JP2021127412A - Thermosetting resin composition for LDS - Google Patents

Abstract

To provide a sheet-like resin composition that prevents cracking and chipping in a sheet and has excellent processing stability for LDS.SOLUTION: A sheet-like thermosetting resin composition for use in laser direct structuring (LDS) comprises an epoxy resin, a (meth)acryl compound, an inorganic filler, a non-conductive metal compound that forms a metal core by irradiation with an active energy ray.SELECTED DRAWING: None

Description

The present invention relates to a thermosetting resin composition for LDS.

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

JP-A-2015-134903

The present inventor has newly considered to provide a sheet-shaped resin composition having excellent processing stability by LDS. Then, it was newly found that it is important to suppress cracking and chipping of the sheet in the sheet-shaped resin composition.

Therefore, the present invention provides a sheet-shaped resin composition in which cracking and chipping of the sheet are suppressed and processing stability by LDS is excellent.

According to the present invention
A sheet-shaped thermosetting resin composition for LDS used for LASER DIRECT STRUCTURING (LDS).
Epoxy resin and
(Meta) acrylic compounds and
Inorganic filler and
Non-conductive metal compounds that form metal nuclei by irradiation with active energy rays,
A thermosetting resin composition for LDS is provided.

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

Further, according to the present invention.
The resin molded product of the present invention having a three-dimensional structure and
It is also possible to obtain a three-dimensional molded circuit component including a three-dimensional circuit formed on the surface of the resin molded product.

Further, according to the present invention.
With the board
With the semiconductor element or semiconductor chip mounted on the substrate,
With a sealing material for sealing the semiconductor element or the semiconductor chip,
Have,
It is also possible to obtain a sealed body in which the sealing material has a sealing layer composed of a cured product of the thermosetting resin composition for LDS according to the present invention.

According to the present invention, it is possible to provide a sheet-shaped resin composition in which cracking or chipping of a sheet is suppressed and processing stability by LDS is excellent.

It is sectional drawing which shows the structural example of the sealing body in this embodiment.

Hereinafter, embodiments of the present invention will be described with reference to specific examples of each component. In addition, in this embodiment, the composition may contain each component individually or in combination of two or more kinds.

(Thermosetting resin composition for LDS)
In the present embodiment, the thermosetting resin composition is a thermosetting resin composition for LDS used for laser direct structuring (LASER DIRECT STRUCTURING: LDS). LDS is one of the methods for manufacturing a three-dimensional molded circuit component (MID). In LDS, specifically, the surface of a resin molded product containing an LDS additive is irradiated with active energy rays to generate metal nuclei, and the metal nuclei are used as seeds by plating treatment such as electroless plating. A plating pattern is formed in the energy ray irradiation region. Conductive members such as wirings and circuits can be formed based on this plating pattern.

In the present embodiment, the thermosetting resin composition for LDS (hereinafter, also simply referred to as “thermosetting resin composition”) is in the form of a sheet, and is filled with an epoxy resin, a (meth) acrylic compound, and an inorganic substance. It contains a material and a non-conductive metal compound that forms a metal nucleus by irradiation with active energy rays.

In the present embodiment, a thermosetting resin composition is used as the resin composition for LDS, its constituent components are appropriately selected, and the thermosetting resin composition is formed into a sheet to crack the sheet. It is possible to obtain a resin composition in which chipping is suitably suppressed and processing stability by LDS is excellent. Therefore, by using the resin composition for LDS in the present embodiment, for example, a sealed body having excellent production stability and processing stability by LDS can be obtained.

