carry out the temperature rising time to a predetermined firing temperature in the range of 15 minutes to 10 hours. The holding time at the firing temperature can be 5 minutes or more, and it is preferably carried out in the range of 5 minutes to 30 hours. In order to efficiently form the copper chromite particles, it is more preferable that the firing temperature holding time is 2 hours or more, and particularly preferably 2 to 15 hours.

[0112] The firing atmosphere is not particularly limited as long as the effects of the present invention can be obtained. For example, an oxygen-containing atmosphere such as air or oxygen, or an inert atmosphere such as nitrogen, argon, or carbon dioxide is preferable, and an air atmosphere is more preferable in consideration of cost.

[0113] The apparatus for firing is not necessarily limited, and a so-called firing furnace can be used. Examples of the firing furnace include a roller hearth kiln, a pusher kiln, a rotary kiln, a tunnel kiln, and a shuttle kiln.

[0114] In this embodiment, when a molybdenum compound is used as a fluxing agent, similar to the conventional flux method, crystal growth can be carried out at a temperature much lower than the melting point of the target compound, and it has the merit that the crystal shape and particle size distribution can be precisely controlled.

[0115] When using a molybdenum compound, the states of the copper compound, the chromium compound, and the molybdenum compound during firing are not particularly limited, as long as the molybdenum compound is present in the same space where it can act on the copper compound and the chromium compound.

[0116] When using a molybdenum compound, there is no particular limitation on the firing temperature conditions, and it is appropriately determined in consideration of the particle diameter, particle size distribution, shape, etc. of the target copper chromite particles. The firing temperature may be 800 °C or higher, or may be 900 °C or higher.

[0117] When using a molybdenum compound, for example, even when the maximum firing temperature for firing the copper compound and the chromium compound is 1500 °C or lower, the formation of copper chromite particles can be carried out efficiently at low cost. Also, even when the firing temperature is much lower than 1500 °C, euhedral copper chromite particles can be formed regardless of the shape of the precursor. Also, from the viewpoint of efficiently producing copper chromite particles, the above firing temperature may be 1500 °C or lower, or may be 1000 °C or lower.

[0118] When using a molybdenum compound, the numerical range of the firing temperature for firing the copper compound and the chromium compound in the firing process may be, for example, 700 to 1500 °C, may be 800 to 1200 °C, may be 900 to 1000 °C, or may be 950 to 1000 °C.

[0119] When using a molybdenum compound, from the viewpoint of production efficiency, the heating rate may be 20 to 600 °C / h, may be 40 to 500 °C / h, may be 100 to 400 °C / h, or may be 200 to 400 °C / h. When the firing rate is within the above range, there is a tendency to form particles with a narrow particle size distribution.

[0120] When using a molybdenum compound, regarding the firing time, it is preferable to carry out the temperature increase time to a predetermined firing temperature in the range of 15 minutes to 10 hours. The holding time at the firing temperature can be 5 minutes or more, and it is preferably carried out in the range of 5 minutes to 30 hours. In order to efficiently form copper chromite particles, it is more preferable that the firing temperature holding time is 2 hours or more, and it is particularly preferable that the firing temperature holding time is 2 to 15 hours.

[0121] When using a molybdenum compound, the firing atmosphere is not particularly limited as long as the effects of the present invention can be obtained. For example, an oxygen-containing atmosphere such as air or oxygen, or an inert atmosphere such as nitrogen, argon, or carbon dioxide is preferable, and an air atmosphere is more preferable in consideration of cost.

[0122] When using a molybdenum compound, the apparatus for firing is not particularly limited, and a so-called firing furnace can be used. The firing furnace is preferably composed of a material that does not react with sublimated molybdenum oxide, and it is preferable to use a highly airtight firing furnace so as to efficiently utilize molybdenum oxide.

[0123] [Cooling step] The method for producing the copper chromite particles may include a cooling step. The cooling step is a step of cooling the copper chromite particles that have grown crystallographically in the firing step.

[0124] The cooling rate is not particularly limited, but it is preferably 1 to 1000 °C / hour, more preferably 5 to 500 °C / hour, and even more preferably 50 to 100 °C / hour. When the cooling rate is 1 °C / hour or more, the production time can be shortened. On the other hand, when the cooling rate is 1000 °C / hour or less, the firing container is less likely to crack due to heat shock and can be used for a long time.

[0125] The cooling method is not particularly limited, and it may be natural cooling or the use of a cooling device.

[0126] [Post-treatment step] In the present embodiment, the method for producing copper chromite particles may further include a post-treatment step of removing at least a part of molybdenum, if necessary, after the firing step.

[0127] Examples of the method for removing at least a part of molybdenum include washing and high-temperature treatment. These can be carried out in combination.

[0128] Since molybdenum can adhere to the surface of copper chromite particles, the molybdenum can be removed by washing with water, an aqueous ammonia solution, an aqueous sodium hydroxide solution, or the like. At this time, by appropriately changing the concentration, usage amount of water, aqueous ammonia solution, aqueous sodium hydroxide solution used, the washing site, washing time, etc., the molybdenum content in the copper chromite particles can be controlled.

[0129] In addition, examples of the high-temperature treatment method include a method of raising the temperature to a temperature equal to or higher than the sublimation point or boiling point of the molybdenum compound.

[0130] [Grinding step] The fired product obtained through the firing step may have the copper chromite particles aggregated and may not satisfy the range of the particle size suitable for the intended use. Therefore, the copper chromite particles may be ground, if necessary, so as to satisfy the range of the suitable particle size. The method for grinding the fired product is not particularly limited, and conventionally known grinding methods such as a ball mill, jaw crusher, jet mill, disk mill, spectromill, grinder, mixer mill, etc. can be applied.

[0131] [Classification step] The fired product containing the copper chromite particles obtained by the firing step may be appropriately classified for adjusting the range of the particle size. "Classification treatment" refers to an operation of grouping particles according to the size of the particles.

