JP7424401B2 - Resin compositions for prepregs, prepregs, metal-clad laminates, printed wiring boards, and semiconductor devices - Google Patents

Description

The present invention relates to a resin composition for substrate materials, a prepreg, a metal-clad laminate, a printed wiring board, and a semiconductor device. More specifically, the present invention relates to a resin composition used for manufacturing a substrate material including a core material, as well as prepregs, metal-clad laminates, printed wiring boards, and semiconductor devices manufactured using this resin composition.

Conventionally, in wiring boards for mounting electronic components, it has been known that a resin paste such as epoxy resin is applied onto an underlying insulating substrate or insulating layer and hardened to form a resin insulating layer. There is. As such a wiring board, for example, a build-up wiring board in which a wiring layer is formed between resin insulation layers and resin insulation layers are laminated, and a printed wiring board in which a resin insulation layer is used as a solder resist layer have been proposed. (For example, Patent Document 1).
In Patent Document 1, light incident on an optical element, light emitted from an optical element, etc. is prevented from being reflected or diffused at a connection between the optical element and a substrate, thereby preventing erroneous input of optical information to the optical element. , it is possible to use a conductive resin composition containing a curable resin, a metal-based conductive filler, and a black colorant as a material for a printed wiring board that can prevent erroneous output of optical information from optical elements. Are listed.

JP2013-91748A

However, the printed wiring boards that have been proposed so far include a black coloring agent in the solder resist layer, and no one has been proposed in which the resin insulating layer itself has low light transmittance.
The present inventors have discovered that malfunctions of optical elements occur due to reflection and diffusion of light emitted from the optical element, and reflection and diffusion of light incident from the surface opposite to the surface on which the optical element is mounted, which can be prevented. The inventors have found that it is sufficient for the substrate itself to have low light transmittance.

As a result of extensive research, the inventors of the present invention discovered that the substrate itself on which the optical element is mounted is made of a material that absorbs light in the wavelength range from ultraviolet to infrared to prevent malfunction of the optical element. They discovered that it can be done and completed the present invention.

According to the present invention, there is provided a resin composition for a substrate material containing a thermosetting resin, an inorganic filler, and a black pigment, wherein a cured product of the composition for a substrate material has a thickness of 400 nm to 1100 nm at a thickness of 60 μm. Provided is a resin composition for a substrate material having a maximum transmittance of 10% or less for light having a wavelength of .

Further, according to the present invention, there is provided a prepreg comprising a fiber base material layer made of a fiber base material impregnated with a resin composition, wherein the resin composition is the resin composition for a substrate material. Ru.

Further, according to the present invention, there is provided a metal-clad laminate including the prepreg described above and a metal foil laminated on the prepreg.

Further, according to the present invention, there is provided a printed wiring board comprising the prepreg molded body and a wiring pattern provided on both surfaces or one side of the molded body.

Further, according to the present invention, there is provided a semiconductor device including the above printed wiring board and a semiconductor element mounted on the printed wiring board.

According to the present invention, a resin composition for a substrate material that absorbs light in a wavelength region ranging from ultraviolet to infrared regions, a prepreg comprising a cured product of the resin composition, a metal-clad laminate, a printed wiring board, and a semiconductor device are provided. provided.

Embodiments of the present invention will be described below.
The resin composition for a substrate material of the present embodiment (hereinafter referred to as a resin composition) includes a thermosetting resin, an inorganic filler, and a black pigment, and the cured product of the resin composition has a thickness of 60 μm. The maximum value of transmittance for light having a wavelength of 400 nm to 1100 nm is 10% or less.

In one embodiment, the resin composition of the present embodiment has a maximum transmittance of 5% or less, preferably 4% or less, for light having a wavelength of 400 nm to 1100 nm at a thickness of 60 μm of the cured product. It is even more preferable. Since the maximum value of the transmittance is 10% or less, when an optical element is mounted on a substrate using this cured product as a core material, reflection and diffusion of the light emitted from the optical element is suppressed, and the surface on which the optical element is mounted is suppressed. Reflection and diffusion of light incident from the opposite surface is prevented. Thereby, malfunction of the optical element due to light can be prevented. Furthermore, since the optical element can be placed at any position, the degree of freedom in arranging the optical element can be increased.

The resin composition of this embodiment contains a black pigment. By including the black pigment, it is possible to reduce the light transmittance in the wavelength range from ultraviolet to infrared. Therefore, when a substrate is manufactured using the cured product of the resin composition as a core material, this substrate does not transmit light in the wavelength range from ultraviolet to infrared, and when an optical element is mounted on this substrate, the optical element Reflection and diffusion of the emitted light are suppressed, thereby reducing malfunctions of the optical elements.

Examples of the thermosetting resin used in the resin composition of this embodiment include epoxy resin, acrylic resin, melamine resin, maleimide resin, phenoxy resin, polyurethane resin, diallyl phthalate resin, and silicone resin. The thermosetting resins may be used alone or in combination of two or more. Among the thermosetting resins, it is preferable to use epoxy resins. Thereby, the dispersibility of the black pigment described below can be improved.

