JP2021195586A - Lds thermosetting resin composition and structure - Google Patents

Abstract

[Problem] To provide a resin composition for LDS that can reduce the wiring width and wiring spacing when forming a plated circuit layer by LDS, and that can improve the surface smoothness of the plated circuit layer formed thereon by making the laser-treated surface of the resin smooth. [Solution] A thermosetting resin composition for LDS used in LASER DIRECT STRUCTURING (LDS), comprising (A) a thermosetting resin, (B) an inorganic filler, (C) a non-conductive metal compound that forms a metal nucleus when irradiated with active energy rays, and (D) a coupling agent, wherein the component (A) comprises one or more selected from the group consisting of epoxy resins and bismaleimide resins, the d50 particle size of the inorganic filler (B) is 3 μm or less, and the d90 particle size of the inorganic filler (B) is 5 μm or less. [Selected Figures] None

Description

The present invention relates to a thermosetting resin composition for LDS and a structure with a plating circuit layer produced using the same.

As a technique relating to a resin material used in LASER DIRECT STRUCTURING (LDS), there are those described in Patent Documents 1 to 3.
Patent Document 1 (Japanese Unexamined Patent Publication No. 2015-134903) describes a fiber-reinforced resin material obtained by impregnating continuous fibers with a thermoplastic resin composition containing an LDS additive, and a polyamide resin is used as the thermoplastic resin. in use.

Patent Document 2 (Japanese Unexamined Patent Publication No. 2015-163682) describes a crystalline cyclic olefin ring-opening polymer hydrogenated product having a repeating unit derived from a polycyclic norbornene-based monomer having three or more rings. A polymer composition containing a specific amount of a glass filler and a metal oxide is described, and it is said that good electrical characteristics (low dielectric positive contact), plating adhesion, and reflow heat resistance can be achieved. Has been done.

In addition, Patent Document 3 (Japanese Patent Laid-Open No. 2017-513794) describes the process of laser direct structuring and many additional functions proved in the art, such as color, flame retardancy, process modification, and smoke. With specific ingredients as a technique for the inorganic encapsulation of metal oxides, mixed metal oxides, and metal compounds, potentially used as additives to provide reduction, antibacterial properties, laser marking, or "activation". Describes the core-shell composite material made.

Japanese Unexamined Patent Publication No. 2015-134903 Japanese Unexamined Patent Publication No. 2015-163682 Special Table 2017-513794

However, when the inventor examined the resin composition applied to LDS, it was improved in terms of miniaturization of the wiring width and wiring interval at the time of circuit formation by LDS and the smoothness of the plating layer surface formed by LDS. It became clear that there was room.
Therefore, according to the present invention, the wiring width and the wiring interval can be reduced when the circuit is formed by the LDS, and the laser-treated surface of the resin material in the LDS is smooth, so that the surface of the plating layer formed on the laser-treated surface is smooth. Provided is a resin composition capable of improving smoothness.

According to the present invention
A thermosetting resin composition for LDS used in LASER DIRECT STRUCTURING (LDS).
(A) Thermosetting resin and
(B) Inorganic filler and
(C) A non-conductive metal compound that forms a metal nucleus by irradiation with active energy rays, and
(D) Containing a coupling agent and
The component (A) contains one or more selected from the group consisting of an epoxy resin and a bismaleimide resin.
Provided is a thermosetting resin composition for LDS, wherein the d50 particle size of the inorganic filler (B) is 3 μm or less, and the d90 particle size of the inorganic filler (B) is 5 μm or less.

Further, according to the present invention.
Resin molded products and
A structure including a plating circuit layer provided on a laser-treated surface of the resin molded product.
A structure is provided in which the resin molded product is made of a cured product of the thermosetting resin composition for LDS.

It should be noted that any combination of these configurations and the conversion of the expression of the present invention between methods, devices and the like are also effective as aspects of the present invention.
For example, according to the present invention, there is provided a resin molded product comprising a cured product of the thermosetting resin composition for LDS according to the present invention.

According to the present invention, when the plating circuit layer is formed by LDS, the wiring width and the wiring interval can be reduced, the laser-treated surface of the resin is smooth, and the surface of the plating circuit layer formed on the surface of the plating circuit layer is smooth. It is possible to provide a resin composition for LDS that can improve smoothness.

Hereinafter, embodiments of the present invention will be described with reference to specific examples of each component. In addition, in this embodiment, the composition may contain each component individually or in combination of two or more kinds.
In the present embodiment, the thermosetting resin composition is a thermosetting resin composition for LDS used for laser direct structuring (LASER DIRECT STRUCTURING: LDS). LDS is one of the methods for manufacturing a three-dimensional molded circuit component (Molded Connect Device: MID). In LDS, specifically, the surface of a resin molded product containing an LDS additive is irradiated with active energy rays to generate metal nuclei, and the metal nuclei are used as seeds by plating treatment such as electroless plating. A plating pattern is formed in the energy ray irradiation area. Conductive members such as wiring and circuits can be formed based on this plating pattern.

(Thermosetting resin composition for LDS)
In the present embodiment, the thermosetting resin composition for LDS (hereinafter, also simply referred to as “thermosetting resin composition”) contains the following components (A) to (D).
(A) Thermosetting resin;
(B) Inorganic filler;
(C) A non-conductive metal compound that forms a metal nucleus by irradiation with active energy rays;
(D) Coupling agent.
In the thermosetting resin composition of the present embodiment, the component (A) contains at least one selected from the group consisting of an epoxy resin and a bismaleimide resin, and the d50 particle size of the inorganic filler (B) is 3 μm. The d90 particle size of the inorganic filler (B) is 5 μm or less.

In the present specification, the d50 particle size means a cumulative 50% particle size measured by a laser diffraction type particle size distribution measuring device, in other words, a particle size in which the cumulative frequency of particle size is 50%. Further, the d90 particle size also means a cumulative 90% particle size.

In the present embodiment, in the thermosetting resin composition, the cured product of the thermosetting resin composition is LDS by appropriately selecting the type of the component (A) and the particle size and particle size distribution of the component (B). When the plating circuit layer is formed, the wiring width and the wiring interval can be reduced, and the smoothness of the laser-treated surface of the resin can be improved.
Hereinafter, each component of the thermosetting resin composition of the present embodiment will be described.

(Ingredient (A))
The component (A) is a thermosetting resin. By using the component (A) in combination with the component (B) having a specific particle size, the wiring width and the wiring interval are reduced when forming a circuit by LDS, and the smoothness of the laser-processed surface is improved. The component (A) contains one or more selected from the group consisting of an epoxy resin and a bismaleimide resin.
Further, from the viewpoint of improving curability, storage stability, heat resistance, moisture resistance, and chemical resistance, the component (A) preferably contains an epoxy resin, and more preferably an epoxy resin.
On the other hand, from the viewpoint of obtaining more excellent heat resistance, the component (A) preferably contains a bismaleimide resin, and more preferably a bismaleimide resin.