[0132] The classification can be performed either wet or dry, but from the perspective of productivity, dry classification is preferred. Dry classification includes classification by sieving, as well as pneumatic classification that classifies based on the difference between centrifugal force and fluid resistance. From the perspective of classification accuracy, pneumatic classification is preferred, and it can be performed using classifiers such as an air classifier utilizing the Coanda effect, a cyclone air classifier, a forced vortex centrifugal classifier, a semi-free vortex centrifugal classifier, etc.

[0133] The above-mentioned grinding process and classification process can be carried out at the necessary stages. By the presence or absence of these grinding and classification and the selection of their conditions, for example, the average particle size of the obtained copper chromite particles can be adjusted.

[0134] The copper chromite particles obtained by the above manufacturing method have little or no aggregation, so they can easily exhibit their original properties, have excellent handleability on their own, and also have excellent dispersibility when dispersed in a dispersion medium and used.

[0135] In addition, according to the manufacturing method of the above copper chromite particles, since copper chromite particles with little or no aggregation can be easily manufactured, even if the above grinding process and classification process are not carried out, there is an excellent advantage that copper chromite particles having the desired excellent properties can be manufactured with high productivity.

[0136] (Resin) The resin constituting the resin composition of the present embodiment is a thermosetting resin, a thermoplastic resin, or an active energy ray curable resin. Further, the above resin may be a polymer, an oligomer, or a monomer.

[0137] (Thermosetting resin) The above thermosetting resin is a resin having the property of being substantially insoluble and infusible when cured by means such as heating, radiation, or a catalyst.

[0138] Examples of the thermosetting resin include known and commonly used resins for use in molding materials and the like. Specifically, for example, novolak type phenol resins such as phenol novolak resin and cresol novolak resin; resol type phenol resins such as unmodified resol phenol resin, and oil-modified resol phenol resin modified with tung oil, linseed oil, walnut oil, etc.; phenol resins; bisphenol type epoxy resins such as bisphenol A epoxy resin and bisphenol F epoxy resin; novolak type epoxy resins such as aliphatic chain-modified bisphenol type epoxy resin, novolak epoxy resin, and cresol novolak epoxy resin; epoxy resins such as biphenyl type epoxy resin, naphthol type epoxy resin, alicyclic compound-modified phenol type epoxy resin, and polyalkylene glycol type epoxy resin; resins having a triazine ring such as urea (carbamide) resin and melamine resin; vinyl resins such as (meth)acrylic resin and vinyl ester resin; unsaturated polyester resin, bismaleimide resin, polyurethane resin, diallyl phthalate resin, silicone resin, resin having a benzoxazine ring, cyanate ester resin, etc. These may be polymers, oligomers, or monomers.

[0139] In addition, the above thermosetting resin may be used together with a curing agent. The curing agent can be used in a known and commonly used combination with the thermosetting resin. For example, when the thermosetting resin is an epoxy resin, any of the compounds commonly used as a curing agent can be used. Examples include amine compounds, amide compounds, acid anhydride compounds, phenol compounds, active ester compounds, etc.

[0140] Specific examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, guanidine derivatives, etc. Specific examples of the amide compound include dicyandiamide, polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine, etc.

[0141] Examples of the acid anhydride compounds include, specifically, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and the like.

[0142] Examples of the phenolic compounds include, specifically, phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl (zairok resin), polyhydric phenol novolak resin synthesized from polyhydric hydroxy compounds typified by resorcinol novolak resin and formaldehyde, naphthol aralkyl resin, trimethylolmethane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin (a polyhydric phenol compound in which phenol nuclei are linked by bismethylene groups), biphenyl-modified naphthol resin (a polyhydric naphthol compound in which phenol nuclei are linked by bismethylene groups), aminotriazine-modified phenol resin (a polyhydric phenol compound in which phenol nuclei are linked by melamine, benzoguanamine, etc.), alkoxy group-containing aromatic ring-modified novolak resin (a polyhydric phenol compound in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked by formaldehyde), and other polyhydric phenol compounds.

[0143] The active ester-based compound is a compound having one or more active ester groups in one molecule. The active ester-based compound is not particularly limited, but compounds having two or more highly reactive ester groups such as phenolic esters, thiophenolic esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds in one molecule are preferably used. The active ester-based compound is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound, and a hydroxy compound and / or a thiol compound. Particularly from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound or its halide and a hydroxy compound is preferred, and an active ester resin obtained from a carboxylic acid compound or its halide and a phenol compound and / or a naphthol compound is more preferred. Also, it may be linear or multi-branched. Further, a carboxylic acid compound having at least two or more carboxy groups in one molecule can have high compatibility with an epoxy resin if it is a compound containing an aliphatic chain, and can have high heat resistance if it is a compound having an aromatic ring.

[0144] Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc., or their halides.

[0145] Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, polyhydroxynaphthylene ether, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-phenol addition type resin, etc.

[0146] As the active ester compound, specifically, an active ester resin containing a dicyclopentadiene-phenol addition structure, an active ester resin containing a naphthalene structure, an active ester resin which is an acetylated product of phenol novolac, an active ester resin which is a benzoylated product of phenol novolac, etc. are preferable. As the active ester resin containing a dicyclopentadiene-phenol addition structure, more specifically, the compound represented by the following formula (21) can be mentioned.

[0147]

Chemical formula

[0148] In the above formula (21), X is a benzene ring, a naphthalene ring, a benzene ring or a naphthalene ring nucleus-substituted with an alkyl group having 1 to 4 carbon atoms, a biphenyl group, Y is a benzene ring, a naphthalene ring, a benzene ring or a naphthalene ring nucleus-substituted with an alkyl group having 1 to 4 carbon atoms, Z is an alkyl group having 1 to 4 carbon atoms, k represents 0 or 1, and n is 0.25 to 3.0 on average as a repeating unit.

[0149] From the viewpoint of reducing the dielectric loss tangent and improving the heat resistance, X is preferably a naphthalene ring, Y is preferably a benzene ring, k is preferably 0, and n is preferably 0.25 to 2.0.

