JP2020132647A - Thermosetting resin molding material for injection molding used in lds, method for manufacturing injection molding using the same, and method for manufacturing mid - Google Patents

Abstract

To provide a thermosetting resin molding material for injection molding used in LDS which is excellent in insulation reliability and connection reliability.SOLUTION: A thermosetting resin molding material for injection molding is a thermosetting resin molding material for injection molding used in LDS, contains a thermosetting resin, an inorganic filler, and an LDS additive composed of a non-conductive metal compound forming a metal core by irradiation with active energy rays, in which a high-type viscosity is 100 Pa s or more and 2,000 Pa s or less, a time Twith a torque value twice or less than the minimum torque value that is measured using a laboratory blast mill is 10 seconds or longer and 60 seconds or shorter, and the minimum torque value is 0.80 N m or more and 25 N m or less.SELECTED DRAWING: None

Description

The present invention relates to a thermosetting resin molding material for injection molding used for LASER DIRECT STRUCTURING, a method for producing an injection molded product using the same, and a method for producing MOLDED INTERCONNECT DEVICE.

As the resin material used for LDS, a fiber-reinforced resin material obtained by impregnating fibers with a thermoplastic resin composition containing an LDS additive is generally used. As a technique of this kind, the one described in Patent Document 1 is known. Patent Document 1 describes a polyamide resin as a thermoplastic resin.

Japanese Unexamined Patent Publication No. 2015-134903

However, as a result of the examination by the present inventor, it has been found that there is room for improvement in the insulation reliability and the connection reliability in the thermoplastic resin molding material containing the LDS additive described in Patent Document 1.
Further, as a type of resin containing an LDS additive, a thermoplastic resin has been studied so far, but a thermosetting resin has not yet been sufficiently studied.

As a result of further studies, the present inventor has realized a molding material suitable for injection molding by appropriately controlling the viscosity and melting characteristics of the thermosetting resin molding material, and the injection molded product obtained by using the molding material can be realized. We have found that the insulation reliability and the connection reliability in the above can be improved, and have completed the present invention.

According to the present invention
A thermosetting resin molding material for injection molding used in LASER DIRECT STRUCTURING (LDS).
Thermosetting resin and
Inorganic filler and
Contains an LDS additive composed of a non-conductive metal compound that forms metal nuclei by irradiation with active energy rays.
The heightened viscosity of the thermosetting resin molding material for injection molding, which is measured under the conditions of a measurement temperature of 150 ° C. and a load of 200 kgf, using a heightened viscosity measuring device is 100 Pa · s or more and 2,000 Pa · s. Is below
The time T ₁ at which the torque value of the injection-molded thermosetting resin molding material measured by the following procedure is twice or less the minimum torque value is 10 seconds or more and 60 seconds or less, and the injection-molding thermosetting is performed. Provided is a thermosetting resin molding material for injection molding, in which the minimum torque value of the sex resin molding material is 0.80 N ・ m or more and 25 N ・ m or less.

Further, according to the present invention.
Provided is a method for manufacturing an injection-molded product, which comprises a step of obtaining an injection-molded product by injection-molding using the thermosetting resin molding material for injection molding.

Further, according to the present invention.
The step of irradiating the surface of the injection-molded product obtained by the above-mentioned method for manufacturing the injection-molded product with active energy rays, and
Provided is a method for producing MOLDED INTERCONNECT DEVICE (MID), which comprises a step of forming a circuit by plating on the surface of the injection-molded article after the step of irradiating the active energy ray.

According to the present invention, there is provided a thermosetting resin molding material for injection molding used for LDS having excellent insulation reliability and connection reliability, a method for manufacturing an injection molded product using the same, and a method for manufacturing MID.

It is a graph which shows typically the relationship between the torque value obtained by the measurement using a laboplast mill, and the measurement time. It is a schematic diagram of the plating pattern for evaluating the connection reliability. It is a schematic diagram of the plating pattern for evaluating the insulation reliability.

The outline of the thermosetting resin molding material of this embodiment will be described.

The thermosetting resin molding material of the present embodiment is a thermosetting resin molding material for injection molding (hereinafter abbreviated as "thermosetting resin molding material") used for LASER DIRECT STRUCTURING (hereinafter abbreviated as "LDS"). is there.

LDS (laser direct structuring) is one of the manufacturing methods of MOLDED INTERCONNECT DEVICE (hereinafter referred to as "MID"). In the manufacturing method of MID (three-dimensional molding circuit component), a metal nucleus is generated on the surface of a resin molded product containing an LDS additive by irradiating with active energy rays, and the metal nucleus is used as a seed, for example, electroless plating. A plating pattern (wiring) can be formed in the energy ray irradiation region by processing or the like.

The thermosetting resin molding material of the present embodiment contains, as an LDS additive, a non-conductive metal compound that forms a metal nucleus by irradiation with active energy rays.
The non-conductive metal compound is not particularly limited as long as it can form a metal nucleus by irradiation with active energy rays. As an example of the non-conductive metal compound, (i) a spinel-type metal oxide, (ii) two or more transition metals selected from Group 3 to Group 12 of the Periodic Table and adjacent to the group. Examples include one or more selected from the group consisting of elemental metal oxides and (iii) tin-containing oxides.

Although the detailed mechanism is not clear, when an active energy ray such as a YAG laser having an absorbable wavelength region is applied to a non-conductive metal compound, the metal nucleus is activated (for example, reduced) and metal plating is performed. It is thought that a possible metal nucleus is produced.

When the surface of a molded product of a thermosetting resin molding material containing a non-conductive metal compound is irradiated with active energy rays, a seed region having a metal core capable of metal plating is formed on the irradiated surface. By utilizing the obtained seed region, it becomes possible to form a plating pattern such as a circuit on the surface of a three-dimensional molded product of a thermosetting resin molding material.

According to the present embodiment, a molding material suitable for injection molding can be realized by appropriately controlling the viscosity and melting characteristics of the thermosetting resin molding material. The high viscosity is used as an index for the state of viscosity, and the lab torque is used as an index for the melting characteristics. By adopting these indexes, it is possible to stably evaluate the state of viscosity and melting characteristics, and by setting the numerical range based on the indexes to an appropriate range, thermosetting resin molding suitable for injection molding is possible. It turned out that the material was obtained. It was found that the injection-molded product obtained by injection-molding such a thermosetting resin molding material is excellent in insulation reliability and connection reliability.

Hereinafter, each component of the thermosetting resin molding material of the present embodiment will be described.

