TW201410777A - Resin composition - Google Patents

Abstract

The subject to be addressed by this invention is to provide a resin composition which can provide the reduced dielectric loss tangent for a cured product of the resin composition and which can inhibit resin residues in through holes after the roughening treatment during the drilling process of the cured product. This invention is a specific resin composition containing an epoxy resin, an active ester compound, and resin residue inhibition ingredients.

Description

Resin composition

The present invention relates to a resin composition. More specifically, it relates to a sheet laminate, a multilayer printed circuit board, and a semiconductor device.

In recent years, the miniaturization and high performance of electronic devices have progressed, and multilayer printed circuit boards have been required to be stratified by a build-up layer, and the wiring has been miniaturized and densified. In addition, in order to reduce transmission loss, it is required to introduce Dielectric tangent is a lower insulating material.

Patent Document 1 discloses a composition for sealing epoxy resin containing an epoxy resin, a curing agent, and carbon black, and describes prevention of aggregation of carbon black. However, the concept of resin residue or low dielectric loss tangent is not revealed or implied at all.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-121010

When the insulating layer of the multilayer printed circuit board is subjected to the opening process, resin residue (smear) is generated in the via hole, and the resin residue must be removed by the roughening treatment step. However, according to the findings of the present inventors, when a multilayer printed circuit board is produced by using a resin composition containing a low dielectric loss tangent of an active ester compound, the via hole is roughened even after the opening of the insulating layer. It is found that it is difficult to remove the resin residue in the via hole.

Therefore, the object of the present invention is to provide a resin composition which can achieve a low dielectric loss tangentiality of a cured product of a resin composition, and which can inhibit the resin residue in the via hole after the roughening process is performed. Things.

In order to solve the above problems, the present inventors have found a specific resin composition containing an epoxy resin, an active ester compound, and a resin residue suppressing component, and have completed the present invention.

In other words, the present invention includes the following contents.

[1] A resin composition comprising (A) an epoxy resin, (B) an active ester compound, and (C) a resin residue inhibiting component, wherein the resin composition has a nonvolatile content of 100% by mass. In the case of (C), the resin residue inhibiting component is 0.001 to 10% by mass.

[2] The resin composition according to the above [1], wherein the resin composition When the nonvolatile content is 100% by mass, the content of the (B) active ester compound is from 1 to 30% by mass.

[3] The resin composition according to the above [1] or [2], wherein the (C) resin residue inhibiting component is an organic resin residue inhibiting component.

[4] The resin composition according to the above [3], wherein the organic resin residue inhibiting component is one or more selected from the group consisting of a pigment, a dye, a rubber particle, an antioxidant, and an infrared ray absorbing agent.

[5] The resin composition according to [3] above, wherein the organic resin residue inhibiting component is a pigment and/or rubber particles.

[6] The resin composition according to [3] above, wherein the organic resin residue inhibiting component is a pigment.

[7] The resin composition according to the above [3], wherein the organic resin residue inhibiting component is one or more selected from the group consisting of a blue pigment, a yellow pigment, a red pigment, and a green pigment.

[8] The resin composition according to [3] above, wherein the organic resin residue inhibiting component is a mixed pigment obtained by mixing a blue pigment, a yellow pigment, and a red pigment.

[9] The resin composition according to any one of the above [1] to [8], which further comprises (D) an inorganic filler.

[10] The resin composition according to [9] above, wherein (D) the inorganic filler has an average particle diameter of 0.01 to 5 μm.

[11] The resin composition according to the above [9] or [10], wherein the content of the inorganic filler in the (D) inorganic filler is 40 to 85% by mass in the case where the nonvolatile content in the resin composition is 100% by mass.

[12] The resin composition according to any one of [9] to [11] wherein the inorganic filler has a carbon amount per unit weight of 0.02 to 3%.

[13] The resin composition according to any one of [1] to [12] wherein the resin composition is cured to form an insulating layer, and the surface of the insulating layer is roughened after the surface of the insulating layer is roughened. Root Mean Square has a thickness Rq of 500 nm or less, and the peeling strength of the conductor layer plated on the surface of the insulating layer and the insulating layer is 0.3 kgf/cm or more, and the dielectric loss tangent of the cured product of the resin composition It is 0.05 or less.

[14] The resin composition according to any one of [1] to [13], which is a resin composition for an insulating layer of a multilayer printed wiring board.

[15] A sheet-like laminate comprising the resin composition according to any one of [1] to [14] above.

[16] A multilayer printed circuit board which is characterized in that the insulating layer is formed by a cured product of the resin composition according to any one of the above [1] to [14].

[17] A semiconductor device characterized by using the multilayer printed circuit board of the above [16].

[18] A method of manufacturing a multilayer printed wiring board, characterized in that a sheet-like laminate material according to the above [15] is laminated on a circuit substrate, and the resin composition is thermally hardened to form an insulating layer, which is formed on the circuit substrate. The upper insulating layer is formed by opening a hole on the support body to form a via hole.

By containing epoxy resin, active ester compound and resin residue The specific resin composition of the slag suppressing component can provide a low dielectric loss tangent to the cured product of the resin composition, and can inhibit the resin in the via hole after the roughening process is performed. A resin composition of the residue.

[Formation of the Invention]

The present invention is a resin composition containing (A) an epoxy resin, (B) an active ester compound, and (C) a resin residue inhibiting component, characterized in that when the nonvolatile content of the resin composition is 100% by mass, (C) The resin residue inhibiting component is 0.001 to 10% by mass.

<(A) Epoxy Resin>

The epoxy resin (A) used in the present invention is not particularly limited, and is preferably an epoxy resin containing two or more epoxy groups in one molecule. Specifically, there are, for example, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AF type epoxy resin, a novolac type epoxy resin, a third butyl-neighbor Hydroquinone type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthyl ether type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type Epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, containing snail Spiro ring epoxy resin, cyclohexane dimethanol type epoxy resin, trimethylol type epoxy resin, halogenated epoxy resin, and the like. These may be used alone or in combination of two or more.

Among these, from the viewpoint of improving heat resistance, improving insulation reliability, and improving adhesion to a metal foil, a bisphenol A type epoxy resin, a naphthol type epoxy resin, a naphthalene type epoxy resin, and a combination are preferable. A benzene type epoxy resin, a naphthyl ether type epoxy resin, a glycidyl ester type epoxy resin, a fluorene type epoxy resin, and an epoxy resin having a butadiene structure. Specifically, for example, there are bisphenol A type epoxy resin ("Epikote 828EL" and "YL980" manufactured by Mitsubishi Chemical Corporation), and bisphenol F type epoxy resin ("jER806H" manufactured by Mitsubishi Chemical Corporation). "YL983U"), naphthalene type difunctional epoxy resin ("HP4032", "HP4032D", "HP4032SS", "EXA4032SS" manufactured by DIC), and naphthalene type tetrafunctional epoxy resin (DIC) "HP4700", "HP4710"), naphthol epoxy resin ("ESN-475V" manufactured by Tohto Kasei Co., Ltd.), epoxy resin with butadiene structure (PB manufactured by Daicel Chemical Industry Co., Ltd.) -3600"), "XX4000", "YX4000H", "YX4000HK" manufactured by Mitsubishi Chemical Corporation ("NC3000H", "NC3000L", "NC3100") manufactured by Nippon Kayaku Co., Ltd. "YL6121", 蒽-type epoxy resin ("YX8800" manufactured by Mitsubishi Chemical Corporation), and naphthyl ether epoxy resin (EXA-7310" and "EXA-7311" manufactured by DIC Corporation "EXA-7311L", "EXA7311-G3"), glycidyl ester epoxy resin ("EX711", "EX721" manufactured by Nagasechemtex Co., Ltd., "R540" by printec )Wait.

Where liquid epoxy resin is used together with solid epoxy resin More preferably, it contains one or more epoxy groups in one molecule, and is a liquid aromatic epoxy resin (hereinafter also referred to as "liquid epoxy resin") at a temperature of 20 ° C and one molecule. An aromatic epoxy resin (hereinafter referred to as "solid epoxy resin") having three or more epoxy groups and being solid at a temperature of 20 ° C. Further, the aromatic epoxy resin referred to in the present invention means an epoxy resin having an aromatic ring structure in its molecule. When the epoxy resin is used in combination with a liquid epoxy resin or a solid epoxy resin, when the resin composition is used in the form of a film, it has moderate flexibility, or the cured product of the resin composition has a moderate breaking strength. The blending ratio (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1:0.1 to 1:4, more preferably in the range of 1:0.1 to 1:2, and more preferably The range is from 1:0.3 to 1:1.8, and more preferably from 1:0.6 to 1:1.5.

In the resin composition of the present invention, when the non-volatile content in the resin composition is 100% by mass, the content of the epoxy resin is from the viewpoint of improving the mechanical strength or the insulating reliability of the cured product of the resin composition. It is preferably from 3 to 40% by mass, more preferably from 5 to 35% by mass, still more preferably from 10 to 30% by mass.