(Epoxy resin)
As the epoxy resin, it is possible to use a monomer, an oligomer, or a polymer having two or more epoxy groups in one molecule. Specific examples of such epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, and bisphenol M type epoxy resin (4). , 4'-(1,3-phenylenediisopridiene) bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4'-(1,4-phenylenediisopridiene) bisphenol type epoxy resin), bisphenol Bisphenol type epoxy resin such as Z type epoxy resin (4,4'-cyclohexidiene bisphenol type epoxy resin); phenol novolac type epoxy resin, brominated phenol novolac type epoxy resin, cresol novolac type epoxy resin, tetraphenol group ethane type Novolak type epoxy resin such as novolak type epoxy resin and novolak type epoxy resin having a fused ring aromatic hydrocarbon structure; biphenyl type epoxy resin; aralkyl type epoxy resin such as xylylene type epoxy resin and biphenyl aralkyl type epoxy resin; naphthylene ether Epoxy resin having a naphthalene skeleton such as type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthalenediol type epoxy resin, bifunctional to tetrafunctional epoxy type naphthalene resin, binaphthyl type epoxy resin, naphthalene aralkyl type epoxy resin; Type epoxy resin; Phenoxy type epoxy resin; Dicyclopentadiene type epoxy resin; Norbornen type epoxy resin; Adamantane type epoxy resin; Fluorene type epoxy resin, phosphorus-containing epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, bisphenol A Novolak type epoxy resin, bixilenol type epoxy resin, trihydroxyphenylmethane type epoxy resin, tetraphenylol ethane type epoxy resin, heterocyclic epoxy resin such as triglycidyl isocyanurate, N, N, N', N'- Epoxy unsaturated double bonds with glycidyl amines such as tetraglycidyl metaxylene diamine, N, N, N', N'-tetraglycidyl bisaminomethylcyclohexane, N, N-diglycidyl aniline, and glycidyl (meth) acrylate. Copolymer with a compound having, epoxy resin having a butadiene structure, diglycidyl etherified product of bisphenol, naphthaleneide One or more selected from the group consisting of all diglycidyl ethers and phenolic glycidyl ethers can be mentioned.

Among these, from the viewpoint of improving the adhesion to the metal pattern and the conductor portion contained in the encapsulant, the epoxy resin is preferably a phenol aralkyl type epoxy resin having a biphenylene skeleton, a biphenyl type epoxy resin, and a tris (hydroxyphenyl). ) One or more selected from the group consisting of methane type epoxy resin, more preferably selected from the group consisting of biphenyl aralkyl type epoxy resin, biphenyl type epoxy resin and trihydroxyphenylmethane type epoxy resin 1 Includes species or two or more. As a result, it is possible to increase the linear expansion and the elastic modulus of the sealed body.

The content of the epoxy resin in the thermosetting resin composition is preferably 1% by mass or more, more preferably 1% by mass or more, based on the entire thermosetting resin composition, from the viewpoint of improving the flexibility of the sheet-shaped encapsulant. Is 3% by mass or more, more preferably 5% by mass or more.
Further, from the viewpoint of improving the reliability of the encapsulant such as a semiconductor package, the content of the epoxy resin is preferably 30% by mass or less, more preferably 20% by mass, based on the entire thermosetting resin composition. Hereinafter, it is more preferably 15% by mass or less.

((Meta) acrylic compound)
Examples of the (meth) acrylic compound include (meth) acrylic resin, (meth) acrylic oligomer, and (meth) acrylic monomer.
From the viewpoint of suppressing cracking and chipping of the sheet, the (meth) acrylic compound preferably contains a (meth) acrylic monomer.
The (meth) acrylic monomer is preferably a monomer having a boiling point higher than that of the solvent used in the production of the sheet-shaped thermosetting resin composition in the present embodiment.
In addition, it suppresses the volatilization of the (meth) acrylic monomer in the manufacturing process of the sheet-shaped thermosetting resin composition, and also interacts by the chemical reaction between the (meth) acrylic monomer and the solvent and the resin composition. From the viewpoint of causing a squeeze, the boiling point of the (meth) acrylic monomer is preferably more than 100 ° C., more preferably 110 ° C. or higher, still more preferably 150 ° C. or higher. By doing so, the sheet-shaped thermosetting resin composition can be made excellent in flexibility to the extent that workability at the time of use can be improved.