[0150] As the active ester compound, the active ester compound disclosed in JP-A-2004-277460 may be used, or a commercially available active ester compound may also be used. Examples of commercially available active ester compounds include active ester hardeners containing a dicyclopentadienyl structure, active ester hardeners containing a naphthalene structure, active ester hardeners containing an acetylated product of phenol novolak, and active ester hardeners containing a benzoylated product of phenol novolak. Active ester hardeners containing a naphthalene structure and active ester hardeners containing a dicyclopenta-dienyl diphenol structure are more preferred. Examples of the active ester hardener containing a dicyclopenta-dienyl diphenol structure include EXB9451, EXB9460, EXB9460S, HPC-8000-65T (manufactured by DIC Corporation), HPC-8000L-65TM (manufactured by DIC Corporation), etc. Examples of the active ester hardener containing a naphthalene structure include EXB9416-70BK, HPC-8900-70BK, HPC-8150-62T (manufactured by DIC Corporation), etc. Examples of the active ester hardener containing an acetylated product of phenol novolak include DC808 (manufactured by Mitsubishi Chemical Corporation), etc. Examples of the active ester hardener containing a benzoylated product of phenol novolak include YLH1026 (manufactured by Mitsubishi Chemical Corporation), etc.

[0151] When the epoxy equivalent of the epoxy resin is set to 1, the reaction equivalent of the active ester compound is preferably from 0.2 to 2, more preferably from 0.3 to 1.5, and still more preferably from 0.4 to 1. Here, the "epoxy equivalent of the epoxy resin" is the total value obtained by dividing the solid mass of each epoxy resin present in the resin composition by the epoxy equivalent for all epoxy resins. Further, the "reaction group" means a functional group capable of reacting with an epoxy group, and the "reaction equivalent of the active ester compound" is the total value obtained by dividing the solid mass of the active ester compound present in the resin composition by the reaction group equivalent.

[0152] These hardeners may be used alone or in combination of two or more.

[0153] In this embodiment, the compounding amounts of the thermosetting resin and the curing agent are not particularly limited. For example, when the curable resin is an epoxy resin, from the viewpoint of obtaining good cured product properties, it is preferable to use an amount such that the active groups in the curing agent are 0.7 to 1.5 equivalents with respect to a total of 1 equivalent of epoxy groups in the epoxy resin.

[0154] Also, if necessary, a curing accelerator can be appropriately used in combination with the thermosetting resin. For example, when the curable resin is an epoxy resin, various curing accelerators can be used. Examples include phosphorus compounds, tertiary amines, imidazoles, metal organic salts, Lewis acids, amine complex salts, and the like.

[0155] Also, if necessary, a curing catalyst can be used in combination with the thermosetting resin at an appropriate time. Examples of the curing catalyst include known and commonly used thermal polymerization initiators and active energy ray polymerization initiators.

[0156] Additional specific examples of the thermosetting resin may also include radical polymerizable resins, anionic polymerizable resins, or cationic polymerizable resins that do not use a curing agent. Exemplifying radical polymerizable resins, radical polymerizable resins; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, s-butyl (meth)acrylate, n-amyl (meth)acrylate, s-amyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, tridecyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, methyl α-hydroxymethylacrylate, ethyl α-hydroxymethylacrylate, t-butyl α-hydroxymethylacrylate, t-amyl α-hydroxymethylacrylate, etc., in addition to 1,4-dioxaspiro[4,5]deca-2-ylmethacrylic acid, (meth)acryloylmorpholine, tetrahydrofurfuryl acrylate, 4-(meth)acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2-methyl-2-cyclohexyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane monomers, oligomers or polymers having a (meth)acrylic acid ester-based skeleton, or epoxy acrylate-based resins, resins having an oxetane-based cyclic skeleton, etc. may be mentioned.

[0157] (Thermoplastic resin) The above thermoplastic resin refers to a resin that can be melt-molded by heating. Specific examples of the thermoplastic resin include polyethylene resin, polypropylene resin, polymethyl methacrylate resin, polyvinyl acetate resin, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, polyvinyl chloride resin, polystyrene resin, polyacrylonitrile resin, polyamide resin, polycarbonate resin, polyacetal resin, polyethylene terephthalate resin, polyphenylene oxide resin, polyphenylene sulfide resin, polysulfone resin, polyethersulfone resin, polyetheretherketone resin, polyallylsulfone resin, thermoplastic polyimide resin, thermoplastic urethane resin, polyaminobismaleimide resin, polyamideimide resin, polyetherimide resin, bismaleimide triazine resin, polymethylpentene resin, fluorinated resin, liquid crystal polymer, olefin-vinyl alcohol copolymer, ionomer resin, polyarylate resin, acrylonitrile-ethylene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer, phenoxy resin, and the like. At least one kind of thermoplastic resin is selected and used, but depending on the purpose, it is also possible to use a combination of two or more kinds of thermoplastic resins.

[0158] (Reactive energy ray curable resin) The reactive energy ray curable resin means a polymerizable compound that is crosslinked and cured by reactive energy rays. Examples of the reactive energy rays include ionizing radiations such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Specific examples of the reactive energy ray curable resin include photopolymerizable prepolymers and photopolymerizable monomers.

[0159] Examples of the photopolymerizable monomer include, for example, unsaturated polyester resins, acrylate resins, polyene / polythiol resins, epoxy resins, aminoalkyd resins, diallyl phthalate resins, furan resins, and the like. These photopolymerizable monomers may be used alone or in combination of two or more.

[0160] In addition, together with these resins, it is also preferable to use monofunctional or polyfunctional monomers, polyfunctional oligomers, and photoinitiators having curability with respect to active energy rays as necessary.

[0161] (Other components) In addition to the copper chromite particles and the resin, the resin composition of the present embodiment may further contain clay minerals, fillers, coupling agents, and other additives as optional components.

[0162] The above clay mineral exhibits a synergistic effect with the copper chromite particles and has a function of improving the plating property and the bonding strength of the plating when LDS is performed on a molded product described later. From the viewpoint of obtaining a practical plating deposition rate for the obtained molded product, it is preferable that the clay mineral is uniformly contained in the resin composition in the same manner as the copper chromite particles.