(Thermosetting resin)
The thermosetting resin molding material contains a thermosetting resin.
As the thermosetting resin, for example, one or two types selected from the group consisting of, for example, epoxy resin, phenol resin, oxetane resin, (meth) acrylate resin, unsaturated polyester resin, diallyl phthalate resin, and maleimide resin. The above can be included.
Among these, a phenol resin or an epoxy resin can be used from the viewpoint of low line expansion, high insulation, and high Tg.

Examples of the phenolic resin include novolak-type phenolic resins such as phenol novolac resin, cresol novolak resin, and bisphenol A-type novolak resin; melted with methylol-type resol resin, dimethylene ether-type resol resin, tung oil, flaxseed oil, walnut oil, and the like. Resol type phenolic resin such as oil-melted resolphenol resin; arylalkylene type phenolic resin and the like can be mentioned. These may be used alone or in combination of two or more. Among these, it is preferable to use a resol type phenol resin from the viewpoint of quick curing.

As the resol type phenol resin, for example, one obtained by reacting phenols and aldehydes under alkaline conditions or weakly acidic conditions is used.

As the above-mentioned phenols, for example, the number of phenol rings may be any of mononuclear, dinuclear or trinuclear, and the number of phenolic hydroxyl groups may be one or two or more.
Examples of the above-mentioned phenols are not particularly limited, but for example, phenol; cresol such as orthocresol, metacresol, paracresol; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6. -Cresol such as 3,5-xylenol; 2,3,5-trimethylphenol, 2-ethylphenol, 4-ethylphenol, 2-isopropylphenol, 4-isopropylphenol, n-butylphenol, isobutylphenol, tert- Alkylphenols such as butylphenol, hexylphenol, octylphenol, nonylphenol, phenylphenol, benzylphenol, cumylphenol, allylphenol, cardanol, ursiol, laccol; naphthols such as 1-naphthol and 2-naphthol; fluorophenols, chlorophenols, bromo Halogenated phenols such as phenol and iodophenol, monovalent phenol substitutions such as p-phenylphenol, aminophenol, nitrophenol, dinitrophenol, trinitrophenol; bisphenol S, bisphenol F, bisphenol A, bisphenol C, bisphenol Z, Bisphenols such as bisphenol E; polyvalent phenols such as resorcin, alkylresorcin, pyrogallol, catechol, alkylcatechol, hydroquinone, alkylhydroquinone, fluoroglusin, dihydroxynaphthalin, and naphthalene; These may be used alone or in combination of two or more. Among these, phenols can include one or more selected from the group consisting of phenol, cresol, xylenol, alkylphenol and bisphenol, and from the viewpoint of low cost, phenol, cresol, butylphenol and bisphenol A can be used. ..

The aldehydes are not particularly limited, but for example, formaldehyde such as formalin and paraformaldehyde; trioxane, acetaldehyde, paraaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glioxal, n-butylaldehyde, etc. Examples thereof include isobutyl aldehyde, tert-butyl aldehyde, capro aldehyde, allyl aldehyde, benz aldehyde, croton aldehyde, achlorine, tetraoxymethylene, phenylacetaldehyde, o-tolu aldehyde and salicyl aldehyde. These aldehydes may be used alone or in combination of two or more. Among these, aldehydes can include formaldehyde or acetaldehyde, and formalin or paraformaldehyde can be used from the viewpoint of productivity and low cost.

Under alkaline conditions, an alkaline catalyst can be used.
The alkaline catalyst is not particularly limited, and examples thereof include amines such as sodium hydroxide, lithium hydroxide, potassium hydroxide, aqueous ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, methylethylamine, and triethylamine. Alkaline earth metal oxides such as calcium, magnesium and barium and alkaline substances such as hydroxide, sodium carbonate and hexamethylenetetramine can be used. These may be used alone or in combination of two or more. For example, sodium hydroxide may be used.

Further, under weakly acidic conditions, a zinc-based catalyst can be used.
The zinc-based catalyst is not particularly limited, and any divalent metal salt catalyst can be used. For example, zinc acetate, zinc formate, or the like can be used. These may be used alone or in combination of two or more. For example, zinc acetate hydrate may be used.

The amount of the alkaline catalyst or the zinc-based catalyst added may be, for example, 0.01% by mass to 20% by mass, preferably 0.1% by mass to 10% by mass, based on 100% by mass of the phenols. Can be done.

The molar ratio of phenols to aldehydes (F / P molar ratio) may be, for example, 0.7 mol to 4.0 mol of aldehydes with respect to 1 mol of phenols, preferably 1.0 mol. It can be up to 3.0 mol. By setting the aldehydes in the above range, the conversion rate of the aldehydes can be increased with respect to 1 mol of the phenols as described above, and the residual unreacted aldehydes can be reduced.

The thermosetting resin molding material can include a resole-type phenol resin as the thermosetting resin.
The lower limit of the content of the resole-type phenol resin is, for example, 60% by mass or more, preferably 70% by mass or more, and more preferably 75% by mass or more with respect to the entire phenol resin (100% by mass). Thereby, the quick-curing property of the sealing resin composition can be enhanced. Thereby, the temperature cycle resistance can be improved. The upper limit of the content of the resole-type phenol resin may be, for example, 100% by mass or less and 95% by mass or less with respect to the entire phenol resin (100% by mass). This makes it possible to balance the physical properties of the molded product of the sealing resin composition.

The above-mentioned resole: novolak content ratio is, for example, 60:40 to 100: 0, more preferably 70:30 to 100: 0, and further preferably 75:25 to 100: 0 in terms of mass. By improving the content ratio of the resole-type phenol resin in the phenol resin in this way, the quick-curing property of the sealing resin composition can be enhanced. Thereby, the temperature cycle resistance can be improved.

In the present specification, "~" means that an upper limit value and a lower limit value are included unless otherwise specified.

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 particularly 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. Novorak type epoxy resin such as type epoxy resin; Polyfunctional epoxy resin such as triphenol methane type epoxy resin, alkyl modified triphenol methane type epoxy resin, etc .; Phenol aralkyl type epoxy having phenylene skeleton Phenol aralkyl type epoxy resin such as resin, naphthol 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 2 amounts Naftor-type epoxy resin such as epoxy resin obtained by glycidyl etherification of the body; Triazine nucleus-containing epoxy resin such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; Arihashi cyclic carbonization such as dicyclopentadiene-modified phenol-type epoxy resin It can contain one or more selected from the group consisting of hydrogen compound modified phenolic epoxy resins. These may be used alone or in combination of two or more.