<(B) Active ester compound>

In the (B) active ester compound of the present invention, a compound having one or more active ester groups in one molecule can reduce the dielectric loss tangent of the resin composition and can reduce the root mean square roughness Rq. (B) The active ester compound can be reacted with an epoxy resin or the like, and a compound having two or more active ester groups in one molecule is preferred. In general, it is preferred to use phenolic esters, thiophenols. (Thiophenol) a compound having two or more ester groups having high reactivity in one molecule such as an ester of an N-hydroxylamine ester or a heterocyclic hydroxy compound.

From the viewpoint of improving heat resistance, an active ester compound obtained by subjecting a carboxylic acid compound and/or a thiocarboxylic acid compound to a condensation reaction with a hydroxy compound and/or a thiol compound is more preferable. Further, it is more preferably an active ester compound obtained by reacting a carboxylic acid compound with one or more selected from the group consisting of a phenol compound, a naphthol compound, and a thiol compound. Further, it is more preferably an aromatic compound having two or more active ester groups in one molecule obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group. In addition, an aromatic compound obtained by reacting a carboxylic acid compound having at least two or more carboxyl groups in one molecule with an aromatic compound having a phenolic hydroxyl group is preferable, and two of the aromatic compounds have one molecule. The above active ester group aromatic compound. Further, it may be linear or branched. In addition, when a carboxylic acid compound having at least two or more carboxyl groups in one molecule is a compound containing an aliphatic chain, compatibility with a resin composition can be improved, and in the case of a compound having an aromatic ring, heat resistance can be improved.

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. Among them, from the viewpoint of heat resistance, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferable, and isophthalic acid and terephthalic acid are more preferable. Specific examples of the thiocarboxylic acid include thioacetic acid, thiobenzoic acid, and the like.

a phenol compound or a naphthol compound, specifically, for example, a pair Hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol , m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, Dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene diol, phenolic, and the like. From the viewpoint of improving heat resistance and improving solubility, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, and phthalic acid are preferred. Phenol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, Tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene diol, phenolic aldehyde, more preferably catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene diphenol, phenolic, More preferably 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, bicyclo Pentadiene diphenol, phenolic, and more preferably 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene diphenol, phenolic, particularly preferred 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene diphenol, particularly preferably dicyclopentadiene diphenol. Specific examples of the thiol compound include benzenedithiol, triazinedithiol and the like. The active ester compound may be used alone or in combination of two or more.

An active ester compound containing a dicyclopentadiene diphenol structure, more specifically. For example, there is a compound of the following formula (1).

(wherein R represents a phenyl group or a naphthyl group, k represents 0 or 1, and the average number of n-type repeating units is 0.05 to 2.5).

From the viewpoint of lowering the dielectric loss tangent and improving the heat resistance, R is preferably a naphthyl group, k is preferably 0, and n is preferably 0.25 to 1.5.

(B) The active ester compound may be an active ester compound disclosed in JP-A-2004-277460, or a commercially available active ester compound. The commercially available active ester compound is specifically preferably an active ester-based hardener containing a dicyclopentadiene diphenol structure, an active ester-based hardener containing a naphthalene structure, and an active ester containing a phenolic acetal-based compound. It is a hardener and an active ester-based hardener containing a phenolic benzamidine compound, and more preferably an active ester-based curing agent containing a naphthalene structure or an active ester-based curing agent containing a dicyclopentadiene diphenol structure. An active ester-based curing agent containing a dicyclopentadiene diphenol structure, for example, EXB 9451, EXB 9460, EXB 9460S, HPC-8000-65T (manufactured by DIC, an active ester-based hardener containing a naphthalene structure, for example EXB9416-70BK (made by DIC), an active ester-based hardener containing phenolic acetamidine, for example, DC808 (manufactured by Mitsubishi Chemical Corporation), an active ester-based hardener containing phenaldehyde-based benzamidine. For example, there are YLH1026 (manufactured by Mitsubishi Chemical Corporation).

(B) the content of the active ester compound to improve heat resistance and When the non-volatile content in the resin composition is 100% by mass, the content of the non-volatile component in the resin composition is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less. In addition, when the nonvolatile content in the resin composition is 100% by mass, it is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more.

Further, when the number of epoxy groups of the epoxy resin (A) is 1, the number of reactive groups of the (B) active ester compound is preferably from 0.2 to 2, more preferably from 0.3 to 1.5, from the viewpoint of improving the mechanical properties of the resin composition. More preferably, it is 0.4~1. Here, the "epoxy group number of epoxy resin" means the value of the solid content of each epoxy resin present in the resin composition divided by the epoxy equivalent value, and the total value of all the epoxy resins. Further, the "reactive group" means a functional group reactive with an epoxy group, and the "reactive group number of the active ester compound" means the mass of the solid portion of the active ester compound present in the resin composition divided by the equivalent of the reactive group equivalent. The total value of all.

<(C) Resin residue inhibiting component>

The resin residue suppressing component used in the present invention can suppress the component of the resin residue of the via hole after the hole-forming process of the cured resin composition and the roughening treatment. Here, the resin residue suppression means either reducing the amount of resin residue generated during the drilling process and more easily removing the resin residue during the roughening treatment. The resin residue suppressing component is, for example, an organic resin residue inhibiting component or an inorganic resin residue suppressing component, and is preferably an organic resin residue suppressing component from the viewpoint of improving the insulating reliability. Specifically, organic The resin residue-preventing component is, for example, a pigment, a dye, a rubber particle, an antioxidant, an infrared ray absorbing agent, or the like, and the inorganic resin residue-suppressing component is, for example, a metal compound powder or a metal powder. (C) The resin residue-inhibiting component is preferably one or more selected from the group consisting of a pigment, a dye, a rubber particle, an antioxidant, and an infrared ray absorbing agent. Among these, from the viewpoint of excellent resin residue suppression performance and excellent peel strength, it is more preferably a pigment and/or rubber particles, and more preferably a pigment. These may be used alone or in combination of two or more.

Examples of the pigment include a blue pigment, a yellow pigment, a red pigment, a black pigment, a green pigment, and the like. The blue pigment is, for example, a pigment such as phthalocyanine, anthraquinone or dioxazine. Examples of the yellow pigment include pigments such as monoazo type, disazo (DISAZO) type, condensed azo type, benzimidazolone type, isoindolinone type, and anthraquinone type. Examples of the red pigment include a monoazo system, a disazo system, an azo lake (AZO LAKE) system, a benzimidazolone system, an anthraquinone system, a diketopyrrolopyrrole system, a condensed azo system, and an anthracene. A pigment such as a lanthanide or a quinacridone. Examples of the black pigment include carbon black, graphite, and the like. The green pigment is, for example, a pigment such as phthalocyanine. One type of the pigment may be used alone or two or more types may be used in combination, and one or more selected from the group consisting of a blue pigment, a yellow pigment, a red pigment, a black pigment, and a green pigment may be appropriately blended. In view of the fact that the insulating reliability can be further improved, it is preferred to use one or more selected from the group consisting of a blue pigment, a yellow pigment, a red pigment, and a green pigment, and more preferably a mixed blue pigment, a yellow pigment, and a red color. A mixed pigment made from pigments. Modulation of mixed blue pigments, yellow pigments and When the mixed pigment of the red pigment is used, the laser during the opening processing can be effectively absorbed, and the mass ratio of the blue pigment, the yellow pigment and the red pigment is preferably 2 to 6 from the viewpoint of suppressing the occurrence of the resin residue. : 5~9:6~10, more preferably 3~5:6~8:7~9.

Examples of the dye include azo (monoazo, disazo, etc.) dyes, azo-methine dyes, anthraquinone dyes, quinoline dyes, ketimine dyes, fluorone dyes, nitro dyes, Xanthene dye, anthraquinone dye, quinone yellow dye, aminoketone dye, methine dye, anthraquinone dye, coumarin dye, perinone dye, triphenyl dye, triallyl methane dye , phthalocyanine dye, indophenol dye, triazine dye, or a mixture thereof.

The rubber particles are, for example, core-shell type rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, acrylic rubber particles, and the like. The core-shell type rubber particles are rubber particles having a core layer and a shell layer, for example, the shell layer of the outer layer is composed of a glassy polymer, the core layer of the inner layer is a two-layer structure composed of a rubbery polymer, or a shell of the outer layer. The layer is composed of a glassy polymer, the intermediate layer is composed of a rubbery polymer, and the core layer is a three-layer structure composed of a glassy polymer.

The antioxidant is, for example, a hindered phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, or the like. Commercially available products are, for example, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] ("IAGANOX 1010" manufactured by CIBA JAPAN Co., Ltd.), 2,2-sulfur Di-dimethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] ("IRGANOX 1035" by CIBA JAPAN), 1,3,5 -three [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-1,3,5-triazine-2,4,6(1H,3H,5H) - Triketone ("ILGANOX 3114" manufactured by CIBA JAPAN Co., Ltd.).

