WO2017199639A1 - Lds用熱硬化性樹脂組成物、樹脂成形品および三次元成形回路部品 - Google Patents
Lds用熱硬化性樹脂組成物、樹脂成形品および三次元成形回路部品 Download PDFInfo
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- WO2017199639A1 WO2017199639A1 PCT/JP2017/014663 JP2017014663W WO2017199639A1 WO 2017199639 A1 WO2017199639 A1 WO 2017199639A1 JP 2017014663 W JP2017014663 W JP 2017014663W WO 2017199639 A1 WO2017199639 A1 WO 2017199639A1
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- thermosetting resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
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- H—ELECTRICITY
- H03—ELECTRONIC CIRCUITRY
- H03K—PULSE TECHNIQUE
- H03K3/00—Circuits for generating electric pulses; Monostable, bistable or multistable circuits
- H03K3/02—Generators characterised by the type of circuit or by the means used for producing pulses
- H03K3/04—Generators characterised by the type of circuit or by the means used for producing pulses by the use, as active elements, of vacuum tubes only, with positive feedback
- H03K3/05—Generators characterised by the type of circuit or by the means used for producing pulses by the use, as active elements, of vacuum tubes only, with positive feedback using means other than a transformer for feedback
- H03K3/06—Generators characterised by the type of circuit or by the means used for producing pulses by the use, as active elements, of vacuum tubes only, with positive feedback using means other than a transformer for feedback using at least two tubes so coupled that the input of one is derived from the output of another, e.g. multivibrator
- H03K3/10—Generators characterised by the type of circuit or by the means used for producing pulses by the use, as active elements, of vacuum tubes only, with positive feedback using means other than a transformer for feedback using at least two tubes so coupled that the input of one is derived from the output of another, e.g. multivibrator monostable
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
- H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0209—Inorganic, non-metallic particles
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0236—Plating catalyst as filler in insulating material
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0239—Coupling agent for particles
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/10—Using electric, magnetic and electromagnetic fields; Using laser light
- H05K2203/107—Using laser light
Definitions
- the present invention relates to a thermosetting resin composition for LDS, a resin molded product, and a three-dimensional molded circuit component.
- Examples of the resin material used in LASER DIRECT STRUCTURING (LDS) include a fiber reinforced resin material in which fibers are impregnated with a thermoplastic resin composition containing an LDS additive.
- a thermoplastic resin composition containing an LDS additive As this type of technology, there is one described in Patent Document 1. According to this document, a polyamide resin is used as the thermoplastic resin.
- thermosetting resin composition for LDS using a thermosetting resin has room for improvement in the characteristic with plating.
- thermosetting resin composition for LDS used for the formation of LASER DIRECT STRUCTURING (LDS), A thermosetting resin; An inorganic filler; A non-conductive metal compound that forms a metal nucleus upon irradiation with active energy rays; A coupling agent, The non-conductive metal compound is Spinel metal oxide, One or more selected from the group consisting of a metal oxide selected from Group 3 to Group 12 of the Periodic Table and the group having two or more adjacent transition metal elements, and a tin-containing oxide Including There is provided a thermosetting resin composition for LDS, wherein the coupling agent contains one or more selected from the group consisting of mercaptosilane, aminosilane, and epoxysilane.
- thermosetting resin composition for LDS a resin molded article provided with a cured product of the above-described thermosetting resin composition for LDS is provided.
- the resin molded product having a three-dimensional structure; There is provided a three-dimensional molded circuit component comprising a three-dimensional circuit formed on the surface of the resin molded product.
- thermosetting resin composition for LDS excellent in properties with plating a resin molded product and a three-dimensional molded circuit component using the same.
- thermosetting resin composition of the embodiment of the present invention is an LDS thermosetting resin composition used for LDS.
- the LDS (LASER DIRECT STRUCTURING (Laser Direct Structuring)) is one of the manufacturing methods of three-dimensional molded circuit parts (MID), and is a resin molded product containing an LDS additive by irradiation with active energy rays.
- a metal nucleus is generated on the surface of the metal, and a plating pattern (wiring) can be formed in the energy ray irradiation region by, for example, electroless plating using the metal nucleus as a seed.
- the thermosetting resin composition of the present embodiment includes a thermosetting resin, an inorganic filler, a non-conductive metal compound that forms a metal nucleus by irradiation with active energy rays, and a coupling agent. it can.
- the non-conductive metal compound acts as the LDS additive and is selected from (i) spinel type metal oxide and (ii) groups 3 to 12 of the periodic table. And one or more selected from the group consisting of (iii) a tin-containing oxide and a metal oxide having two or more transition metal elements adjacent to the group.
- the coupling agent may contain one or more selected from the group consisting of mercaptosilane, aminosilane, and epoxysilane.
- the non-conductive metal compound is not particularly limited as long as it can form a metal nucleus by irradiation with active energy rays.
- active energy rays such as a YAG laser having an absorbable wavelength region
- the metal nucleus is activated (for example, reduced) )
- Metal nuclei capable of metal plating are considered to be generated.
- a seed region having a metal nucleus capable of metal plating is formed on the irradiated surface. It is formed. By using the obtained seed region, it is possible to form a plating pattern such as a circuit on the surface of the cured product of the thermosetting resin composition.
- thermosetting resin composition by selecting an appropriate coupling agent in the thermosetting resin composition, it is possible to improve the properties with plating in the cured product of the thermosetting resin composition.
- thermosetting resin composition of the present embodiment will be described.
- thermosetting resin composition of the present embodiment contains a thermosetting resin.
- thermosetting resin include one or two selected from the group consisting of, for example, epoxy resins, phenol resins, oxetane resins, (meth) acrylate resins, unsaturated polyester resins, diallyl phthalate resins, and maleimide resins.
- epoxy resins for example, epoxy resins, phenol resins, oxetane resins, (meth) acrylate resins, unsaturated polyester resins, diallyl phthalate resins, and maleimide resins.
- an epoxy resin from the viewpoint of improving curability, storage stability, heat resistance, moisture resistance, and chemical resistance.
- the epoxy resin contained in the thermosetting resin monomers, oligomers and polymers generally having two or more epoxy groups in one molecule can be used, and the molecular weight and molecular structure are not particularly limited.
- the epoxy resin is, for example, a biphenyl type epoxy resin; a bisphenol type epoxy resin such as a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, or a tetramethylbisphenol F type epoxy resin; a stilbene type epoxy resin; a phenol novolac type epoxy.
- novolak type epoxy resin such as cresol novolak type epoxy resin
- polyfunctional epoxy resin such as trisphenol type epoxy resin exemplified by triphenolmethane type epoxy resin, alkyl-modified triphenolmethane type epoxy resin, etc .
- having phenylene skeleton Phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin having phenylene skeleton, phenol aralkyl type epoxy resin having biphenylene skeleton, bif Phenol aralkyl type epoxy resins such as naphthol aralkyl type epoxy resins having a nylene skeleton
- naphthol type epoxy resins such as dihydroxynaphthalene type epoxy resins and epoxy resins obtained by glycidyl etherification of dihydroxynaphthalene dimers; triglycidyl isocyanurate; Triazine nucleus-containing epoxy resins such as monoallyl diglycidyl isocyan
- the epoxy resin may include one or more selected from the group consisting of orthocresol novolac type epoxy resins, phenol aralkyl resin type epoxy resins having a biphenylene skeleton, and triphenylmethane type epoxy resins.