[0163] As the clay mineral, those having a layered and cleavable property are used. The clay mineral is not particularly limited, and examples thereof include carbonate minerals and silicate minerals.

[0164] The above fillers are not particularly limited, and examples thereof include fibrous fillers such as carbon fiber, silane glass fiber, ceramic fiber, aramid fiber, metal fiber, potassium titanate fiber, silicon carbide fiber, and calcium silicate (wollastonite); glass beads, glass flakes, barium sulfate, clay, pyrophyllite, bentonite, sericite, attapulgite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, glass beads, zeolite, calcium sulfate, mica, and other non-fibrous fillers. These fillers may be used alone or in combination of two or more. These fillers have functions such as further imparting mechanical strength to the molded product.

[0165] Examples of the coupling agent include, as a silane coupling agent, epoxy group-containing alkoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; isocyanato group-containing alkoxysilane compounds such as γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, and γ-isocyanatopropyltrichlorosilane; amino group-containing alkoxysilane compounds such as γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, and γ-aminopropyltrimethoxysilane; and hydroxyl group-containing alkoxysilane compounds such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyltriethoxysilane. These silane coupling agents may be used alone or in combination of two or more. These coupling agents have a function of imparting adhesiveness to dissimilar materials to the molded product and also imparting mechanical strength.

[0166] Examples of other additives include curing agents, curing accelerators, mold release agents, flame retardants, light stabilizers, heat stabilizers, alkalis, elastomers, titanium oxide, antioxidants, hydrolysis resistance improvers, matting agents, ultraviolet absorbers, nucleating agents, plasticizers, dispersants, antistatic agents, anti-coloring agents, anti-gelling agents, and coloring agents.

[0167] <Properties of the resin composition> The resin composition of this embodiment is excellent in the dispersibility of copper chromite particles in the resin composition. By using a resin composition excellent in the dispersibility of copper chromite particles, when the LDS technique is applied to a molded product obtained by curing the resin composition, plating binds uniformly, and further, an MID excellent in the adhesion of the plating can be obtained. The dispersibility of copper chromite particles in the resin composition can be evaluated, for example, by observing the aggregated particles in the dispersion when the resin composition is dispersed in a solvent, observing the aggregated particles and the metal element distribution in the color development product obtained by molding the resin composition into a sheet shape, or measuring the surface roughness of the resin cured product obtained by curing the resin composition.

[0168] When evaluating the dispersibility by observing the aggregated particles in the color development product, it can be evaluated based on the following criteria. The color development product is prepared by the method described in the examples below. [Evaluation Criteria] A (Excellent): The color development product has a uniform coating film without color unevenness and no streaks due to poor dispersion. B (Good): The color development product has a uniform coating film without color unevenness, but there are slightly streaks due to poor dispersion. C (Unacceptable): Streaks or color unevenness are observed in the color development product.

[0169] The resin composition of this embodiment is preferably "A" or "B" according to the above evaluation criteria, and more preferably "A". If it is a resin composition having the above characteristics, since the dispersibility of copper chromite particles is excellent, when the resin composition of this embodiment is subjected to LDS, plating binds uniformly, and furthermore, excellent adhesion is exhibited.

[0170] Also, as a method for evaluating the dispersibility of copper chromite particles in the resin composition, it may be evaluated by metal element analysis. In this case, the variation of the elements is evaluated from the profile showing the peak intensities of Cu and Cr, and if it is unevenly distributed in part, it can be determined that the dispersibility is poor. Specifically, it can be evaluated by the method described in the examples.

[0171] Also, the dispersion state of copper chromite particles in the resin composition can also be evaluated by calculating the surface roughness. Specifically, it can be confirmed by preparing a cured product of the resin composition and calculating the roughness of the surface of the cured product. The occurrence of unevenness on the surface of the cured product means that there are aggregates (secondary particles) or coarse particles (primary particles) due to insufficient control of the particle size and particle size distribution.

[0172] As a method for measuring the surface roughness, it can be carried out in accordance with JIS B0601 (1994). The cured product of the resin composition can be produced based on the method described in the resin molded product described later.

[0173] In addition, it can also be evaluated by dropping or applying a color-developing composition in which copper chromite particles, a water-soluble binder, a dispersant, and an antifoaming agent are mixed onto a substrate and observing the surface state of the cured coating film.

[0174] Examples of the water-soluble binder include styrene acrylic resin emulsion, (meth)acrylate resin emulsion, polybutadiene resin emulsion, and the like.

[0175] Examples of the dispersant include phosphate-based ones, and among them, sodium hexametaphosphate and sodium pyrophosphate are preferable.

[0176] As the antifoaming agent, a silicone antifoaming agent is preferably mentioned, and any of an emulsified dispersion type and a solubilized type can be used.

[0177] <Manufacturing method of resin composition> The manufacturing method of the resin composition of this embodiment is not particularly limited. For example, it can be obtained by mixing the above-mentioned copper chromite particles and the above-mentioned resin. The mixing method is not particularly limited, and mixing is carried out by a known and commonly used method. Specifically, for example, when a thermoplastic resin is used as the resin, the copper chromite particles and the thermoplastic resin are sufficiently melt-kneaded using an extruder, kneader, roll, etc. as necessary until they become uniform, and the kneaded product is cooled to obtain it. The shape of the obtained resin composition may be any shape such as pellet shape when a thermoplastic resin is used, and when a thermosetting resin is used, it may be pulverized into an appropriate size and formed into a tablet shape using a tableting machine or the like.

[0178] <Use> The resin molded article obtained by curing the resin composition of the present embodiment can be provided with a metal layer by selectively laser-direct structuring (LDS) its surface. Therefore, it can be suitably used for built-in antennas, touch sensors, circuit lines of chip packages, communication devices, devices that require antenna circuits, capacitors, conductors, connectors, semiconductors, LED elements, etc.