Examples of the infrared ray absorbing agent include a phthalocyanine compound, a ruthenium compound, and a nickel complex. Commercially available products include, for example, IR-14 (manufactured by Nippon Shokubai Co., Ltd.), TX-HA-1 (manufactured by Nippon Shokubai Co., Ltd.), and the like.

Examples of the metal compound powder include titanium oxides such as titanium oxide, magnesium oxides such as magnesium oxide, iron oxides such as iron oxide, nickel oxides such as nickel oxide, zinc oxides such as manganese dioxide and zinc oxide, and the like. Cobalt oxide such as cerium oxide, aluminum oxide, rare earth oxide or cobalt oxide, tin oxide such as tin oxide, tungsten oxide such as tungsten oxide, tantalum carbide, tungsten carbide, boron nitride, tantalum nitride, nitrogen Titanium, aluminum nitride, barium sulfate, rare earth acid sulfide, or a mixture of such powders, and the like.

The metal powder is, for example, silver, aluminum, lanthanum, cobalt, copper, iron, magnesium, manganese, molybdenum, nickel, palladium, iridium, ruthenium, tin, titanium, vanadium, tungsten, zinc, or a powder of such alloys or mixtures thereof. .

(C) The content of the resin residue-inhibiting component is preferably 10% by mass or less, more preferably 5% by mass or less, more preferably 5% by mass or less, based on 100% by mass of the nonvolatile component in the resin composition, from the viewpoint of preventing deterioration of the cured material property. It is preferably 4% by mass or less, more preferably 3% by mass or less, and particularly preferably 2% by mass or less. In addition, it is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and still more preferably 0.02% by mass or more, based on 100% by mass of the nonvolatile component in the resin composition, from the viewpoint of improving the resin residue suppressing energy. More preferably, it is 0.05% by mass or more, and more preferably 0.08% by mass. In particular, it is particularly preferably 0.1% by mass or more.

<(D) Inorganic filler>

The resin composition of the present invention may further contain (D) an inorganic filler in order to lower the linear thermal expansion coefficient and improve the resin residue removal property during the roughening treatment. (D) inorganic fillers such as cerium oxide, aluminum oxide, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, titanium Barium strontium, barium titanate, calcium titanate, magnesium titanate, barium titanate, titanium oxide, barium zirconate, calcium zirconate, and the like. Among them, cerium oxide is preferred. Further, the cerium oxide is preferably amorphous cerium oxide, pulverized cerium oxide, molten cerium oxide, crystalline cerium oxide, synthetic cerium oxide, hollow cerium oxide or the like, and molten cerium oxide is more preferable. Further, the cerium oxide is preferably spherical cerium oxide. These may be used alone or in combination of two or more. Commercially available spherical molten cerium oxide is, for example, "SO-C2" or "SO-C1" manufactured by Admatechs.

(D) The average particle diameter of the inorganic filler is not particularly limited, and from the viewpoint of forming fine wiring on the insulating layer, the upper limit of the average particle diameter of the inorganic filler increases the total surface area of the inorganic filler to suppress opening. The resin residue at the time of processing is preferably 5 μm or less, more preferably 3 μm or less, more preferably 1 μm or less, more preferably 0.7 μm or less, more preferably 0.5 μm or less, and particularly preferably 0.4 μm or less. The following is particularly good for μm. On the other hand, when the epoxy resin composition is used as a varnish, the epoxy resin composition is preferably a thickness of 0.01 μm or more and 0.03 μm or more from the viewpoint of preventing the viscosity of the varnish from increasing and the workability is lowered. For more Preferably, it is more preferably 0.05 μm or more, more preferably 0.07 μm or more, and particularly preferably 0.1 μm or more. The average particle size of the above inorganic filler material can be obtained by laser diffraction according to the Mie scattering theory. Determined by scattering method. Specifically, the particle size distribution of the inorganic filler is determined on a volume basis by a laser diffraction type particle size distribution measuring apparatus, and the median diameter can be measured as an average particle diameter. The measurement sample is preferably one in which the inorganic filler is dispersed in water by ultrasonic waves. For the laser diffraction type particle size distribution measuring apparatus, LA-500, 750, 950, etc., manufactured by Horiba, Ltd., can be used.

(D) The content of the inorganic filler is not particularly limited, and from the viewpoint of preventing the flexibility of the resin composition as a film form, when the nonvolatile content in the resin composition is 100% by mass, it is preferably 85 mass. % or less, more preferably 80% by mass or less, still more preferably 75% by mass or less. Moreover, from the viewpoint of lowering the thermal expansion coefficient of the insulating layer, the total surface area of the inorganic filler is increased, the resin residue at the time of opening processing is suppressed, and the resin residue is easily removed during the roughening treatment, and the nonvolatile content in the resin composition is When it is 100% by mass, it is preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, and still more preferably 70% by mass or more.

(D) The inorganic filler is preferably an amine-based decane-based coupling agent, a urea-based decane-based coupling agent, an epoxy decane-based coupling agent, a mercapto decane-based coupling agent, or decane from the viewpoint of improving moisture resistance and dispersibility. A coupling agent, a vinyl decane coupling agent, a styryl decane coupling agent, an acrylate decane coupling agent, an isocyanate decane coupling agent, a sulfur decane coupling agent, an organic decane compound, a titanate Coupling agent, etc. The surface treatment agent is subjected to surface treatment. Among them, the inorganic filler is surface-treated with an organic decazane compound, and then surface-treated with a decane coupling agent to further improve the moisture resistance or dispersibility of the inorganic filler. These may be used alone or in combination of two or more.

Specifically, for example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-aminopropyldiethoxymethyldecane, N-phenyl-3- Aminopropyltrimethoxydecane, N-methylaminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-amine Amino decane coupling agent such as ethyl ethyl)-3-aminopropyl dimethoxymethyl decane, ureido decane coupling agent such as 3-ureidopropyltriethoxy decane, and 3-shrinkage Glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethoxydiethoxydecane, 3-glycidoxypropyl ( An epoxy decane coupling agent such as dimethoxy)methyl decane, glycidyl butyl trimethoxy decane or 2-(3,4-ethoxycyclohexyl)ethyltrimethoxy decane, 3- A mercapto decane coupling agent such as mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, 3-mercaptopropylmethyldimethoxydecane, 11-decylundecyltrimethoxydecane , methyltrimethoxydecane, octadecyltrimethoxyanthracene a decane coupling agent such as phenyltrimethoxydecane, methacryloxypropyltrimethoxydecane, imidazolium, triazine decane, tert-butyltrimethoxydecane, or vinyl a vinyl decane coupling agent such as trimethoxy decane, vinyl triethoxy decane or vinyl methyl diethoxy decane; or a styryl decane coupling agent such as p-styryl trimethoxy decane; 3-propenyloxypropyltrimethoxy Decane, 3-methacryloxypropyltrimethoxydecane, 3-methylpropenyloxypropyldimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3 - an acrylate decane coupling agent such as methacryloxypropyl diethoxy decane or an isocyanate decane coupling agent such as 3-isocyanate propyl trimethoxy decane or bis(triethoxy decyl propyl propyl) a thiononane coupling agent such as disulfide or bis(triethoxydecylpropyl)tetrasulfide, hexamethyldioxane, 1,3-divinyl-1,1,3,3-tetra Methyldiazepine, hexaphenyldioxane, triazane, cyclotriazane, 2,2,4,4,6,6-hexamethylcyclotriazane, octamethyl Cyclotetradecane, hexabutyldiazepine, hexaoctyldioxane, 1,3-diethyltetramethyldiazepine, 1,3-di-n-octyltetramethyl Dioxane, 1,3-diphenyltetramethyldiazepine, 1,3-dimethyltetraphenyldiazepine, 1,3-diethyltetramethyldiazepine, 1,1,3,3-tetraphenyl-1,3-dimethyldiazepine, 1,3-dipropyltetramethyldiazepine, hexamethylcyclotriazane, dimethyl Aminotrimethylhydrazine An organic sulfonium compound such as azide or tetramethyldiazane, a tetra-n-butyl titanate dimer, a titanium i-propoxy octanediol, or a tetra-n-butyl titanic acid Ester, titanium octanediol, titanium diisopropoxide bis (triethanol valerate), titanium dihydroxydilactic acid, dihydroxy bis(ammonium lactate) titanium, bis(dioctyl pyrophosphate) extended ethyl titanium Acid ester, bis(dioctyl pyrophosphate)oxyacetate titanate, titanium tri-n-butoxy monostearate, tetra-n-butyl titanate, tetrakis(2-ethylhexyl) titanate , tetraisopropylbis(dioctylphosphonate) titanate, tetraoctylbis(di(tridecyl)phosphate) titanate, tetrakis(2,2-diallyloxymethyl- 1-butyl)bis(bis(tridecyl))phosphate titanate, isopropyl trioctylide titanate, isopropyl tricumylphenyl titanate, isopropyl Triisostearyl decyl titanate, isopropyl isostearyl decyl bis decyl decyl titanate, isopropyl dimethyl propylene decyl isostearyl decyl titanate, isopropyl tris(II) Octyl phosphate) titanate, isopropyl tris(dodecyl)benzenesulfonate titanate, isopropyl tris(dioctyl pyrophosphate) titanate, isopropyl tris(N- A titanate coupling agent such as guanidinoethyl.aminoethyl) titanate or the like. Among these, the amino decane-based coupling agent is excellent in moisture resistance, dispersibility, and properties of a cured product. Therefore, the organic decazane compound is preferred because it is excellent in improving the dispersibility of the resin varnish. For the commercial product of the surface treatment agent, "KBM403" (3-glycidoxypropyltrimethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyl) manufactured by Shin-Etsu Chemical Co., Ltd. "Methoxy decane", "KBE903" (3-aminopropyltriethoxy decane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-amino group) manufactured by Shin-Etsu Chemical Co., Ltd. Propyltrimethoxydecane) and the like.

