TWI620781B - Resin composition - Google Patents

Abstract

The problem to be solved by the present invention is to provide a resin composition capable of achieving a low dielectric loss tangent of a hardened material of a resin composition and a resin residue in a via hole after the hardened material is subjected to hole-opening processing and roughening treatment. .

The present invention is a specific resin composition containing an epoxy resin, an active ester compound, and a resin residue suppression component.

Description

Resin composition

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

In recent years, the miniaturization and high performance of electronic devices have progressed. Multilayer printed circuit boards are required to be multi-layered (Build up layer), miniaturized and high-density wiring. In addition, in order to reduce transmission loss, media are required. Insulation material with low electrical loss tangent.

Patent Document 1 discloses an epoxy resin composition for sealing containing an epoxy resin, a hardener, and carbon black, and describes preventing the aggregation of carbon black. However, the concept of resin residue or low dielectric loss tangent is not disclosed or suggested at all.

[Prior technical literature] [Patent Literature]

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

When the insulating layer of the multilayer printed circuit board is subjected to hole processing, resin residues may be generated in the via holes, and the resin residues must be removed in a roughening process. However, according to the findings of the present inventors, when using a resin composition containing a low dielectric loss tangent of an active ester compound to make a multilayer printed circuit board, the via hole is roughened even after the opening of the insulating layer is processed. It will be found that it is difficult to remove the resin residue in the via hole.

Therefore, the problem to be solved by the present invention is to provide a resin composition that can achieve a low dielectric loss tangent of a hardened material of a resin composition, and can suppress the opening of the hardened material and roughening the resin residue in the via hole. Thing.

As a result of intensive studies 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 completed the present invention.

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

[1] A resin composition characterized by a resin composition containing (A) an epoxy resin, (B) an active ester compound, and (C) a resin residue suppressing component, and a non-volatile content of the resin composition is 100% by mass (C) The resin residue suppression component is 0.001 to 10% by mass.

[2] The resin composition according to the aforementioned item [1], wherein when the non-volatile content in the resin composition is 100% by mass, the content of the (B) active ester compound It is 1 to 30% by mass.

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

[4] The resin composition according to the item [3], wherein the organic resin residue suppressing component is one or more members selected from the group consisting of a pigment, a dye, a rubber particle, an antioxidant, and an infrared absorber.

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

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

[7] The resin composition according to the item [3], wherein the organic resin residue suppression 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 the item [3], wherein the organic resin residue suppression 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 items [1] to [8], which further contains (D) an inorganic filler.

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

[11] The resin composition according to the item [9] or [10], wherein when the non-volatile content in the resin composition is 100% by mass, the content of the (D) inorganic filler is 40 to 85% by mass.

[12] The resin composition according to any one of the items [9] to [11], wherein The carbon content per unit weight of the inorganic filler is 0.02 to 3%.

[13] The resin composition according to any one of the above items [1] to [12], wherein the resin composition is hardened to form an insulating layer, and the surface of the insulating layer is roughened after the surface of the insulating layer is roughened. The Root Mean Square has a thickness Rq of 500 nm or less. The peel strength of the conductive layer and the insulating layer obtained by plating on the surface of the insulating layer is 0.3 kgf / cm or more. The dielectric loss tangent of the hardened material of the resin composition is tangent. It is 0.05 or less.

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

[15] A sheet-like laminated material characterized by containing the resin composition according to any one of the items [1] to [14].

[16] A multilayer printed circuit board characterized by forming an insulating layer from a hardened product of the resin composition as described in any one of [1] to [14] above.

[17] A semiconductor device characterized by using a multilayer printed circuit board as described in [16] above.

[18] A method for manufacturing a multilayer printed circuit board, which is characterized in that the sheet-like laminated material as described in [15] above is laminated on a circuit board, and the resin composition is heat cured to form an insulating layer. An insulating layer is formed on the support to form a via hole.

By providing a specific resin composition containing an epoxy resin, an active ester compound, and a resin residue suppressing component, it is possible to provide the resin group Resin composition of hardened product with low dielectric loss tangent, and resin residue in the via hole after roughening treatment can be suppressed by hardening the hardened product.

[Mode for Carrying Out the Invention]

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

<(A) epoxy resin>

The (A) epoxy resin used in the present invention is not particularly limited, and an epoxy resin containing two or more epoxy groups in one molecule is preferred. 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 phenolic epoxy resin, and a third butyl-ortho Resorcinol epoxy resin, naphthol epoxy resin, naphthalene epoxy resin, naphthyl ether epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, cresol novolac type Epoxy resin, biphenyl type epoxy resin, anthracene type epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, containing spiral Spiro ring epoxy resin, cyclohexanedimethanol epoxy resin, trimethylol epoxy resin, halogenated epoxy resin, etc. These can be used singly or in combination of two or more kinds.