Examples of the (meth) acrylic monomer include 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, and 2- (meth). ) Acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylmethylhexahydrophthalic acid, 2- (meth) acryloyloxypropylmethylhexahydrophthalic acid, 2- (meth) acryloylxyethylphthalic acid , 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxyethyl tetrahydrophthalic acid, 2- (meth) acryloyloxypropyltetrahydrophthalic acid, 2- (meth) acryloyloxyethyl methyltetrahydrophthalic acid Acid, 2- (meth) acryloyloxypropylmethyltetrahydrophthalic acid, 2-hydroxy-1,3-di (meth) acryloxypropane, tetramethylol methanetri (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, glycerindi (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, 1,4-cyclohexanedimethanol Mono (meth) acrylate, ethyl-α- (hydroxymethyl) (meth) acrylate, 4-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( Meta) acrylate, Tarsal butyl (meth) acrylate, Isodecyl (meth) acrylate, Lauryl (meth) acrylate, Tridecyl (meth) acrylate, Cetyl (meth) acrylate, Stearyl (meth) acrylate, Isoamyl (meth) acrylate, Isostearyl (Meta) acrylate, behenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, other alkyl (meth) acrylate, cyclohexyl (meth) acrylate, tarsalbutylcyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, trimethylpropantri (meth) acrylate, zincmo No (meth) acrylate, zinc di (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, neopentyl glycol (meth) acrylate, trifluoroethyl (meth) acrylate, 2,2,3,3 -Tetrafluoropropyl (meth) acrylate, 2,2,3,3,4,4-hexafluorobutyl (meth) acrylate, perfluorooctyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, ethylene glycol di ( Meta) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1, 3-Butandiol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) Acrylate, methoxypolyalkylene glycol mono (meth) acrylate, octoxypolyalkylene glycol mono (meth) acrylate, lauroxypolyalkylene glycol mono (meth) acrylate, stearoxypolyalkylene glycol mono (meth) acrylate, allyloxypolyalkylene glycol Mono (meth) acrylate, nonylphenoxypolyalkylene glycol mono (meth) acrylate, N, N'-methylenebis (meth) acrylamide, N, N'-ethylenebis (meth) acrylamide, 1,2-di (meth) acrylamide ethylene Glycol, di (meth) acryloyloxymethyltricyclodecane, 2- (meth) acryloyloxyethyl, N- (meth) acryloyloxyethyl maleimide, N- (meth) acryloyloxyethyl hexahydrophthalimide, N- Examples thereof include polyfunctional monomers such as (meth) acryloyloxyethyl phthalimide, N-vinyl-2-pyrrolidone, ethoxylated bisphenol A (meth) acrylate, and propoxylated bisphenol A (meth) acrylate.

The content of the (meth) acrylic monomer in the thermosetting resin composition is preferably 0.01% by mass or more with respect to the entire thermosetting resin composition from the viewpoint of suppressing cracking or chipping of the sheet. , More preferably 0.05% by mass or more, still more preferably 0.5% by mass or more.
From the same viewpoint, the content of the (meth) acrylic monomer is preferably 3% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass, based on the entire thermosetting resin composition. % Or less.

(Inorganic filler)
The inorganic filler can be used, for example, as a semiconductor encapsulating material. Specific examples of the inorganic filler include fused crushed silica, fused spherical silica, crystalline silica, secondary agglomerated silica and other silica; alumina; titanium white; aluminum hydroxide; talc; clay; mica; glass fiber and the like. .. Among these, silica is preferable, and molten spherical silica is more preferable. Moreover, it is preferable that the particle shape is infinitely spherical. Further, the inorganic filling amount can be increased by mixing particles having different particle sizes, but the average particle size d ₅₀ is preferably 0.01 μm or more from the viewpoint of improving the filling property in a narrow region. It is more preferably 0.1 μm or more, still more preferably 1 μm or more, and preferably 150 μm or less, more preferably 100 μm or less, still more preferably 50 μm or less, still more preferably 20 μm or less, and even more preferably. Is 10 μm or less.
The average particle size d ₅₀ of the inorganic filler can be measured using, for example, a laser diffraction type particle size distribution measuring device (LA-500, manufactured by HORIBA).

The content of the inorganic filler in the thermosetting resin composition is preferably 50% by mass or more, more preferably 50% by mass or more, based on the entire thermosetting resin composition from the viewpoint of suppressing cracking or chipping of the sheet. It is 55% by mass or more, more preferably 62% by mass or more.
Further, from the viewpoint of improving the filling property of the sealing material, the content of the inorganic filler is preferably 93% by mass or less, more preferably 90% by mass or less, and further, with respect to the entire thermosetting resin composition. It is preferably 85% by mass or less.

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

The non-conductive metal compound is selected from, for example, (i) a spinel-type metal oxide, and (ii) groups 3 to 12 of the periodic table, and two or more transition metals having the group adjacent to each other. Includes one or more selected from the group consisting of elemental metal oxides and (iii) tin-containing oxides.

In the above (i), the spinel type structure is _{one of the typical crystal structure types found in compound AB 2} O ₄ type compounds (A and B are metal elements). The spinel structure may be either a forward spinel structure or an inverted spinel structure (B (AB) O ₄ ) in which A and B are partially exchanged, 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 enhancing the adhesion to the copper plating pattern.