Specifically, the above-mentioned epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, bisphenol M type epoxy resin (4,4'-(1, 3-phenylene diisopridiene) bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4'-(1,4-phenylene diisopridiene) bisphenol type epoxy resin), bisphenol Z type epoxy resin (4, Bisphenol-type epoxy resins such as 4'-cyclohexydiene bisphenol-type epoxy resins; phenol novolac-type epoxy resins, cresol novolak-type epoxy resins, tetraphenol-based ethane-type novolak-type epoxy resins, novolacs having a condensed ring aromatic hydrocarbon structure Novolac-type epoxy resins such as type epoxy resins; biphenyl-type epoxy resins; aralkyl-type epoxy resins such as xylylene-type epoxy resins and biphenylaralkyl-type epoxy resins; naphthylene ether-type epoxy resins, naphthol-type epoxy resins, naphthalene diol-type epoxy resins, Epoxy resins having a naphthalene skeleton such as difunctional to tetrafunctional epoxy naphthalene resins, binaphthyl epoxy resins, naphthalene aralkyl epoxy resins, naphthalene-modified cresol novolak epoxy resins; anthracene epoxy resins; phenoxy epoxy resins; dicyclopentadiene Type epoxy resins; norbornene type epoxy resins; adamantane type epoxy resins; fluorene type epoxy resins and the like. The epoxy resins may be used alone or in combination of two or more.

Among epoxy resins, bisphenol-type epoxy resins, novolac-type epoxy resins, biphenyl-type epoxy resins, aralkyl-type epoxy resins, and naphthalene-type epoxy resins are selected from the viewpoint of further improving the heat resistance and insulation reliability of cured resin compositions. , anthracene type epoxy resin, and dicyclopentadiene type epoxy resin are preferred, and aralkyl type epoxy resin, novolak type epoxy resin having a condensed ring aromatic hydrocarbon structure, and naphthalene type epoxy resin. More preferably, one or more selected from the group consisting of:

As the bisphenol A epoxy resin, "Epicote 828EL" and "YL980" manufactured by Mitsubishi Chemical Corporation can be used. As the bisphenol F type epoxy resin, "jER806H" and "YL983U" manufactured by Mitsubishi Chemical Corporation, "EPICLON 830S" manufactured by DIC Corporation, etc. can be used. As the bifunctional naphthalene type epoxy resin, "HP4032", "HP4032D", "HP4032SS", etc. manufactured by DIC Corporation can be used. As the tetrafunctional naphthalene type epoxy resin, "HP4700" and "HP4710" manufactured by DIC Corporation can be used. As the naphthol type epoxy resin, "ESN-475V" manufactured by Nippon Steel Chemical Co., Ltd., "NC7000L" manufactured by Nippon Kayaku Co., Ltd., etc. can be used. Aralkyl type epoxy resins include "NC3000", "NC3000H", "NC3000L", "NC3000S", "NC3000S-H", "NC3100" manufactured by Nippon Kayaku Co., Ltd., and "ESN-170" manufactured by Nippon Steel Chemical Co., Ltd. ”, “ESN-480”, etc. can be used. As the biphenyl type epoxy resin, "YX4000", "YX4000H", "YX4000HK", "YL6121", etc. manufactured by Mitsubishi Chemical Corporation can be used. As the anthracene type epoxy resin, "YX8800" manufactured by Mitsubishi Chemical Corporation, etc. can be used. As the naphthylene ether type epoxy resin, "HP6000", "EXA-7310", "EXA-7311", "EXA-7311L", "EXA7311-G3", etc. manufactured by DIC Corporation can be used.

Among these epoxy resins, aralkyl epoxy resins are particularly preferred. Thereby, the moisture absorption solder heat resistance and flame retardance of the cured product of the resin composition can be further improved.

The aralkyl type epoxy resin is represented by the following general formula (1), for example.

（上記一般式（１）中、ＡおよびＢは、ベンゼン環、ビフェニル構造等の芳香族環を表す。またＡおよびＢの芳香族環の水素が置換されていてもよい。置換基としては、例えば、メチル基、エチル基、プロピル基、フェニル基等が挙げられる。ｎは繰返し単位を表し、例えば、１～１０の整数である。）

(In the above general formula (1), A and B represent an aromatic ring such as a benzene ring or a biphenyl structure. Furthermore, hydrogen in the aromatic rings of A and B may be substituted. As a substituent, Examples include methyl group, ethyl group, propyl group, phenyl group, etc. n represents a repeating unit and is, for example, an integer from 1 to 10.)

Specific examples of aralkyl-type epoxy resins include the following formulas (1a) and (1b).

（式（１ａ）中、ｎは、１～５の整数を示す。）

(In formula (1a), n represents an integer from 1 to 5.)

（式（１ｂ）中、ｎは、１～５の整数を示す。）

(In formula (1b), n represents an integer from 1 to 5.)