[0179] <Resin molded article> In the present embodiment, the resin molded article is a cured product of the resin composition of the above-described present embodiment.

[0180] The method for obtaining a resin molded article from the resin composition of the present embodiment is not particularly limited, and known methods can be appropriately employed. For example, when the resin constituting the resin composition of the present embodiment is a thermosetting resin or a thermoplastic resin, methods such as injection molding, injection compression molding, transfer molding and other mold molding methods, extrusion molding, sheet molding, thermoforming, rotational molding, lamination molding, press molding, blow molding, melt molding, etc. can be mentioned. Also, when the resin constituting the resin composition of the present embodiment is an active energy ray curable resin, the resin composition can be cured by irradiating the resin composition with active energy rays. The light wavelength during photocuring can be appropriately adjusted according to the type of resin used. Also, as the light used for curing, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, an argon laser, a helium-cadmium laser, etc. can be used.

[0181] By roughening the surface layer of the obtained molded article and further performing a plating treatment, plating can be deposited only on the roughened region.

[0182] Examples of the method for roughening the surface layer of the molded article include lasers. The wavelength of the laser can be appropriately selected from the range of 150 to 12,000 nm, preferably 185 nm, 248 nm, 254 nm, 308 nm, 355 nm, 532 nm, 1,064 nm or 10,600 nm.

[0183] When a laser is irradiated onto a molded article, only the surface layer portion irradiated with the laser is activated. In this activated state, plating can be formed by performing plating treatment.

[0184] The plating treatment may be either electrolytic plating or electroless plating. By the aforementioned laser irradiation, the surface layer of the molded article is roughened, and a part of the activated copper oxide chromium particles in the resin composition is exposed. As a result, during the plating treatment, the plating is deposited only in the roughened region, and it becomes possible to form a circuit or the like. There is no particular limitation on the plating solution, and a known plating solution can be appropriately used, and a plating solution containing a required metal component such as Cu, Ni, or Ag can be used.

[0185] <Structural body> Also, in the present embodiment, the resin molded article may be provided on a base material. That is, it may be a structural body having a base material and a resin molded article formed by curing the resin composition of the present embodiment on at least a part of the surface of the base material. In the case of the above aspect, since it is only necessary to form a layer containing an additive (copper oxide chromium particles) on the surface of the base material, there is no need to add the additive to the base material portion, the addition amount of the additive can be reduced, and the cost during MID production can be reduced.

[0186] The material of the base material constituting the structural body of the present embodiment is not particularly limited, and for example, resin, glass, metal, ceramic, etc. can be used. Examples of the resin include thermoplastic resins and thermosetting resins. Specific examples of the thermoplastic resin and the thermosetting resin are the same as those described above. These resins may be used alone or in combination of two or more. Further, the base material may be a foamed molded body of these resins.

[0187] Also in the said structural body, by performing laser direct structuring on the surface on which the resin molded article is formed, the surface layer is roughened, and further by performing plating treatment, plating can be deposited only in the roughened region.

[0188] The thickness of the resin molded product formed on the surface of the base material is not particularly limited, but for example, it is preferably 0.1 to 300 μm, more preferably 1 to 200 μm, and even more preferably 10 to 200 μm. The thickness of the resin molded product can be measured, for example, by a stylus profiler.

[0189] (Method for manufacturing the structure) The above structure can be obtained by forming a resin molded product obtained by curing the resin composition of the present embodiment on the surface of the base material.

[0190] As a method for forming the above resin molded product on at least a part of the surface of the base material, for example, a method of applying the resin composition of the present embodiment to the surface of the base material and curing it can be mentioned. As a method for applying the resin composition of the present embodiment onto the base material, known methods can be used. For example, dip coating, spin coater, bar coater, blade coater, curtain coater, screen printing machine, etc. can be used. The resin composition of the present embodiment can be cured by thermosetting or photocuring the applied resin composition. The conditions for thermosetting and photocuring can be appropriately set according to the type of resin used.

[0191] Also, in the present embodiment, the above resin composition may be dissolved in a solvent to form a varnish-like resin composition, and then applied to and formed on the base material. The solvent may be an organic solvent or an inorganic solvent such as water. The organic solvent is not particularly limited, and examples thereof include alcohols such as methanol, ethanol, propanol, isopropyl alcohol, butanol, hexanol, heptanol, octanol, decanol, cyclohexanol, terpineol, 1-methoxy-2-propanol, etc.; glycols such as ethylene glycol, propylene glycol, etc.; ketones such as acetone, ethyl ketone, methyl ethyl ketone, diethyl ketone, etc.; esters such as ethyl acetate, butyl acetate, benzyl acetate, etc.; ether alcohols such as methoxyethanol, ethoxyethanol, etc.; ethers such as dioxane, tetrahydrofuran, etc.; glycol ether solvents such as propylene glycol monomethyl ether, etc.; acid amides such as N,N-dimethylformamide, etc.; aromatic hydrocarbons such as benzene, toluene, xylene, trimethylbenzene, dodecylbenzene, etc.; organic chlorine compounds such as chloroform, chlorobenzene, orthodichlorobenzene, etc.; long-chain alkanes such as hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, octadecane, nonadecane, eicosane, trimethylpentane, etc.; and cyclic alkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, etc.

[0192] Furthermore, when the resin composition is in the form of a varnish, a dispersant may be added. As the dispersant, known ones can be appropriately used. Examples thereof include polymer dispersants such as urethane-based dispersants, acrylic-based dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene diester-based dispersants, polyether phosphate-based dispersants, polyester phosphate-based dispersants, sorbitan aliphatic ester-based dispersants, aliphatic-modified polyester-based dispersants, etc.

[0193] When the resin composition of the present embodiment is in a varnish form, the method of mixing the resin composition and the solvent is not particularly limited. For example, a method of mixing using a mixer such as a paint conditioner, bead mill, ball mill, blender mill, three-roll mill, ultrasonic homogenizer, etc. can be used.

[0194] Further, the above-mentioned structure may be obtained by curing the resin composition of the present embodiment into a film form to obtain a resin film and attaching the resin film to the surface of a substrate.