The thermosetting resin molding material may contain a phenol resin alone as the thermosetting resin, or may contain two or more kinds of epoxy resin, phenol resin and the like.

In the present embodiment, the lower limit of the content of the thermosetting resin is, for example, 5% by mass or more, preferably 10% by mass or more, and more preferably 15% by mass or more with respect to the entire thermosetting resin molding material. .. Thereby, the fluidity at the time of molding can be improved. Therefore, it is possible to improve the filling property and the molding stability. On the other hand, the upper limit of the content of the thermosetting resin is, for example, 50% by mass or less, preferably 45% by mass or less, and more preferably 25% by mass or less with respect to the entire thermosetting resin molding material. As a result, moisture resistance reliability and reflow resistance can be improved. Further, by controlling the content of the thermosetting resin within such a range, it is possible to contribute to the suppression of warpage of the molded product.

In the present embodiment, the content of the thermosetting resin molding material with respect to the whole refers to the content of the thermosetting resin molding material with respect to the entire solid content excluding the solvent when the solvent is contained. The solid content of the thermosetting resin molding material refers to the non-volatile content in the thermosetting resin molding material, and refers to the balance excluding volatile components such as water and solvent.

(LDS additive)
The thermosetting resin molding material contains a non-conductive metal compound as an LDS additive.
Specific examples of the non-conductive metal compound include two or more transition metal elements selected from, for example, spinel-type metal oxides and groups 3 to 12 of the periodic table, and the groups are adjacent to each other. It can contain one or more selected from the group consisting of metal oxides having, and tin-containing oxides. These may be used alone or in combination of two or more.

As the spinel-type metal oxide, for example, the spinel-type structure is one of the typical crystal structure types found in AB ₂ O ₄ type compounds (A and B are metal elements) of compound oxides. is there. Either a forward spinel structure or an inverted spinel structure (B (AB) O ₄ ) in which A and B are partially exchanged) may be used, but the forward spinel structure can be used more preferably. 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 non-conductive metal compound 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 adhesion to the copper plating pattern.

In addition to copper and chromium, trace amounts of metal atoms such as antimony, tin, lead, indium, iron, cobalt, nickel, zinc, cadmium, silver, bismuth, arsenic, manganese, magnesium, and calcium are used as the metal atoms. It may be contained. These trace metal atoms may exist as oxides. In addition, 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.

In the present embodiment, 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 has, for example, an unirradiated region on the surface of the cured product of the thermosetting resin molding material in a high oxide state by appropriately controlling the dispersibility of the thermosetting resin molding material. Can exist in. As an example of the spinel-type metal oxide as described above, for example, Japanese Patent No. 3881338 is described.

The metal oxide having the 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. .. Here, the metal belonging to the transition metal element can be expressed as containing a metal of group n in the periodic table and a 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.

Examples of the metals belonging to Group n in the above periodic table include Group 3 (scandium, ittrium), Group 4 (titanium, zirconium, etc.), Group 5 (vanadium, niobium, etc.), Group 6 (chromium, molybdenum, etc.), and 7. Group 8 (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 (group 12) Zinc, cadmium, etc.), Group 13 (aluminum, gallium, indium, etc.).

Examples of group n + 1 metals in the periodic table include groups 4 (titanium, gallium, etc.), group 5 (vanadium, niobium, etc.), group 6 (chromium, molybdenum, etc.), group 7 (manganese, etc.), and 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.).
As an example of the metal oxide having the above transition metal element as described above, for example, Japanese Patent No. 3881338 is described.

The tin-containing oxide is a metal oxide containing at least tin. As the metal atom constituting the tin-containing oxide, antimony may be used in addition to tin. Such tin-containing oxides can contain tin oxide and antimony oxide.

For example, 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, antimony oxide, lead oxide and / or copper oxide. The tin-containing oxide may contain trace metal atoms exemplified by spinel-type metal oxides. Further, the tin-containing oxide may be used in combination with the spinel-type metal oxide or the metal oxide having the transition metal element.

The lower limit of the content of the non-conductive metal compound (LDS additive) is, for example, 0.1% by mass or more, preferably 0.3% by mass or more, based on the entire thermosetting resin molding material. , More preferably 0.5% by mass or more. As a result, in the cured product of the thermosetting resin molding material, the plating characteristics can be improved. The upper limit of the content of the non-conductive metal compound is, for example, 10.0% by mass or less, preferably 8.0% by mass or less, more preferably 8.0% by mass or less, based on the entire thermosetting resin molding material. Is 6.0% by mass or less. As a result, in the cured product of the thermosetting resin molding material, it is possible to suppress a decrease in insulating property and an increase in dielectric loss tangent. Further, when the non-conductive metal compound is non-spherical, the fluidity of the thermosetting resin molding material can be improved.

The thermosetting resin molding material of the present embodiment may contain at least one kind of organic thermostable metal chelate complex salt in addition to the above-mentioned non-conductive metal compound.

(Inorganic filler)
The thermosetting resin molding material includes an inorganic filler.
As the inorganic filler, a fibrous, plate-shaped or spherical inorganic filler can be used. These may be used alone or in combination of two or more.

Examples of the fibrous inorganic filler include glass fibers, carbon fibers, asbestos fibers, metal fibers, wallastnite, attapulsite, sepiolite, rock wool, aluminum borate whiskers, potassium titanate fibers, calcium carbonate whiskers, and titanium oxide. Examples include whiskers and ceramic fibers.

Examples of the plate-shaped inorganic filler or granular inorganic filler include kaolin clay, calcium carbonate, zinc oxide, calcium silicate hydrate, mica, glass flakes, glass powder, magnesium carbonate, silica, titanium oxide, and alumina. Aluminum hydroxide, magnesium hydroxide, barium sulfate, calcium sulfate, calcium sulfite, zinc borate, barium metaborate, aluminum borate, calcium borate, sodium borate, aluminum nitride, boron nitride, silicon nitride, fibrous inorganic Examples include crushed fillers. The thermosetting resin molding material containing the phenol resin may contain glass fibers.

Among these, it is preferable to use spherical silica such as crushed silica, spherical silica, and crystalline silica as the inorganic filler. These may be fused silica. By using the spherical inorganic filler, the dispersibility of the thermosetting resin molding material can be improved.