As the epoxy resin other than the above, a novolac type epoxy resin having a condensed ring aromatic hydrocarbon structure is preferable. Thereby, heat resistance and low thermal expansion properties can be further improved.

The novolac type epoxy resin having a condensed ring aromatic hydrocarbon structure is naphthalene, anthracene, phenanthrene, tetracene, chrysene, pyrene, triphenylene, tetraphene, or other novolac type epoxy resin having a condensed ring aromatic hydrocarbon structure. . Novolak-type epoxy resins having a condensed ring aromatic hydrocarbon structure have excellent low thermal expansion properties because a plurality of aromatic rings can be regularly arranged. In addition, it has a high glass transition temperature, so it has excellent heat resistance. Furthermore, because the molecular weight of the repeating structure is large, it has superior flame retardancy compared to conventional novolak-type epoxy resins.

A novolak type epoxy resin having a condensed ring aromatic hydrocarbon structure is an epoxidized novolak type phenol resin synthesized from a phenol compound, an aldehyde compound, and a condensed ring aromatic hydrocarbon compound.

The maleimide group of a maleimide compound has a five-membered ring planar structure, and the double bond of the maleimide group easily interacts between molecules and is highly polar. It exhibits strong intermolecular interactions and can suppress molecular movement. Therefore, by containing the maleimide compound, the resin composition can lower the linear expansion coefficient of the resulting cured product, improve the glass transition temperature, and further improve heat resistance.

As the maleimide compound, a maleimide compound having at least two maleimide groups in the molecule is preferred. Examples of maleimide compounds having at least two maleimide groups in the molecule include 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, 2,2-bis[4-(4-maleimide) phenoxy)phenyl]propane, bis-(3-ethyl-5-methyl-4-maleimidophenyl)methane, 4-methyl-1,3-phenylenebismaleimide, N,N'-ethylene dimaleimide, N,N'- Hexamethylene dimaleimide, bis(4-maleimidophenyl) ether, bis(4-maleimidophenyl) sulfone, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, bisphenol A diphenyl ether bismaleimide, etc. Examples include compounds having two maleimide groups in the molecule, and compounds having three or more maleimide groups in the molecule such as polyphenylmethane maleimide.

One of these can be used alone, or two or more can be used in combination. Among these maleimide compounds, 4,4'-diphenylmethane bismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, and bis-(3-ethyl- Preferred are 5-methyl-4-maleimidophenyl)methane, polyphenylmethanemaleimide, and bisphenol A diphenyl ether bismaleimide.

Examples of the phenoxy resin include phenoxy resins having a bisphenol skeleton, phenoxy resins having a naphthalene skeleton, phenoxy resins having an anthracene skeleton, and phenoxy resins having a biphenyl skeleton. Furthermore, a phenoxy resin having a structure having multiple types of these skeletons can also be used.

Among these, it is preferable to use a phenoxy resin having a biphenyl skeleton and a bisphenol S skeleton. The rigidity of the biphenyl skeleton can increase the glass transition temperature of the phenoxy resin, and the presence of the bisphenol S skeleton can improve the adhesion between the phenoxy resin and metal. As a result, it is possible to improve the heat resistance of the cured product of the resin composition, and when manufacturing a circuit board using the cured product of the resin composition as a resin insulating layer, it is possible to improve the adhesion of the wiring layer to the resin insulating layer. can improve sex. Furthermore, it is also preferable to use a phenoxy resin having a bisphenol A skeleton and a bisphenol F skeleton. Thereby, it is possible to further improve the adhesion of the wiring layer to the resin insulating layer when manufacturing the circuit board.

Further, it is also preferable to use a phenoxy resin having a bisphenolacetophenone structure represented by the following general formula (X).

(In the formula, R1 may be the same or different from each other and is a group selected from a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen element, and R2 is a hydrogen atom, a group having 1 or less carbon atoms, (R3 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and m is an integer of 0 to 5.)

Since the phenoxy resin containing the bisphenolacetophenone structure has a bulky structure, it has excellent solvent solubility and compatibility with the thermosetting resin component to be blended. Furthermore, since a uniform rough surface with low roughness can be formed, it is excellent in forming fine wiring.

A phenoxy resin having a bisphenolacetophenone structure can be synthesized by a known method such as a method of increasing the molecular weight of an epoxy resin and a phenol resin with a catalyst.

The phenoxy resin having a bisphenolacetophenone structure may contain a structure other than the bisphenolacetophenone structure of general formula (X), and the structure is not particularly limited, but may include bisphenol A type, bisphenol F type, bisphenol S type, biphenyl type, phenol novolac type, and cresol novolac type structures. Among these, those containing a biphenyl type structure are preferred because they have a high glass transition temperature.