Moreover, the amount of carbon per unit weight of the inorganic filler after the surface treatment by the solvent (for example, methyl ethyl ketone) can be measured as the inorganic filler after the surface treatment with the surface treatment agent. Here, the "amount of carbon per unit weight of the inorganic filler" means that the amount of carbon (g) bonded to the inorganic filler 1g is expressed as a percentage. Specifically, a sufficient amount of MEK was added as a solvent to the inorganic filler which was surface-treated with a surface treatment agent, and ultrasonic cleaning was performed at 25 ° C for 5 minutes. After removing the supernatant and drying the solid component, the amount of carbon per unit weight of the inorganic filler was measured using a carbon analyzer. For the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

The amount of carbon per unit weight of the inorganic filler is increased from The viewpoint of the dispersibility of the inorganic filler or the root mean square roughness after the roughening treatment of the cured product is preferably 0.02% or more, more preferably 0.05% or more, still more preferably 0.1% or more. Further, from the viewpoint of preventing the melt viscosity of the resin varnish or the melt viscosity of the film form, it is preferably 3% or less, more preferably 2% or less, still more preferably 1% or less.

<(E) hardening accelerator>

The resin composition of the present invention may further contain (E) a curing accelerator in order to adjust the curing time, the curing temperature, and the like. (E) The curing accelerator is not particularly limited, and examples thereof include an imidazole-based hardening accelerator, an amine-based curing accelerator, an organic phosphine (PHOSPHINE) compound, and an organic phosphonium salt compound. These may be used alone or in combination of two or more.

The imidazole-based hardening accelerator is, for example, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2 - dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl- 2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1- Cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidin trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4 -diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl- (1')]-Ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s- Triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole three Polycyanate adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrole [ Imidazole compound of 1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, etc., and imidazole An adduct of a compound and an epoxy resin. These may be used alone or in combination of two or more.

The amine-based hardening accelerator may, for example, be a trialkylamine such as triethylamine or tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6 or -gin (dimethyl group). An amine compound such as aminomethyl)phenol or 1,8-diazabicyclo(5,4,0)-undecene (hereinafter abbreviated as DBU). These may be used alone or in combination of two or more.

Examples of the organic phosphine compound and the organic phosphonium salt compound include TPP, TPP-K, TPP-S, TPTP-S, TBP-DA, TPP-SCN, and TPTP-SCN (Beixing Chemical Industry Co., Ltd.). These may be used alone or in combination of two or more.

(E) The content of the hardening accelerator is preferably from 0.01 to 3% by mass, more preferably from 0.01 to 3% by mass, based on 100% by mass of the nonvolatile matter in the resin composition, from the viewpoint of storage stability of the resin varnish or efficiency of curing. 0.1 to 2% by mass.

<(F) Thermoplastic Resin>

The resin composition of the present invention further contains (F) a thermoplastic resin, and the viscosity of the resin varnish obtained from the resin composition can be adjusted to an appropriate range, whereby the flexibility of the cured product can be improved. The thermoplastic resin is not particularly limited, and examples thereof include a phenoxy resin, a polyacetonitrile acetal resin, and a polyfluorene resin. An amine resin, a polyamidoximine resin, a polyamide resin, a polyether oxime resin, a polyfluorene resin, a polybutadiene resin, an ABS resin, or the like. Among them, from the viewpoint of improving the flexibility of the cured product and contributing to the adhesion, the phenoxy resin and the polyethylene acetal resin are more preferable, and the phenoxy resin is more preferable. These may be used alone or in combination of two or more. The thermoplastic resin preferably has a glass transition temperature of 80 ° C or higher.

The weight average molecular weight of the thermoplastic resin is preferably in the range of 5,000 to 800,000, more preferably in the range of 10,000 to 200,000, still more preferably in the range of 15,000 to 150,000, and more preferably in the range of 20,000 to 100,000. When it is in this range, the film forming ability or the effect of improving the mechanical strength can be sufficiently exhibited, and the compatibility with the epoxy resin can be improved. The weight average molecular weight of the present invention is measured by a gel permeation chromatography (GPC) method (in terms of polystyrene). The weight average molecular weight measured by the GPC method, specifically, the LC-9A/RID-6A manufactured by Shimadzu Corporation, and the Shodex K-800P/K-804L manufactured by Showa Denko Co., Ltd. /K-804L, the mobile phase was measured at a column temperature of 40 ° C using chloroform or the like, and the weight average molecular weight was calculated using a calibration curve of standard polystyrene.

The phenoxy resin has, for example, a bisphenol A skeleton selected from the group consisting of a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a phenolic skeleton, a biphenyl skeleton, an anthracene skeleton, a dicyclopentadiene skeleton, and norbornene. One or more skeletons of a skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The phenoxy resin may be used in combination of two or more kinds. The terminal of the phenoxy resin may be any one of a phenolic hydroxyl group, an epoxy group and the like. Commercial products such as Mitsubishi Chemical Co., Ltd. 1256, 4250 (Phenoxy resin containing a bisphenol A skeleton), YX8100 (a phenoxy resin containing a bisphenol S skeleton) manufactured by Mitsubishi Chemical Corporation, and YX6954 (a benzene containing a bisphenol acetophenone skeleton) manufactured by Mitsubishi Chemical Corporation Oxygen resin). Commercially available products include FX280, FX293 manufactured by Nippon Steel Chemical Co., Ltd., YL7553, YL6954, YL6794, YL7213, YL7290, and YL7482 manufactured by Mitsubishi Chemical Corporation.

Specific examples of the polyethyl fluorene acetal resin include, for example, an electrochemical industry, a butadiene 4000-2, a 5000-A, a 6000-C, a 6000-EP, and a Sekisui Chemical Industry Co., Ltd. Lec BH series, BX series, KS series, BL series, BM series, etc. Specific examples of the polyimide resin include, for example, RIKACOAT SN20 and RIKACOAT PN20 manufactured by Nippon Chemical and Chemical Co., Ltd. Further, a linear polyimine obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid dianhydride (described in JP-A-2006-37083) contains polyfluorene A modified polyimine such as a polyimine of the oxyalkylene skeleton (described in JP-A-2002-12667, JP-A-2000-319386, etc.). Specific examples of the polyamidoximine resin include, for example, polyamine amidoxime "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. In addition, modified polyamidoquinone imines such as polyacrylamide skeletons "KS9100" and "KS9300" which are made of a polysiloxane chain made by Hitachi Chemical Co., Ltd. Specific examples of the polyether oxime resin include polyether oxime "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like. Specific examples of the polyanthracene resin, for example, polypethane manufactured by Solven Advanced Polymers "P1700", "P3500", etc.

The content of the thermoplastic resin is not particularly limited, and is preferably from 0.5 to 30% by mass based on 100% by mass of the nonvolatile content in the resin composition from the viewpoint of the adjustment of the melt viscosity of the sheet-like laminate or the adjustment of the viscosity of the resin varnish. %, more preferably 1 to 20% by mass.

<(G) hardener>

The resin composition of the present invention may further contain (G) a hardener. Thereby, the insulation reliability, peeling strength, and mechanical properties of the cured product of the resin composition can be improved. (G) The curing agent is not particularly limited, and examples thereof include a phenol-based curing agent, a cyanate-based curing agent, a benzoxazine-based curing agent, and an acid anhydride-based curing agent. These may be used alone or in combination of two or more. Among them, a phenol-based curing agent and a cyanate-based curing agent are preferred from the viewpoint of improving resin residue removal property and improving dielectric properties.