As the epoxy resin, a monomer, an oligomer, or a polymer having two or more epoxy groups in one molecule can be used in general, and the molecular weight and molecular structure thereof are not limited.
The epoxy resin is, for example, a biphenyl type epoxy resin; a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol type epoxy resin such as a tetramethyl bisphenol F type epoxy resin; a stillben type epoxy resin; a phenol novolac type epoxy resin, a cresol novolac type. Novolak type epoxy resin such as epoxy resin; Polyfunctional epoxy resin such as triphenol methane type epoxy resin exemplified by alkyl modified triphenol methane type epoxy resin; Phenol aralkyl type epoxy resin having phenylene skeleton , Phenol aralkyl type epoxy resin having a phenylene skeleton, phenol aralkyl type epoxy resin having a biphenylene skeleton, naphthol aralkyl type epoxy resin having a biphenylene skeleton; dihydroxynaphthalene type epoxy resin, dihydroxynaphthalene dimer Naftor-type epoxy resin such as epoxy resin obtained by glycidyl etherification; Triazine core-containing epoxy resin such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; Arihashi cyclic hydrocarbon such as dicyclopentadiene-modified phenol-type epoxy resin Includes one or more selected from the group consisting of compound modified phenolic epoxy resins.

Of these, the novolak type epoxy resin and polyfunctionality are used from the viewpoint of suppressing warpage of the molded body obtained by curing the thermosetting resin composition and improving the balance of various properties such as filling property, heat resistance and moisture resistance. An epoxy resin and a phenol aralkyl type epoxy resin can be preferably used. Further, from the same viewpoint, the epoxy resin preferably contains one or more selected from the group consisting of an orthocresol novolac type epoxy resin, a phenol aralkyl type epoxy resin having a biphenylene skeleton, and a triphenylmethane type epoxy resin, and more. It preferably comprises one or more selected from the group consisting of orthocresol novolac type epoxy resins and phenol aralkyl type epoxy resins having a biphenylene skeleton.

Further, the bismaleimide resin is a (co) polymer of a compound having two or more maleimide groups.
The compound having two or more maleimide groups includes, for example, at least one of the compound represented by the following general formula (1) and the compound represented by the following general formula (2). Thereby, the glass transition temperature of the cured product of the thermosetting resin composition can be increased, and the heat resistance of the cured product can be more effectively improved.

In the above general formula (1), R ¹ is a divalent organic group having 1 or more carbon atoms and 30 or less carbon atoms, and may contain one or more of an oxygen atom and a nitrogen atom. From the viewpoint of improving the heat resistance of the cured product, ^{it is more preferable that R 1} is an organic group containing an aromatic ring. In the present embodiment, as R ¹ , for example, a structure such as the following general formula (1a) or (1b) can be exemplified.

In the above general formula (1a), R ³¹ is a divalent organic group having 1 or more and 18 or less carbon atoms which may contain one or more of an oxygen atom and a nitrogen atom. Further, each of the plurality of R ^32s is an independently hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 or more and 4 or less carbon atoms.

In the above general formula (1b), a plurality of Rs exist independently, and R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group, and is preferably a hydrogen atom. Further, m is an average value, which is a number of 1 or more and 5 or less, preferably a number larger than 1 and 5 or less, more preferably a number larger than 1 and 3 or less, and further preferably a number larger than 1 and 2 or less. be.

Examples of the compound represented by the above general formula (1) that can be applied in the present embodiment include compounds represented by the following formulas (1-1) to (1-3).

In the general formula (2), a plurality of R ² are each independently substituted or unsubstituted at least 1 but no greater than 4 hydrogen or C hydrocarbon group. n is an average value, which is a number of 0 or more and 10 or less, preferably 0 or more and 5 or less.

Further, the component (A) may further contain another thermosetting resin. Examples of such thermosetting resins include unsaturated polyester resins such as benzoxazine resins, phenol resins, urea (urea) resins, and melamine resins, polyurethane resins, diallyl phthalate resins, silicone resins, cyanate resins, and polyimide resins. One or more selected from the group consisting of polyamideimide resin and benzocyclobutene resin can be mentioned.

The content of the component (A) in the thermosetting resin composition is relative to the entire thermosetting resin composition from the viewpoint of improving the fluidity at the time of molding and improving the filling property and the molding stability. It is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 2.5% by mass or more.
On the other hand, from the viewpoint of improving moisture resistance reliability and reflow resistance, and from the viewpoint of suppressing warpage of the molded product, the content of the component (A) is preferably 15% by mass with respect to the entire thermosetting resin composition. % Or less, more preferably 14% by mass or less, still more preferably 13% by mass or less.
Here, in the present embodiment, the content with respect to the entire thermosetting resin composition means the entire solid content of the thermosetting resin composition excluding the solvent when the thermosetting resin composition contains a solvent. Refers to the content for. The solid content of the thermosetting resin composition refers to the non-volatile content in the thermosetting resin composition, and refers to the balance excluding volatile components such as water and solvent.

(Component (B))
The component (B) is an inorganic filler. The component (B) consists of, for example, fused silica such as molten crushed silica and fused spherical silica; silica such as crystalline silica and amorphous silica; silicon dioxide; alumina; aluminum hydroxide; silicon nitride; and aluminum nitride. Includes one or more selected materials. From the viewpoint of favoring the mechanical properties or thermal properties of the cured product of the thermosetting resin composition, the component (B) preferably contains silica such as fused crushed silica, fused spherical silica, and crystalline silica, and more preferably. It is silica.

In the present embodiment, the d50 particle size of the component (B) is 3 μm from the viewpoint of reducing the wiring width and wiring interval (line and space) when forming a circuit by LDS and improving the smoothness of the laser-processed surface. The particle size of d90 is 5 μm or less. The d50 particle size of the component (B) is preferably 2.8 μm or less, more preferably 2.6 or less, and even more preferably 2.4 μm or less. The particle size of the component (B) d90 is preferably 4.5 μm or less, more preferably 4 μm or less, and even more preferably 3.5 μm or less. The lower limit of the d50 particle size of the component (B) is, for example, 0.5 μm or more from the viewpoint of availability and handleability. The lower limit of the d90 particle size of the component (B) is, for example, 1 μm or more from the viewpoint of availability and handleability.

In a preferred embodiment, the proportion of particles having a particle size of 5 μm or more and 20 μm or less in the component (B) reduces the wiring width and wiring spacing (L / S, line and space) when forming a circuit by LDS. From the viewpoint and from the viewpoint of improving the surface smoothness of the laser-treated surface of the resin composition, it is 20% by volume or less, more preferably 10% by volume or less, and even more, with respect to the total of the component (B). It is preferably 5% by volume or less.