The content of the bisphenolacetophenone structure of general formula (X) in the phenoxy resin containing a bisphenolacetophenone structure is not particularly limited, but is preferably 5 mol% or more and 95 mol% or less, more preferably 10 mol% or more and 85 mol%. or less, more preferably 15 mol% or more and 75 mol% or less. When the content is at least the above lower limit, the effect of improving the heat resistance and moisture resistance reliability of the cured product of the resulting resin composition can be sufficiently exhibited. Moreover, the solvent solubility of a resin composition can be improved as content is below the said upper limit.

The weight average molecular weight (Mw) of the phenoxy resin is not particularly limited, but is preferably 5,000 or more and 100,000 or less, more preferably 10,000 or more and 70,000 or less, and even more preferably 20,000 or more and 50,000 or less. When Mw is below the above upper limit, compatibility with other resins and solubility in solvents can be improved. When it is at least the above lower limit, film formability is improved and it is possible to suppress occurrence of defects when used for manufacturing circuit boards.

The content of the phenoxy resin is not particularly limited, but is preferably 0.5% to 40% by weight of the resin composition excluding fillers, and more preferably 1% to 20% by weight. When the content is at least the above lower limit, it is possible to suppress a decrease in the mechanical strength of the insulating resin layer and a decrease in plating adhesion to the conductor circuit. When it is below the above upper limit, an increase in the coefficient of thermal expansion of the resin insulating layer can be suppressed, and the heat resistance can be reduced.

Inorganic fillers used in the resin composition of the present embodiment include silicates such as talc, fired clay, unfired clay, mica, and glass; oxides such as titanium oxide, alumina, boehmite, silica, and fused silica; Carbonates such as calcium carbonate, magnesium carbonate, hydrotalcite; hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide; sulfates or sulfites such as barium sulfate, calcium sulfate, calcium sulfite; zinc borate , borates such as barium metaborate, aluminum borate, calcium borate, sodium borate; nitrides such as aluminum nitride, boron nitride, silicon nitride, carbon nitride; titanates such as strontium titanate, barium titanate Examples include. The fillers may be used alone or in combination of two or more. It is preferable to use silica as the filler.

Examples of the black pigment used in the resin composition of the present embodiment include inorganic oxides such as black titanium oxide; carbon compounds such as carbon black, graphite, fullerene, and carbon fiber. Among these, black titanium oxide is preferred as the black pigment. Black titanium oxide is a titanium oxide represented by _{Ti n} O _{2n-1 (} n is a positive integer). It is preferable to include titanium oxide Ti _n O _2n-1 (n is an integer of 2 or more and 6 or less). Since such black titanium oxide is highly dispersed in the resin composition, it is possible to reduce the light transmittance of the resulting resin composition.

The upper limit of the average particle diameter of black titanium oxide is not particularly limited, but is preferably 2.0 μm or less, more preferably 1.9 μm or less, and even more preferably 1.8 μm or less. Thereby, the dispersibility of black titanium oxide in the resin composition can be improved. Further, the lower limit of the average particle diameter of black titanium oxide is not particularly limited, but is preferably 0.1 μm or more, and more preferably 0.2 μm or more, for example. Black titanium oxide having such an average particle size is preferable from the viewpoint of ease of manufacture and handling.

In this embodiment, black titanium oxide is preferably blended in an amount of 1% by weight or more and 10% by weight or less based on the entire solid content of the resin composition. By using black titanium oxide in such a content, the light transmittance of the resulting resin composition can be adjusted to a desired range.

The resin composition of this embodiment may contain a curing agent, if necessary. As curing agents that can be used, for example, phenol resins, benzoxazine resins, cyanate resins, active ester resins, etc. can be used. As the curing agent, for example, it is preferable to use cyanate resin. Thereby, the black titanium oxide can be suitably dispersed in the resin composition, and the cured product of the resin composition obtained has a high glass transition temperature Tg, high rigidity, and low linear expansion.

The above-mentioned phenolic resins are monomers, oligomers, and polymers having two or more phenolic hydroxyl groups in one molecule, and specifically include novolak-type phenolic resins such as phenol novolac resins, cresol novolac resins, and naphthol novolac resins; Polyfunctional phenolic resins such as methane-type phenolic resins; modified phenolic resins such as terpene-modified phenolic resins and dicyclopentadiene-modified phenolic resins; phenolic aralkyl resins having a phenylene skeleton and/or biphenylene skeleton, and phenol aralkyl resins having a phenylene and/or biphenylene skeleton Aralkyl type resins such as naphthol aralkyl resins; bisphenol compounds such as bisphenol A and bisphenol F; and the like. The phenol resins may be used alone or in combination of two or more. Note that the phenol resin preferably includes a liquid phenol resin that is liquid at room temperature of 25°C.