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

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

The metal oxide having the transition metal element of (ii) is selected from the groups 3 to 12 of the periodic table, and the metal oxide having two or more transition metal elements adjacent to the group is selected. Is. Here, the metal belonging to the transition metal element can be expressed as containing 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.

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

Group n + 1 metals in the periodic table include, for example, Group 4 (titanium, zirconium, etc.), Group 5 (vanadium, niobium, etc.), Group 6 (chromium, molybdenum, etc.), Group 7 (manganese, etc.), Group 8 (iron, etc.). , 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 transition metal element as described above, for example, those described in JP-A-2004-534408 can be mentioned.

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

The content of the non-conductive metal compound in the thermosetting resin composition is adjusted with respect to the entire thermosetting resin composition from the viewpoint of improving the plating characteristics in the cured product of the thermosetting resin composition. For example, it is 2% by mass or more, preferably 4% by mass or more, and more preferably 8% by mass or more. Further, in the cured product of the thermosetting resin composition, from the viewpoint of suppressing a decrease in insulating property and an increase in dielectric tangent, and when the shape of the non-conductive metal compound is non-spherical, the thermosetting resin composition From the viewpoint of improving the fluidity, the content of the non-conductive metal compound is, for example, 20% by mass or less, preferably 18% by mass or less, more preferably 18% by mass or less, based on the entire thermosetting resin composition. It is 15% by mass or less.

Further, the total content of the inorganic filler and the non-conductive metal compound in the thermosetting resin composition is preferable with respect to the entire thermosetting resin composition from the viewpoint of improving the resin mechanical properties and the resin strength. It is 60% by mass or more, more preferably 70% by mass or more, and further preferably 75% by mass or more.
From the viewpoint of improving moldability, the total content of the inorganic filler and the non-conductive metal compound is preferably 98% by mass or less, more preferably 95% by mass, based on the entire thermosetting resin composition. % Or less, more preferably 90% by mass or less.

(Other ingredients)
In the present embodiment, the thermosetting resin composition may contain components other than the above-mentioned components.
For example, the thermosetting resin composition may further contain at least one of a curing agent and a curing accelerator.

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

Heavy addition hardeners include, for example, aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), metaxylerylene diamine (MXDA), diaminodiphenylmethane (DDM), m-phenylenediamine (MPDA), In addition to aromatic polyamines such as diaminodiphenylsulfone (DDS), polyamine compounds containing dicyandiamide (DICY), organic acid dihydrazide and the like; alicyclic acids such as hexahydrophthalic anhydride (HHPA) and methyltetrahydrophthalic anhydride (MTHPA). Acid anhydrides containing anhydrides, aromatic acid anhydrides such as trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), benzophenone tetracarboxylic acid (BTDA); trihydroxyphenylmethane type phenolic resin, biphenyl aralkyl Aralkyl type phenol resin such as mold, novolak type phenol resin, polyvinyl phenol, etc. Phenolic resin curing agent; polymercaptan compound such as polysulfide, thioester, thioether; isocyanate compound such as isocyanate prepolymer, blocked isocyanate; carboxylic acid-containing polyester Includes one or more selected from the group consisting of organic acids such as resins.

Catalytic curing agents are tertiary amine compounds such as, for example, benzyldimethylamine (BDMA), 2,4,6-trisdimethylaminomethylphenol (DMP-30); 2-methylimidazole, 2-ethyl-4- Includes one or more selected from the group consisting of imidazole compounds such as methylimidazole (EMI24); _{Lewis acids such as the BF 3 complex.}

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

Among these, the thermosetting resin composition preferably contains a phenol resin curing agent from the viewpoint of improving the reliability of the encapsulant such as a semiconductor package.

The content of the curing agent in the thermosetting resin composition is higher than that of the entire thermosetting resin composition from the viewpoint of realizing excellent fluidity at the time of molding and improving the filling property and moldability. It is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, and even more preferably 3% by mass or more.
Further, from the viewpoint of improving the moisture resistance reliability and reflow resistance of the electronic components contained in the encapsulant and from the viewpoint of suppressing the warp of the encapsulant, the content of the curing agent is the thermosetting resin composition. It is preferably 15% by mass or less, more preferably 12% by mass or less, and further preferably 8% by mass or less with respect to the whole.