In a preferred embodiment, the proportion of particles having a particle size of 1 μm or more and 20 μm or less in the component (B) reduces the wiring width and wiring spacing (L / S, line and space) when forming a circuit by LDS. From the viewpoint, it is 40% by volume or more, more preferably 70% by volume or more, based on the whole of the component (B). The proportion of particles having a particle size of 1 μm or more and 20 μm or less in the component (B) is 95% by volume or less from the viewpoint of improving moldability.

The d10 particle size of the component (B) is, for example, 0.03 μm or more, preferably 0.05 μm or more, more preferably 0.1 μm or more, still more preferably 0.3 μm or more, from the viewpoint of improving moldability. ..
On the other hand, from the viewpoint of reducing the plating wiring width after laser processing, the d10 particle size of the component (B) is preferably 3 μm or less, more preferably 2.0 μm or less, still more preferably 1.0 μm or less, still more. It is preferably 0.8 μm or less.

The maximum diameter dmax of the component (B) is preferably 5.0 μm or less, more preferably 4.5 μm or less, still more preferably, from the viewpoint of reducing the plating circuit wiring width and improving the smoothness of the laser-processed surface. Is 4 μm or less.

Here, the particle size distribution of the inorganic filler can be measured on a volume basis by using a commercially available laser diffraction type particle size distribution measuring device (for example, SALD-7000 manufactured by Shimadzu Corporation).

The content of the component (B) in the thermosetting resin composition is preferably 50% by mass or more with respect to the entire thermosetting resin composition from the viewpoint of improving the heat resistance and moisture resistance of the cured product. It is more preferably 60% by mass or more, still more preferably 70% by mass or more.
On the other hand, from the viewpoint of more effectively improving the fluidity and filling property of the thermosetting resin composition at the time of molding, the content of the component (B) is preferably 90 with respect to the entire thermosetting resin composition. It is 0% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less.

(Component (C))
The component (C) is a non-conductive metal compound that forms a metal nucleus by irradiation with active energy rays. Such compounds act as LDS additives. The component (C) is not limited as long as it can form a metal nucleus by irradiation with active energy rays. Although the detailed mechanism is not clear, such non-conductive metal compounds are activated (for example, reduced) when irradiated with active energy rays such as a YAG laser having an absorbable wavelength region. ), It is considered that a metal nucleus capable of metal plating is generated. Then, when the surface of the cured product of the thermosetting resin composition in which the non-conductive metal compound is dispersed is irradiated with active energy rays, a seed region having a metal nucleus capable of metal plating is formed on the irradiated surface. Will be done. By utilizing the obtained seed region, it becomes possible to form a plating pattern such as a circuit on the surface of the cured product of the thermosetting resin composition.

The component (C) is selected from, for example, (i) a spinel-type metal oxide, (ii) groups 3 to 12 of the periodic table, and two or more transition metal elements to which the group is adjacent. Includes one or more selected from the group consisting of metal oxides having, and (iii) tin-containing oxides.

In the above (i), the spinel type structure is one of the typical crystal structure types found in AB2O4 type compounds (A and B are metal elements) which are compound oxides. The spinel structure may be either a forward spinel structure or an inverted spinel structure (B (AB) O4) in which A and B are partially exchanged), but a forward spinel structure can be more preferably used. In this case, A of the forward spinel structure may be copper.

As the metal atom constituting the spinel-type metal oxide, for example, copper or chromium can be used. That is, the component (C) can contain a spinel-type metal oxide containing copper or chromium. For example, copper can be used as the metal atom from the viewpoint of enhancing the adhesion to the copper plating pattern.

In addition to copper and chromium, it contains trace amounts of metal atoms such as antimony, tin, lead, indium, iron, cobalt, nickel, zinc, cadmium, silver, bismuth, arsenic, manganese, magnesium, and calcium. May be. These trace metal atoms may exist as oxides. Further, the content of trace metal atoms can be 0.001% by mass or less with respect to the total amount of metal atoms in the metal oxide.

Spinel-type metal oxides are thermally highly stable and can be durable in acidic or alkaline aqueous metallization baths. The spinel-type metal oxide, for example, by appropriately controlling the dispersibility of the thermosetting resin composition, can be applied to the unirradiated region on the surface of the cured product of the thermosetting resin composition in a high oxide state. Can exist. As an example of the spinel-type metal oxide as described above, for example, those described in JP-A-2004-534408 can be mentioned.

The metal oxide having the transition metal element of (ii) is selected from Group 3 to Group 12 of the Periodic Table, and the metal oxide having two or more transition metal elements adjacent to the group is selected. Is. Here, the metal belonging to the transition metal element can be expressed as containing the metal of group n in the periodic table and the metal of group n + 1. As the metal oxide having the transition metal element, the oxides of these metals may be used alone or in combination of two or more.

Metals belonging to Group n of the periodic table include, for example, Group 3 (scandium, ittrium), Group 4 (titanium, zirconium, etc.), Group 5 (vanadium, niobium, etc.), Group 6 (chromium, molybdenum, etc.), Group 7. Group 8 (iron, ruthenium, etc.), Group 9 (cobalt, rhodium, iridium, etc.), Group 10 (nickel, palladium, platinum), Group 11 (copper, silver, gold, etc.), Group 12 (zinc) , Cadmium, etc.), Group 13 (aluminum, gallium, indium, etc.).

Group n + 1 metals in the periodic table include, for example, Group 4 (titanium, zirconium, etc.), Group 5 (vanadium, niobium, etc.), Group 6 (chromium, molybdenum, etc.), Group 7 (manganese, etc.), Group 8 (iron, etc.). , Luthenium, etc.), Group 9 (cobalt, rhodium, iridium, etc.), Group 10 (nickel, palladium, platinum), Group 11 (copper, silver, gold, etc.), Group 12 (zinc, cadmium, etc.), Group 13 (aluminum, etc.) , Gallium, indium, etc.).
As an example of the metal oxide having the transition metal element as described above, for example, those described in JP-A-2004-534408 can be mentioned.

The tin-containing oxide of (iii) is a metal oxide containing at least tin. The metal atom constituting the tin-containing oxide may contain antimony in addition to tin. Such tin-containing oxides can contain tin oxide and antimony oxide. More specifically, 90% by mass or more of the metal component contained in the tin-containing oxide may be tin, and 5% by mass or more may be antimony. The tin-containing oxide may further contain lead and / or copper as a metal component. Specifically, in the metal component contained in the tin-containing oxide, for example, 90% by mass or more is tin, 5 to 9% by mass is antimony, and the range is 0.01 to 0.1% by mass. It contains lead and can contain copper in the range of 0.001 to 0.01% by mass. Such tin-containing oxides can contain, for example, tin oxide and antimony oxide, and one or more of lead oxide and copper oxide. The tin-containing oxide may contain trace metal atoms exemplified by the spinel-type metal oxide.
Further, the tin-containing oxide may be used in combination with the spinel-type metal oxide of the above (i) or the metal oxide having the transition metal element of the above (ii).