Specifically, the above-mentioned benzoxazine resins include o-cresolaniline type benzoxazine resin, m-cresolaniline type benzoxazine resin, p-cresolaniline type benzoxazine resin, phenol-aniline type benzoxazine resin, phenol-methyl Amine type benzoxazine resin, phenol-cyclohexylamine type benzoxazine resin, phenol-m-toluidine type benzoxazine resin, phenol-3,5-dimethylaniline type benzoxazine resin, bisphenol A-aniline type benzoxazine resin, bisphenol A- Amine type benzoxazine resin, bisphenol F-aniline type benzoxazine resin, bisphenol S-aniline type benzoxazine resin, dihydroxydiphenylsulfone-aniline type benzoxazine resin, dihydroxydiphenyl ether-aniline type benzoxazine resin, benzophenone type benzoxazine resin, biphenyl type benzoxazine resin, bisphenol AF-aniline type benzoxazine resin, bisphenol A-methylaniline type benzoxazine resin, phenol-diaminodiphenylmethane type benzoxazine resin, triphenylmethane type benzoxazine resin, and phenolphthalein type benzoxazine resin, etc. can be mentioned.
Furthermore, as commercially available benzoxazine resins, for example, BF-BXZ, BS-BXZ, BA-BXZ (all manufactured by Konishi Kagaku Kogyo Co., Ltd.), etc. can be used.

As the cyanate resin, cyanate ester resin can be used.
Specifically, the cyanate ester resins include bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4, 4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate) phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5- Difunctional cyanate resins such as dimethylphenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether; phenol Polyfunctional cyanate resins derived from novolak, cresol novolac, phenolic resins containing dicyclopentadiene structures, etc.; prepolymers in which a portion of the above-exemplified cyanate ester resins are triazinized, and the like.
Here, as commercially available cyanate ester resins, for example, PT30, BA230, DT-4000, DT-7000 manufactured by Lonza Japan, etc. can be used.

Specifically, the active ester resin has an ester group with high reaction activity such as a phenol ester compound, a thiophenol ester compound, an N-hydroxyamine ester compound, a compound in which a heterocyclic hydroxy group is esterified, An epoxy resin having a curing effect can be used.
As the active ester resin, it is preferable to use, for example, one obtained from a carboxylic acid compound and a hydroxy compound among the above specific examples. Here, specific examples of the hydroxy compound include phenol compounds, naphthol compounds, and the like.

Specific examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.
In addition, specific examples of the above-mentioned phenol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, and o-cresol. , m-cresol, p-cresol, catechol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyl diphenol, phenol novolak, and the like.
Further, specific examples of the naphthol compounds include α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene.

The resin composition of this embodiment may contain further components such as a curing accelerator, a coloring agent, a coupling agent, a leveling agent, and a flame retardant, as necessary.

As the curing accelerator, one that accelerates the reaction between the epoxy resin and the curing agent can be used. Specific examples of curing accelerators include organic metals such as zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, zinc octylate, cobalt (II) bisacetylacetonate, and cobalt (III) trisacetylacetonate. salts, triethylamine, tributylamine, tertiary amines such as diazabicyclo[2,2,2]octane, tetraphenylphosphonium tetraphenylborate (TPP-K), tetraphenylphosphonium tetrakis(4-methylphenyl)borate (TPP -MK), quaternary phosphonium compounds such as bis(naphthalene-2,3-dioxy)phenylsilicate adduct of tetraphenylphosphonium, 2-phenyl-4-methylimidazole, 2-ethyl-4-ethylimidazole, 2 - Imidazoles such as phenyl-4-ethylimidazole, 2-phenyl-4-methyl-5-hydroxyimidazole, and 2-phenyl-4,5-dihydroxyimidazole, phenolic compounds such as phenol, bisphenol A, and nonylphenol, acetic acid, benzoic Examples thereof include acids, organic acids such as salicylic acid and para-toluenesulfonic acid, and onium salt compounds.

The onium salt compound used as the curing accelerator is not particularly limited, but for example, a compound represented by the following general formula (2) can be used.

（上記一般式（２）中、Ｐはリン原子、Ｒ３、Ｒ４、Ｒ５およびＲ６は、それぞれ、置換もしくは無置換の芳香環または複素環を有する有機基、あるいは置換もしくは無置換の脂肪族基を示し、互いに同一であっても異なっていてもよい。Ａ－は分子外に放出しうるプロトンを少なくとも１個以上分子内に有するｎ（ｎ≧１）価のプロトン供与体のアニオン、またはその錯アニオンを示す）

(In the above general formula (2), P is a phosphorus atom, R3, R4, R5 and R6 are each an organic group having a substituted or unsubstituted aromatic ring or a heterocycle, or a substituted or unsubstituted aliphatic group. A- is an anion of an n-valent proton donor (n≧1) that has at least one proton that can be released outside the molecule, or a complex thereof. (indicates anion)

The lower limit of the content of the curing accelerator may be, for example, 0.01% by weight or more, preferably 0.05% by weight or more, based on 100% by weight of the total solid content of the thermosetting resin composition. You can also use it as By setting the content of the curing accelerator to the above lower limit or more, the curability of the thermosetting resin composition can be improved more effectively. On the other hand, the upper limit of the content of the curing accelerator may be, for example, 2.5% by weight or less, preferably 1% by weight or less, based on 100% by weight of the total solid content of the thermosetting resin composition. good. By controlling the content of the curing accelerator to be less than or equal to the above upper limit, the storage stability of the thermosetting resin composition can be improved.