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

The 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; 5.4.0] One selected from nitrogen atom-containing compounds such as amidines and tertiary amines such as undecene-7, benzyldimethylamine and 2-methylimidazole, and quaternary salts of the above amidines and amines, or Two or more types can be included. Among these, it is more preferable to contain a phosphorus atom-containing compound from the viewpoint of improving curability. Further, from the viewpoint of improving the balance between moldability and curability, it has latent properties such as a tetra-substituted phosphonium compound, a phosphobetaine compound, an adduct of a phosphine compound and a quinone compound, and an adduct of a phosphonium compound and a silane compound. It is more preferable to include one.

From the viewpoint of making the curing characteristics of the thermosetting resin composition more preferable, the curing accelerator preferably contains organic phosphine, and more preferably organic phosphine. Examples of the organic phosphine include a first phosphine such as ethylphosphine and phenylphosphine; a second phosphine such as dimethylphosphine and diphenylphosphine; and a third phosphine such as trimethylphosphine, triethylphosphine, tributylphosphine and triphenylphosphine. The organic phosphine is preferably a third phosphine, more preferably triphenylphosphine.

When the thermosetting resin composition contains a curing accelerator, the content of the curing accelerator is preferably 0 with respect to the entire thermosetting resin composition from the viewpoint of effectively improving the curability during molding. It is 0.05% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.15% by mass or more.
Further, from the viewpoint of improving the fluidity during molding, the content of the curing accelerator is preferably 1% by mass or less, more preferably 0.8% by mass, based on the entire thermosetting resin composition. Hereinafter, it is more preferably 0.5% by mass or less.

Further, the thermosetting resin composition may contain at least one kind of organic thermostable metal chelate complex salt in addition to the above-mentioned non-conductive metal compound.

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

Further, the thermosetting resin composition preferably does not contain carbon such as carbon black used as the colorant from the viewpoint of improving the plating characteristics.

In the present embodiment, as a method for producing a sheet-shaped thermosetting resin composition, for example, a solution obtained by previously melt-mixing and dissolving-mixing each component, additive, etc. is prepared by using a coater to prepare polyethylene. Examples thereof include a method of applying the film on a base material such as a terephthalate (PET) film to form a sheet.

The sheet thickness of the thermosetting resin composition is preferably 10 μm or more, more preferably 30 μm or more, still more preferably 50 μm, from the viewpoint of suppressing cracking or chipping of the sheet and improving the processing stability by LDS. That is all.
Further, from the viewpoint of suppressing the formation of voids when the solvent or the like is volatilized, the sheet thickness of the thermosetting resin composition is preferably 300 μm or less, more preferably 200 μm or less, still more preferably 150 μm or less.

The glass transition temperature of the cured product of the thermosetting resin composition is preferably 100 ° C. or higher, more preferably 110 ° C. or higher, still more preferably 120 ° C. or higher, from the viewpoint of improving heat resistance.
Further, from the viewpoint of improving the reliability of the encapsulant such as a semiconductor package, the glass transition temperature of the cured product of the thermosetting resin composition is preferably 200 ° C. or lower, more preferably 190 ° C. or lower, and further preferably 190 ° C. or lower. It is 180 ° C. or lower.

The coefficient of linear expansion of the cured product of the thermosetting resin composition in a temperature range lower than the glass transition temperature is preferably 5 ppm / ° C. or higher, more preferably 7 ppm / ° C. from the viewpoint of improving the dimensional stability of the sealed body. Above, more preferably 10 ppm / ° C. or more.
From the same viewpoint, the coefficient of linear expansion of the cured product of the thermosetting resin composition in a temperature region lower than the glass transition temperature is preferably 30 ppm / ° C. or less, more preferably 25 ppm / ° C. or less, still more preferably. It is 20 ppm / ° C or less.

Here, for the measurement of the glass transition temperature and the coefficient of linear expansion, a cured product of the thermosetting resin composition obtained at a molding temperature of 175 ° C. for 3 minutes and a post-mold cure (PMC) of 175 ° C. for 4 hours is used. ..
The glass transition temperature and the coefficient of linear expansion are measured by thermomechanical analysis (TMA, specifically, TMA6100 manufactured by Hitachi High-Technologies Corporation) at a heating rate of 10 ° C./min.

The flexural modulus of the cured product of the thermosetting resin composition is preferably 5 GPa or more, more preferably 8 GPa or more, still more preferably 12 GPa or more, from the viewpoint of improving the mechanical strength of the encapsulant.
Further, from the viewpoint of suppressing warpage of a sealed body such as a semiconductor package, the flexural modulus of the cured product of the thermosetting resin composition is preferably 30 GPa or less, more preferably 25 GPa or less, still more preferably 20 GPa or less. Is.
Here, for the measurement of the flexural modulus of the cured product of the thermosetting resin composition, the cured product of the thermosetting resin composition obtained at a molding temperature of 175 ° C. for 3 minutes and PMC 175 ° C. for 4 hours is used. ..
The flexural modulus is measured at room temperature (25 ° C.) using a universal tester (specifically, a Tensilon universal material tester manufactured by AND).