The upper limit of the average particle size D50 of the inorganic filler is, for example, 30 μm or less, preferably 28 μm or less, and more preferably 26 μm or less. This makes it possible to narrow the width of the obtained circuit pattern in the cured product of the thermosetting resin molding material. On the other hand, the lower limit of the average particle size D50 of the inorganic filler is not particularly limited, but is, for example, 0.1 μm or more, preferably 0.5 μm or more, and more preferably 1.0 μm or more. As a result, the melt viscosity of the thermosetting resin molding material can be appropriately controlled, so that the moldability of injection molding can be improved.

The upper limit of D90 of the inorganic filler is, for example, 100 μm or less, preferably 80 μm or less, and more preferably 60 μm or less. As a result, in the cured product of the thermosetting resin molding material, the surface roughness of the cured product after laser processing can be reduced, so that the plating characteristics can be improved. On the other hand, the lower limit of D90 of the inorganic filler is not particularly limited, but may be, for example, 1 μm or more, 3 μm or more, 10 μm or more, or 20 μm or more. As a result, the fluidity of the thermosetting resin molding material can be improved, and the moldability can be improved 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. As a result, it is possible to suppress variations in the surface roughness of the cured product of the thermosetting resin molding material, so that the plating characteristics can be improved. Further, the lower limit of the particle size distribution width (D90 / D50) of the inorganic filler may be, for example, 1 or more.

In the present embodiment, the inorganic fillers D50 and D90 can measure the particle size distribution of particles on a volume basis using a commercially available laser diffraction type particle size distribution measuring device (for example, SALD-7000 manufactured by Shimadzu Corporation). it can. Here, the obtained median diameter (D50) can be used as the average particle size.

The lower limit of the content of the filler is, for example, 50% by mass or more, preferably 60% by mass or more, and more preferably 65% by mass or more with respect to 100% by mass of the solid content of the thermosetting resin molding material. .. As a result, the mechanical strength of the cured product of the thermosetting resin molding material can be increased, and a thermosetting resin molding material suitable for the molding material can be realized. On the other hand, the upper limit of the content of the filler is not particularly limited with respect to 100% by mass of the solid content of the thermosetting resin molding material, but is, for example, 90% by mass or less, preferably 80% by mass or less, more preferably. Is 75% by mass or less. As a result, it is possible to improve the manufacturing stability while suppressing the increase in viscosity.

(Hardener)
When the thermosetting resin molding material contains the phenol resin as the thermosetting resin, the amine-based curing agent can be contained as the curing agent.

The amine-based curing agent is not limited, and a conventionally known amine-based curing agent used for curing the novolak type phenol resin can be used.
Specifically, hexamethylenetetramine, hexamethoxymethylolmelamine and the like can be used as the amine-based curing agent. As the amine-based curing agent, for example, hexamethylenetetramine is preferably used.

The content of the amine-based curing agent is, for example, 7 parts by mass to 30 parts by mass, and more preferably 10 parts by mass to 25 parts by mass with respect to the entire phenol resin (100% by mass). By setting the value within the above numerical range, good curability can be obtained.

When the thermosetting resin molding material contains the epoxy resin as the thermosetting resin, at least the following polyaddition type curing agent, catalytic type curing agent, and condensation type curing agent are used as the curing agent. One or more can be used. These may be used alone or in combination of two or more.

The heavy addition type curing agent used as the curing agent is, for example, an aliphatic polyamine such as diethylenetriamine (DETA), triethylenetetramine (TETA), metaxylerylene diamine (MXDA), diaminodiphenylmethane (DDM), m-phenylene. In addition to aromatic polyamines such as diamine (MPDA) and diaminodiphenylsulfone (DDS), polyamine compounds containing dicyandiamide (DICY), organic acid dihydrazide, etc .; hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MTHPA), etc. Acid anhydrides containing alicyclic acid anhydrides, trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), aromatic acid anhydrides such as benzophenone tetracarboxylic acid (BTDA); novolak type phenolic resin, A group consisting of phenolic resin-based curing agents such as polyvinylphenol and aralkyl-type phenolic resin; polymercaptan compounds such as polysulfide, thioester and thioether; isocyanate compounds such as isocyanate prepolymer and blocked isocyanate; and organic acids such as carboxylic acid-containing polyester resin. It can include one or more selected from.

The catalytic curing agent used as the curing agent is a tertiary amine compound such as benzyldimethylamine (BDMA), 2,4,6-trisdimethylaminomethylphenol (DMP-30); 2-methylimidazole, 2 Imidazole compounds such as −ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole; triphenylphosphine, tri-p-tolylphosphine, tetraphenylphosphonium / tetraphenylborate, triphenylphosphine / triphenylborane, 1, It can contain one or more selected from the group consisting of organic phosphorus compounds such as 2-bis- (diphenylphosphine) ethane; Lewis acids such as BF3 complex.

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.

Among these, it is more preferable to contain a phenolic resin-based curing agent from the viewpoint of improving the balance of flame resistance, moisture resistance, electrical properties, curability, storage stability and the like. As the phenolic 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 particularly limited.
The phenolic resin-based curing agent used as the curing agent of the present embodiment is, for example, a novolak-type phenol resin such as phenol novolac resin, cresol novolak resin, or bisphenol novolak; a polyfunctional phenol such as polyvinylphenol or triphenol methane-type phenol resin. Resin; Modified phenol resin such as terpen-modified phenol resin, dicyclopentadiene-modified phenol resin; Phenolic aralkyl resin having phenylene skeleton and / or biphenylene skeleton, phenol aralkyl type phenol resin such as naphthol aralkyl resin having phenylene and / or biphenylene skeleton It can contain one or more selected from the group consisting of bisphenol compounds such as bisphenol A and bisphenol F. Among these, from the viewpoint of suppressing warpage of the molded product, it is more preferable to include 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 triphenylmethane type phenol resin modified with formaldehyde can be preferably used.

In the present embodiment, the lower limit of the content of the curing agent is, for example, preferably 0.5% by mass or more, more preferably 1% by mass or more, based on the entire thermosetting resin molding material. It is particularly preferable that it is 1.5% by mass or more. As a result, excellent fluidity can be realized at the time of molding, and the filling property and moldability can be improved. On the other hand, the upper limit of the content of the curing agent is, for example, preferably 9% by mass or less, more preferably 8% by mass or less, and 7% by mass or less, based on the entire thermosetting resin molding material. It is particularly preferable to have. As a result, the moisture resistance reliability and reflow resistance of the electronic component can be improved. Further, by controlling the content of the curing agent within such a range, it is possible to contribute to the suppression of warpage of the obtained molded product.