As the coloring agent, a black dye or a black pigment other than the above-mentioned black pigment can be used. Specific examples of the black dye include metal complex black dyes such as azo-based, organic black dyes such as anthraquinone-based compounds, and more specifically, Kayaset Black A-N (Nippon Kayaku Co., Ltd.). (manufactured by Nippon Kayaku Co., Ltd.), Kayaset Black G (manufactured by Nippon Kayaku Co., Ltd.), and the like. In this embodiment, one or more types of black dye may be used.

Examples of the coupling agent include silane coupling agents such as epoxy silane coupling agents, cationic silane coupling agents, and aminosilane coupling agents, titanate coupling agents, and silicone oil type coupling agents. The coupling agents may be used alone or in combination of two or more.

The resin composition for circuit boards in this embodiment includes thermoplastic resins such as polyimide resin, polyamideimide resin, polyphenylene oxide resin, polyethersulfone resin, polyester resin, polyethylene resin, and polystyrene resin, styrene-butadiene copolymer, and styrene. - Thermoplastic elastomers such as polystyrene-based thermoplastic elastomers such as isoprene copolymers, polyolefin-based thermoplastic elastomers, polyamide-based elastomers, and polyester-based elastomers - Diene systems such as polybutadiene, epoxy-modified polybutadiene, acrylic-modified polybutadiene, and methacrylic-modified polybutadiene An elastomer may also be used in combination.

The resin composition of this embodiment is provided as a varnish-like composition by dissolving and dispersing the raw ingredients in a solvent.
Specific examples of the solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethyl acetate, heptane, cyclohexane, cyclohexanone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, cellosolve series, carbitol series, and anisole. , and N-methylpyrrolidone. The solvents may be used alone or in combination of two or more.

(Method for producing resin composition for substrate material)
The thermosetting resin composition of this embodiment can be prepared using the above-mentioned raw material components, for example, by an ultrasonic dispersion method, a high-pressure collision dispersion method, a high-speed rotation dispersion method, a bead mill method, a high-speed shear dispersion method, and a rotation-revolution dispersion method. It can be prepared by dissolving, mixing, and stirring in a solvent using various mixers such as.
As a method for producing a resin composition for a substrate material, it is important to dissolve and disperse the black pigment in a solvent, and then dissolve and disperse raw components of the resin composition for the substrate material other than the black pigment. This allows the black pigment to be highly dispersed in the resin composition for substrate materials compared to conventional resin compositions for substrate materials.
As a method for dissolving and dispersing the black pigment in a solvent, it is preferable to use, for example, ultrasonic dispersion. Thereby, the black pigment can be more highly dispersed in the resin composition for substrate material.
In addition, from the viewpoint of improving the dispersibility of the black pigment, the time for ultrasonic dispersion is preferably 30 minutes or more and 60 minutes or less, for example. Thereby, it is possible to reduce the light transmittance while reducing the content of the black pigment.

The resin composition of this embodiment can be used to produce a substrate material. For example, the resin composition of this embodiment is used to produce a molded article of the resin composition. Methods for molding the resin composition include, but are not particularly limited to, transfer molding, injection molding, and potting molding (liquid injection molding). As one mode of molding to obtain a molded body by the transfer molding method, the curable resin composition preformed into a tablet of an arbitrary size is charged into a preheated transfer molding machine, and the attached arbitrary An example of this method is to transfer the material to a mold having the same shape and material by applying pressure with a plunger.

Alternatively, the resin composition of this embodiment can be used to produce prepreg. The prepreg is produced, for example, by immersing a fiber base material in the resin composition (varnish-like) of this embodiment. The fiber base materials used for prepreg include glass fiber base materials such as glass woven fabric and glass non-woven fabric, polyamide resin fibers such as polyamide resin fibers, aromatic polyamide resin fibers, and fully aromatic polyamide resin fibers, polyester resin fibers, Synthetic fiber base materials consisting of woven or nonwoven fabrics whose main components are aromatic polyester resin fibers, polyester resin fibers such as fully aromatic polyester resin fibers, polyimide resin fibers, fluororesin fibers, etc., kraft paper, and cotton linters. Examples include organic fiber base materials such as paper base materials whose main components are paper, mixed paper of linter and kraft pulp, and the like.

In one embodiment, the prepreg may have a structure in which a fiber base material layer made of the above fiber base material impregnated with the above resin composition and a resin layer made of the above resin composition are laminated. . The thickness of the resin layer is 1 μm or more and 50 μm or less, preferably 10 μm or more and 40 μm or less. By setting the thickness of the resin layer to be equal to or greater than the above lower limit, the transmittance of the resin layer can be lowered. Moreover, when the thickness of the resin layer exceeds the above upper limit, the water absorption rate of the resin layer increases. Therefore, by setting the thickness of the resin layer to be equal to or less than the above upper limit, deterioration of moisture absorption and heat resistance can be avoided.