- the lower limit of the content of the thermosetting resin is preferably 1% by mass or more, more preferably 2% by mass or more, based on the entire thermosetting resin composition. It is particularly preferably 5% by mass or more. Thereby, the fluidity
- the upper limit of the content of the thermosetting resin is, for example, preferably 15% by mass or less, more preferably 14% by mass or less, with respect to the entire thermosetting resin composition. It is particularly preferable that the content is not more than mass%. Thereby, moisture resistance reliability and reflow resistance can be improved.
- thermosetting resin in such a range.
- content with respect to the whole thermosetting resin composition refers to content with respect to the whole solid content except the solvent of a thermosetting resin composition, when a solvent is included.
- the solid content of the thermosetting resin composition refers to the non-volatile content in the thermosetting resin composition and refers to the remainder excluding volatile components such as water and solvent.
- the thermosetting resin composition of the present embodiment can contain a curing agent.
- the curing agent can be roughly classified into three types, for example, a polyaddition type curing agent, a catalyst type curing agent, and a condensation type curing agent. These may be used alone or in combination of two or more.
- polyaddition type curing agent used as the curing agent examples include aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylylenediamine (MXDA), diaminodiphenylmethane (DDM), and m-phenylene.
- aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylylenediamine (MXDA), diaminodiphenylmethane (DDM), and m-phenylene.
- aromatic polyamines such as diamine (MPDA) and diaminodiphenylsulfone (DDS)
- polyamine compounds including dicyandiamide (DICY) and organic acid dihydrazide hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MTHPA), etc.
- Acid anhydrides including aromatic acid anhydrides such as alicyclic acid anhydrides, trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), benzophenone tetracarboxylic acid (BTDA); Phenolic resin-based curing agents such as polyethylene resins, polyvinylphenols, aralkyl-type phenolic resins; polymercaptan compounds such as polysulfides, thioesters, and thioethers; isocyanate compounds such as isocyanate prepolymers and blocked isocyanates; organic acids such as carboxylic acid-containing polyester resins One type or two or more types selected from the group consisting of:
- BDMA benzyldimethylamine
- DMP-30 2,4,6-trisdimethylaminomethylphenol
- 2-methylimidazole, 2 Imidazole compounds such as ethyl-4-methylimidazole (EMI24)
- EMI24 ethyl-4-methylimidazole
- Lewis acids such as BF3 complexes.
- the condensation type curing agent used as the curing agent is, for example, one or two types 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. The above can be included.
- 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.
- the phenol resin-based curing agent for example, monomers, oligomers and polymers generally having two or more phenolic hydroxyl groups in one molecule can be used, and the molecular weight and molecular structure are not particularly limited.
- the phenol resin-based curing agent used as the curing agent of the present embodiment include novolak-type phenol resins such as phenol novolak resin, cresol novolak resin, and bisphenol novolak; and polyfunctional phenols such as polyvinylphenol and triphenolmethane-type phenol resin.
- Modified phenol resin such as terpene modified phenol resin and dicyclopentadiene modified phenol resin
- Phenol aralkyl type phenol resin such as phenol aralkyl resin having phenylene skeleton and / or biphenylene skeleton, naphthol aralkyl resin having phenylene and / or biphenylene skeleton
- One or more selected from the group consisting of bisphenol compounds such as bisphenol A and bisphenol F may be included.
- a novolak type phenol resin, a polyfunctional type phenol resin, and a phenol aralkyl type phenol resin are included from a viewpoint of suppressing the curvature of a molded object.
- a phenol novolak resin, a phenol aralkyl resin having a biphenylene skeleton, and a triphenylmethane type phenol resin modified with formaldehyde can be preferably used.
- the lower limit of the content of the curing agent is, for example, preferably 0.5% by mass or more, and more preferably 1% by mass or more, with respect to the entire thermosetting resin composition. It is particularly preferably 1.5% by mass or more.
- liquidity can be implement
- the upper limit of the content of the curing agent is preferably 9% by mass or less, more preferably 8% by mass or less, and more preferably 7% by mass with respect to the entire thermosetting resin composition. The following is particularly preferable. Thereby, the moisture resistance reliability and reflow resistance of an electronic component can be improved. Moreover, it is possible to contribute to suppression of the curvature of the molded object obtained by controlling content of a hardening
- the thermosetting resin composition of the present embodiment contains a nonconductive metal compound.
- the non-conductive metal compound include, for example, a spinel metal oxide, selected from Group 3 to Group 12 of the periodic table, and two or more transition metal elements adjacent to the group.
- One or more selected from the group consisting of metal oxides and tin-containing oxides can be included.
- the spinel type structure is one of the typical crystal structure types found in the compound of AB 2 O 4 type (A and B are metal elements) as a double oxide. is there.
- a and B are metal elements
- Either a forward spinel structure or a reverse spinel structure (B (AB) O 4 ) in which A and B are partially exchanged may be used, but a forward spinel structure can be more preferably used.
- a in the forward spinel structure may be copper.
- the metal atom constituting the spinel metal oxide for example, copper or chromium can be used. That is, the nonconductive metal compound can contain a spinel type metal oxide containing copper or chromium. For example, from the viewpoint of adhesion with a copper plating pattern, copper can be used as the metal atom.
- the above metal atoms include trace amounts of metal atoms such as antimony, tin, lead, indium, iron, cobalt, nickel, zinc, cadmium, silver, bismuth, arsenic, manganese, magnesium, and calcium. You may contain. These trace metal atoms may exist as oxides. Moreover, content of a trace metal atom can be 0.001 mass% or less with respect to the whole metal atom in a metal oxide, respectively.
- the spinel type metal oxide has high thermal stability and can have durability in an acidic or alkaline aqueous metallization bath.
- the spinel-type metal oxide is an unirradiated region on the surface of the cured product of the thermosetting resin composition in a high oxide state, for example, by appropriately controlling the dispersibility of the thermosetting resin composition.
- An example of the above spinel type metal oxide is described in, for example, Japanese Patent No. 3881338.
- the metal oxide having a transition metal element is a metal oxide selected from Group 3 to Group 12 of the periodic table and having two or more transition metal elements adjacent to the group.
- the metal belonging to the transition metal element can be expressed as containing an n-group metal and an n + 1 group metal in the periodic table.
- these metal oxides may be used alone or in combination of two or more.
- Examples of metals belonging to Group n of the periodic table include Group 3 (scandium, yttrium), Group 4 (titanium, zirconium, etc.), Group 5 (vanadium, niobium, etc.), Group 6 (chromium, molybdenum, etc.), 7 Group (such as manganese), Group 8 (such as iron and ruthenium), Group 9 (such as cobalt, rhodium, and iridium), Group 10 (nickel, palladium, platinum), Group 11 (such as copper, silver, and gold), Group 12 ( Zinc, cadmium, etc.) and group 13 (aluminum, gallium, indium, etc.).
- Examples of the metal of group n + 1 of the periodic table include group 4 (titanium, zirconium, etc.), group 5 (vanadium, niobium, etc.), group 6 (chromium, molybdenum, etc.), group 7 (manganese, etc.), 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.).