Among them, from improving heat resistance, improving insulation reliability, From the viewpoint of improving adhesion with metal foil, bisphenol A epoxy resin, naphthol epoxy resin, naphthalene epoxy resin, biphenyl epoxy resin, and naphthyl ether epoxy resin are preferred. Glycidyl epoxy resin, anthracene epoxy resin, epoxy resin with butadiene structure. Specifically, for example, there are bisphenol A type epoxy resin ("Epikote 828EL" and "YL980" manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resin ("jER806H" manufactured by Mitsubishi Chemical Corporation), "YL983U"), naphthalene-type bifunctional epoxy resin ("HP4032", "HP4032D", "HP4032SS", "EXA4032SS") manufactured by DIC (share) "HP4700", "HP4710"), naphthol-type epoxy resin ("ESN-475V" manufactured by Tohto Kasei Co., Ltd.), epoxy resin with butadiene structure ("PB" manufactured by Daicel Chemical Industry Co., Ltd.) -3600 "), biphenyl epoxy resin (" NC3000H "," NC3000L "," NC3100 "manufactured by Nippon Kayaku Co., Ltd.," YX4000 "," YX4000H "," YX4000HK "manufactured by Mitsubishi Chemical Co., Ltd. , "YL6121"), anthracene-based epoxy resin ("YX8800" manufactured by Mitsubishi Chemical Corporation), dnaphthyl ether epoxy resin ("EXA-7310", "EXA-7311" manufactured by DIC) , "EXA-7311L", "EXA7311-G3"), glycidyl epoxy resin (nagasechemtex (stock) "EX711", "EX721", (stock) printec "R540") Wait.

Among them, it is preferable to use a liquid epoxy resin and a solid epoxy resin in combination, and it is more preferable that the epoxy resin contains two or more epoxy groups in one molecule. A liquid aromatic epoxy resin (hereinafter also referred to as a "liquid epoxy resin") at a temperature of 20 ° C and a solid aromatic fragrance having three or more epoxy groups in one molecule at a temperature of 20 ° C Family epoxy resin (hereinafter referred to as "solid epoxy resin"). The term "aromatic epoxy resin" as used in the present invention means an epoxy resin having an aromatic ring structure in the molecule. When the epoxy resin is a combination of a liquid epoxy resin and a solid epoxy resin, when the resin composition is used in the form of a film, it has a moderate flexibility, or a cured product of the resin composition has a moderate breaking strength. , Its blending ratio (liquid epoxy resin: solid epoxy resin) is based on mass ratio, preferably in the range of 1: 0.1 ~ 1: 4, more preferably in the range of 1: 0.1 ~ 1: 2, and more It is preferably in the range of 1: 0.3 to 1: 1.8, and more preferably in the range of 1: 0.6 to 1: 1.5.

In the resin composition of the present invention, from the viewpoint of improving the mechanical strength or insulation reliability of the hardened material of the resin composition, when the non-volatile content in the resin composition is 100% by mass, the content of (A) the epoxy resin is It is preferably 3 to 40% by mass, more preferably 5 to 35% by mass, and even more preferably 10 to 30% by mass.

<(B) Active ester compound>

The (B) active ester compound in the present invention is a compound having one or more active ester groups in one molecule, which can reduce the dielectric loss tangent of the resin composition, and can make the root mean square roughness Rq small. (B) The active ester compound can react with epoxy resin and the like, and a compound having two or more active ester groups in one molecule is preferred. Generally speaking, it is preferable to use phenolic esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxy compound esters. Compounds such as compounds having two or more highly reactive ester groups in one molecule.

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. Still more preferred is an active ester compound obtained by reacting a carboxylic acid compound with one or two or more selected from a phenol compound, a naphthol compound, and a thiol compound. Still more preferred is an aromatic compound having two or more active ester groups in one molecule obtained by reacting a carboxylic acid compound and an aromatic compound having a phenolic hydroxyl group. In addition, it is particularly preferable that the carboxylic acid compound having at least two carboxyl groups in one molecule and the aromatic compound having a phenolic hydroxyl group react with each other, and that the aromatic compound has two in one molecule. An aromatic compound of the above active ester group. Moreover, it may be linear or branched. In addition, when a carboxylic acid compound having at least two carboxyl groups in one molecule is a compound containing an aliphatic chain, compatibility with a resin composition can be improved, and when a compound has 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, pyromellitic acid, and the like. Among these, from the viewpoint of heat resistance, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferred, and isophthalic acid and terephthalic acid are more preferred. Specific examples of the thiocarboxylic acid include thioacetic acid and thiobenzoic acid.

Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, Methylated bisphenol S, phenol, o-methyl Phenol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene , Dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, resorcinol (Phloroglucin), benzenetriol, dicyclopentadienediol, phenolic, etc. 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 phthalate are preferred. Phenol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, Tetrahydroxybenzophenone, resorcinol, pyroglycerol, dicyclopentadienediphenol, phenolic form, more preferably catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, resorcinol, benzenetriol, dicyclopentadienediphenol, phenolic, and, More preferred are 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, and bicyclic Pentadiene, phenol, and more preferably 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadienediphenol, and phenolaldehyde, particularly preferably 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene diphenol, and dicyclopentadiene diphenol is particularly preferred. Specific examples of the thiol compound include benzenedithiol and triazinedithiol. The active ester compound may be used singly or in combination of two or more kinds.

More specifically, the active ester compound containing a dicyclopentadiene diphenol structure. For example, there are compounds of the following formula (1).

(In the formula, R represents a phenyl group and 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 reducing the dielectric loss tangent and improving heat resistance, R is preferably a naphthyl group, k is preferably 0, and n is preferably 0.25 to 1.5.

(B) As the active ester compound, the active ester compound disclosed in Japanese Patent Application Laid-Open No. 2004-277460 may be used, or a commercially available active ester compound may be used. Commercially available active ester compounds are specifically preferably active ester-based hardeners containing a dicyclopentadiene diphenol structure, active ester-based hardeners containing a naphthalene structure, and active esters containing an acetamidate of a phenolic compound. Type hardeners, active ester hardeners containing benzamidine compounds containing phenolic form, more preferably active ester hardeners containing a naphthalene structure, and active ester hardeners containing a dicyclopentadiene diphenol structure. Active ester hardeners containing a dicyclopentadiene diphenol structure include, for example, EXB 9451, EXB 9460, EXB 9460S, HPC-8000-65T (manufactured by DIC (stock), active ester hardeners containing a naphthalene structure, for example There is EXB9416-70BK (manufactured by DIC), and active ester-based hardeners containing acetic acid compounds of phenolic compounds. For example, there is YLH1026 (Mitsubishi Chemical Corporation).

(B) The content of the active ester compound, from the viewpoint of improving heat resistance and suppressing the occurrence of resin residue, the non-volatile components in the resin composition are When it is 100% by mass, it is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less. From the viewpoint of improving the peel strength, when the non-volatile 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 even more preferably 5% by mass or more.

In addition, when the epoxy group number of the (A) epoxy resin is 1, from the viewpoint of improving the mechanical properties of the resin composition, the number of reactive groups of the (B) active ester compound is preferably 0.2 to 2, and more preferably 0.3 to 1.5. It is more preferably 0.4 to 1. Here, the "epoxy number of epoxy resin" refers to a value obtained by dividing the solid content of each epoxy resin present in the resin composition by the epoxy equivalent, and the total value for all epoxy resins. The "reactive group" refers to a functional group capable of reacting with an epoxy group, and the "reactive group number of the active ester compound" refers to a value obtained by dividing the solid content mass of the active ester compound present in the resin composition by the equivalent of the reactive group. The total value of all.

<(C) Resin residue suppression component>

The resin residue-suppressing component used in the present invention is a component that can suppress the resin residue of the through-holes of the hardened product of the resin composition after roughening treatment. Here, the term "resin residue suppression" refers to either of reducing the amount of resin residues generated during the hole-opening process and making it easier to remove the resin residues during roughening. The resin residue suppression component includes, for example, an organic resin residue suppression component and an inorganic resin residue suppression component. From the viewpoint of improving insulation reliability, an organic resin residue suppression component is preferred. Specifically, the organic resin residue suppression component includes, for example, pigments, dyes, rubber particles, and antioxidants. Chemical agents, infrared absorbers, etc., and the inorganic resin residue suppressing components include, for example, metal compound powders and metal powders. (C) The resin residue suppressing component is preferably one or more selected from the group consisting of pigments, dyes, rubber particles, antioxidants, and infrared absorbers. Among these, pigments and / or rubber particles are more preferable, and pigments are more preferable from the viewpoints of excellent resin residue suppression performance and excellent peel strength. These can be used singly or in combination of two or more kinds.