In one embodiment, the resin composition described above is used to make a metal clad laminate. In this embodiment, the metal-clad laminate can be produced by laminating metal foil on at least one surface of the cured prepreg described above. Metal-clad laminates are produced, for example, by layering metal foil on both upper and lower surfaces or on one side of the outside of the above-mentioned prepreg or a laminate made of two or more prepregs, and bonding these together under high vacuum conditions using a laminator or Becquerel device. Alternatively, it can be produced by directly stacking metal foil on both upper and lower surfaces or on one side of the outside of the prepreg, and then heating and press-molding a laminate in which the prepreg and metal foil are stacked.

Examples of metals constituting the metal foil include copper, copper alloy, aluminum, aluminum alloy, silver, silver alloy, gold, gold alloy, zinc, zinc alloy, nickel, nickel alloy, tin, Examples include tin-based alloys, iron, iron-based alloys, Fe-Ni-based alloys such as Kovar (trade name), 42 alloy, Invar, and Super Invar, W, and Mo. Among these, copper or a copper alloy is preferred because it has excellent conductivity, is easy to form a circuit by etching, and is inexpensive.

In one embodiment, a printed wiring board is produced using the prepreg or metal-clad laminate described above. The printed wiring board of this embodiment includes the above-described prepreg molded body and a wiring pattern provided on both sides or one side of the molded body. Other configurations of the printed wiring board of this embodiment are not particularly limited, and may include various conventionally known parts or may be subjected to various processing. The printed wiring board of this embodiment can be used as a component for fixing semiconductor elements (electronic components) such as LSIs, resistive elements, capacitors, and inductors, and for connecting the semiconductor elements (electronic components) with wiring. . In the printed wiring board of the present invention, a wiring pattern is formed on one or both sides of the above-mentioned prepreg molded body or the above-mentioned metal-clad laminate using a known method such as a subtractive method, an additive method, or a semi-additive method. It can be manufactured by

In one embodiment, a semiconductor device is provided that includes the above-described printed wiring board and a semiconductor element mounted on the printed wiring board. Specific examples of semiconductor elements include LSIs, resistance elements, capacitors, and inductors. Other configurations of the semiconductor device of the present invention are not particularly limited, and may include conventionally known semiconductor device members in addition to the semiconductor element. Examples of such semiconductor device members include lead wiring, wire wiring, control elements, heat sinks, conductive members, die bonding materials, bonding pads, and the like.

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

EXAMPLES Hereinafter, the present invention will be explained in detail using Examples, but the present invention is not limited to the description of these Examples.

(Examples 1 to 5, Comparative Example 1, and Reference Example 1)
(Preparation of thermosetting resin composition)
For Examples and Comparative Examples, varnish-like thermosetting resin compositions were prepared.
First, the black pigment in the amount listed in Table 1 was dissolved in a mixed solvent of methyl isobutyl ketone and cyclohexanone (methyl isobutyl ketone: cyclohexanone = 26:9) using a high-speed stirring device, and then for 30 minutes. It was made into a slurry by ultrasonic dispersion. Next, components other than the black pigment in the amounts listed in Table 1 were dissolved and dispersed in the slurry using a high-speed stirring device to prepare resin varnishes of Examples and Comparative Examples.

(thermosetting resin)
Thermosetting resin 1: Phenol aralkyl type epoxy resin having a biphenylene skeleton (manufactured by Nippon Kayaku Co., Ltd., NC-3000H, epoxy equivalent weight 275, weight average molecular weight 2000)
Thermosetting resin 2: Modified biphenol type epoxy resin (manufactured by Mitsubishi Chemical Corporation, YX6900BH45)
Thermosetting resin 3 _: A _maleimide compound ₍ BMI- 2300, manufactured by Daiwa Kasei Kogyo Co., Ltd., Mw=750)

(hardening agent)
Phenolic curing agent 1: Cyanate resin (manufactured by LONZA, Primaset PT-30)
Phenol curing agent 2: Phenol resin curing agent (manufactured by Nippon Kayaku Co., Ltd., GPH-103)
Phenol curing agent 3: Phenol resin curing agent (manufactured by Daiwa Kasei Kogyo Co., Ltd., DABPA)
(Inorganic filler)
Inorganic filler 1: Silica particles (manufactured by Admatex, SC4050-KNR)
Inorganic filler 2: Silica particles (manufactured by Admatex, YA050C-HHA)
(colorant)
Black dye 1: Anthraquinone compound (Nippon Kayaku Co., Ltd., Kayaset Black AN)
Black pigment 2: Black titanium oxide (manufactured by Ako Kasei Co., Ltd., Tilack D)
Black pigment 3: Carbon black (manufactured by Mitsubishi Chemical Corporation, MA600)
(hardening accelerator)
Curing accelerator 1: Bis(naphthalene-2,3-dioxy)phenylsilicate adduct of tetraphenylphosphonium (manufactured by Sumitomo Bakelite)
(coupling agent)
Coupling agent 1: Epoxysilane type coupling agent (manufactured by Momentive Performance Materials, A-187)
(Leveling agent)
Leveling agent 1: Leveling agent (manufactured by BIC Chemie)

(prepreg)
In Examples and Comparative Examples, the glass cloth (cloth type #1078, E glass, basis weight 48 g/m ² ) was impregnated with the resin varnish by applying the obtained resin varnish to a glass cloth. Thereafter, it was dried in a heating oven at 180° C. for 2 minutes to obtain a prepreg with a thickness of 70 μm.