The content of the component (C) in the thermosetting resin composition is such that the thermosetting resin composition has good plating characteristics on the laser-treated surface of the cured product with respect to the entire thermosetting resin composition. From this point of view, for example, it is 2% by mass or more, preferably 4% by mass or more, and more preferably 8% by mass or more. Further, in the cured product of the thermosetting resin composition, from the viewpoint of suppressing a decrease in insulating property and an increase in dielectric loss tangent, and when the shape of the component (C) is non-spherical, the flow of the thermosetting resin composition From the viewpoint of improving the properties, the content of the component (C) is, for example, 20% by mass or less, preferably 18% by mass or less, and more preferably 15% by mass with respect to the entire thermosetting resin composition. % Or less.

Further, the total content of the component (B) and the component (C) in the thermosetting resin composition is preferable with respect to the entire thermosetting resin composition from the viewpoint of improving the resin mechanical properties and the resin strength. It is 60% by mass or more, more preferably 65% by mass or more.
On the other hand, from the viewpoint of improving moldability, the total content of the component (B) and the component (C) is preferably 95% by mass or less, more preferably 90% by mass, based on the entire thermosetting resin composition. % Or less.

(Component (D))
The component (D) is a coupling agent. The component (D) is preferably one or more selected from the group consisting of mercaptosilane, aminosilane and epoxysilane from the viewpoint of improving mold moldability by optimizing the viscosity of the thermosetting resin composition. including. From the viewpoint of continuous moldability, mercaptosilane is preferable, from the viewpoint of fluidity, secondary aminosilane is preferable, and from the viewpoint of adhesion, epoxysilane is preferable.

Among these, examples of the epoxy silane include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and β- (3,4-epoxycyclohexyl) ethyl. Examples thereof include trimethoxysilane, and γ-glycidoxypropylmethyldimethoxysilane is preferable.

Examples of aminosilanes include phenylaminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, and N-β (aminoethyl). -Γ-Aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N- Examples thereof include (6-aminohexyl) 3-aminopropyltrimethoxysilane, N- (3- (trimethoxysilylpropyl) -1,3-benzenedimethanane, etc., preferably N-phenyl-γ-aminopropyltri. It is ethoxysilane. It may be used as a latent aminosilane coupling agent in which the primary amino moiety of aminosilane is protected by reacting with ketone or aldehyde. Further, aminosilane may have a secondary amino group.

Further, examples of the mercaptosilane include γ-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane, as well as bis (3-triethoxysilylpropyl) tetrasulfide and bis (3-triethoxysilylpropyl) disulfide. Examples thereof include a silane coupling agent that exhibits the same function as the mercaptosilane coupling agent by thermal decomposition, and γ-mercaptopropyltrimethoxysilane is preferable.

These silane coupling agents may be blended with those that have been hydrolyzed in advance. These silane coupling agents may be used alone or in combination of two or more.

The content of the component (D) in the thermosetting resin composition is adjusted with respect to the entire thermosetting resin composition from the viewpoint of improving the injection moldability by increasing the flow flow length of the thermosetting resin composition. It is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more.
On the other hand, from the viewpoint of suppressing an increase in water absorption of the cured product of the thermosetting resin composition and obtaining good rust resistance, the content of the component (D) is higher than that of the entire thermosetting resin composition. It is preferably 1% by mass or less, more preferably 0.8% by mass or less, still more preferably 0.6% by mass or less.

(Other ingredients)
In the present embodiment, the thermosetting resin composition may contain components other than the above-mentioned components (A) to (D).
For example, the thermosetting resin composition may further contain (E) a curing accelerator.

(Ingredient (E))

The component (E) is a curing accelerator. The curing accelerator may be any as long as it promotes the cross-linking reaction between the thermosetting resin and the curing agent, and those used in general thermosetting resin compositions can be used.

The component (E) is a phosphorus atom-containing compound such as an organic phosphine, a tetra-substituted phosphonium compound, a phosphobetaine compound, an adduct of a phosphine compound and a quinone compound, and an adduct of a phosphonium compound and a silane compound; 1,8-diazabicyclo. [5.4.0] One selected from nitrogen atom-containing compounds such as amidines and tertiary amines such as undecene-7, benzyldimethylamine and 2-methylimidazole, and quaternary salts of the above amidines and amines. Alternatively, two or more types can be included. Among these, it is more preferable to contain a phosphorus atom-containing compound from the viewpoint of improving curability. Further, from the viewpoint of improving the balance between moldability and curability, it has latent properties such as a tetra-substituted phosphonium compound, a phosphobetaine compound, an adduct of a phosphine compound and a quinone compound, and an adduct of a phosphonium compound and a silane compound. It is more preferable to include one. From a similar point of view, component (E) preferably comprises one or more selected from tetraphenylphosphonium bis (naphthalene-2,3-dioxy) phenylsilicate and traphenylphosphonium-4,4'-sulfonyldiphenolate. ..

Examples of the organic phosphine include a first phosphine such as ethylphosphine and phenylphosphine; a second phosphine such as dimethylphosphine and diphenylphosphine; and a third phosphine such as trimethylphosphine, triethylphosphine, tributylphosphine and triphenylphosphine.

Examples of the tetra-substituted phosphonium compound include compounds represented by the following general formula (6).

(In the above general formula (6), P represents a phosphorus atom. R ⁴ , R ⁵ , R ⁶ and R ⁷ represent an aromatic group or an alkyl group. A is selected from a hydroxyl group, a carboxyl group and a thiol group. Represents an anion of an aromatic organic acid having at least one functional group in the aromatic ring. AH is an aromatic having at least one functional group selected from a hydroxyl group, a carboxyl group, and a thiol group in the aromatic ring. Represents an organic acid. X and y are numbers 1 to 3, z is a number 0 to 3, and x = y.)

The compound represented by the general formula (6) can be obtained, for example, as follows, but is not limited thereto. First, a tetra-substituted phosphonium halide, an aromatic organic acid and a base are mixed uniformly with an organic solvent to generate an aromatic organic acid anion in the solution system. Then, water can be added to precipitate the compound represented by the general formula (6). In the compound represented by the general formula (6), R ⁴ , R ⁵ , R ⁶ and R ⁷ bonded to the phosphorus atom are phenyl groups, and AH is a compound having a hydroxyl group in the aromatic ring, that is, phenols. Yes, and A is preferably an anion of the phenols. Examples of the phenols include monocyclic phenols such as phenol, cresol, resorcin, and catechol, condensed polycyclic phenols such as naphthol, dihydroxynaphthalene, and anthraquinol, and bisphenols such as bisphenol A, bisphenol F, and bisphenol S. Examples thereof include polycyclic phenols such as phenylphenol and biphenol.