The thermosetting resin molding material of the present embodiment may contain components other than the above-mentioned components as long as the object of the present invention is not impaired. Examples of other components include additives such as elastomers, curing accelerators, resin components, mold release agents, low stress agents, pigments, flame retardants, adhesion improvers, and silane coupling agents. The thermosetting resin molding material may contain a solvent.

The thermosetting resin molding material of the present embodiment may contain an elastomer, if necessary.
The elastomer is not particularly limited, and examples thereof include acrylic nitrile butadiene rubber, isoprene, styrene butadiene rubber, and ethylene propylene rubber. Of these, acrylonitrile butadiene rubber is preferable. In particular, toughness can be imparted by using an elastomer.

The thermosetting resin molding material of the present embodiment may contain a curing aid, if necessary. The curing aid can be used in combination with the above curing agent. As a result, thermal stability and curability can be improved.

The curing accelerator is not particularly limited, and ordinary curing aids can be used, for example, oxides or hydroxides of alkaline earth metals such as magnesium oxide, calcium hydroxide, and barium hydroxide, and salicylic acid. , Aromatic carboxylic acids such as benzoic acid can be exemplified.

Specifically, as the low stress agent, a silicone compound such as silicone oil or silicone rubber can be used.

As the release agent, for example, natural wax such as carnauba wax, synthetic wax such as montanic acid ester wax, higher fatty acids such as calcium stearate and zinc stearate and metal salts thereof, paraffin and the like can be used.

As the pigment, for example, carbon black or niglosin can be used.

Examples of the silane coupling agent include epoxy group-containing alkoxys such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Silane compounds; mercapto group-containing alkoxysilane compounds such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) ) Ureido group-containing alkoxysilane compounds such as aminopropyltrimethoxysilane; γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxy Isocyanato group-containing alkoxysilane compounds such as silane, γ-isocyanatopropyl ethyldimethoxysilane, γ-isocyanatopropyl ethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane; γ-aminopropyltriethoxysilane, γ- (2-) Amino group-containing alkoxysilane compounds such as aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane; γ-hydroxypropyltrimethoxysilane, γ-hydroxy Examples thereof include hydroxyl group-containing alkoxysilane compounds such as propyltriethoxysilane. These may be used alone or in combination of two or more.

The thermosetting resin molding material of the present embodiment can also be used in combination with known resin materials for the purpose of modifying properties and the like. Examples of such resin components include resins having a triazine ring such as urea resin and melamine resin, bismaleimide resin, polyurethane resin, silicone resin, resin having a benzoxazine ring, cyanate ester resin, and polyvinyl butyral resin. , Polyvinyl acetate resin can be mentioned. Further, if necessary, these plurality of types can be used in combination.

Next, the characteristics of the thermosetting resin molding material of the present embodiment will be described.

The lower limit of the high viscosity of the thermosetting resin molding material is 100 Pa · s or more, preferably 200 Pa · s or more, and more preferably 300 Pa · s or more. On the other hand, the upper limit of the high viscosity is 2,000 Pa · s or less, preferably 1,800 Pa · s or less, and more preferably 1,500 Pa · s or less.

As the high viscosity, a value measured for the thermosetting resin molding material using a high viscosity measuring device under the conditions of a measurement temperature of 150 ° C. and a load of 200 kgf is used.

The lower limit of the time T ₁ in which the torque value of the thermosetting resin molding material is twice or less the minimum torque value is, for example, 10 seconds or longer, preferably 11 seconds or longer, and more preferably 15 seconds or longer. On the other hand, the upper limit of the time T ₁ is, for example, 60 seconds or less, preferably 50 seconds or less, more preferably 40 seconds or less, and further preferably 30 seconds or less.

The lower limit of the minimum torque value in the thermosetting resin molding material is 0.80 N · m or more, preferably 1.0 N · m or more, and more preferably 1.5 N · m or more. On the other hand, the upper limit of the minimum torque value is 25 N ・ m or less, preferably 23 N ・ m or less, and more preferably 20 N ・ m or less.

The time T ₁ and the minimum torque value are measured according to the following procedure.
First, using a laboplast mill, the torque value of the thermosetting resin molding material is measured over time under the conditions of a rotation speed of 30 rpm and a measurement temperature of 150 ° C. The measurement start point of the laboplast mill measurement is P ₁ , the point where the torque value is the minimum torque value is P _3, and the point where the torque value is twice the minimum torque value between P ₁ and P ₃ is P. _2, and the point where torque value after a P ₃ is twice the minimum torque value and P _4. The measurement start point P ₁ of the lab plast mill measurement is a point where the material is put into the lab plast mill, the torque suddenly rises, and then the torque starts to fall. The time from P ₃ to P ₄ is defined as the time T _{1 in} which the torque value is twice or less the minimum torque value.

Regarding the thermosetting resin molding material, the thermosetting resin suitable for injection molding is suitable for injection molding by setting the high viscosity within the above numerical range and setting the time T ₁ and the minimum torque value as the lab torque within the above numerical range. A molding material can be realized. Further, it is possible to improve the insulation reliability and the connection reliability of the injection-molded product obtained by injection-molding such a thermosetting resin molding material.

The glass transition temperature of the cured product of the thermosetting resin molding material is, for example, 150 ° C. to 300 ° C., preferably 180 ° C. to 280 ° C., and more preferably 200 ° C. to 260 ° C. By setting the value to the above lower limit or more, an injection-molded product having excellent heat resistance can be obtained.

The upper limit of the average linear expansion coefficient of 40 ° C. to 150 ° C. in the flow direction of the cured product of the thermosetting resin molding material for injection molding is, for example, 20 ppm / ° C. or lower, preferably 19 ppm / ° C. or lower, more preferably 18 ppm. It is below / ° C. As a result, an injection-molded product with excellent dimensional stability can be realized. On the other hand, the lower limit of the average coefficient of linear expansion from 40 ° C. to 150 ° C. in the flow direction may be, for example, 8 ppm or more, preferably 10 ppm or more, more preferably 12 ppm or more.

The upper limit of the dielectric loss tangent at a frequency of 1 GHz of the cured product of the thermosetting resin molding material may be, for example, 0.05 or less, 0.04 or less, and the lower limit thereof may be, for example, 0.001 or more. .. By setting the value to the above upper limit or less, a molded product having excellent insulation reliability can be realized.

The upper limit of the hygroscopicity of the cured product of the thermosetting resin molding material may be, for example, 0.5% or less, 0.4% or less, and the lower limit thereof may be, for example, 0.05% or more. By setting the value to the above upper limit or less, a molded product having excellent insulation reliability can be realized.