- An example of the metal oxide having the transition metal element as described above is described in, for example, Japanese Patent No. 3881338.
- the tin-containing oxide is a metal oxide containing at least tin.
- Antimony may be used as the metal atom constituting the tin-containing oxide in addition to tin.
- Such a tin-containing oxide can contain tin oxide and antimony oxide.
- 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.
- This tin-containing oxide may further contain lead and / or copper as a metal component.
- 90% by mass or more is tin, 5 to 9% by mass is antimony, and in the range of 0.01 to 0.1% by mass.
- Such tin-containing oxides can contain, for example, tin oxide, antimony oxide, lead oxide and / or copper oxide.
- the said tin containing oxide may contain the trace metal atom illustrated by the spinel type metal oxide.
- the tin-containing oxide may be used in combination with the spinel metal oxide or the metal oxide having the transition metal element.
- the lower limit of the content of the nonconductive metal compound is, for example, 3% by mass or more, preferably 5% by mass or more, and more preferably 8% by mass or more, with respect to the entire thermosetting resin composition. It is. Thereby, in the hardened
- the upper limit of content of the said nonelectroconductive metal compound is 20 mass% or less with respect to the whole thermosetting resin composition, for example, Preferably it is 18 mass% or less, More preferably, it is 15 mass % Or less.
- thermosetting resin composition in the hardened
- thermosetting resin composition of the present embodiment may contain at least one organic heat-stable metal chelate complex salt in addition to the above non-conductive metal compound.
- the thermosetting resin composition of the present embodiment can contain an inorganic filler.
- the inorganic filler include one or two selected from the group consisting of fused silica such as fused crushed silica and fused spherical silica, silica such as crystalline silica, alumina, aluminum hydroxide, silicon nitride, and aluminum nitride. More than one type of inorganic filler can be included. Among these, as the inorganic filler, silica such as fused crushed silica, fused spherical silica, and crystalline silica is preferably used, and fused spherical silica is more preferably used. By using a spherical inorganic filler, the dispersibility of the thermosetting resin composition can be improved.
- the upper limit of the average particle diameter D50 of the inorganic filler is, for example, 30 ⁇ m or less, preferably 20 ⁇ m or less, and more preferably 10 ⁇ m or less.
- the lower limit value of the average particle diameter D50 of the inorganic filler is not particularly limited, but is, for example, 0.01 ⁇ m or more, preferably 0.05 ⁇ m or more, and more preferably 0.1 ⁇ m or more.
- the upper limit value of D90 of the inorganic filler is, for example, 80 ⁇ m or less, preferably 70 ⁇ m or less, and more preferably 60 ⁇ m or less.
- the lower limit value of D90 of the inorganic filler is not particularly limited, but may be, for example, 1 ⁇ m or more, 3 ⁇ m or more, 10 ⁇ m or more, or 20 ⁇ m or more.
- liquidity of a thermosetting resin composition can be made favorable, and it becomes possible to improve a moldability more effectively.
- the upper limit of the particle size distribution width (D90 / D50) of the inorganic filler is, for example, 10 or less, preferably 9 or less, and more preferably 8 or less. Thereby, since the variation in the surface roughness of the hardened
- D50 and D90 of the inorganic filler can be measured by measuring the particle size distribution on a volume basis using a commercially available laser diffraction particle size distribution measuring device (for example, SALD-7000, manufactured by Shimadzu Corporation). it can.
- the obtained median diameter (D50) can be an average particle diameter.
- thermosetting resin composition of the present embodiment can contain a curing accelerator.
- a curing accelerator what is necessary is just to accelerate
- the curing accelerator 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, an adduct of a phosphonium compound and a silane compound; , 8-diazabicyclo [5.4.0] undecene-7, benzyldimethylamine, 2-methylimidazole and the like, and selected from nitrogen-containing compounds such as amidine and tertiary amine, and quaternary salts of the amidine and amine One type or two or more types can be included.
- 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, an adduct of
- a phosphorus atom containing compound is included from a viewpoint of improving curability.
- it has latent properties such as tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds. It is more preferable to include those.
- Examples of the organic phosphine that can be used in the thermosetting resin composition of the present embodiment include a first phosphine such as ethylphosphine and phenylphosphine; a second phosphine such as dimethylphosphine and diphenylphosphine; trimethylphosphine, triethylphosphine, and tributyl. Third phosphine such as phosphine and triphenylphosphine can be used.
- thermosetting resin composition of the present embodiment examples include compounds represented by the following 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.
- 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, where x and y are numbers from 1 to 3, z is a number from 0 to 3, and x y.
- the compound represented by General formula (6) is obtained as follows, for example, it is not limited to this. First, a tetra-substituted phosphonium halide, an aromatic organic acid and a base are mixed in an organic solvent and mixed uniformly to generate an aromatic organic acid anion in the solution system. Then, when water is added, the compound represented by the general formula (6) can be precipitated.
- R 4 , R 5 , R 6 and R 7 bonded to the phosphorus atom are phenyl groups
- AH is a compound having a hydroxyl group in an aromatic ring, that is, phenols.
- A is preferably an anion of the phenol.
- phenols examples include monocyclic phenols such as phenol, cresol, resorcin, and catechol, condensed polycyclic phenols such as naphthol, dihydroxynaphthalene, and anthraquinol, bisphenols such as bisphenol A, bisphenol F, and bisphenol S, Examples include polycyclic phenols such as phenylphenol and biphenol.
- thermosetting resin composition of the present embodiment examples include compounds represented by the following 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 represents a number of 0 to 5
- g represents 0 to A number of 3.
- the compound represented by the general formula (7) is obtained, for example, as follows. First, it is obtained through a step of bringing a triaromatic substituted phosphine, which is a third phosphine, into contact with a diazonium salt and replacing the triaromatic substituted phosphine with a diazonium group of the diazonium salt.
- a triaromatic substituted phosphine which is a third phosphine
- the present invention is not limited to this.
- thermosetting resin composition of the present embodiment examples include compounds represented by the following 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 the same as each other.
- R 13 , R 14 and R 15 each represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms and may be the same or different from each other, and R 14 and R 15 are bonded to each other. And may have a circular structure.
- Examples of the phosphine compound used as an adduct of a phosphine compound and a quinone compound include an aromatic ring such as triphenylphosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, trinaphthylphosphine, and tris (benzyl) phosphine.
- aromatic ring such as triphenylphosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, trinaphthylphosphine, and tris (benzyl) phosphine.
- Those having a substituent or a substituent such as an alkyl group and an alkoxyl group are preferred, and examples of the substituent such as an alkyl group and an alkoxyl group include those having 1 to 6 carbon atoms. From the viewpoint of availability, triphenyl
- examples of the quinone compound used for the adduct of the phosphine compound and the quinone compound include benzoquinone and anthraquinones, and among them, p-benzoquinone is preferable from the viewpoint of storage stability.
- the adduct can be obtained by contacting and mixing in a solvent capable of dissolving both organic tertiary phosphine and benzoquinone.
- the solvent is preferably a ketone such as acetone or methyl ethyl ketone, which has low solubility in the adduct.
- the present invention is not limited to this.