In Examples and Comparative Examples, the following evaluations were performed. The evaluation results are shown in Table 1.

(Dispersibility 24 hours after preparation)
After the obtained resin varnish was allowed to stand still for 24 hours, the degree of dispersion was visually confirmed. In Table 1, the results are shown in Table 1 as "○" indicates that the resin solid content is uniformly dispersed, and as "x" indicates that the resin solid content is sedimented.

(cured prepreg product)
The obtained prepreg was heat-treated at 220° C. for 2 hours to obtain a cured prepreg (thickness: 60 μm) of a thermosetting resin composition.

(transmittance)
Transmittance was evaluated for the cured prepregs of each Example and Comparative Example. Details will be explained below.
The transmittance of the measurement sample was measured using an ultraviolet-visible near-infrared spectrophotometer (manufactured by JASCO Corporation, V-670). Note that the measurement wavelength was 400 nm to 1100 nm. The evaluation results are shown in Table 1 below. Note that the unit of maximum transmittance is %.

(Glass transition temperature, storage modulus at 30°C)
A test piece of 8 mm x 40 mm was cut out from the obtained prepreg cured product, and the test piece was subjected to dynamic viscoelasticity measurement (DMA device, TA Instruments, Q800) at a heating rate of 5°C/ Dynamic viscoelasticity was measured at a frequency of 1 Hz and a storage modulus at 30°C was calculated. Moreover, the glass transition temperature was set as the temperature at which the loss tangent tan δ shows the maximum value.

(Coefficient of linear expansion (CTE))
A 4 mm x 20 mm test piece was prepared from the obtained prepreg cured product. This test piece was subjected to thermomechanical analysis using a thermomechanical analyzer TMA (manufactured by TA Instruments, Q400) under the conditions of a temperature range of 30 to 300°C, a heating rate of 10°C/min, a load of 10 g, and a tensile mode. (TMA) was measured for two cycles. From this result, the average value of the coefficient of linear expansion (CTE) in the plane direction (XY direction) in the range from 30° C. to 250° C. in the second cycle was calculated. In addition, the value of the second cycle was adopted as the linear expansion coefficient.

(Measurement of volume resistivity)
Volume resistivity was measured in accordance with JIS K 6911. The test pieces used were those cut out to a size of 10 cm x 10 cm from the prepreg cured products obtained in Examples and Comparative Examples. The results are shown in Table 1.

As shown in Table 1, the resin varnishes of each example had excellent dispersibility. In addition, the prepreg cured products of each example have a transmittance of 10% or less for light with a wavelength of 400 nm to 1100 nm, and also have excellent properties such as high volume resistivity, high glass transition temperature, low linear expansion, and high rigidity. It had physical properties. As a result, when a semiconductor device is manufactured by mounting an optical element on a printed wiring board having the prepreg cured product of each example as an insulating layer, a highly reliable semiconductor device in which malfunction of the optical element is suppressed can be realized. it is conceivable that.

Claims (8)

thermosetting resin;
Inorganic filler and
A resin composition for prepreg comprising a black pigment,
A resin composition for prepregs, wherein the cured product of the resin composition for prepregs has a maximum transmittance of 10% or less for light with a wavelength of 400 nm to 1100 nm at a thickness of 60 μm. The resin composition for prepreg according to claim 1 , wherein the thermosetting resin contains an epoxy resin. The resin composition for prepreg according to claim 1 or 2 , further comprising a curing agent. A prepreg comprising a fiber base material layer made of a fiber base material impregnated with a resin composition,
A prepreg, wherein the resin composition is the prepreg resin composition according to any one of claims 1 to 3 . Further comprising a resin layer laminated on at least one surface of the fiber base layer,
The resin layer is made of the prepreg resin composition according to any one of claims 1 to 3 ,
The prepreg according to claim 4 , wherein the resin layer has a thickness of 1 μm or more and 50 μm or less. The prepreg according to claim 4 or 5 ,
A metal-clad laminate, comprising a metal foil laminated on the prepreg. A printed wiring board comprising the prepreg molded body according to claim 5 and a wiring pattern provided on both surfaces or one side of the molded body. The printed wiring board according to claim 7 ,
A semiconductor device comprising: a semiconductor element mounted on the printed wiring board.