[0195] The above-mentioned resin film can be obtained, for example, by applying the resin composition of the present embodiment in a film form on a predetermined base to form and cure a coating film.

[0196] An adhesive layer may be provided on one surface of the obtained resin film. By providing an adhesive layer, the adhesiveness when the resin film is attached to the substrate can be enhanced. The adhesive layer is not particularly limited as long as it has adhesiveness between the resin film (layer of the resin composition) and the substrate.

Examples

[0197] Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the following, "parts" and "%" are based on mass unless otherwise specified.

[0198] <Synthesis of copper chromite particles> (Synthesis Example 1) 7.95 parts of copper(II) oxide (reagent manufactured by Kanto Chemical Co., Inc., CuO) and chromium(III) oxide (reagent manufactured by Kanto Chemical Co., Inc., Cr 2 O 3)15.20 parts, 1.16 parts of molybdenum trioxide (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.), 30 parts of ion-exchanged water, and 120 parts of 5 mmφ zirconia beads were charged into a 100 ml polypropylene bottle, and mixed and pulverized for 120 minutes using a paint shaker to obtain a mixture. The obtained mixture was transferred to a metal bath and dried in an oven at 120 °C, and the dried product was pulverized with a mixer (manufactured by Osaka Chemical Co., Ltd.). The pulverized raw material was put into a crucible and fired in a ceramic electric furnace at 950 °C for 10 hours. The temperature was raised at 5 °C / min. After the temperature was lowered, the crucible was taken out to obtain a black powder. Subsequently, the black powder was dispersed in 300 mL of 0.25% aqueous ammonia, and the dispersion solution was stirred at room temperature (25 to 30 °C) for 2 hours, passed through a 100 μm sieve, and the aqueous ammonia was removed by filtration, followed by washing with water and drying to obtain copper oxide chromium particles. As a result of XRF and XPS analysis of the particles, Cu 1 was 33.7% by mass, Cu 2 was 62.7% by mass, Mo 1 was 0.2% by mass, Mo 2 was 5.4% by mass. Note that the meanings of "Cu 1 ", "Cu 2 ", "Mo 1 ", and "Mo 2 " are as described in the column of the above (copper oxide chromium particles). In addition, the results of SEM observation of the obtained copper oxide chromium particles are shown in Fig. 1.

[0199] (Synthesis Example 2) Copper oxide chromium particles were obtained in the same manner as in Example 1 except that the amount of molybdenum trioxide used was changed to 2.32 parts. As a result of XRF and XPS analysis of the particles, Cu 1 was 33.4% by mass, Cu 2 was 71.7% by mass, Mo 1 was 0.3% by mass, Mo 2 was 3.9% by mass. In addition, the results of SEM observation of the obtained copper oxide chromium particles are shown in Fig. 2.

[0200] (Synthesis Example 3) A mixture of 38.6 parts of sodium molybdate dihydrate (reagent manufactured by Kanto Chemical) and 14.4 parts of molybdenum trioxide (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.) was placed in a crucible and fired at 700 °C for 5 hours in a ceramic electric furnace to obtain 49.0 parts of Na 2 Mo 2 O 7 . 7.95 parts of copper(II) oxide (reagent manufactured by Kanto Chemical Co., Inc., CuO), 15.20 parts of chromium(III) oxide (reagent manufactured by Kanto Chemical Co., Inc., Cr 2 O 3 ), 2.32 parts of the Na 2 Mo 2 O 7 obtained above, 30 parts of ion-exchanged water, and 120 parts of 5 mmφ zirconia beads were charged into a 100 ml polypropylene bottle and mixed and pulverized for 120 minutes using a paint shaker to obtain a mixture. The obtained mixture was transferred to a metal bath and dried in an oven at 120 °C, and the dried product was pulverized with a mixer (manufactured by Osaka Chemical). The pulverized raw material was placed in a crucible and fired at 950 °C for 10 hours in a ceramic electric furnace. The temperature was raised at 5 °C / min. After the temperature was lowered, the crucible was taken out to obtain a black powder. Subsequently, the black powder was dispersed in 300 mL of 0.25% aqueous ammonia, the dispersion solution was stirred at room temperature (25 to 30 °C) for 2 hours, passed through a 100 μm sieve, and the aqueous ammonia was removed by filtration, followed by washing with water and drying to obtain copper chromite particles. As a result of XRF and XPS analysis of the particles, Cu 1 was 33.3% by mass, Cu 2 was 64.4% by mass, Mo 1 was 0.1% by mass, and Mo 2 was 0.8% by mass. Further, the results of SEM observation of the obtained copper chromite particles are shown in Figure 3.

[0201] (Synthesis Example 4) 7.95 parts of copper(II) oxide (reagent manufactured by Kanto Chemical Co., Inc., CuO), 15.20 parts of chromium(III) oxide (reagent manufactured by Kanto Chemical Co., Inc., Cr 2 O 3)15.20 parts, 1.16 parts of molybdenum trioxide (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.), 30 parts of ion-exchanged water, and 120 parts of 5 mmφ zirconia beads were charged into a 100 ml polypropylene bottle and mixed and pulverized for 120 minutes using a paint shaker to obtain a mixture. The obtained mixture was transferred to a metal bath and dried in an oven at 120 °C, and the dried product was pulverized with a mixer (manufactured by Osaka Chemical Co., Ltd.). The pulverized raw material was put into a crucible and fired at 900 °C for 10 hours in a ceramic electric furnace. The temperature was raised at 5 °C / min. After the temperature was lowered, the crucible was taken out to obtain a black powder. Subsequently, the black powder was dispersed in 300 mL of 0.25% aqueous ammonia, and the dispersion solution was stirred at room temperature (25 to 30 °C) for 2 hours, passed through a 100 μm sieve, and the aqueous ammonia was removed by filtration, followed by washing with water and drying to obtain copper oxide chromium particles. As a result of XRF and XPS analysis of the particles, Cu 1 was 32.9 mass%, Cu 2 was 55.9 mass%, Mo 1 was 0.1 mass%, Mo 2 was 0.3 mass%. Also, the results of SEM observation of the obtained copper oxide chromium particles are shown in Figure 4.