- 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, ie, 1,
- a compound in which 4-benzoquinone and triphenylphosphine are added is preferable in that it reduces the thermal elastic modulus of the cured product of the thermosetting resin composition.
- thermosetting resin composition of the present embodiment examples include compounds represented by the following general formula (9).
- R 16 , R 17 , R 18 and R 19 are each an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group. Represents a group, which may be the same or different from each other, wherein R 20 is an organic group bonded to the groups Y 2 and Y 3.
- R 21 represents the groups Y 4 and Y 5 ; Y 2 and Y 3 represent a group formed by releasing a proton from a proton donating group, 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 a group formed by releasing a proton from a proton donating group, and groups Y 4 and Y 5 in the same molecule are combined with a silicon atom to form a chelate structure.
- R 20, and R 21 are mutually Or different mere, Y 2, Y 3, Y 4 and Y 5 may .Z 1 also being the same or different organic group having an aromatic ring or a heterocyclic ring or fat, A group.
- examples of R 16 , R 17 , R 18 and R 19 include 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.
- 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.
- R 20 is an organic group bonded to Y 2 and Y 3.
- R 21 is an organic group that binds to groups Y 4 and Y 5 .
- Y 2 and Y 3 are groups formed by proton-donating groups releasing protons, and groups Y 2 and Y 3 in the same molecule are combined with a silicon atom to form a chelate structure.
- Y 4 and Y 5 are groups formed by proton-donating groups releasing protons, and groups Y 4 and Y 5 in the same molecule are combined with 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.
- the proton donor releases two protons.
- the proton donor is preferably an organic acid having at least two carboxyl groups or hydroxyl groups in the molecule, and further has a carboxyl group or hydroxyl group on the adjacent carbon constituting the 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.
- 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 Roxy-2-naphthoic acid, chloranilic acid, tannic acid, 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2-propanediol, glycerin, etc., among these, catechol, 1,2- Dihydroxynaphthalene and 2,3-dihydroxynaphthalene are more preferable.
- 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, a butyl group, Aliphatic hydrocarbon groups such as hexyl group and octyl group, aromatic hydrocarbon groups such as phenyl group, benzyl group, naphthyl group and biphenyl group, glycidyloxy groups such as glycidyloxypropyl group, mercaptopropyl group and aminopropyl group Reactive groups such as mercapto groups, alkyl groups having amino groups, and vinyl groups.
- methyl groups, ethyl groups, phenyl groups, naphthyl groups, and biphenyl groups are preferred from the viewpoint of thermal stability. More preferable.
- a silane compound such as phenyltrimethoxysilane and a proton donor such as 2,3-dihydroxynaphthalene are added to a flask containing methanol, and then dissolved.
- Sodium methoxide-methanol solution is added dropwise with stirring.
- crystals are precipitated. The precipitated crystals are filtered, washed with water, and vacuum dried to obtain an adduct of a phosphonium compound and a silane compound.
- the content of the curing accelerator is preferably 0.1% by mass or more, more preferably 0.15% by mass or more, based on the entire thermosetting resin composition. It is particularly preferably 25% by mass or more.
- content of a hardening accelerator is 1 mass% or less with respect to the whole thermosetting resin composition, and it is more preferable that it is 0.8 mass% or less.
- thermosetting resin composition of this embodiment can contain a coupling agent.
- the coupling agent may include one or more selected from the group consisting of mercaptosilane, aminosilane, and epoxysilane.
- Examples of the epoxy silane include ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltri And methoxysilane.
- Examples of the aminosilane include phenylaminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxysilane, N- ⁇ .
- aminoethyl ⁇ -aminopropylmethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltriethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropyltriethoxysilane N- (6-aminohexyl) 3-aminopropyltrimethoxysilane, N- (3- (trimethoxysilylpropyl) -1,3-benzenedimethanane, etc.
- the primary amino moiety of aminosilane is a ketone.
- aminosilane coupling agent As the aminosilane may have a secondary amino group.
- the mercaptosilane include ⁇ -mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfide, and bis (3-triethoxysilylpropyl) disulfide.
- silane coupling agents that exhibit the same function as a mercaptosilane coupling agent by thermal decomposition. These silane coupling agents may be preliminarily hydrolyzed.
- silane coupling agents may be used alone or in combination of two or more.
- the moldability is optimized by optimizing the viscosity of the thermosetting resin composition. Can be improved.
- Mercaptosilane is preferable from the viewpoint of continuous moldability, secondary aminosilane is preferable from the viewpoint of fluidity, and epoxysilane is preferable from the viewpoint of adhesion.
- thermosetting resin composition As a lower limit of content of the said coupling agent, 0.01 mass% or more is preferable with respect to the whole thermosetting resin composition, More preferably, it is 0.05 mass% or more, Most preferably, it is 0.1 mass. % Or more. Thereby, since the flow flow length of a thermosetting resin composition can be lengthened, injection moldability can be improved.
- an upper limit of content of a coupling agent 1 mass% or less is preferable with respect to the whole thermosetting resin composition, More preferably, it is 0.8 mass% or less, Most preferably, it is 0.6 mass. % Or less. Thereby, the water absorption of the hardened
- thermosetting resin composition of the present embodiment may contain additives such as a mold release agent, a flame retardant, an ion scavenger, a colorant, a low stress agent, and an antioxidant as necessary. it can. These may be used alone or in combination of two or more.
- the mold release agent is, for example, one or two kinds selected from natural waxes such as carnauba wax, synthetic waxes such as montanic ester wax and polyethylene oxide wax, higher fatty acids such as zinc stearate and metal salts thereof, and paraffin.
- 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 a hydrous oxide of an element selected from magnesium, aluminum, bismuth, titanium, and zirconium.
- the colorant may include one or more selected from carbon black, bengara, and titanium oxide.
- the low stress agent may include one or more selected from silicone compounds such as polybutadiene compounds, acrylonitrile butadiene copolymer compounds, silicone oils, and silicone rubbers.
- thermosetting resin composition of the present embodiment can be configured not to contain carbon such as carbon black used as the colorant. Thereby, the characteristic with plating can be improved.
- thermosetting resin composition of the present embodiment will be described.
- the lower limit of the spiral flow flow length of the thermosetting resin composition of the present embodiment is, for example, 50 cm or more, preferably 55 cm or more, and more preferably 60 cm or more. Thereby, the fluidity
- the upper limit value of the spiral flow flow length is not particularly limited, but may be, for example, 200 cm or less.
- the spiral flow flow length can be measured according to the EMMI-1-66 method under conditions of a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a holding time of 120 seconds.
- thermosetting resin composition of this embodiment As a manufacturing method of the thermosetting resin composition of this embodiment, a mixture is obtained by mixing each component of the said thermosetting resin composition by a well-known means, for example. Furthermore, a kneaded product is obtained by melt-kneading the mixture.
- a kneading method for example, an extrusion kneader such as a single-screw kneading extruder, a biaxial kneading extruder, or a roll kneader such as a mixing roll can be used, but a twin-screw kneading extruder is used. It is preferable.
- the kneaded product After cooling, the kneaded product can be made into a predetermined shape.
- thermosetting resin composition of this embodiment you may have predetermined
- a thermosetting resin composition suitable for known molding methods such as transfer molding, injection molding, and compression molding can be obtained.