The above glass transition temperature, linear expansion coefficient, dielectric tangent and moisture absorption rate can be measured using a test piece (cured product of thermosetting resin molding material) obtained by the following procedure. Measurement of glass transition temperature or linear expansion coefficient An as-molded product (10 mm × 80 mm × 4 mmt) was obtained by transfer molding at 175 ° C. for 3 minutes using a thermosetting resin molding material, and this as-molded product was used at 180 ° C. for 8 hours. A test piece is obtained by post-curing treatment under curing conditions.
Regarding the measurement of hygroscopicity, a test piece (φ50 mm, 4 mmt) is obtained by injection transfer molding at 175 ° C. for 3 minutes using a thermosetting resin molding material.
Regarding the measurement of the dielectric constant, an injection-molded product (□ 120 mm, 1.5 mmt) is obtained by injection-molding at 175 ° C. for 60 seconds using a thermosetting resin molding material, and this injection-molded product is cut out. Then, a strip-shaped test piece (□ 100 mm, 1.5 mmt) is obtained.

In the present embodiment, for example, the type and blending amount of each component contained in the thermosetting resin molding material, the preparation method of the thermosetting resin molding material, and the like are appropriately selected to increase the viscosity and torque value. , Glass transition temperature, average linear expansion coefficient, dielectric loss tangent and moisture absorption rate can be controlled. Among these, for example, the use of phenol resin and selection of its type, the content ratio of resole-type phenol resin, the type and content of inorganic filler are appropriately selected, and the like, the above-mentioned high viscosity, torque value, etc. The factors for setting the glass transition temperature, the average linear expansion coefficient, the dielectric loss tangent and the moisture absorption rate within the desired numerical ranges can be mentioned.

Next, a method for producing the thermosetting resin molding material of the present embodiment will be described.
The thermosetting resin molding material of the present embodiment can be produced by using a known method.
As an example of the method for producing the thermosetting resin molding material, each of the above components is melt-kneaded in advance with a kneader, a roll, or the like, and then uniformly mixed with other raw materials, or all the raw materials to be blended are rolled. It is obtained by granulating or pulverizing after melt-kneading with a kneading device such as a conida or a twin-screw extruder alone or in combination with a roll and another mixing device. The shape is not particularly limited.

The method for producing an injection-molded product of the present embodiment can include a step of obtaining an injection-molded product by injection-molding using the thermosetting resin molding material for injection molding of the present embodiment. Hereinafter, injection molding will be described.
First, the injection molding machine is connected to a mold having a molding space such as a gate, a runner, and a cavity.
The injection molding machine includes, for example, a cylinder, a screw that can rotate in the cylinder, an inlet that can charge the thermosetting resin molding material into the cylinder, a heater that heats the thermosetting resin molding material through the cylinder, and a cylinder. It is equipped with a nozzle that sends the molding material kneaded inside to the mold. The screw may be provided with a check valve at the tip.

Subsequently, the thermosetting resin molding material is put into the heated injection molding machine. The thermosetting resin molding material is kneaded by a screw in a cylinder while being heated by a heater and passes through a kneading region.
The thermosetting resin molding material that has passed through the kneading region reaches the nozzle region where the nozzles are present. As a result, the thermosetting resin molding material is injected into the mold through the nozzle by the pressure of the screw.
The thermosetting resin molding material ejected from the nozzle is cured while flowing into the molding region of the mold. Here, the molding region is a molding space for the mold. A heat medium such as hot water flows inside the mold, whereby the temperature of the molding space can be kept constant.

As described above, a molded product (injection resin molded product) obtained by injection molding the thermosetting resin molding material of the present embodiment can be obtained. The shape of the resin molded product is not particularly limited as long as it has a three-dimensional structure, but it may have a curved surface in part.

In the present embodiment, the three-dimensional molded circuit component (MID) has three elements of a three-dimensional shape, the resin molded product, and a three-dimensional circuit. For example, a metal film is formed on the surface of the resin molded product having a three-dimensional structure. It is a component formed by the circuit. Specifically, 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. By using such a three-dimensional molded circuit component (MID), it is possible to effectively utilize the space, reduce the number of components, and reduce the weight, thinness, and length.

The method for manufacturing the MID of the present embodiment is a step of irradiating the surface of the injection-molded product obtained by the method of manufacturing the injection-molded product with an active energy ray and a step of irradiating the surface of the injection-molded product with an active energy ray. A step of forming a circuit by a plating process on the surface of the above can be included. A surface cleaning step may be added before the plating process.

By using a known LDS method, metal nuclei are generated on the surface of a cured product (resin molded product having a three-dimensional structure) of a thermosetting resin molding material containing an LDS additive by active energy rays, and the metal nuclei are generated. A plating pattern (wiring) can be formed in the energy ray irradiation region by, for example, electroless plating treatment or the like.

As the active energy ray, 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. The wavelength of the laser is not particularly specified, but is, for example, 200 nm to 12000 nm. Of these, preferably 248 nm, 308 nm, 355 nm, 532 nm, 1064 nm or 10600 nm may be used.

As the plating treatment, either electric field plating or electroless plating may be used. A circuit (plating layer) can be formed by subjecting the above-mentioned laser-irradiated region to a plating treatment. The plating solution is not particularly specified, and a known plating solution can be widely used, and a plating solution in which copper, nickel, gold, silver, and palladium are mixed as metal components may be used.

In the present embodiment, the resin molded product (cured product of thermosetting resin molding material) is not limited to the final product, but may also include composite materials and various parts. The resin molded product can be used as a component of a portable electronic device, a vehicle and a medical device, an electronic component including other electric circuits, a semiconductor encapsulant, and a composite material for forming the same. 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. Further, the present invention is not limited to the above-described embodiment, and modifications, improvements, etc. within the range in which the object of the present invention can be achieved are included in the present invention.

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.

<Preparation of thermosetting resin molding material>
(Examples 1 to 6, Comparative Example 1)
A granular thermosetting resin molding material is obtained by kneading a material mixture containing each component according to the blending amounts shown in Table 1 below with heating rolls having different rotation speeds and pulverizing the sheet-like cooled material. It was.
The kneading conditions of the heating roll were such that the rotation speed was 20/14 rpm on the high speed side / low speed side, the temperature was 80/20 ° C. on the high speed side / low speed side, and the kneading time was 5 to 10 minutes.