The minimum melt viscosity of the thermosetting resin composition is preferably 5 Pa · s or more, more preferably 10 Pa · s or more, still more preferably 20 Pa · s or more, from the viewpoint of suppressing entrainment voids.
Further, from the viewpoint of improving the filling property into a narrow portion such as chip filling property, the minimum melt viscosity of the thermosetting resin composition is preferably 80 Pa · s or less, more preferably 70 a · s or less, and further preferably 70 a · s or less. It is 60 Pa · s or less.
Here, the minimum melt viscosity of the thermosetting resin composition is a condition of a frequency of 10 Hz, a strain control of 0.1%, and a sample size of 20 mmφ × thickness of 0.1 mm using a viscosity / viscoelasticity measuring device (MARS manufactured by HAAKE). Measured by.

(Resin molded product)
In the present embodiment, the resin molded product is a cured product of a thermosetting resin composition containing an LDS additive, and specifically, is a resin molded product having a three-dimensional structure. The shape of the resin molded product is not limited as long as it has a three-dimensional structure, and may have a curved surface in part, for example.
Further, the resin molded product composed of the cured product of the thermosetting resin composition is not limited to the final product, but may also include composite materials and various parts. The 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. Hereinafter, a sealed body will be described as an example of such a material.

(Encapsulant)
FIG. 1 is a cross-sectional view showing a configuration example of a sealed body according to the present embodiment. The sealing body 110 shown in FIG. 1 has a substrate 101, a semiconductor element 103 mounted on the substrate 101, and a sealing material (sealing layer 111) for sealing the semiconductor element 103. The sealing layer 111 is composed of a cured product of a thermosetting resin composition containing an LDS additive.
In the sealing body 110, since the sealing layer 111 is exposed in a predetermined region on the surface of the sealing material, the sealing body 110 can be preferably used for the MID described below.

Specific examples of the sealing body 110 include a semiconductor device, and more specifically, a molded circuit component and various semiconductor packages.
Specific examples of molded circuit parts include those used for automobile members.
Further, as specific examples of semiconductor packages, MAP (Mold Array Package), QFP (Quad Flat Package), SOP (Small Outline Package), CSP (Chip Size Package), QFN (Quad Flat Non-leaded Package), SON (Small) Outline Non-leaded Package), BGA (Ball Grid Array), LF-BGA (Lead Flame BGA), FCBGA (Flip Chip BGA), MAPBGA (Molded Array Process BGA), eWLB (Embedded Wafer-Level BGA), Fan-In Semiconductor packages such as type eWLB and Fan-Out type eWLB; SIP (System In package) and the like can be mentioned.

The board 101 is, for example, a wiring board such as an interposer, or a lead frame. The semiconductor element 103 is electrically connected to the substrate 101 by, for example, wire bonding or flip chip connection. The semiconductor element 103 may be mounted on the substrate 101 in the form of a semiconductor package.

The sealing body 110 can be obtained, for example, by a manufacturing method including the following steps.
(Step 1) A step of preparing a substrate 101 on which the semiconductor element 103 is mounted (Step 2) A step of sealing the semiconductor element 103 with a sealing layer 111 so as to cover the surface of the semiconductor element 103.

Here, step 1 can be performed according to a conventional method.
Further, examples of the sealing method in step 2 include compression molding and becquerel pressing.
In the present embodiment, since the sealing material contains the sealing layer 111, cracking and chipping of the sealing layer 111 are suppressed, and the processing stability by LDS is excellent. Therefore, the sealing body 110 is excellent in manufacturing stability and processing stability by LDS.

Although FIG. 1 illustrates a configuration in which the sealing material is composed of one sealing layer 111, the sealing material may be configured to have a plurality of sealing layers. At this time, for example, the sealing layer forming the outermost layer of the sealing body may be a cured product of the thermosetting resin composition for LDS. Further, the entire plurality of sealed bodies can be composed of a cured product of a thermosetting resin composition for LDS.