- the granular thermosetting resin composition is a pulverized product obtained by pulverizing the obtained kneaded product, and the granular thermosetting resin composition is a powder of the thermosetting resin composition.
- thermosetting resin composition (Powdered kneaded product) Agglomerated solids or granules obtained by a known granulation method, tablet-like thermosetting resin composition is a thermosetting resin composition at high pressure It is a shaped body shaped to have a predetermined shape by tableting, and the sheet-like thermosetting resin composition is, for example, a sheet-shaped or a roll-curable thermosetting resin composition It means a resin film made of a material.
- the thermosetting resin composition in the form of powder, granules, tablets or sheets may be in a semi-cured state (B stage state).
- thermosetting resin composition in the present embodiment examples 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 including a cured product of the thermosetting resin composition.
- the shape of the resin molded product in the present embodiment is not particularly limited as long as it has a three-dimensional structure, but may have a curved surface in part.
- a three-dimensional molded circuit component (MOLDED INTERCONNECT DEVICE (hereinafter referred to as “MID”)) has a three-dimensional shape, the above-mentioned resin molded product, and a three-dimensional circuit.
- a three-dimensional resin This is a part formed with a metal film on the surface of a molded product.
- the three-dimensional molded circuit component can include, for example, a resin molded product having a three-dimensional structure and a three-dimensional circuit formed on the surface of the resin molded product.
- LDS of this embodiment is one of the manufacturing methods of MID, and it is applied to the surface of the cured product (three-dimensional structure resin molded product) of the thermosetting resin composition containing the LDS additive by active energy rays.
- a metal nucleus is generated, and a plating pattern (wiring) can be formed in the energy beam irradiation region by, for example, electroless plating treatment using the metal nucleus as a seed.
- the manufacturing process of MID is based on the production of a thermosetting resin composition used for LDS, the molding of the thermosetting resin composition, the irradiation of active energy rays on the obtained resin molded product, and the plating treatment. Circuit formation can be included. A surface cleaning step may be added before the plating process.
- a laser can be used as the active energy ray.
- the laser can be appropriately selected from known lasers such as YAG laser, excimer laser, and electromagnetic radiation, and YGA laser is preferable.
- the wavelength of the laser is not particularly defined, but is, for example, 200 nm to 12000 nm. Among these, preferably 248 nm, 308 nm, 355 nm, 532 nm, 1064 nm or 10600 nm may be used.
- plating treatment either electroplating or electroless plating may be used.
- a circuit (plating layer) can be formed by performing a plating process on the region irradiated with the laser.
- the plating solution is not particularly defined, and a known plating solution can be widely used.
- a plating solution in which copper, nickel, gold, silver, and palladium are mixed as a metal component may be used.
- the resin molded product (cured product of the thermosetting resin composition) is not limited to the final product, and may include composite materials and various parts.
- the resin molded product can be used as a component for portable electronic devices, vehicles and medical devices, electronic components including other electric circuits, semiconductor sealing materials, and composite materials for forming these.
- the MID can be applied to a mobile phone, a smartphone, a built-in antenna, a sensor, or a semiconductor device.
- thermosetting resin composition The raw materials having the blending amounts shown in Tables 1 to 3 below were mixed using a mixer at room temperature, and then roll kneaded at 70 to 100 ° C. Subsequently, after cooling the obtained kneaded material, this was grind
- Thermosetting resin 1 phenol aralkyl resin type epoxy resin having biphenylene skeleton (Nippon Kayaku Co., Ltd., NC3000, epoxy equivalent 276 g / eq, softening point 58 ° C.)
- Thermosetting resin 2 Orthocresol novolac type epoxy resin (“EOCN1020” manufactured by Nippon Kayaku Co., Ltd., softening point 55 ° C., epoxy equivalent 196, chloride ion amount 5.0 ppm)
- Thermosetting resin 3 Triphenylmethane type epoxy resin (manufactured by Mitsubishi Chemical Corporation, 1032H-60, epoxy equivalent 171 g / eq, softening point 60 ° C.)
- Thermosetting resin 4 biphenyl type epoxy resin (Japan Epoxy Resin Co., Ltd., YX4000HK, softening point 105 ° C., epoxy equivalent 193) (Curing agent) Curing agent 1:
- Curing agent 3 Triphenylmethane type phenol resin modified with formaldehyde (HE910-20, manufactured by Air Water Co., Ltd.) (Inorganic filler)
- Inorganic filler 1 fused spherical silica (average particle diameter D50: 3.4 ⁇ m, D90: 6.8 ⁇ m, D90 / D50: 2.0, particles exceeding 12 ⁇ m, 0.5% by mass or less, manufactured by Tatsumori Co., Ltd., MUF-4V)
- Inorganic filler 2 fused spherical silica (average particle size D50: 0.9 ⁇ m, D90: 1.6 ⁇ m, D90 / D50: 1.8, manufactured by Admatechs, SD2500-SQ)
- Inorganic filler 3 fused spherical silica (average particle size D50: 6.2 ⁇ m, D90: 20.4
- Curing accelerator 2 Tetraphenylphosphonium • 4,4′-sulfonyldiphenolate represented by the following structural formula (14) obtained by the following production method [Method of synthesizing curing accelerator 2] A separable flask equipped with a stirrer was charged with 37.5 g (0.15 mol) of 4,4′-bisphenol S and 100 ml of methanol, dissolved by stirring at room temperature, and 4.0 g of sodium hydroxide in 50 ml of methanol in advance while stirring. A solution in which (0.1 mol) was dissolved was added.
- Coupling agent 1 phenylaminopropyltrimethoxysilane (CF4083 manufactured by Toray Dow Corning Co., Ltd.)
- Coupling agent 2 ⁇ -glycidoxypropyltrimethoxysilane (GPS-M manufactured by Chisso Corporation)
- Coupling agent 3 ⁇ -mercaptopropyltrimethoxysilane (S810 manufactured by Chisso Corporation)
- Carbon 1 Carbon black (trade name carbon # 5 manufactured by Mitsubishi Chemical Corporation)
- Mold release agent 1 Glycerin trimontanate (manufactured by Clariant Japan Co., Ltd., Recolbe WE4)
- Silicone oil 1 Silicone oil (FZ-3730 manufactured by Toray Dow Corning Co., Ltd.)
- Low stress agent 1 epoxidized polybutadiene (JP-200, epoxidized polybutadiene manufactured by Nippon Soda, Td5: 245 ° C) Flame retardant 1: Aluminum
- thermosetting resin composition of Comparative Example 1 was produced in the same manner as in Example 1 except that the coupling agent was not added.
- the thermosetting resin composition of Comparative Example 2 was produced in the same manner as in Example 1 except that the nonconductive metal compound was not added.
- Resin molded products were obtained by transfer molding the thermosetting resin compositions of Examples 1 to 21, Reference Examples 1 to 3, and Comparative Examples 1 and 2, respectively.
- the surface of the resin molded product obtained in Examples 1 to 21 was irradiated with a YAG laser, and it was found that the characteristics with plating in the laser irradiation region were better than those of Comparative Examples 1 and 2, respectively. .
- thermosetting resin composition of each Example was evaluated using thermosetting resin composition of each Example and each reference example.