Examples of the phosphobetaine compound include compounds represented by the following general formula (7).

(In the above general formula (7), P represents a phosphorus atom. R ⁸ represents an alkyl group having 1 to 3 carbon atoms, R ⁹ represents a hydroxyl group. F is a number from 0 to 5, and g is 0 to 0. It is a number of three.)

The compound represented by the general formula (7) can be obtained, for example, as follows. First, it is obtained through a step of contacting a tri-aromatic substituted phosphine, which is a tertiary phosphine, with a diazonium salt, and substituting the tri-aromatic substituted phosphine with the diazonium group of the diazonium salt. However, it is not limited to this.

Examples of the adduct of the phosphine compound and the quinone compound include compounds represented by the following general formula (8).

(In the above general formula (8), P represents a phosphorus atom. R ¹⁰ , R ¹¹ and R ¹² represent an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, and are identical to each other. ^{R 13} , R ¹⁴ and R ¹⁵ represent hydrogen atoms or hydrocarbon groups having 1 to 12 carbon atoms, which may be the ^{same or different from each other, and R 14} and R ¹⁵ are bonded to each other. It may have a annular structure.)

Examples of the phosphin compound used as an adduct between the phosphin compound and the quinone compound include triphenylphosphine, tris (alkylphenyl) phosphin, tris (alkoxyphenyl) phosphin, trinaphthylphosphine, tris (benzyl) phosphine and the like. Substituents or those having a substituent such as an alkyl group or an alkoxyl group are preferable, and examples of the substituent such as an alkyl group and an alkoxyl group include those having 1 to 6 carbon atoms. Triphenylphosphine is preferred from the standpoint of availability.

Examples of the quinone compound used as an adduct of the phosphin compound and the quinone compound include benzoquinone and anthraquinone, and among them, p-benzoquinone is preferable from the viewpoint of storage stability.

As a method for producing an adduct of a phosphine compound and a quinone compound, the adduct can be obtained by contacting and mixing in a solvent in which both organic tertiary phosphine and benzoquinones can be dissolved. As the solvent, ketones such as acetone and methyl ethyl ketone, which have low solubility in adducts, are preferable. However, it is not limited to this.

In the compound represented by the general formula (8), the compounds in which R ¹⁰ , R ¹¹ and R ¹² bonded to the phosphorus atom are phenyl groups and R ¹³ , R ¹⁴ and R ¹⁵ are hydrogen atoms, that is, 1, A compound to which 4-benzoquinone and triphenylphosphine are added is preferable in that it lowers the thermal elasticity of the cured product of the thermosetting resin composition.

Examples of the adduct of the phosphonium compound and the silane compound that can be used in the thermosetting resin composition of the present embodiment include compounds represented by the following general formula (9), and tetraphenylphosphonium bis is preferable. (Naphthalene-2,3-dioxy) Phenyl silicate can be mentioned.

(In the above general formula (9), P represents a phosphorus atom and Si represents a silicon atom. R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are organic groups or fats having an aromatic ring or a heterocyclic ring, respectively. Represents a group group and may be the same or different from each other. In the formula, R ²⁰ is an organic group bonded to the groups Y ² and Y ^{3. In the formula, R 21} is a group Y ⁴ and Y ⁵ . ^{Y 2} and Y ³ are organic groups to be bonded. Y 2 and Y 3 represent a group formed by a proton donor group releasing a proton, ^{and groups Y 2} and Y ³ in the same molecule are bonded to a silicon atom to form a chelate structure. Y ⁴ and Y ⁵ represent groups formed by the proton donor group releasing a proton, and the groups Y ⁴ and Y ⁵ in the same molecule combine with a silicon atom to form a chelate structure. There are. R ²⁰ , and R ²¹ may be the same or different from each other ^{, and Y 2} , Y ³ , Y ⁴ and Y ⁵ may be the same or different from each other. Z1 is an aromatic ring or It is an organic group having a heterocycle or an aliphatic group.)

In the general formula (9), R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ include, for example, a phenyl group, a methylphenyl group, a methoxyphenyl group, a hydroxyphenyl group, a naphthyl group, a hydroxynaphthyl group, a benzyl group and a methyl group. , Ethyl group, n-butyl group, n-octyl group, cyclohexyl group, etc. Among these, alkyl group such as phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, hydroxynaphthyl group, alkoxy group, etc. , An aromatic group having a substituent such as a hydroxyl group or an unsubstituted aromatic group is more preferable.

Further, in the general formula (9), R ²⁰ is an organic group bonded to ^{Y 2} and Y ^3. Similarly, R ²¹ is an organic group that binds to groups Y ⁴ and Y ^5. Y ² and Y ³ are groups formed by a proton donor group releasing a proton, and the groups Y ² and Y ³ in the same molecule are bonded to a silicon atom to form a chelate structure. Similarly, Y ⁴ and Y ⁵ are groups formed by a proton donor group releasing a proton, and the groups Y ⁴ and Y ⁵ in the same molecule are bonded to a silicon atom to form a chelate structure. The groups R ²⁰ and R ²¹ may be the same or different from each other, and the groups Y ² , Y ³ , Y ⁴ and Y ⁵ may be the same or different from each other. ^{In such a group represented by −Y 2} −R ²⁰ −Y ³ − and Y ⁴ −R ²¹ −Y ⁵ − in the general formula (9), the proton donor releases two protons. As the proton donor, an organic acid having at least two carboxyl groups or hydroxyl groups in the molecule is preferable, and further, a carboxyl group or a hydroxyl group is added to an adjacent carbon constituting an aromatic ring. An aromatic compound having at least two is preferable, and an aromatic compound having at least two hydroxyl groups on adjacent carbons constituting the aromatic ring is more preferable, for example, catechol, pyrogallol, 1,2-dihydroxynaphthalene, 2,3-dihydroxy. Naphthalene, 2,2'-biphenol, 1,1'-bi-2-naphthol, salicylic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chloranilic acid, tannic acid, 2-hydroxybenzyl Examples thereof include alcohol, 1,2-cyclohexanediol, 1,2-propanediol and glycerin, but among these, catechol, 1,2-dihydroxynaphthalene and 2,3-dihydroxynaphthalene are more preferable.