(MID)
The MID has three elements of a three-dimensional shape, the resin molded product, and a three-dimensional circuit. For example, the MID is a component in which a circuit is formed of a metal film on the surface of a resin molded product having a three-dimensional structure. Specifically, the MID can include a resin molded product having a three-dimensional structure and a three-dimensional circuit formed on the surface of the resin molded product. By using such an MID, the space can be effectively utilized, the number of parts can be reduced, and the size can be reduced. The MID can also be applied to mobile phones, smartphones, built-in antennas, sensors, and semiconductor devices.

The MID can be obtained, for example, by subjecting the above-mentioned resin molded product to the LDS.
In the present embodiment, the manufacturing process of MID is carried out by producing a thermosetting resin composition used for LDS, molding the thermosetting resin composition, irradiating the obtained resin molded product with active energy rays, and plating treatment. Each step of circuit formation can be included. Further, a surface cleaning step may be added before the plating process.

As the active energy ray to irradiate the resin molded product, for example, a laser can be used. The laser can be appropriately selected from known lasers such as a YAG laser, an excimer laser, and an electromagnetic ray, and a YGA laser is preferable. Further, the wavelength of the laser is not defined, but is, for example, 200 nm to 12000 nm. Of these, preferably 248 nm, 308 nm, 355 nm, 532 nm, 1064 nm or 10600 nm may be used.

As the plating treatment, either electroplating 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. As the plating solution, 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.

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

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

(Examples 1 to 3)
The thermosetting resin compositions for LDS of each example were prepared and evaluated according to the formulations shown in Table 1. The components used in each example are as follows.

(raw materials)
(Epoxy resin)
Epoxy resin 1: Biphenyl aralkyl type epoxy resin, NC-3000L, Nippon Kayaku company epoxy resin 2: Biphenyl type epoxy resin, YX4000HK, Mitsubishi Chemical company epoxy resin 3: Trihydroxyphenylmethane type epoxy resin, 1032H-60, Made by Mitsubishi Chemical Corporation (hardener)
Curing agent 1: Trihydroxyphenylmethane type phenol resin, HE910-20, Air Water Chemical Inc. curing agent 2: Biphenyl aralkyl type phenol resin, MEH-7851SS, Showa Kasei (curing accelerator)
Curing Accelerator 1: Triphenylphosphine (inorganic filler)
Inorganic filler 1: Fused spherical silica, MUF-046, manufactured by Ryumori Co., Ltd., average particle size 4.1 μm
((Meta) acrylic monomer)
(Meta) Acrylic Monomer 1: Trimethylolpropane Trimethacrylate, Light Ester TMP, manufactured by Kyoeisha Chemical Co., Ltd., boiling point 200 ° C or higher (additive)
Additive 1 (LDS additive): Inorganic composite oxide, Black3702, manufactured by Asahi Kasei Kogyo Co., Ltd.

(Preparation of thermosetting resin composition)
First, the resin mixture obtained by kneading each raw material component excluding the solvent and the acrylic monomer according to the blending amounts shown in Table 1 below is dissolved in a predetermined amount of propylene glycol monomethyl ether and the amount of acrylic monomer shown in Table 1. A varnish was prepared.
Next, the prepared varnish was applied to the upper surface of a PET film (TR1 manufactured by Unitika Ltd.) with a die coater, and then dried until the propylene glycol monomethyl ether volatilized. By doing so, each resin sheet of Examples 1 to 3 was prepared. The thickness of each of the obtained resin sheets was 100 μm, and the width was 500 mm.

(Glass transition temperature, coefficient of linear expansion)
The thermosetting resin composition obtained in each example was compression molded at a molding temperature of 175 ° C. for 3 minutes and PMC 175 ° C. for 4 hours to obtain a cured product.
With TMA (TMA6100, manufactured by Hitachi High-Technologies Corporation), the glass transition temperature of the cured product and the linear expansion coefficient in the temperature range below the glass transition temperature were measured at a heating rate of 10 ° C./min.

(Flexural modulus)
The thermosetting resin composition obtained in each example was compression molded at a molding temperature of 175 ° C. for 3 minutes and PMC 175 ° C. for 4 hours to obtain a cured product.
The flexural modulus of the cured product was measured at room temperature (25 ° C.) using a universal testing machine (Tensilon universal material testing machine manufactured by AND).

(Minimum melt viscosity)
The measurement was performed using a viscosity / viscoelasticity measuring device (MARS manufactured by HAAKE) under the conditions of frequency 10 Hz, strain control 0.1%, sample size 20 mmφ × thickness 0.1 mm.