- spiral flow The spiral flow flow length was measured using the obtained thermosetting resin composition under the conditions of a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a holding time of 120 seconds in accordance with the EMMI-1-66 method.
- the surface of the obtained resin molded product was irradiated with a YAG laser, and the plating property in the laser irradiation region was evaluated according to the following criteria. ⁇ : There is no unevenness on the plating surface ⁇ : Some unevenness is visible on the plating surface, but there is no unplated part ⁇ : There is unevenness on the plating surface, but there is no unplated part ⁇ : Severe unevenness appears on the plating surface Yes
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Abstract
Description
LASER DIRECT STRUCTURING(LDS)の形成に用いるLDS用熱硬化性樹脂組成物であって、
熱硬化性樹脂と、
無機充填材と、
活性エネルギー線の照射により金属核を形成する非導電性金属化合物と、
カップリング剤と、を含み、
前記非導電性金属化合物が、
スピネル型の金属酸化物、
周期表第3族~第12族の中から選択されており、かつ当該族が隣接する2以上の遷移金属元素を有する金属酸化物、および
錫含有酸化物からなる群から選択される一種以上を含み、
前記カップリング剤が、メルカプトシラン、アミノシランおよびエポキシシランからなる群から選択される一種以上を含む、LDS用熱硬化性樹脂組成物が提供される。
三次元構造を有する上記樹脂成形品と、
前記樹脂成形品の表面に形成された三次元回路と、を備える、三次元成形回路部品が提供される。
本実施形態の熱硬化性樹脂組成物は、LDSに用いるLDS用熱硬化性樹脂組成物である。当該LDS(LASER DIRECT STRUCTURING(レーザーダイレクトストラクチャリング))とは、三次元成形回路部品(MID)の製造方法の一つであり、活性エネルギー線を照射して、LDS添加剤を含有する樹脂成形品の表面に金属核を生成し、その金属核をシードとして、例えば無電解めっき処理等により、エネルギー線照射領域にめっきパターン(配線)を形成することができる。
本実施形態において、上記非導電性金属化合物は、上記LDS添加剤として作用し、(i)スピネル型の金属酸化物、(ii)周期表第3族~第12族の中から選択されており、かつ当該族が隣接する2以上の遷移金属元素を有する金属酸化物、および(iii)錫含有酸化物からなる群から選択される一種以上を含むことができる。また、上記カップリング剤は、メルカプトシラン、アミノシランおよびエポキシシランからなる群から選択される一種以上を含むことができる。
上記熱硬化性樹脂としては、例えば、たとえばエポキシ樹脂、フェノール樹脂、オキセタン樹脂、(メタ)アクリレート樹脂、不飽和ポリエステル樹脂、ジアリルフタレート樹脂、およびマレイミド樹脂からなる群から選択される一種類または二種類以上を含むことができる。これらの中でも、硬化性、保存性、耐熱性、耐湿性、および耐薬品性を向上させる観点から、エポキシ樹脂を含むことがとくに好ましい。
成形体の反り抑制や、充填性、耐熱性、耐湿性等の諸特性のバランスを向上させる観点からは、これらのうち、ノボラック型エポキシ樹脂、多官能エポキシ樹脂、およびフェノールアラルキル型エポキシ樹脂を用いることができる。また、上記エポキシ樹脂としては、オルソクレゾールノボラック型エポキシ樹脂、ビフェニレン骨格を有するフェノールアラルキル樹脂型エポキシ樹脂およびトリフェニルメタン型エポキシ樹脂からなる群から選択される一種以上を含むことができる。このようなエポキシ樹脂とカップリング剤との適切に選択することにより、熱硬化性樹脂組成物の硬化物におけるめっき付き特性を向上させることができる。
本実施形態において、熱硬化性樹脂組成物全体に対する含有量とは、溶媒を含む場合には、熱硬化性樹脂組成物のうちの溶媒を除く固形分全体に対する含有量を指す。熱硬化性樹脂組成物の固形分とは、熱硬化性樹脂組成物中における不揮発分を指し、水や溶媒等の揮発成分を除いた残部を指す。
上記硬化剤としては、たとえば重付加型の硬化剤、触媒型の硬化剤、および縮合型の硬化剤の3タイプに大別することができる。これらを単独で用いても2種以上を組み合わせて用いてもよい。
本実施形態の硬化剤として用いられるフェノール樹脂系硬化剤は、たとえば、フェノールノボラック樹脂、クレゾールノボラック樹脂、ビスフェノールノボラック等のノボラック型フェノール樹脂;ポリビニルフェノール、トリフェノールメタン型フェノール樹脂等の多官能型フェノール樹脂;テルペン変性フェノール樹脂、ジシクロペンタジエン変性フェノール樹脂等の変性フェノール樹脂;フェニレン骨格及び/又はビフェニレン骨格を有するフェノールアラルキル樹脂、フェニレン及び/又はビフェニレン骨格を有するナフトールアラルキル樹脂等のフェノールアラルキル型フェノール樹脂;ビスフェノールA、ビスフェノールF等のビスフェノール化合物からなる群から選択される一種類または二種類以上を含むことができる。これらの中でも、成形体の反りを抑制する観点からは、ノボラック型フェノール樹脂、多官能型フェノール樹脂およびフェノールアラルキル型フェノール樹脂を含むことがより好ましい。また、フェノールノボラック樹脂、ビフェニレン骨格を有するフェノールアラルキル樹脂、ホルムアルデヒドで変性したトリフェニルメタン型フェノール樹脂が好ましく使用することができる。
非導電性金属化合物の具体例としては、例えば、スピネル型の金属酸化物、周期表第3族~第12族の中から選択されており、かつ当該族が隣接する2以上の遷移金属元素を有する金属酸化物、および錫含有酸化物からなる群から選択される一種以上を含むことができる。
以上のような上記遷移金属元素を有する金属酸化物の一例としては、例えば、特許3881338号に記載されている。
上記無機充填材としては、たとえば、溶融破砕シリカ及び溶融球状シリカ等の溶融シリカ、結晶シリカ等のシリカ、アルミナ、水酸化アルミニウム、窒化珪素、および窒化アルミからなる群から選択される一種類または二種類以上の無機充填材を含むことができる。この中でも、無機充填材として、溶融破砕シリカ、溶融球状シリカ、結晶シリカ等のシリカを用いることが好ましく、溶融球状シリカを用いることがより好ましい。球状の無機充填材を用いることにより、熱硬化性樹脂組成物の分散性を向上させることができる。