^{Further, Z 1} in the general formula (9) represents an organic group or an aliphatic group having an aromatic ring or a heterocyclic ring, and specific examples thereof include a methyl group, an ethyl group, a propyl group and a butyl group. An aliphatic hydrocarbon group such as a hexyl group and an octyl group, an aromatic hydrocarbon group such as a phenyl group, a benzyl group, a naphthyl group and a biphenyl group, a glycidyloxy group such as a glycidyloxypropyl group, a mercaptopropyl group and an aminopropyl group. , A mercapto group, a reactive substituent such as an alkyl group having an amino group and a vinyl group, etc. Among these, a methyl group, an ethyl group, a phenyl group, a naphthyl group and a biphenyl group are selected from the viewpoint of thermal stability. , More preferred.

As a method for producing an adduct of a phosphonium compound and a silane compound, a silane compound such as phenyltrimethoxysilane and a proton donor such as 2,3-dihydroxynaphthalene are added to a flask containing methanol and dissolved, and then at room temperature. The sodium methoxide-methanol solution is added dropwise with stirring. Further, a solution prepared in advance in which a tetra-substituted phosphonium halide such as tetraphenylphosphonium bromide is dissolved in methanol is added dropwise to the solution under stirring at room temperature to precipitate crystals. The precipitated crystals are filtered, washed with water and vacuum dried to obtain an adduct of a phosphonium compound and a silane compound. However, it is not limited to this.

When the thermosetting resin composition contains the component (E), the content of the component (E) is preferable with respect to the entire thermosetting resin composition from the viewpoint of effectively improving the curability at the time of molding. Is 0.1% by mass or more, more preferably 0.15% by mass or more, still more preferably 0.25% by mass or more.
On the other hand, from the viewpoint of improving the fluidity during molding, the content of the curing accelerator is preferably 1% by mass or less, more preferably 0.8% by mass, based on the entire thermosetting resin composition. It is as follows.

Further, the thermosetting resin composition may contain at least one kind of organic heat-stable metal chelate complex salt in addition to the non-conductive metal compound of the component (C).

Further, the thermosetting resin composition may further contain a curing agent. The curing agent can be roughly classified into three types, for example, a polyaddition type curing agent, a catalytic type curing agent, and a condensation type curing agent. These may be used alone or in combination of two or more.

The heavy addition type curing agent is, for example, an aliphatic polyamine such as diethylenetriamine (DETA), triethylenetetramine (TETA), metaxylerylene diamine (MXDA), diaminodiphenylmethane (DDM), m-phenylenediamine (MPDA), In addition to aromatic polyamines such as diaminodiphenylsulfone (DDS), polyamine compounds containing dicyandiamide (DICY), organic acid dihydrazide and the like; alicyclic acids such as hexahydroanhydride phthalic acid (HHPA) and methyltetrahydroanhydride phthalic acid (MTHPA). Acid anhydrides including anhydrous, aromatic acid anhydrides such as trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), benzophenone tetracarboxylic acid (BTDA); novolak type phenolic resin, polyvinylphenol, aralkyl type Phenolic resin-based curing agent such as phenol resin; Polymercaptan compound such as polysulfide, thioester, thioether; isocyanate compound such as isocyanate prepolymer and blocked isocyanate; Includes species or two or more.

The catalytic curing agent is a tertiary amine compound such as benzyldimethylamine (BDMA), 2,4,6-trisdimethylaminomethylphenol (DMP-30); 2-methylimidazole, 2-ethyl-4- Includes one or more selected from the group consisting of imidazole compounds such as methylimidazole (EMI24); Lewis acids such as BF3 complex.

The condensation type curing agent includes, for example, one or more selected from the group consisting of a resol type phenol resin; a urea resin such as a methylol group-containing urea resin; and a melamine resin such as a methylol group-containing melamine resin.

Among these, it is more preferable to contain a phenol resin-based curing agent from the viewpoint of improving the balance of flame resistance, moisture resistance, electrical characteristics, curability, storage stability and the like. As the phenol resin-based curing agent, for example, a monomer, an oligomer, or a polymer having two or more phenolic hydroxyl groups in one molecule can be used, and the molecular weight and molecular structure thereof are not limited.
The phenol resin-based curing agent is, for example, a novolak type phenol resin such as a phenol novolak resin, a cresol novolak resin, or a bisphenol novolak; a polyfunctional phenol resin such as a polyvinyl phenol or a triphenol methane type phenol resin; a terpene-modified phenol resin or a dicyclo. Modified phenol resins such as pentadiene-modified phenolic resins; phenol formaldehyde resins having a phenylene skeleton and / or biphenylene skelesin, phenol formaldehyde resins such as phenylene and / or naphthol aralkyl resins having biphenylene skeletrons; bisphenols such as bisphenol A and bisphenol F. Includes one or more selected from the group consisting of compounds. Among these, from the viewpoint of suppressing warpage of the molded body, it is more preferable to contain a novolak type phenol resin, a polyfunctional phenol resin and a phenol aralkyl type phenol resin. Further, a phenol novolac resin, a phenol aralkyl resin having a biphenylene skeleton, and a formaldehyde-modified triphenylmethane-type phenol resin can also be preferably used.

The content of the curing agent in the thermosetting resin composition is such that the content of the curing agent is higher than that of the entire thermosetting resin composition from the viewpoint of realizing excellent fluidity at the time of molding and improving fillability and moldability. It is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 1.5% by mass or more.
On the other hand, the content of the curing agent is preferable with respect to the entire thermosetting resin composition from the viewpoint of improving the moisture resistance reliability and reflow resistance of the electronic component and from the viewpoint of suppressing the warp of the obtained molded product. Is 9% by mass or less, more preferably 8% by mass or less, still more preferably 7% by mass or less.

Further, the thermosetting resin composition of the present embodiment contains, if necessary, additives such as a mold release agent, a flame retardant, an ion scavenger, a colorant, a low stress agent and an antioxidant. be able to. These may be used alone or in combination of two or more.
The amount of each of these components in the thermosetting resin composition can be about 0.01 to 2% by mass, respectively, with respect to the entire thermosetting resin composition.

The release agent is selected from, for example, natural waxes such as carnauba wax; montanic acid ester waxes such as glycerin trimontanic acid ester, synthetic waxes such as polyethylene oxide wax; higher fatty acids such as zinc stearate and their metal salts; and paraffin. Can include one type or two or more types.
The flame retardant can include, for example, one or more selected from aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, and phosphazene.
The ion scavenger may contain one or more selected from hydrotalcites or hydrotalcites of elements selected from magnesium, aluminum, bismuth, titanium and zirconium.
The colorant may contain one or more selected from carbon black, red iron oxide, and titanium oxide.
The low stress agent may contain one or more selected from a polybutadiene compound; an acrylonitrile butadiene copolymer compound; a silicone compound such as silicone oil and silicone rubber.

Further, the thermosetting resin composition of the present embodiment is preferably configured not to contain carbon such as carbon black used as the colorant from the viewpoint of improving the plating characteristics.