[0202] (Synthesis Example 5) 7.95 parts of copper(II) oxide (reagent manufactured by Kanto Chemical Co., Inc., CuO), chromium(III) oxide (reagent manufactured by Kanto Chemical Co., Inc., Cr 2 O 3)15.20 parts, 2.32 parts of molybdenum trioxide (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.), 30 parts of ion-exchanged water, and 120 parts of 5 mmφ zirconia beads were charged into a 100 ml polypropylene bottle, mixed and pulverized for 120 minutes using a paint shaker to obtain a mixture. The obtained mixture was transferred to a metal bath and dried in an oven at 120 °C, and the dried product was pulverized with a mixer (manufactured by Osaka Chemical Co., Ltd.). The pulverized raw material was put into a crucible and fired in a ceramic electric furnace at 950 °C for 10 hours. The temperature increase was carried out at 5 °C / min. After the temperature decrease, the crucible was taken out to obtain a black powder. Subsequently, the black powder was dispersed in 300 mL of 0.25% aqueous ammonia, the dispersion solution was stirred at room temperature (25 - 30 °C) for 2 hours, passed through a 100 μm sieve, and the aqueous ammonia was removed by filtration, followed by washing with water and drying to obtain copper oxide chromium particles. As a result of XRF and XPS analysis of the particles, Cu 1 was 33.2 mass%, Cu 2 was 61.6 mass%, Mo 1 was 0.2 mass%, Mo 2 was 2.7 mass%. Also, the results of SEM observation of the obtained copper oxide chromium particles are shown in Fig. 5.

[0203] (Synthesis Example 6) A mixture of 38.6 parts of sodium molybdate dihydrate (reagent manufactured by Kanto Chemical Co., Inc.) and 14.4 parts of molybdenum trioxide (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.) was put into a crucible and fired in a ceramic electric furnace at 700 °C for 5 hours. 49.0 parts of Na 2 Mo 2 O 7 was obtained. 7.95 parts of copper(II) oxide (reagent manufactured by Kanto Chemical Co., Inc., CuO), 15.20 parts of chromium(III) oxide (reagent manufactured by Kanto Chemical Co., Inc., Cr 2 O 3 ), and the above-mentioned Na 2 Mo 2 O 72.32 parts, 30 parts of ion-exchanged water, and 120 parts of 5 mmφ zirconia beads were charged into a 100 ml polypropylene bottle, mixed and pulverized for 120 minutes using a paint shaker to obtain a mixture. The obtained mixture was transferred to a metal bath and dried in an oven at 120 °C, and the dried product was pulverized with a mixer (manufactured by Osaka Chemical). The pulverized raw material was placed in a crucible and fired at 900 °C for 10 hours in a ceramic electric furnace. The temperature was raised at 5 °C / min. After the temperature was lowered, the crucible was taken out to obtain a black powder. Subsequently, the black powder was dispersed in 300 mL of 0.25% aqueous ammonia, the dispersion solution was stirred at room temperature (25 - 30 °C) for 2 hours, passed through a 100 μm sieve, and the aqueous ammonia was removed by filtration, followed by washing with water and drying to obtain copper oxide chromium particles. As a result of XRF and XPS analysis of the particles, Cu 1 was 33.4 mass%, Cu 2 was 51.2 mass%, Mo 1 was 0.1 mass%, Mo 2 was 0.9 mass%. Also, the results of SEM observation of the obtained copper oxide chromium particles are shown in Fig. 6.

[0204] (Synthesis Example 7) 7.95 parts of copper(II) oxide (reagent manufactured by Kanto Chemical Co., Inc., CuO), 15.20 parts of chromium(III) oxide (reagent manufactured by Kanto Chemical Co., Inc., Cr 2 O 3 ), 30 parts of ion-exchanged water, and 120 parts of 5 mmφ zirconia beads were charged into a 100 ml polypropylene bottle, mixed and pulverized for 120 minutes using a paint shaker to obtain a mixture. The obtained mixture was transferred to a metal bath and dried in an oven at 120 °C, and the dried product was pulverized with a mixer (manufactured by Osaka Chemical). The pulverized raw material was placed in a crucible and fired at 900 °C for 10 hours in a ceramic electric furnace. The temperature was raised at 5 °C / min. After the temperature was lowered, the crucible was taken out to obtain a dark green powder. Subsequently, the dark green powder was dispersed in 300 mL of 0.25% aqueous ammonia, the dispersion solution was stirred at room temperature (25 - 30 °C) for 2 hours, passed through a 100 μm sieve, and the aqueous ammonia was removed by filtration, followed by washing with water and drying to obtain a dark green powder. Also, the results of SEM observation of the obtained copper oxide chromium particles are shown in Fig. 7.

[0205] (Synthesis Example 8) 4.78 parts of copper(II) oxide (reagent manufactured by Kanto Chemical Co., Inc., CuO), and chromium(III) oxide (reagent manufactured by Kanto Chemical Co., Inc., Cr 2 O 3 ) 15.00 parts, 0.02 part of molybdenum trioxide (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.), 0.20 part of zinc oxide (reagent manufactured by Kanto Chemical Co., Inc., ZnO), 30 parts of ion-exchanged water, and 120 parts of 5 mmφ zirconia beads were charged into a 100 ml polypropylene bottle, mixed and pulverized for 120 minutes using a paint shaker to obtain a mixture. The obtained mixture was transferred to a metal bath and dried in an oven at 120 °C, and the dried product was pulverized with a mixer (manufactured by Osaka Chemical Co., Ltd.). The pulverized raw material was placed in a crucible and fired at 900 °C for 10 hours in a ceramic electric furnace. The temperature was raised at 5 °C / min. After cooling, the crucible was taken out to obtain a black powder. Subsequently, the black powder was dispersed in 300 mL of 0.25% aqueous ammonia, and the dispersion solution was stirred at room temperature (25 to 30 °C) for 2 hours, passed through a 100 μm sieve, and the aqueous ammonia was removed by filtration, followed by washing with water and drying to obtain copper chromite particles. As a result of XRF and XPS analysis of the particles, Mo 1 was 0.1% by mass, and Mo 2 was 10.0% by mass. The results of SEM observation of the obtained copper chromite particles are shown in Fig. 8.