The phenolic curing agent is not particularly limited, and examples thereof include a phenol resin, a phenol resin containing a triazine skeleton, a naphthol phenol resin, a naphthol aralkyl resin, a naphthol resin containing a triazine skeleton, and a biphenyl aralkyl type. Phenolic resin, etc. Examples of the biphenyl aralkyl type phenol resin include "MEH-7700", "MEH-7810", "MEH-7851" (made by Megumi Kasei Co., Ltd.), NHN", "CBN", and "GPH" (Japanese). "Nanopharmaceutical"), naphthol aralkyl type resins such as "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN375", "SN395" (Dongdu Huacheng (Stock), phenolic resin, for example, "TD2090" (made by DIC), containing a triazine skeleton Examples of the phenol resin include "LA3018", "LA7052", "LA7054", and "LA1356" (made by DIC). The phenolic curing agent may be used alone or in combination of two or more.

The cyanate-based curing agent is not particularly limited, and examples thereof include a phenolic type (phenol type phenol type, alkyl phenol type, etc.) cyanate type curing agent, a dicyclopentadiene type cyanate type curing agent, and a bisphenol type. A cyanate-based curing agent (such as a bisphenol A type, a bisphenol F type, or a bisphenol S type), and a part of the triazine-based prepolymer. The weight average molecular weight of the cyanate-based curing agent is not particularly limited, and is preferably 500 to 4,500, more preferably 600 to 3,000. Specific examples of the cyanate-based curing agent include bisphenol A dicyanate and polyphenol cyanate (oligo(3-methylene-1,5-phenylene), 4,4' -methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2- Bis(4-cyanate) phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1, 3-bis(4-cyanate phenyl-1-(methylethylidene))benzene, bis(4-cyanate phenyl) sulfide, bis(4-cyanate phenyl) ether, etc. a polyfunctional cyanate resin derived from a bifunctional cyanate resin, a phenolic aldehyde, a cresol novolak, a phenol resin having a dicyclopentadiene structure, or the like, and a part of the cyanate resin pre-polymerized by triazine These may be used alone or in combination of two or more. Commercially available cyanate resins include, for example, Phenol Novolac type polyfunctional cyanate resin (manufactured by Lonza Japan Co., Ltd., PT30, cyanic acid). Ester equivalent 124), part or all of bisphenol A dicyanate is triazineated to form a terpolymer prepolymer (manufactured by Lonza Japan Co., Ltd., BA230, cyanate equivalent 232), containing two Cyclopentane A cyanate resin of a diene structure (manufactured by Lonza Japan Co., Ltd., DT-4000, DT-7000) or the like.

The benzoxazine-based curing agent is not particularly limited, and specific examples thereof include F-a, P-d (manufactured by Shikoku Chemical Co., Ltd.), and HFB2006M (manufactured by Showa Polymer Co., Ltd.).

The content of the (G) curing agent in the resin composition is not particularly limited, and from the viewpoint of preventing the cured product of the resin composition from becoming brittle, it is preferably 0.5 to 10% by mass based on 100% by mass of the nonvolatile component in the resin composition. %, more preferably 1 to 6 mass%.

<Other ingredients>

The resin composition of the present invention may be blended with, for example, a maleimide compound, a diene propylene quinone imine (NADIIMIDE) compound, a vinyl benzyl resin, or ethylene, as long as it does not inhibit the effects of the present invention. An organic filler such as a thermosetting component such as a benzyl ether resin, a tantalum powder, a tolerant powder or a fluorine powder, an adhesion promoter such as Orben or Benton, a polyfluorene-based, a fluorine-based or a polymer-based antifoaming agent; A tackifier such as a flattening agent, an imidazole-based compound, a thiazole-based compound, a triazole-based or a decane-based coupling agent, a phosphorus-based compound, and a flame retardant such as a metal hydroxide.

The resin composition of the present invention is suitably mixed with the above components, and if necessary, by a mixing means such as a three-roller, a ball mill, a bead mill, a sand mill, or a stirring means such as a super mixer or a planetary mixer. Mix or mix to make a resin varnish. The cured product of the resin composition of the present invention can achieve low dielectric loss tangential, and can inhibit the hardened material from being opened Resin residue in the via hole after hole processing and roughening treatment.

The dielectric loss tangent of the cured product of the resin composition of the present invention can be measured by the method described in <Measurement of dielectric loss tangent> to be described later. Specifically, it can be measured by a cavity resonator perturbation method at a frequency of 5.8 GHz and a measurement temperature of 23 °C. From the viewpoint of preventing high frequency heat generation, signal delay, and signal noise reduction, the dielectric loss tangent is preferably 0.05 or less, more preferably 0.04 or less, still more preferably 0.03 or less, and still more preferably 0.02 or less. It is 0.01 or less. Further, the lower limit of the dielectric loss tangent is not particularly limited, but is preferably 0.001 or more.

The root mean square roughness Rq of the cured product of the resin composition of the present invention can be measured by the measurement method described in <Measurement of the root mean square roughness (Rq) described later. The surface of the insulating layer after the roughening treatment is preferably fine concavo-convex from the viewpoint of reducing the loss of the electric signal. The compactness of the unevenness of the surface of the insulating layer is exhibited, for example, the root mean square roughness Rq. By this index, not only the average value of the unevenness of the surface of the insulating layer but also the surface of the insulating layer became a close uneven shape. Specifically, the resin composition is cured to form an insulating layer, and the root mean square roughness Rq of the surface of the insulating layer after the roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, and further preferably It is 300 nm or less, more preferably 200 nm or less, and particularly preferably 100 nm or less. Further, the lower limit value is preferably 5 nm or more, more preferably 10 nm or more, and still more preferably 20 nm or more from the viewpoint of obtaining good adhesion to the plated conductor layer.

The peeling strength of the cured product of the resin composition of the present invention can be determined by the measurement of the peeling strength (peeling strength) of the plated conductor layer described later. The measurement method described is measured. Specifically, the resin composition is cured to form an insulating layer, and the peeling strength of the conductor layer obtained by plating and the insulating layer on the surface of the insulating layer after the roughening treatment is preferably 0.3 kgf/cm or more. It is 0.5 kgf/cm or more, and more preferably 0.6 kgf/cm or more. Further, the upper limit is not particularly limited, and is generally 1.2 kgf/cm or less.

The use of the resin composition of the present invention is not particularly limited. For example, it can be used for a sheet-like laminate such as a film or a prepreg, a circuit board (for laminate use, multilayer printed circuit board use, etc.), and a solder resist. The bottom underfill, the wafer bonding material, the semiconductor sealing material, the buried resin, the component embedding resin, and the like require a wide range of uses of the resin composition. Among them, the resin composition of the present invention can suppress the resin residue in the via hole after the roughening process and the roughening treatment, thereby improving the plating adhesion force in the via hole and preventing the occurrence of voids in the via hole. The communication between the insulating layers of the multi-layer printed circuit board formed in multiple stages can be ensured. In other words, when the multilayer printed wiring board is manufactured, it can be suitably used as a resin composition for forming an insulating layer (a resin composition for an insulating layer of a multilayer printed wiring board), and can be more suitably used as a resin for forming a conductor layer by plating. The composition (a resin composition for an insulating layer of a multilayer printed wiring board for forming a conductor layer by plating) is used. The resin composition of the present invention can be applied to a circuit board to form an insulating layer in a varnish state. However, it is generally industrially used in the form of a sheet-like laminate which is followed by a film or a prepreg. The softening point of the resin composition is preferably from 40 to 150 ° C from the viewpoint of the lamination property of the sheet-like laminate.

<Sheet laminate] (following the film)

In the embodiment, the sheet-like laminate of the present invention is a film. The adhesive film is formed on the support to form a resin composition layer. The adhesive film can be prepared by a method known to those skilled in the art, for example, by dissolving a resin composition in an organic solvent to prepare a resin varnish which is applied to a support, heated, or blown using a die coater or the like. The organic solvent is dried by hot air or the like to form a resin composition layer.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, and the like. Carbamates such as acetates, cellosolves, butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methyl A guanamine-based solvent such as pyrrolidone or the like. The organic solvent may be used in combination of two or more kinds.

The drying conditions are not particularly limited, and the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less, and dried. The amount of the organic solvent in the varnish varies depending on the boiling point of the organic solvent. For example, a varnish containing 30 to 60% by mass of an organic solvent is dried at 50 to 150 ° C for about 3 to 10 minutes to form a resin composition layer.

Next, the thickness of the resin composition layer formed in the film is preferably equal to or greater than the thickness of the conductor layer. The thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, and therefore the resin composition layer preferably has a thickness of 10 to 100 μm. From the viewpoint of film formation, it is more preferably 15 to 80 μm.

The support body is, for example, polyethylene, polypropylene, polyvinyl chloride, or the like. A film of a polyolefin, a film of a polyester such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") or polyethylene naphthalate, a polycarbonate film, or a polyimide film. Plastic film. A release paper, a metal foil such as a copper foil or an aluminum foil, or the like can also be used. Among them, from the viewpoint of general availability, a plastic film is preferred, and a polyethylene terephthalate film is more preferred. The support and the protective film described later may be subjected to surface treatment such as electron impact (mad) treatment or corona treatment. Further, a release agent such as a polyoxymethylene resin release agent, an alkyd resin release agent, or a fluororesin release agent may be applied to the release treatment.