As a method for producing a thermosetting resin composition of the present embodiment, for example, each component of the thermosetting resin composition is mixed by a known means to obtain a mixture. Further, the mixture is melt-kneaded to obtain a kneaded product. As a kneading method, for example, an extrusion kneader such as a single-screw kneading extruder or a twin-screw kneading extruder or a roll-type kneading machine such as a mixing roll can be used, but a twin-screw kneading extruder is used. Is preferable. After cooling, the kneaded product can be shaped into a predetermined shape.

The thermosetting resin composition obtained in the present embodiment contains the components (A) to (D), and the type of the component (A) and the size of the component (B) are appropriately selected, so that the curing thereof is performed. When the material is plated with LDS to form a circuit layer, the wiring width and the wiring interval can be reduced, and the smoothness of the laser-treated surface of the cured product can be improved. As a result, the surface smoothness of the plating circuit layer formed on the laser-treated surface of the cured product can be improved, and the plating circuit layer having excellent reliability can be formed.

The shape of the thermosetting resin composition may have a predetermined shape such as powdery granules, granules, tablets or sheets. This makes it possible to obtain a thermosetting resin composition suitable for known molding methods such as transfer molding, injection molding, and compression molding.
Here, the powder-granular thermosetting resin composition is a pulverized product obtained by crushing the obtained kneaded product, and the granular thermosetting resin composition is a powder (powder) of the thermosetting resin composition. Agglomerates obtained by solidifying (granular kneaded products) or granules obtained by a known granulation method, and a tablet-shaped thermosetting resin composition is a thermosetting resin composition that is tableted at high pressure. It is a molded body that is shaped to have a predetermined shape by molding, and the sheet-shaped thermosetting resin composition is, for example, from a thermosetting resin composition having a sheet-like shape or a roll-like shape that can be rolled up. It means that it is a resin film.
In the present embodiment, the thermosetting resin composition in the form of powder granules, granules, tablets or sheets may be in a semi-cured state (B stage state).

(Structure with plated circuit layer and its manufacturing method)
A structure with a plating circuit layer produced by irradiating the surface of a resin molded product formed from the thermosetting resin composition of the present embodiment with a laser and then applying a metal to form a plating circuit layer. The manufacturing method will be described below.

Examples of the method for forming the thermosetting resin composition in the method for producing the structure of the present embodiment include mold formation such as injection molding and transfer molding. By using such a molding method, it is possible to produce a resin molded product containing a cured product of the thermosetting resin composition.

In the present embodiment, the resin molded product is a cured product of a thermosetting resin composition containing an LDS additive, and specifically, is a resin molded product having a three-dimensional structure. As long as it has a three-dimensional structure, the shape of the resin molded product is not limited, and for example, it may have a curved surface in part.
MID can be obtained by subjecting the resin molded product to LDS.
The MID has three elements of a three-dimensional shape, the resin molded product, and a three-dimensional circuit. For example, the MID is a component in which a circuit is formed of a metal film on the surface of a resin molded product having a three-dimensional structure. Specifically, the MID can include a resin molded product having a three-dimensional structure and a three-dimensional circuit formed on the surface of the resin molded product. By using such an MID, the space can be effectively utilized, the number of parts can be reduced, and the size can be reduced.

In the present embodiment, the manufacturing process of MID is based on preparation of a thermosetting resin composition used for LDS, molding of this thermosetting resin composition, irradiation of the obtained resin molded product with active energy rays, and plating treatment. Each step of circuit formation can be included. Further, a surface cleaning step may be added before the plating treatment.

As the active energy ray to irradiate the resin molded product, for example, a laser can be used. The laser can be appropriately selected from known lasers such as a YAG laser, an excimer laser, and an electromagnetic ray, and a YGA laser is preferable. Further, the wavelength of the laser is not defined, but is, for example, 200 nm to 12000 nm. Of these, 248 nm, 308 nm, 355 nm, 532 nm, 1064 nm or 10600 nm may be preferably used.
In the present embodiment, the thermosetting resin composition contains the components (A) to (D), and the type of the component (A) and the size of the component (B) are appropriately selected. The wiring width and the wiring interval when forming a circuit by laser irradiation on the resin molded product can be reduced, and the laser irradiation surface of the resin molded product can be smoothed.
The surface roughness Ra (arithmetic mean roughness) of the laser-irradiated surface of the resin molded product is, for example, 3 μm or less, preferably 2.5 μm or less, and more preferably 2.0 μm or less. The lower limit of the surface roughness Ra of the laser irradiation surface is not particularly limited, but is, for example, 1.0 μm or more. When the surface roughness Ra of the laser irradiation surface is within the above range, the smoothness of the surface of the plating circuit layer formed on the plating circuit layer described below is improved, and thus the structure with a plating circuit obtained can be obtained. Improves electrical reliability. The surface roughness Rz (maximum height roughness) of the laser-irradiated surface of the resin molded product is, for example, 55 μm or less, preferably 50 μm or less, and more preferably 45 μm or less. The lower limit of the surface roughness Rz of the laser irradiation surface is not particularly limited, but is, for example, 30 μm or more. When the surface roughness Rz of the laser irradiation surface is in the above range, the smoothness of the surface of the plating circuit layer formed on the surface roughness Rz is improved, and the electrical reliability of the obtained structure with a plating circuit is improved. ..

As the plating treatment, either electroplating or electroless plating may be used. A plating circuit layer can be formed by subjecting the above-mentioned laser-irradiated region to a plating treatment. As the plating solution, a known plating solution can be widely adopted, and a plating solution in which copper, nickel, gold, silver, and palladium are mixed may be used as the metal component. The thickness of the plating circuit layer obtained by the plating treatment can be, for example, in the range of 1 μm to 30 μm.
In the present embodiment, the thermosetting resin composition contains the components (A) to (D), and the type of the component (A) and the size of the component (B) are appropriately selected. Therefore, this resin molding The laser irradiation surface of an object can be smoothed.

In the present embodiment, the structure composed of the cured product of the thermosetting resin composition is not limited to the final product, but may also include composite materials and various parts. The structure can be used as a component for high frequency modules, portable electronic devices, vehicles and medical devices, electronic components including other electric circuits, semiconductor encapsulants, and composite materials for forming them. The MID can also be applied to mobile phones, smartphones, built-in antennas, sensors, and semiconductor devices.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the description of these Examples.

(Examples 1 to 4, Comparative Example 1)
The thermosetting resin compositions for LDS of each example were prepared and evaluated according to the formulations shown in Table 1. The components used in each example are as follows.