(Comparative Examples 1 and 2)
The raw materials in the blending amounts shown in Table 1 below were mixed at room temperature using a mixer, and then roll-kneaded at 70 to 100 ° C. Then, after cooling the obtained kneaded product, it was pulverized to obtain a powdery and granular thermosetting resin molding material. Then, tablet-shaped thermosetting resin molding material was obtained by tablet molding at high pressure.

Hereinafter, each component in Table 1 is shown.
(Thermosetting resin)
-Phenolic resin 1: Resol type phenol resin (Sumitomo Bakelite Co., Ltd., R-25)
-Phenolic resin 2: Resol type phenol resin (manufactured by Sumitomo Bakelite, PR-51723)
-Phenolic resin 3: Novolac type phenol resin (manufactured by Sumitomo Bakelite, PR-51470)
-Phenolic resin 4: Novolac type phenol resin (manufactured by Sumitomo Bakelite, A-1087)
-Phenolic resin 5: Novolac type phenol resin (manufactured by Sumitomo Bakelite, PR-HF-3)
-Epoxy resin 1: Orthocresol novolac type epoxy resin (manufactured by DIC, EPICLON N-670)
-Epoxy resin 2: Orthocresol novolac type epoxy resin (manufactured by Nippon Kayakusha, EOCN-1020)
(Thermoplastic resin)
・ Polyamide resin 1:10 nylon

(Hardening aid)
-Curing aid 1: Slaked lime-Curing aid 2: 2-Phenyl-4-methylimidazole (manufactured by Shikoku Chemicals Corporation, 2P4MZ)
-Curing aid 3: Triphenylphosphine (manufactured by Hokuko Chemical Co., Ltd., TPP)

(Inorganic filler)
-Inorganic filler 1: Spherical silica (manufactured by Denki Kagaku Kogyo Co., Ltd., FB-950, average particle size D ₅₀ = 26 μm)
-Inorganic filler 2: Spherical silica (manufactured by Admatex, SD2500-SQ, average particle size D ₅₀ = 0.9 μm)
-Inorganic filler 3: Spherical silica (manufactured by Admatex, FEB24S5, average particle size D ₅₀ = 12.3 μm)
-Inorganic filler 4: crushed silica (manufactured by Ryumori Seisakusho, RD-8, average particle size D ₅₀ = 15 μm)
-Inorganic filler 5: Glass fiber (average diameter: 11 μm, average length: 3 mm)
-Inorganic filler 6: Glass fiber (manufactured by Nippon Electric Glass Co., Ltd., 03T-296GH, fiber diameter: 10 μm)
-Inorganic filler 7: Wallastnite (average diameter: 10 μm, average length: 50 μm)
-Inorganic filler 8: talc (manufactured by Hayashi Kasei Co., Ltd., Micron White 5000S)
-Inorganic filler 9: Calcium carbonate (manufactured by Nitto Flourka Co., Ltd.)

(Non-conductive metal compound: LDS additive)
-Non-conductive metal compound 1: Black 30C965: CuCr ₂ O ₄ (Shefard color company, powder)

(Additive)
-Silicone oil 1: Silicone oil (manufactured by Toray Dow, FZ-3730)
-Release agent 1: Montanic acid ester wax (manufactured by Clariant Japan, Recolve WE-4)
-Release agent 2: Montanate (manufactured by Nitto Kasei Kogyo, CS8CP)
-Release agent 3: Calcium stearate (manufactured by Nitto Kasei Kogyo Co., Ltd.)
-Silane coupling agent 1: γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-903)
・ Pigment 1: Carbon black (manufactured by Mitsubishi Chemical Corporation, # 5)

The following evaluation items were evaluated using the obtained thermosetting resin molding material.
The results are shown in Table 1. In Table 1, "-" indicates that no evaluation was made.

(Lab torque)
Using a lab plast mill (4C150 manufactured by Toyo Seiki Seisakusho Co., Ltd.), the torque value of the obtained thermosetting resin molding material was measured over time under the conditions of a rotation speed of 30 rpm and a measurement temperature of 150 ° C.
As shown in FIG. 1, the measurement start point of the lab plast mill measurement is P ₁ , the point where the torque value becomes the minimum torque value is P _3, and the torque value is the minimum torque value between P ₁ and P ₃ . The point where the torque value is doubled is P _2, and the point where the torque value becomes twice the minimum torque value after passing through P ₃ is defined as P ₄ .
Measurement start point P ₁ of the Laboplastomill measurement material was put into Labo Plastomill, after rapid torque rises, and the point where torque begins to drop. The time from P ₃ to P ₄ was defined as the time T _{1 in} which the torque value was twice or less the minimum torque value. The results are shown in Table 1. The unit of time T ₁ is seconds, and the unit of the minimum torque value is Nm.

(High viscosity)
Using a high-grade viscosity measuring device (high-grade flow tester, Shimadzu Corporation, CFT-100EX), heat under the conditions of measurement temperature 150 ° C., load 200 kgf, nozzle dimensions: diameter 1.0 mm x length 10 mm. The melt viscosity of the curable resin molding material was measured.

(Coefficient of linear expansion, glass transition temperature)
Using the obtained thermosetting resin molding material, transfer molding was performed at 175 ° C. for 3 minutes to prepare an as-molded test piece having a length × width × thickness: 10 mm × 80 mm × 4 mmt.
Further, the obtained as-mold test piece was subjected to post-curing treatment under curing conditions of 180 ° C. for 8 hours to prepare a post-curing test piece. Using a thermomechanical analyzer (manufactured by Seiko Instruments Co., Ltd., product name: TMA / SS-6000) in the flow direction from the center of the surface of the obtained post-curing test piece, the temperature was raised to 5 ° C./min, 40. The average coefficient of linear expansion when measured under the temperature range of ° C to 150 ° C was α ₁ (ppm / ° C), and the average coefficient of linear expansion in the flow direction and the orthogonal direction was α 2.
Further, from the above TMA measurement, the temperature corresponding to the bending point was defined as the glass transition point temperature (Tg).

(Injection moldability)
Using the obtained thermosetting resin molding material, using a 100 ton horizontal hydraulic injection molding machine, mold temperature: 175 ° C, cylinder tip temperature: 90 ° C, injection pressure upper limit: 150 MPa, holding pressure: 50 MPa The ISO dumbbell test piece (resin molded product) was molded under the molding conditions of.
At this time, the injection moldability was evaluated based on the following evaluation criteria.
〇: Molding was possible, and no appearance defects were observed.
Δ: Molding was possible, but poor filling and lack of gas occurred on the appearance.
X: Molding was not possible.