(Plating property)
The resin composition obtained in each example was molded and cured under the condition of 175 ° C. to obtain a cured product. The surface of the obtained cured product was irradiated with a YAG laser (wavelength 1064 nm), electroless copper plating was performed, and the plating property in the laser irradiation region 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 can be

(Presence or absence of cracks)
(When wrapped around a cylinder)
After using the resin sheets of each example formed on a PET film (TR1 manufactured by Unitika Ltd.) in a size of 300 mm in width and 1 m in length according to the above method, once wound around a cylinder having a diameter of 3 inches at room temperature. , The resin sheet was spread out and the presence or absence of cracks was visually confirmed.

(At the time of disconnection)
Using the resin sheet 10 cm × 10 cm of each example formed on a PET film (TR1 manufactured by Unitika Ltd.) according to the above method, after cutting with scissors at room temperature, cracks (cracks) at the cut portion. The presence or absence of was visually confirmed.

(Slit part cracked and chipped)
On the PET film (TR1 manufactured by Unitika Ltd.), the resin sheet 10 cm × 10 cm cut portion (slit portion) of each example formed according to the above method is cut (slit) while being heated to the temperature shown in Table 1. I did it. Here, the heating was performed by bringing a hot plate heated to the temperature shown in Table 1 into contact with the slit portion. The presence or absence of cracks or chips in the cut portion (slit portion) was visually confirmed. Here, the heating temperature indicates the set temperature of the hot plate, not the resin temperature of the slit portion.

From Table 1, the resin compositions obtained in each example preferably suppressed cracking and chipping of the sheet and were excellent in plating property.

101 Substrate 103 Semiconductor element 110 Encapsulant 111 Encapsulating layer

Claims (11)

A sheet-shaped thermosetting resin composition for LDS used for LASER DIRECT STRUCTURING (LDS).
Epoxy resin and
(Meta) acrylic compounds and
Inorganic filler and
Non-conductive metal compounds that form metal nuclei by irradiation with active energy rays,
A thermosetting resin composition for LDS. The thermosetting resin composition for LDS according to claim 1, wherein the (meth) acrylic compound is a (meth) acrylic monomer. The thermosetting resin composition for LDS according to claim 2, wherein the (meth) acrylic monomer has a boiling point higher than 100 ° C. Claims 1 to 3 wherein the epoxy resin contains one or more selected from the group consisting of a phenol aralkyl type epoxy resin having a biphenylene skeleton, a biphenyl type epoxy resin, and a tris (hydroxyphenyl) methane type epoxy resin. The thermosetting resin composition for LDS according to any one item. The thermosetting resin composition for LDS according to any one of claims 1 to 4, further comprising a curing agent. The thermosetting resin composition for LDS according to any one of claims 1 to 5, further comprising a curing accelerator. Thermomechanical analysis (TMA) of the cured product of the thermosetting resin composition for LDS obtained at a molding temperature of 175 ° C. for 3 minutes and a post-mold cure (PMC) of 175 ° C. for 4 hours. The thermosetting resin composition for LDS according to any one of claims 1 to 6, wherein the glass transition temperature measured at 10 ° C./min is 100 ° C. or higher and 200 ° C. or lower. Thermomechanical analysis (TMA) of the cured product of the thermosetting resin composition for LDS obtained at a molding temperature of 175 ° C. for 3 minutes and a post-mold cure (PMC) of 175 ° C. for 4 hours. The thermosetting resin for LDS according to any one of claims 1 to 7, wherein the linear expansion coefficient in the temperature region below the glass transition temperature measured at 10 ° C./min is 5 ppm / ° C. or higher and 30 ppm / ° C. or lower. Composition. The flexural modulus of the cured product of the thermosetting resin composition for LDS obtained at a molding temperature of 175 ° C./3 minutes and a post-mold cure (PMC) of 175 ° C. for 4 hours is 5 GPa as measured by a universal tester. The thermosetting resin composition for LDS according to any one of claims 1 to 8, which is 30 GPa or less. The LDS for LDS according to any one of claims 1 to 9, wherein the minimum melt viscosity of the thermosetting resin composition for LDS measured by a viscosity / viscoelasticity measuring device is 5 Pa · s or more and 80 Pa · s or less. Thermosetting resin composition. The thermosetting resin composition for LDS according to any one of claims 1 to 10, wherein the sheet thickness is 10 μm or more and 300 μm or less.

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