The thickness of the support is not particularly limited, and when the hole is processed by the support, even if the energy of the laser irradiation is large, the resin residue is less likely to remain, and the occurrence of resin residue can be suppressed, and preferably 10 μm or more. More preferably, it is 20 μm or more, and more preferably 30 μm or more. Moreover, from the viewpoint of improving the cost performance or opening the hole from the support, the hole can be effectively opened, preferably 150 μm or less, more preferably 100 μm or less, still more preferably 50 μm or less.

The protective film according to the support may be laminated on the opposite side of the surface of the resin composition layer which is adhered to the support. At this time, the film then includes a support, a resin composition layer formed on the support, and a protective film formed on the resin composition layer. The thickness of the protective film is not particularly limited and is, for example, 1 to 40 μm. By laminating the protective film, it is possible to prevent dust or the like from adhering to the surface of the resin composition layer or causing scratches. The film can then be wound into a roll for storage.

(prepreg)

In the embodiment, the sheet-like laminate of the present invention is a prepreg. The prepreg can be produced by impregnating the resin composition of the present invention into a sheet-like reinforcing substrate by a hot melt method or a solvent method, and heating to cause semi-hardening. In other words, a prepreg in which the resin composition of the present invention is impregnated into a sheet-like reinforcing substrate can be formed. As the sheet-like reinforcing substrate, for example, a glass cloth or an aromatic polyamide fiber can be used, and it is often used as a fiber for a prepreg. Further, it is preferred that a prepreg is formed on the support.

The hot melt method does not require the resin composition to be dissolved in the organic solvent, but is applied to the support and then laminated to the sheet-like reinforcing substrate, or directly applied to the sheet-like reinforcing material by a die coater. A method of manufacturing a prepreg, such as a substrate. Further, the solvent method is a method in which a resin varnish is prepared by dissolving a resin in an organic solvent, immersing the flaky reinforcing substrate in the varnish, impregnating the flaky reinforcing substrate with a resin varnish, and drying the resin in the same manner as the adhesive film. Further, a continuous film can be produced by continuous thermal lamination on both sides of the sheet-like reinforcing substrate under heating and pressurization conditions. A support or a protective film or the like can also be used similarly to the adhesive film.

<Multilayer printed circuit board using sheet laminates>

Next, a method of manufacturing a multilayer printed wiring board using the sheet-like laminate produced as described above will be described.

First, a sheet laminate is laminated on one or both sides of a circuit board using a vacuum laminator. The substrate for the circuit board includes, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, BT resin substrate, thermosetting polyphenylene ether substrate, and the like. The circuit board refers to a conductor layer (circuit) in which a pattern is processed on one or both sides of the substrate. Further, in the multilayer printed wiring board in which the conductor layer and the insulating layer are laminated to each other, one or both of the outermost layers of the multilayer printed circuit board are formed into a patterned conductor layer (circuit), and are also included in In the circuit substrate here. Further, the surface of the conductor layer may be subjected to a roughening treatment in advance by a blackening treatment, copper etching or the like.

When the sheet-like laminate has a protective film, the sheet-like laminate and the circuit board can be preheated if necessary, and the sheet-like laminate can be laminated on the circuit board while being pressurized and heated. In a preferred embodiment, the sheet-like laminate of the present invention is laminated to a circuit substrate by vacuum lamination under reduced pressure. The conditions for lamination are not particularly limited. For example, the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C, and the pressing pressure (laminating pressure) is preferably 1 to 11 kgf/cm ² (9.8 × 10 ^{4 ).} ~107.9 × 10 ⁴ N/m ² ), the pressure-bonding time (lamination time) is preferably from 5 to 180 seconds, and lamination is preferably carried out under reduced pressure of air pressure of 20 mmHg (26.7 hPa) or less. Further, the lamination method may be a batch type or a continuous type using a roll. Vacuum lamination can be carried out using a commercially available vacuum laminator. Commercially available vacuum laminating machines include a vacuum laminating machine manufactured by Nichigo-morton Co., Ltd., a vacuum press laminator manufactured by Nihon Seiki Co., Ltd., a roll drying applicator manufactured by Hitachi Industries, and Hitachi AIC (stock) vacuum laminator and the like.

After laminating the sheet-like laminate material on the circuit board, it was cooled to near room temperature, and when the support was peeled off, the resin composition was thermally cured to form an insulating layer. Thereby, an insulating layer can be formed on the circuit substrate. Thermal hardening The conditions may be appropriately selected in accordance with the type and content of the resin component in the resin composition, preferably from 150 ° C to 220 ° C, from 20 to 180 minutes, more preferably from 160 ° C to 210 ° C, and 30 °. Choose from a range of 120 minutes. After the formation of the insulating layer, the support is not peeled off before the curing, and may be peeled off at this time if necessary.

Further, the sheet-like laminate was laminated on one side or both sides of the circuit board using a vacuum hot press. The laminating step of heating and pressurizing under reduced pressure can be carried out using a general vacuum hot press. For example, a metal plate such as a heated SUS plate is pressed from the side of the support layer. The pressurization condition is such that the degree of pressure reduction is usually 1 × 10 ^-2 MPa or less, preferably 1 × 10 ^-3 MPa or less. Although heating and pressurization can be performed in one stage, it is preferable to divide the conditions into two or more stages from the viewpoint of controlling the bleeding of the resin. For example, the pressurization in the first stage is carried out at a temperature of 70 to 150 ° C and a pressure of 1 to 15 kgf/cm ² , and the second stage of pressurization is carried out at a temperature of 150 to 200 ° C and a pressure of 1 to 40 kgf/cm. The range of ² is better. The time of each stage is preferably 30 to 120 minutes. Thus, by thermally hardening the resin composition layer, an insulating layer can be formed on the circuit board. Commercially available vacuum hot presses are, for example, MNPC-V-750-5-200 (manufactured by Nihon Seiki Co., Ltd.), VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.), and the like.

Next, the insulating layer formed on the circuit board is subjected to a hole forming process to form a via hole and a via hole. The drilling process is performed by a known method such as drilling, laser, plasma, or the like, and if necessary, the method can be combined to perform the drilling process. Among them, laser hole drilling such as carbon dioxide gas laser and YAG laser is the most common method. Also, the present invention The lamella laminate is laminated on the circuit substrate, and the resin composition layer is thermally cured to form an insulating layer, and the insulating layer formed on the circuit substrate is formed by opening the hole on the support to form a via hole. Preferably, the circuit board is preferably peeled off after the opening process. In this way, the via hole is formed by the opening process on the support, and the occurrence of resin residue can be suppressed. Further, in order to reduce the thickness of the multilayer printed circuit board, the diameter of the via hole is preferably 15 to 70 μm, more preferably 20 to 65 μm, still more preferably 25 to 60 μm.

Next, the surface of the insulating layer is roughened. The dry roughening treatment is, for example, a plasma treatment, and the wet roughening treatment is performed, for example, by swelling treatment of a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid. method. It is preferable to use any of the dry type and the wet type roughening treatment, but the wet type roughening treatment forms a convex-concave anchor on the surface of the insulating layer and at the same time removes the resin residue in the via hole. In the swelling treatment of the swelling liquid, the insulating layer is immersed in the swelling liquid at 50 to 80 ° C for 5 to 20 minutes (preferably 55 to 70 ° C, 8 to 15 minutes). The swelling liquid is, for example, an alkali solution, a surfactant solution or the like, and is preferably an alkali solution such as a sodium hydroxide solution or a potassium hydroxide solution. Commercially available swelling liquids include, for example, Swelling Dip Securiganth P, Swelling Dip Securiganth SBU manufactured by Atotech Japan Co., Ltd., and the like. In the roughening treatment of the oxidizing agent, the insulating layer is immersed in the oxidizing agent solution at 60 to 80 ° C for 10 to 30 minutes (preferably 70 to 80 ° C, 15 to 25 minutes). The oxidizing agent is, for example, an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide/sulfuric acid, and nitrate. Acid, etc. Further, the concentration of the permanganate in the alkaline permanganic acid solution is preferably 5 to 10% by weight. Commercially available oxidizing agents, such as Concentrate manufactured by Atotech Japan. Basic permanganic acid solution such as Compact CP, Dosing Solution Securiganth P, etc. The insulating layer is immersed in the neutralizing solution at 30 to 50 ° C for 3 to 10 minutes (preferably 35 to 45 ° C, 3 to 8 minutes) in a neutralization solution. The neutralizing liquid is preferably an acidic aqueous solution, and a commercial product such as a reduction solution manufactured by Atotech Japan Co., Ltd. Securiganth P.