In Table 1, in Comparative Example 2, the viscosity was too low to backflow in the cylinder, and in Comparative Example 3, the viscosity was too high to inject the material from the cylinder. Comparative Examples 2 and 3 that could not be injection-molded could not evaluate the following plating property, insulation reliability, and connection reliability.

(Plating property)
Using the obtained thermosetting resin molding material, using a 100 ton horizontal hydraulic injection molding machine, mold temperature: 175 ° C, cylinder tip temperature: 90 ° C, injection pressure upper limit: 200 MPa, holding pressure: 50 MPa 120 × 1.5 mmt (resin molded product) was molded under the molding conditions of. The surface of this resin molded product was irradiated with a YAG laser, and a plating pattern was formed in the laser irradiation region to produce a molded circuit product A. The plating property of this molded circuit product A was evaluated according to the following criteria.
◎: No unevenness on the plated surface ○: Some unevenness is visible on the plated surface but no unplated part △: Unevenness is visible on the plated surface but no unplated part ×: Severe unevenness is visible on the plated surface Yes

(Connection reliability)
A molding circuit product B having a plating pattern shown in FIG. 2 was produced in the same manner as in the production of the above-mentioned (plating property) molding circuit product A. FIG. 2 is a schematic diagram showing an outline of a plating pattern for evaluating connection reliability. FIG. 2B is an enlarged view of the α region of FIG. 2A.
Fluctuations in resistance were evaluated over time under the conditions of (i) 150 ° C. for 1000 hours, (ii) 85 ° C., 80% for 1000 hours, and (iii) −40 ° C. to 150 ° C. for 500 cycles.

In Examples 1 to 6, it was found that the increase in resistance value from the initial stage was suppressed even under the conditions (i) to (iii) above.

(Insulation reliability)
A molded circuit product C having a plating pattern (line and space) shown in FIG. 3 was produced in the same manner as in the production of the molded circuit product A (plating property) described above. FIG. 3 is a schematic view showing an outline of a plating pattern for evaluating insulation reliability.
(A) L / S = 200 μm / 200 μm, (B) L / S = 100 μm / 300 μm, (C) L / S = 100 μm / 200 μm, (D) L / S = 100 μm / 100 μm, 85 in line and space The fluctuation of the resistance value was evaluated over time under the conditions of 1000 hours at 80% and DC: 15V.

In Examples 1 to 6, it was found that the fluctuation of the resistance value from the initial stage was suppressed even under the conditions (A) to (C) above.

It was found that the thermosetting resin molding materials of Examples 1 to 6 were excellent in injection molding as compared with Comparative Examples 2 and 3, and were excellent in connection reliability as compared with Comparative Example 1. Since the thermosetting resin molding material of such an example is excellent in plating property, it was found that it can be suitably used as a thermosetting resin molding material for injection molding used for LDS.

Claims (10)

A thermosetting resin molding material for injection molding used in LASER DIRECT STRUCTURING (LDS).
Thermosetting resin and
Inorganic filler and
Contains an LDS additive composed of a non-conductive metal compound that forms metal nuclei by irradiation with active energy rays.
The heightened viscosity of the thermosetting resin molding material for injection molding, which is measured under the conditions of a measurement temperature of 150 ° C. and a load of 200 kgf, using a heightened viscosity measuring device is 100 Pa · s or more and 2,000 Pa · s. Is below
The time T ₁ at which the torque value of the injection-molded thermosetting resin molding material measured by the following procedure is twice or less the minimum torque value is 10 seconds or more and 60 seconds or less, and the injection-molding thermosetting is performed. A thermosetting resin molding material for injection molding, wherein the minimum torque value of the sex resin molding material is 0.80 Nm or more and 25 Nm or less.
(procedure)
Using a laboplast mill, the torque value of the thermosetting resin molding material for injection molding is measured over time under the conditions of a rotation speed of 30 rpm and a measurement temperature of 150 ° C.
The measurement start point of the laboplast mill measurement is P ₁ , the point where the torque value is the minimum torque value is P _3, and the point where the torque value is twice the minimum torque value between P ₁ and P ₃ is P. _2, and the point where torque value after a P ₃ is twice the minimum torque value and P _4.
The measurement start point P ₁ of the lab plast mill measurement is a point where the material is put into the lab plast mill, the torque suddenly rises, and then the torque starts to fall.
The time from P ₃ to P ₄ is defined as the time T _{1 in} which the torque value is twice or less the minimum torque value. The thermocurable resin molding material for injection molding according to claim 1.
A thermosetting resin molding material for injection molding, wherein the thermosetting resin contains a resole-type phenol resin. The thermosetting resin molding material for injection molding according to claim 1 or 2.
The content of the LDS additive is 0.1% by mass or more and 10.0% by mass or less with respect to the entire thermosetting resin molding material for injection molding. Thermosetting resin molding material for injection molding. The thermosetting resin molding material for injection molding according to any one of claims 1 to 3.
A thermosetting resin molding material for injection molding, wherein the glass transition temperature of the cured product of the thermosetting resin molding material for injection molding is 150 ° C. or higher. The thermosetting resin molding material for injection molding according to any one of claims 1 to 4.
A thermosetting resin molding material for injection molding, wherein the cured product of the thermosetting resin molding material for injection molding has an average linear expansion coefficient of 40 ° C. to 150 ° C. in the flow direction of 20 ppm / ° C. or less. The thermosetting resin molding material for injection molding according to any one of claims 1 to 5.
A thermosetting resin molding material for injection molding, wherein the cured product of the thermosetting resin molding material for injection molding has a dielectric loss tangent of 0.05 or less at a frequency of 1 GHz. The thermosetting resin molding material for injection molding according to any one of claims 1 to 6.
A thermosetting resin molding material for injection molding, wherein the moisture absorption rate of the cured product of the thermosetting resin molding material for injection molding is 0.5% or less. The thermosetting resin molding material for injection molding according to any one of claims 1 to 7.
The content of the inorganic filler is 50% by mass or more and 90% by mass or less with respect to the entire thermosetting resin molding material for injection molding. Thermosetting resin molding material for injection molding. A method for producing an injection-molded product, which comprises a step of obtaining an injection-molded product by injection-molding using the thermosetting resin molding material for injection molding according to any one of claims 1 to 8. A step of irradiating the surface of the injection-molded product obtained by the method for producing an injection-molded product according to claim 9 with active energy rays, and
A method for producing MOLDED INTERCONNECT DEVICE (MID), which comprises a step of forming a circuit by plating on the surface of the injection-molded article after the step of irradiating the active energy ray.

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