[0206] <Preparation of Resin Composition> (Example 1) 20.0 parts of copper chromite particles obtained in Synthesis Example 1, 70 parts of an epoxy resin (manufactured by DIC Corporation, product number EPICLON HP-7200-75M), 80 parts of a phenol resin (manufactured by DIC Corporation, product number PR-100L-50P), 30 parts of mica (manufactured by Yamaguchi Mica Co., Ltd., product number A-3), and 0.3 part of a curing accelerator (2-ethyl-4-methylimidazole, manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 300 parts of propylene glycol monomethyl ether and 5 parts of an acrylic monomer (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester TMPT) to obtain a varnish-like resin composition. Next, the varnish-like resin composition was applied onto the upper surface of an LCP film (manufactured by Kuraray Co., Ltd., Vectra CTQ-100) using an applicator, and then dried until propylene glycol monomethyl ether volatilized, and further heated at 180°C for 120 minutes to cure the resin composition. Thus, a film-shaped resin molded article having a cured resin formed on the LCP film was obtained. Here, the thickness of the film-shaped resin molded article was 150 μm.

[0207] (Examples 2 to 6, Comparative Examples 1 and 2) A varnish-like resin composition was prepared in the same procedure as in Example 1 except that the type of copper chromite particles was changed as shown in Table 2. Next, the varnish-like resin composition was applied onto an LCP film, dried, and heated to obtain a film-shaped resin molded article.

[0208] [Measurement of particle size distribution of copper chromite oxide particles] Using a laser diffraction dry particle size distribution analyzer (HELOS (H3355)&RODOS manufactured by Nippon Laser Co., Ltd.), the particle size distribution of the copper chromite oxide particles obtained above was measured under the conditions of a dispersion pressure of 3 bar and a suction pressure of 90 mbar. The particle diameter at the point where the volume integration % distribution curve intersects the horizontal axis at 50% was determined as D50. Note that D10 and D90 were also determined by the same method.

[0209] [SPAN value] The spread (SPAN) of the particle size distribution of the copper chromite oxide particles was determined by the following conversion formula. SPAN = (D90 - D10) / D50

[0210] [Crystal structure analysis: XRD (X-ray diffraction) method] The copper chromite oxide particles were filled into a measurement sample holder with a depth of 0.5 mm, and it was set in a wide-angle X-ray diffraction (XRD) apparatus (UltimaIV manufactured by Rigaku Corporation). Measurement was performed under the conditions of Cu / Kα ray, 40 kV / 40 mA, a scan speed of 2° / min, and a scan range of 10 to 70° to identify the crystal structure.

[0211] [Appearance evaluation of color-developed product] For the color-developed product obtained above, visual evaluation was performed according to the following items. [Evaluation Criteria] A (Excellent): The color-developed product has a uniform coating film without color unevenness and no streaks due to poor dispersion. B (Good): The color-developed product has a uniform coating film without color unevenness, but there are slightly streaks due to poor dispersion. C (Poor): Streaks or color unevenness are visible in the color-developed product.

[0212] [Metal Element Analysis Evaluation] <Preparation of Sample> The color-developed product obtained above was fixed to an aluminum plate, and gold was coated on the coating film surface of the color-developed product using a magnetron sputtering device (manufactured by Vacuum Device Co., Ltd.) to obtain a measurement sample.

[0213] <Sample Measurement Method> For the above measurement sample, using a desktop SEM (JCM-7000, manufactured by JEOL), under the condition of an acceleration voltage of 15 kV, as shown in Fig. 9, while scanning the surface linearly for about 1 mm, the intensity in the energy region corresponding to the characteristic X-rays of Cr-Kα and Cu-Kα was measured.

[0214] <Metal Element Analysis Evaluation> Regarding the profile showing the peak intensities of Cr and Cu at each point on the surface of the obtained sample (the starting point and the ending point of reference numeral 130 in Fig. 9), evaluation was performed according to the following items, and the results are shown in Table 2. Also, the line profiles of Cr and Cu in Examples 1, 4, 5 and Comparative Example 1 are shown in Figs. 10 to 17. [Profile Evaluation Criteria] A (Excellent): The peaks of Cr and Cu are not unevenly distributed, and the variation in peak intensity is small. B (Good): The peaks of Cr and Cu are partially unevenly distributed, but the variation in peak intensity is small. C (Poor): The peaks of Cr and Cu are unevenly distributed, and the variation in peak intensity is large.

[0215]

Table 1

[0216]

Table 2

[0217] As shown in Tables 1 and 2, Examples 1 to 6 containing copper chromite particles having a specific particle size distribution had both appearance evaluation and elemental analysis evaluation of B or higher, indicating excellent dispersibility. Since the resin compositions of Examples 1 to 6 are excellent in the dispersibility of copper chromite particles, it is expected that when the resin composition is cured and used for LDS, an MID showing excellent plating characteristics can be obtained. In addition, in Comparative Examples 1 and 2, since the spread of the particle size distribution of the copper chromite particles exceeded 2.00, the appearance evaluation and elemental analysis evaluation were inferior to those of the examples.

Explanation of Signs

[0218] 100 PET film 110 Resin molded product 120 Scanning direction of SEM

Claims

Claim 1 A resin composition containing copper chromite particles and a resin, in the volume-based particle size distribution of the copper chromite particles obtained by the laser diffraction scattering method, when the particle sizes at which the cumulative frequencies from the small particle size side are 10%, 50%, and 90% are D10, D50, and D90, respectively, the spread of the particle size distribution SPAN = (D90 - D10) / D50 is 2.00 or less.

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