Next, a conductor layer is formed on the insulating layer by dry plating or wet plating. Dry plating can be carried out by a conventional method such as vapor deposition, sputtering, or ion plating. The wet plating system combines electroless plating and electrolytic plating to form a conductor layer, and forms a plating resist having a pattern opposite to that of the conductor layer, and a method of forming a conductor layer only by electroless plating. Subsequent pattern formation methods, for example, a subtractive process, an additive process, and the like which are well known to those skilled in the art can be used. By repeating the above-described series of steps a plurality of times, a multi-stage laminated build-up multilayer printed circuit board can be manufactured. The present invention can suppress the occurrence of resin residue, and thus can ensure the communication-to-layer communication between layers. Accordingly, the lamella laminate of the present invention can be suitably used to form buildup layers of multilayer printed circuit boards.

<semiconductor device>

A semiconductor device can be fabricated using the multilayer printed circuit board of the present invention. At the conduction point of the multilayer printed circuit board of the present invention, a semiconductor wafer can be fabricated by mounting a semiconductor wafer. The so-called "conduction point" means "in a multilayer printed circuit board. The point at which the electrical signal is transmitted, which can be at the surface, or at a point where it is buried. Further, the semiconductor wafer is not particularly limited as long as it is an electronic circuit element made of a semiconductor.

The method of mounting the semiconductor wafer in the manufacture of the semiconductor device of the present invention is not particularly limited as long as the semiconductor wafer can effectively function, and specifically, for example, a wire bonding mounting method, a flip chip mounting method, and an increase in no bumps. A method of mounting a layer (BBUL), a method of mounting an anisotropic conductive film (ACF), a method of mounting a non-conductive film (NCF), and the like.

[Examples]

Hereinafter, the present invention will be described in detail by way of comparative examples, but the invention is not limited thereto. In the following description, "parts" means "parts by mass".

<Measurement method. Evaluation method>

First, explain the various measurement methods. Evaluation method.

<Resin residue evaluation>

For the adhesive films obtained in the respective Examples and Comparative Examples, the resin residue (smear) was evaluated in accordance with the following.

(1) Production of circuit board

A circuit pattern is formed by etching on both sides of a glass cloth substrate epoxy resin acryl-coated copper laminate (copper foil thickness 18 μm, substrate thickness 0.8 mm, Matsushita Electric Co., Ltd. R5715ES), using a microetching agent (MEC (share) system CZ8100) roughened to produce a circuit board.

(2) followed by lamination of the film

The adhesive film produced in each of the examples and the comparative examples was laminated on both sides of the circuit board produced in the above (1) using a batch type vacuum pressure laminator MVLP-500 (trade name, manufactured by Konica Minolta Co., Ltd.). . The lamination was carried out by pressure reduction for 30 seconds, pressure of 13 hPa or less, and then pressure bonding at 100 ° C, 30 seconds, and pressure of 0.74 MPa.

(3) Hardening of the resin composition layer

In Examples 1 to 8 and Comparative Example 1, the PET film was peeled off from the film after lamination, and the resin composition layer was cured at 170 ° C for 30 minutes to form an insulating layer. In Example 9, an unexposed PET film was obtained, and the resin composition layer was cured at 170 ° C for 30 minutes to form an insulating layer.

(4) Via hole formation

Using a CO ₂ laser processing machine (YB-HCS03T04) made by a Panasonic welding system (share), the insulating layer was opened and formed on the surface of the insulating layer under the conditions of a frequency of 1000 Hz, a pitch width of 13 μsec, and a number of impacts of 3. The via hole has a via hole having a diameter of 60 μm. In Example 9, the PET film was thereafter peeled off.

(5) roughening treatment

The circuit substrate was immersed in a swelling solution, that is, Atotech Japan's Swelling Dip Securiganth P at 60 ° C for 10 minutes. Then at 80 ° C, in the roughening liquid (oxidant), namely Atotech Japan (shares) Concentrate. The mixture was immersed in a compact P (KMnO ₄ : 60 g/L, NaOH: 40 g/L aqueous solution) for 20 minutes. Finally, at 40 ° C, in the neutralization solution, namely Atotech Japan (shares) Reduction Solution. Immerse in Securiganth P for 5 minutes.

(6) Evaluation of the residue at the bottom of the via hole

The periphery of the bottom of the via hole was observed using a scanning electron microscope (SEM), and the resulting image was measured for the maximum resin residue length from the wall surface at the bottom of the via hole. ○○ indicates that the maximum resin residue length is less than 2 μm, ◎ indicates that the maximum resin residue length is 2 μm or more and less than 3.5 μm, and ○ indicates that the maximum resin residue length is 3.5 μm or more and less than 5 μm, and × indicates the maximum resin residue. The length is 5 μm or more.

<Measurement of tensile peel strength (peel strength) of the plated conductor layer, measurement of root mean square roughness (Rq), and evaluation of insulation reliability> (1) Bottom processing of laminate

A glass cloth substrate having an internal circuit formed of an epoxy resin-coated copper laminate (a thickness of 18 μm of copper foil, a residual copper ratio of 60%, a substrate thickness of 0.3 mm, and R5715ES manufactured by Matsushita Electric Co., Ltd.) is immersed in the MEC. In the CZ8100 system, the copper surface is roughened.

(2) followed by lamination of the film

The adhesive film produced in each of the examples and the comparative examples was laminated on both surfaces of a laminate using a batch type vacuum pressure laminator MVLP-500 (manufactured by a famous machine). The lamination was carried out by pressure reduction for 30 seconds, pressure of 13 hPa or less, and then pressure bonding at 100 ° C and a pressure of 0.74 MPa for 30 seconds.

(3) Hardening of the resin composition layer

The PET film was peeled off from the film after lamination, and the resin composition was cured at 170 ° C for 30 minutes.

(4) roughening treatment

The laminate was immersed in Swelling Dip Securiganth P containing diethylene glycol monobutyl ether in a swelling solution, namely Atotech Japan (stock) at 60 ° C for 10 minutes, followed by a crude solution at 80 ° C, ie Atotech Concentrate of Japan. The mixture was immersed in a compact P (KMnO ₄ : 60 g/L, NaOH: 40 g/L aqueous solution) for 20 minutes. Finally, at 40 ° C, in the neutralization solution, namely Atotech Japan (shares) Reduction Solution. Immerse in Securiganth P for 5 minutes. This roughened laminate was used as sample A.

(5) Forming by semi-additive process plating

In order to form a circuit on the surface of the insulating layer, the laminate is immersed in a solution for electroless plating containing PdCl ₂ and then immersed in an electroless copper plating solution. After annealing at 150 ° C for 30 minutes, an etching resist was formed, and a pattern was formed by etching, and then copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 30 μm. Next, annealing treatment was performed at 180 ° C for 60 minutes. This laminate was used as sample B.

(6) Determination of root mean square roughness (Rq value)

For the sample A, a non-contact surface roughness meter (WYKO NT3300, manufactured by Veeco Instruments Co., Ltd.) was used, and the Rq value was obtained by a VSI contact mode, a 50-fold lens, and a measurement range of 121 μm × 92 μm. Then, the average value of each of 10 points was obtained as a measured value.

(7) Determination of peeling strength (Peel strength) of the plated conductor layer

On the conductor layer of the sample B, a portion having a width of 10 mm and a length of 100 mm was applied, and the end was peeled off to hold the holder (T.S. E, Auto com type test machine AC-50C-SL) The load (kgf/cm) when peeling 35 mm in the vertical direction at a speed of 50 mm/min was measured at room temperature.

(8) Evaluation of insulation reliability

A circular resist tape (made by Nitto Denko Co., Ltd., ELEP MASKING N380) was attached to the conductor layer of the sample B, and immersed in an aqueous solution of ferrous chloride for 30 minutes. The conductor layer of the portion where the photoresist tape was not attached was removed, and an evaluation substrate in which a circular conductor layer was formed on the insulating layer was produced. Then, one portion of the insulating layer is removed to expose the copper foil at the bottom. The exposed copper foil and the circular conductor layer are connected by wiring (metal wire). The wiring of the evaluation substrate was connected to a DC power source (TP018-3D, manufactured by Kobelco Seisakusho Co., Ltd.), and a voltage of 200 hours and 3.3 V was supplied under conditions of 130 ° C and 85% RH. After 200 hours, the resistance value was measured. When the resistance value was 1.0 × 10 ⁸ Ω or more, the evaluation was "○", and 1.0 × 10 ⁷ Ω or more and less than 1.0 × 10 ⁸ Ω were evaluated as "△". The 1.0 × 10 ⁷ Ω is evaluated as "X".

<Measurement of dielectric loss tangent>

The adhesive film obtained in each of the examples and the comparative examples was thermally cured at 190 ° C for 90 minutes, and the PET film was peeled off to obtain a sheet-like cured product. The cured product was cut into a test piece having a width of 2 mm and a length of 80 mm, and a cavity resonance device permeation method CP521 and a network analyzer E8362B manufactured by Agilent Technologies were used to form a cavity resonance using Kanto Electronics Application Development Co., Ltd. The device perturbation method measures the dielectric loss tangent (tan δ) at a measurement frequency of 5.8 GHz. Two test pieces were measured, and the average value was calculated.