上記硬化促進剤としては、熱硬化性樹脂と硬化剤との架橋反応を促進させるものであればよく、一般の熱硬化性樹脂組成物に使用するものを用いることができる。
一方で、硬化促進剤の含有量は、熱硬化性樹脂組成物の全体に対して1質量%以下であることが好ましく、0.8質量%以下であることがより好ましい。硬化促進剤の含有量を上記上限値以下とすることにより、成形時における流動性の向上を図ることができる。
上記カップリング剤は、メルカプトシラン、アミノシランおよびエポキシシランからなる群から選択される一種以上を含むことができる。
また、上記アミノシランとしては、例えば、フェニルアミノプロピルトリメトキシシラン、γ-アミノプロピルトリエトキシシラン、γ-アミノプロピルトリメトキシシラン、N-β(アミノエチル)γ-アミノプロピルトリメトキシシラン、N-β(アミノエチル)γ-アミノプロピルメチルジメトキシシラン、N-フェニル-γ-アミノプロピルトリエトキシシラン、N-フェニル-γ-アミノプロピルトリメトキシシラン、N-β(アミノエチル)γ-アミノプロピルトリエトキシシラン、N-(6-アミノヘキシル)3-アミノプロピルトリメトキシシラン、N-(3-(トリメトキシシリルプロピル)-1,3-ベンゼンジメタナン等が挙げられる。アミノシランの1級アミノ部位をケトン又はアルデヒドを反応させて保護した潜在性アミノシランカップリング剤として用いてもよい。また、アミノシランとしては、2級アミノ基を有してもよい。
また、上記メルカプトシランとしては、例えば、γ-メルカプトプロピルトリメトキシシラン、3-メルカプトプロピルメチルジメトキシシランのほか、ビス(3-トリエトキシシリルプロピル)テトラスルフィド、ビス(3-トリエトキシシリルプロピル)ジスルフィドのような熱分解することによってメルカプトシランカップリング剤と同様の機能を発現するシランカップリング剤など、が挙げられる。
これらのシランカップリング剤は予め加水分解反応させたものを配合してもよい。これらのシランカップリング剤は1種類を単独で用いても2種類以上を併用してもよい。
本実施形態において、カップリング剤として、メルカプトシラン、アミノシランおよびエポキシシランからなる群から選択される一種以上を含むことにより、熱硬化性樹脂組成物の粘度を最適にすることにより、金型成形性を向上させることができる。
本実施形態の熱硬化性樹脂組成物には、必要に応じて、たとえば、離型剤、難燃剤、イオン捕捉剤、着色剤、低応力剤および酸化防止剤等の添加剤を含有することができる。これらを単独で用いても2種以上を組み合わせて用いてもよい。
上記難燃剤は、たとえば、水酸化アルミニウム、水酸化マグネシウム、ホウ酸亜鉛、モリブデン酸亜鉛、ホスファゼンから選択される1種類または2種類以上を含むことができる。
上記イオン捕捉剤は、ハイドロタルサイト類またはマグネシウム、アルミニウム、ビスマス、チタン、ジルコニウムから選ばれる元素の含水酸化物から選択される1種類または2種類以上を含むことができる。
上記着色剤は、カーボンブラック、ベンガラ、酸化チタンから選択される1種類または2種類以上を含むことができる。
上記低応力剤は、ポリブタジエン化合物、アクリロニトリルブタジエン共重合化合物、シリコーンオイル、シリコーンゴム等のシリコーン化合物から選択される1種類または2種類以上を含むことができる。
本実施形態の熱硬化性樹脂組成物の形状としては、例えば、粉粒状、顆粒状、タブレット状またはシート状等の所定の形状を有していてもよい。これにより、トランスファー成形、射出成形、および圧縮成形等の公知の成形方法に適する熱硬化性樹脂組成物を得ることができる。
本実施形態において、粉粒状の熱硬化性樹脂組成物とは、得られた混練物を粉砕した粉砕物であり、顆粒状の熱硬化性樹脂組成物とは、熱硬化性樹脂組成物の粉末(粉粒状の混練物)同士を固めた凝集体または公知の造粒法で得られた造粒物であり、タブレット状の熱硬化性樹脂組成物とは、熱硬化性樹脂組成物を高圧で打錠成形することによって所定形状を有するように造形された造形体であり、シート状の熱硬化性樹脂組成物とは、例えば、枚葉状または巻き取り可能なロール状を有する熱硬化性樹脂組成物からなる樹脂膜であることを意味する。
本実施形態において、粉粒状、顆粒状、タブレット状またはシート状の、熱硬化性樹脂組成物は、半硬化状態(Bステージ状態)であってもよい。
(熱硬化性樹脂組成物の調製)
下記の表1~3に示す配合量の各原材料を、常温でミキサーを用いて混合した後、70~100℃でロール混練した。次いで、得られた混練物を冷却した後、これを粉砕して、粉粒状の熱硬化性樹脂組成物を得た。次いで、高圧で打錠成形することによってタブレット状の熱硬化性樹脂組成物を得た。
熱硬化性樹脂1:ビフェニレン骨格を有するフェノールアラルキル樹脂型エポキシ樹脂(日本化薬株式会社製、NC3000、エポキシ当量276g/eq、軟化点58℃)
熱硬化性樹脂2:オルソクレゾールノボラック型エポキシ樹脂(日本化薬(株)製「EOCN1020」、軟化点55℃、エポキシ当量196、塩素イオン量5.0ppm)
熱硬化性樹脂3:トリフェニルメタン型エポキシ樹脂(三菱化学株式会社製、1032H-60。エポキシ当量171g/eq、軟化点60℃)
熱硬化性樹脂4:ビフェニル型エポキシ樹脂(ジャパンエポキシレジン(株)製、YX4000HK、軟化点105℃、エポキシ当量193)
(硬化剤)
硬化剤1:ビフェニレン骨格を有するフェノールアラルキル樹脂(明和化成株式会社製、MEH-7851SS、水酸基当量203g/eq)
硬化剤2:フェノールノボラック樹脂(住友ベークライト(株)製PR-HF-3(フェノールノボラック樹脂、水酸基当量105g/eq、軟化点80℃))
硬化剤3:ホルムアルデヒドで変性したトリフェニルメタン型フェノール樹脂(エア・ウォーター(株)製、HE910-20)
(無機充填材)
無機充填材1:溶融球状シリカ(平均粒径D50:3.4μm、D90:6.8μm、D90/D50:2.0、12μmを超える粒子0.5質量%以下、(株)龍森製、MUF-4V)
無機充填材2:溶融球状シリカ(平均粒径D50:0.9μm、D90:1.6μm、D90/D50:1.8、アドマテックス(株)製、SD2500-SQ)
無機充填材3:溶融球状シリカ(平均粒径D50:6.2μm、D90:20.4μm、D90/D50:3.3、24μmを超える粒子0.5質量%以下、アドマテックス(株)製、FEB24S5)
無機充填材4:溶融球状シリカ(平均粒径D50:12.3μm、D90:36.8μm、D90/D50:3.0、45μmを超える粒子0.5質量%以下、アドマテックス(株)製、FED45S2)
無機充填材5:溶融球状シリカ(平均粒径D50:7.2μm、D90:43.9μm、D90/D50:6.1、電気化学工業株式会社製、FB-105FD)
無機充填材6:溶融球状シリカ(平均粒径D50:0.8μm、D90:1.3μm、D90/D50:1.7、(株)アドマテックス製、SC2500SQ)