(Inorganic filler)
Inorganic filler 1: Amorphous silica / crystalline silica, MUF-4V, manufactured by Ryumori Co., Ltd., average particle diameter 3.8 μm, specific surface area 4.0 m ² / g
Inorganic filler 2: Silicon dioxide, SC-2500-SQ, manufactured by Admatex, average particle diameter 0.6 μm, specific surface area 6.4 m ² / g
Inorganic filler 3: Silicon dioxide, SC-5500-SQ, manufactured by Admatex, average particle diameter 1.6 μm, specific surface area 4.4 m ² / g
Inorganic filler 4: Silicon dioxide, TS-6026, manufactured by Micron Company, average particle size 9.0 μm, specific surface area 3.4 m ² / g
Inorganic filler 5: Silicon dioxide, TS-3100, manufactured by Micron Company, average particle diameter 2.0 μm, specific surface area 10 m ² / g
Inorganic filler 6: Amorphous silica / crystalline silica, MUF-2BV, manufactured by Ryumori Co., Ltd., average particle diameter 1.2 μm, specific surface area 6.4 m ² / g
Inorganic filler 7: silica, UF-305, manufactured by Tokuyama Corporation, average particle diameter 2.7 μm, specific surface area 2.1 m ² / g

(Coupling agent)
Coupling agent 1: 3-glycidoxypropyltrimethoxysilane, S510, manufactured by Chisso Coupling agent 2: N-phenyl-γ-aminopropyltrimethoxysilane, CF-4083, manufactured by Toray Dow Corning

(Thermosetting resin)
Epoxy resin 1: Biphenylene skeleton-containing phenol aralkyl type epoxy resin, NC3000, manufactured by Nippon Kayaku Co., Ltd.

(Hardener)
Hardener 1: Biphenylene skeleton-containing phenol formaldehyde, MEH-7851SS, manufactured by Meiwa Kasei Co., Ltd.

(Hardening accelerator)
Curing Accelerator 1: Tetraphenylphosphonium Bis (Naphthalene-2,3-dioxy) Phenylsilicate Curing Accelerator 2: Tetraphenylphosphonium-4,4'-Sulfonyldiphenolate

(Release agent)
Release Agent 1: Glycerin Trimontanic Acid Ester, Recolve-WE-4, manufactured by Clariant Japan

(Additive: non-conductive metal compound)
Additive 1: Inorganic composite oxide, Black3702, manufactured by Asahi Kasei Kogyo Co., Ltd.

(silicone)
Silicone 1: Polyoxyalkylene epoxy modified dimethylpolysiloxane, FZ-3730, manufactured by Toray Dow Corning

(Preparation of thermosetting resin composition)
The raw materials in the blending amounts shown in Table 1 were mixed at room temperature using a mixer, and then rolled and kneaded at 70 to 100 ° C. Then, after cooling the obtained kneaded product, it was pulverized to obtain a powdery and granular thermosetting resin composition. Then, by tableting and molding at high pressure, a tablet-shaped thermosetting resin composition was obtained.

(Measurement of size of inorganic filler)
The d10, d50, and d90 of the entire inorganic filler used in each example were measured by a laser diffraction type particle size distribution measuring device (SALD-7000, manufactured by Shimadzu Corporation).

(Evaluation method)
(L / S)
The resin composition obtained in each example was used under the condition of 175 ° C. using a transfer molding machine to obtain a molded product having a thickness of 50 mm × 50 mm × thickness 2 μm. The surface of the obtained resin molded product was irradiated with a UV laser, circuits with each line width were created, and the narrowest pitched ones with good conduction were shown in Table 1 as the results of each example. Described as.
The evaluation levels were 7 levels of L / S = 17, 20, 30, 40, 50, 75, and 100 μm.

(Measurement of surface roughness)
The resin composition obtained in each example was used under the condition of 175 ° C. using a transfer molding machine to obtain a molded product having a thickness of 50 mm × 50 mm × thickness 2 μm. The surface of the obtained resin molded product was irradiated with a UV laser, and the surface roughness of the laser-irradiated surface was measured using a laser microscope (manufactured by KEYENCE CORPORATION, VK-X100). The maximum height roughness Rz (μm) and the arithmetic mean roughness Ra (μm) are shown in Table 1.

(Smoothness of plating layer)
The resin composition obtained in each example was used under the condition of 175 ° C. using a transfer molding machine to obtain a molded product having a thickness of 50 mm × 50 mm × thickness 2 μm. The surface of the obtained resin molded product is irradiated with a UV laser, and then electroless copper plating is performed, and the surface roughness of the obtained plated surface is measured with a laser microscope (manufactured by KEYENCE CORPORATION, VK-X100). ) Was measured. "X" when the arithmetic average roughness Ra is 3 μm or more, which is coarser than the surface roughness of the laser-irradiated surface of the resin molded product, “○” when Ra is less than 3 μm and 2 μm or more, and “○” when Ra is less than 2 μm. The evaluation results are shown in Table 1 as "◎".

From Table 1, the resin compositions obtained in each example were excellent in the balance between the effects of narrowing the L / S pitch and the smoothness of the laser-treated surface, as compared with those obtained in the comparative examples.

Claims (9)

A thermosetting resin composition for LDS used in LASER DIRECT STRUCTURING (LDS).
(A) Thermosetting resin and
(B) Inorganic filler and
(C) A non-conductive metal compound that forms a metal nucleus by irradiation with active energy rays, and
(D) Containing a coupling agent and
The component (A) contains one or more selected from the group consisting of an epoxy resin and a bismaleimide resin.
A thermosetting resin composition for LDS, wherein the d50 particle size of the inorganic filler (B) is 3 μm or less, and the d90 particle size of the inorganic filler (B) is 5 μm or less. The LDS according to claim 1, wherein the proportion of particles having a particle size of 5 μm or more and 20 μm or less in the inorganic filler (B) is 20% by volume or less with respect to the entire inorganic filler (B). Thermosetting resin composition. (E) The thermosetting resin composition for LDS according to claim 1 or 2, further comprising a curing accelerator. The thermosetting resin composition for LDS according to any one of claims 1 to 3, wherein the inorganic filler (B) contains silica. The thermosetting for LDS according to any one of claims 1 to 4, wherein the inorganic filler (B) is 50% by mass or more and 90% by mass or less with respect to the entire thermosetting resin composition for LDS. Sex resin composition. The total content of the inorganic filler (B) and the non-conductive metal compound (C) in the thermosetting resin composition for LDS is 60 mass with respect to the entire thermosetting resin composition for LDS. The thermosetting resin composition for LDS according to any one of claims 1 to 5, wherein the content is% or more and 95% by mass or less. Resin molded products and
A structure including a plating circuit layer provided on a laser-treated surface of the resin molded product.
A structure in which the resin molded product is a cured product of the thermosetting resin composition for LDS according to any one of claims 1 to 6. The structure according to claim 7, wherein the surface roughness Ra of the laser-treated surface of the resin molded product is 3 μm or less. The structure according to claim 7 or 8, wherein the thickness of the plating circuit layer is 1 μm or more and 30 μm or less.