(Example 1)

Liquid bisphenol A type epoxy resin (epoxy equivalent 180, Mitsubishi Chemical (parts) "828US") 10 parts, biphenyl type epoxy resin (epoxy equivalent 291, Nippon Chemical Co., Ltd. "NC3000H") 20 parts in methyl ethyl ketone (hereinafter referred to as "MEK") 15 parts of 15 parts of cyclohexanone were stirred and dissolved by heating. Further, an active ester compound ("HPC8000-65T" manufactured by DIC), an active ester equivalent of 223, a 65% toluene solution of a solid fraction, and 28 parts of a cresol resin containing triazine ("LA3018-50P") ", a phenol equivalent of 151, a 50% solid solution of 2-methoxypropanol), 7 parts, a hardening accelerator (manufactured by Kwong Wing Chemical Industry Co., Ltd., "4-dimethylaminopyridine"), 0.1 part, Spherical cerium oxide (average particle size 0.5 μm, treated with "amino-based decane" "SO-C2", (manufactured by admatechs), carbon content per unit weight of 0.18%) 140 parts, phenoxy resin (YL7553BH30, solid content 30 mass 1:1 solution of MEK and cyclohexanone, weight average molecular weight of 40,000), 7 parts, blue pigment (manufactured by Daisei Seiki Co., Ltd., cyanine blue 4920), 0.04 parts, yellow pigment (BASF, Paliotol Yellow) K1841) 0.07 parts, 0.08 parts of a red pigment (manufactured by Clariant Japan Co., Ltd., PV Fast Pink E01), and uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish. Next, the resin was varnished on a polyethylene terephthalate film (thickness: 38 μm, hereinafter abbreviated as "PET film"), and applied to a die coater to have a resin thickness after drying of 40 μm to 80 to 120 ° C. (Average 100 ° C) was dried for 6 minutes to obtain a sheet-like adhesive film.

(Example 2)

In addition to the blue pigment of Example 1, 0.04 parts, yellow pigment 0.07 A resin varnish was prepared in the same manner as in Example 1 except that 0.08 parts of the red pigment and 0.4 parts of the red pigment were changed to 0.4 parts of a blue pigment, 0.66 parts of a yellow pigment, and 0.84 parts of a red pigment. Next, a film was obtained in the same manner as in Example 1.

(Example 3)

A resin varnish was produced in the same manner as in Example 1 except that 0.04 parts of the blue pigment of Example 1, 0.07 parts of a yellow pigment, and 0.08 parts of a red pigment were changed to 0.9 parts of a blue pigment, 1.4 parts of a yellow pigment, and 1.6 parts of a red pigment. Next, a film was obtained in the same manner as in Example 1.

(Example 4)

A resin varnish was produced in the same manner as in the Example except that 0.04 parts of the blue pigment of Example 1, 0.07 parts of a yellow pigment, and 0.08 parts of a red pigment were changed to 3 parts of carbon black. Next, a film was obtained in the same manner as in Example 1.

(Example 5)

A resin varnish was prepared in the same manner as in Example 1 except that 0.04 parts of the blue pigment of Example 1, 0.07 parts of a yellow pigment, and 0.08 parts of a red pigment were changed to 3.5 parts of rubber particles ("AC3816N" manufactured by Gansu Chemical Co., Ltd.). Next, a film was obtained in the same manner as in Example 1.

(Example 6)

In addition to 0.04 parts of the blue pigment of Example 1, 0.07 parts of the yellow pigment, and 0.08 parts of the red pigment were changed to antioxidants (BASF) A resin varnish was produced in the same manner as in Example 1 except for 3.5 parts of "IRGANOX 1010". Next, a film was obtained in the same manner as in Example 1.

(Example 7)

In the same manner as in Example 1, except that 0.04 parts of the blue pigment of Example 1, 0.07 parts of the yellow pigment, and 0.08 parts of the red pigment were changed to 3.5 parts of an infrared ray absorbing agent ("IR-14" manufactured by Nippon Shokubai Co., Ltd.). Make a resin varnish. Next, a film was obtained in the same manner as in Example 1.

(Example 8)

In addition, 140 parts of spherical cerium oxide (average particle diameter: 0.5 μm, treated with an amine decane "SO-C2", manufactured by Admatechs, 0.18% by weight per unit weight) of Example 2 was changed to spherical cerium oxide ( A resin varnish was produced in the same manner as in Example 2 except that the average particle diameter was 0.25 μm, and 100 parts of carbon (0.8% by weight per unit weight) of "SO-C1" and (manufactured by Admatechs) were treated with an amino decane. Next, a film was obtained in the same manner as in Example 1.

(Example 9)

The same adhesive film as in Example 2 was used.

(Comparative Example 1)

A resin varnish was produced in the same manner as in Example 1 except that 0.04 parts of the blue pigment of Example 1 and 0.07 parts of a yellow pigment and 0.08 parts of a red pigment were not added. Next, a film was obtained in the same manner as in Example 1.

The results are shown in Table 1.

As is apparent from Table 1, the examples are low dielectric loss tangent, and the resin residue in the via holes is excellent in suppression. Further, Examples 1 to 3 and 5 to 9 were particularly excellent in insulation reliability, and the results of the resin residues of Examples 3, 8, and 9 were further suppressed. On the other hand, in Comparative Example 1, although the dielectric loss tangent was low, there was a result of residual resin residue.

[Industrial availability]

The present invention can provide a resin composition and a lamellar laminate which can achieve a low dielectric loss tangentiality of a cured product of a resin composition, and can inhibit a resin residue in a via hole after the roughening treatment of the cured product by the opening process. Materials, multilayer printed circuit boards, semiconductor devices. In addition, it is possible to provide electric appliances such as computers, mobile phones, digital cameras, televisions, and the like, or vehicles such as motorcycles, automobiles, electric cars, ships, and airplanes.

Claims (18)

A resin composition comprising a resin composition of (A) an epoxy resin, (B) an active ester compound, and (C) a resin residue inhibiting component, wherein when the nonvolatile content of the resin composition is 100% by mass, C) The resin residue inhibiting component is 0.001 to 10% by mass. In the resin composition of the first aspect of the invention, wherein the nonvolatile content in the resin composition is 100% by mass, the content of the (B) active ester compound is from 1 to 30% by mass. The resin composition of the first aspect of the invention, wherein the (C) resin residue inhibiting component is an organic resin residue inhibiting component. The resin composition according to the third aspect of the invention, wherein the organic resin residue inhibiting component is one or more selected from the group consisting of a pigment, a dye, a rubber particle, an antioxidant, and an infrared ray absorbing agent. The resin composition of claim 3, wherein the organic resin residue inhibiting component is a pigment and/or rubber particles. The resin composition of claim 3, wherein the organic resin residue inhibiting component is a pigment. The resin composition of the third aspect of the invention, wherein the organic resin residue inhibiting component is one or more selected from the group consisting of a blue pigment, a yellow pigment, a red pigment, and a green pigment. The resin composition of claim 3, wherein the organic resin residue inhibiting component is a mixed pigment obtained by mixing a blue pigment, a yellow pigment, and a red pigment. For example, the resin composition of claim 1 of the patent scope is further contained (D) Inorganic filler. The resin composition of claim 9, wherein (D) the inorganic filler has an average particle diameter of 0.01 to 5 μm. In the resin composition of the ninth aspect of the invention, wherein the non-volatile content in the resin composition is 100% by mass, the content of the (D) inorganic filler is from 40 to 85% by mass. The resin composition of claim 9, wherein the inorganic filler has a carbon content per unit weight of 0.02 to 3%. The resin composition of claim 1, wherein the resin composition is hardened to form an insulating layer, and the surface of the insulating layer is roughened by a root mean square (Root Mean Square) Rq When the thickness is 500 nm or less, the peeling strength of the conductor layer obtained by plating the surface of the insulating layer and the insulating layer is 0.3 kgf/cm or more, and the dielectric loss tangent of the cured product of the resin composition is 0.05 or less. The resin composition of claim 1 is a resin composition for an insulating layer of a multilayer printed circuit board. A sheet-like laminate comprising the resin composition according to any one of claims 1 to 14. A multilayer printed circuit board characterized in that the insulating layer is formed by a cured product of the resin composition according to any one of claims 1 to 14. A semiconductor device characterized by using a multilayer printed circuit board as claimed in claim 16. A method of manufacturing a multilayer printed circuit board, the characteristics of which will be The sheet-like laminate material of claim 15 is laminated on the circuit substrate, and the resin composition is thermally hardened to form an insulating layer. For the insulating layer formed on the circuit substrate, the via hole is formed by the support body to form a via hole. .