無機充填材7:溶融球状シリカ(平均粒径D50:1.0μm、D90:4.0μm、D90/D50:3.8、(株)アドマテックス製、SC5500SQ)
(非導電性金属化合物)
非導電性金属化合物1:Black 30C965:CuCr2O4(Shephred color company製)
非導電性金属化合物2:Black 1G:CuCr2O4(Shephred color company製)
(硬化促進剤)
硬化促進剤1:下記の製造方法で得られた下記構造式(16)で示されるテトラフェニルホスホニウムビス(ナフタレン-2,3-ジオキシ)フェニルシリケート
メタノール1800gを入れたフラスコに、フェニルトリメトキシシラン249.5g、2,3-ジヒドロキシナフタレン384.0gを加えて溶かし、次に室温攪拌下28%ナトリウムメトキシド-メタノール溶液231.5gを滴下した。さらにそこへ予め用意したテトラフェニルホスホニウムブロマイド503.0gをメタノール600gに溶かした溶液を室温攪拌下滴下すると結晶が析出した。析出した結晶を濾過、水洗、真空乾燥し、桃白色結晶の硬化促進剤1を得た。
硬化促進剤2:下記の製造方法で得られた下記構造式(14)で示されるテトラフェニルホスホニウム・4,4'-スルフォニルジフェノラート
撹拌装置付きのセパラブルフラスコに4,4'-ビスフェノールS37.5g(0.15モル)、メタノール100mlを仕込み、室温で撹拌溶解し、更に攪拌しながら予め50mlのメタノールに水酸化ナトリウム4.0g(0.1モル)を溶解した溶液を添加した。次いで予め150mlのメタノールにテトラフェニルホスホニウムブロマイド41.9g(0.1モル)を溶解した溶液を加えた。しばらく攪拌を継続し、300mlのメタノールを追加した後、フラスコ内の溶液を大量の水に撹拌しながら滴下し、白色沈殿を得た。沈殿を濾過、乾燥し、白色結晶の硬化促進剤2を得た。
(カップリング剤)
カップリング剤1:フェニルアミノプロピルトリメトキシシラン(東レ・ダウコーニング(株)製CF4083)
カップリング剤2:γ-グリシドキシプロピルトリメトキシシラン(チッソ(株)製GPS-M)
カップリング剤3:γ-メルカプトプロピルトリメトキシシラン(チッソ(株)製S810)
(添加剤)
カーボン1:カーボンブラック(三菱化学株式会社製商品名カーボン#5)
離型剤1:グリセリントリモンタン酸エステル(クラリアントジャパン(株)製、リコルブWE4)
シリコーンオイル1:シリコーンオイル(東レ・ダウコーニング(株)製FZ-3730
低応力剤1:エポキシ化ポリブタジエン(JP-200、日本曹達製エポキシ化ポリブタジエン、Td5:245℃)
難燃剤1:水酸化アルミニウム(住友化学(株)製、商品名CL303)
比較例1の熱硬化性樹脂組成物は、カップリング剤を添加しなかった点を除いて実施例1と同様にして作製した。比較例2の熱硬化性樹脂組成物は、非導電性金属化合物を添加しなかった点を除いて、実施例1と同様にして作製した。
スパイラルフロー流動長は、得られた熱硬化性樹脂組成物を使用し、EMMI-1-66法に従い、金型温度175℃、注入圧力6.9MPa、保圧時間120秒の条件で測定した。
得られた樹脂成形品の表面に対して、YAGレーザーを照射し、そのレーザー照射領域におけるめっき付き性について、以下の判断基準で評価した。
◎:めっき表面にムラ無し
○:めっき表面に多少のムラが見えるがめっき未着部分はなし
△:めっき表面にムラが見えるがめっき未着部分はなし
×:めっき表面にひどいムラが見えめっき未着部あり
Claims (16)
- LASER DIRECT STRUCTURING(LDS)に用いるLDS用熱硬化性樹脂組成物であって、
熱硬化性樹脂と、
無機充填材と、
活性エネルギー線の照射により金属核を形成する非導電性金属化合物と、
カップリング剤と、を含み、
前記非導電性金属化合物が、
スピネル型の金属酸化物、
周期表第3族~第12族の中から選択されており、かつ当該族が隣接する2以上の遷移金属元素を有する金属酸化物、および
錫含有酸化物からなる群から選択される一種以上を含み、
前記カップリング剤が、メルカプトシラン、アミノシランおよびエポキシシランからなる群から選択される一種以上を含む、LDS用熱硬化性樹脂組成物。 - 請求項1に記載のLDS用熱硬化性樹脂組成物であって、
前記無機充填材の平均粒径D50が30μm以下である、LDS用熱硬化性樹脂組成物。 - 請求項1または2に記載のLDS用熱硬化性樹脂組成物であって、
前記無機充填材のD90が80μm以下である、LDS用熱硬化性樹脂組成物。 - 請求項1から3のいずれか1項に記載のLDS用熱硬化性樹脂組成物であって、
前記無機充填材の粒度分布幅(D90/D50)が10以下である、LDS用熱硬化性樹脂組成物。 - 請求項1から4のいずれか1項に記載のLDS用熱硬化性樹脂組成物であって、
前記非導電性金属化合物の含有量が、当該LDS用熱硬化性樹脂組成物全体に対して、3質量%以上20質量%以下である、LDS用熱硬化性樹脂組成物。 - 請求項1から5のいずれか1項に記載のLDS用熱硬化性樹脂組成物であって、
EMMI-1-66法に従い、金型温度175℃、注入圧力6.9MPa、保圧時間120秒の条件で測定される、当該LDS用硬化性樹脂組成物のスパイラルフロー流動長が50cm以上である、LDS用熱硬化性樹脂組成物。 - 請求項1から6のいずれか1項に記載のLDS用熱硬化性樹脂組成物であって、
カーボンを含まない、LDS用熱硬化性樹脂組成物。 - 請求項1から7のいずれか1項に記載のLDS用熱硬化性樹脂組成物であって、
前記非導電性金属化合物が、銅またはクロムを含む前記スピネル型の金属酸化物を含有する、LDS用熱硬化性樹脂組成物。 - 請求項1から8のいずれか1項に記載のLDS用熱硬化性樹脂組成物であって、
前記無機充填材が、シリカを含む、LDS用熱硬化性樹脂組成物。 - 請求項1から9のいずれか1項に記載のLDS用熱硬化性樹脂組成物であって、
前記熱硬化性樹脂が、エポキシ樹脂を含む、LDS用熱硬化性樹脂組成物。 - 請求項10に記載のLDS用熱硬化性樹脂組成物であって、
前記エポキシ樹脂が、オルソクレゾールノボラック型エポキシ樹脂、ビフェニレン骨格を有するフェノールアラルキル樹脂型エポキシ樹脂、およびトリフェニルメタン型エポキシ樹脂からなる群から選択される一種以上を含む、LDS用熱硬化性樹脂組成物。 - 請求項1から11のいずれか1項に記載のLDS用熱硬化性樹脂組成物であって、
硬化剤をさらに含む、LDS用熱硬化性樹脂組成物。 - 請求項1から12のいずれか1項に記載のLDS用熱硬化性樹脂組成物であって、
硬化促進剤を含む、LDS用熱硬化性樹脂組成物。 - 請求項1から13のいずれか1項に記載のLDS用熱硬化性樹脂組成物であって、
粉粒状、顆粒状、タブレット状またはシート状である、LDS用熱硬化性樹脂組成物。 - 請求項1から14のいずれか1項に記載のLDS用熱硬化性樹脂組成物であって、
LDS用熱硬化性樹脂組成物の硬化物を備える、樹脂成形品。 - 三次元構造を有する請求項15に記載の樹脂成形品と、
前記樹脂成形品の表面に形成された三次元回路と、を備える、三次元成形回路部品。
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