Examples of the pigment include a blue pigment, a yellow pigment, a red pigment, a black pigment, and a green pigment. Examples of the blue pigment include phthalocyanine-based, anthraquinone-based, and dioxazine-based pigments. Examples of yellow pigments include monoazo-based, disazo-based, condensed azo-based, benzimidazolone-based, isoindolinone-based, and anthraquinone-based pigments. Examples of red pigments are monoazo-based, disazo-based, azo lake (AZO LAKE) -based, benzimidazolone-based, fluorene-based, diketopyrrolopyrrole-based, condensed azo-based, anthracene Pigments such as quinone and quinacridone. Examples of the black pigment include carbon black and graphite. Examples of the green pigment include phthalocyanine-based pigments. One kind of pigment may be used, or two or more kinds may be used in combination, and one or more kinds 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. Among them, from the viewpoint of further improving insulation reliability, it is preferred to use one or more members selected from the group consisting of blue pigments, yellow pigments, red pigments, and green pigments, and more preferably to use a mixture of blue pigments, yellow pigments, and red pigments. A pigment made from pigments. In addition, when a mixed pigment made by mixing blue pigment, yellow pigment, and red pigment is prepared, it can effectively absorb Laser, from the viewpoint of more inhibiting the occurrence of resin residue, the mass ratio of blue pigment, yellow pigment and red pigment is preferably 2 ~ 6: 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 Dyes, Naphthalene Dyes, Quinoline Yellow Dyes, Amino Ketone Dyes, Methylene Dyes, Perylene Dyes, Coumarin Dyes, Perinone Dyes, Triphenyl Dyes, Triallyl Methane Dyes , Phthalocyanine dyes, indoxyl dyes, triazine dyes, or mixtures thereof.

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

Examples of the antioxidant include hindered phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Commercial products include, for example, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] ("IRGANOX 1010" manufactured by CIBA JAPAN) and 2,2-sulfur Substituted-dimethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] ("IRGANOX 1035" by CIBA JAPAN), 1, 3, 5 -Tris [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] -1,3,5-tris Azine-2,4,6 (1H, 3H, 5H) -trione ("IRGANOX 3114" manufactured by CIBA JAPAN).

Examples of the infrared absorber include a phthalocyanine-based compound, an anthraquinone compound, and a nickel complex. Commercial products include, for example, IR-14 (manufactured by Japan Catalysts Co., Ltd.) and TX-HA-1 (manufactured by Japan Catalysts Co., Ltd.).

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, zinc oxide, and the like. Silicon oxide, aluminum oxide, rare earth oxide, cobalt oxide such as cobalt oxide, tin oxide such as tin oxide, tungsten oxide such as tungsten oxide, silicon carbide, tungsten carbide, boron nitride, silicon nitride, nitrogen Titanium nitride, aluminum nitride, barium sulfate, rare-earth acid sulfide, or a mixture of these powders.

Examples of metal powder include silver, aluminum, bismuth, cobalt, copper, iron, magnesium, manganese, molybdenum, nickel, palladium, antimony, silicon, tin, titanium, vanadium, tungsten, zinc, or powders of alloys or mixtures thereof. .

(C) The content of the resin residue inhibiting component is, from the viewpoint of preventing deterioration in hardened properties, preferably 100% by mass or less, more preferably 5% by mass or less, and more preferably 100% by mass of the nonvolatile matter in the resin composition. 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, from the viewpoint of improving the resin residue suppression performance, it is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.02% by mass or more, with respect to 100% by mass of the nonvolatile matter in the resin composition. It is more preferably 0.05% by mass or more, still more preferably 0.08% by mass or more, and 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 reduce the linear thermal expansion rate and improve the resin residue removal property during roughening treatment. (D) The inorganic fillers include, for example, silicon dioxide, aluminum oxide, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, and titanium. Barium acid, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate and the like. Among them, silicon dioxide is preferred. In addition, amorphous silicon dioxide, pulverized silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, hollow silicon dioxide, etc. are preferred, and fused silicon dioxide is more preferred. The silica is preferably spherical silica. These can be used singly or in combination of two or more kinds. Commercially available spherical fused silica includes, for example, "SO-C2" and "SO-C1" manufactured by Admatechs.

(D) The average particle diameter of the inorganic filler is not particularly limited. 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 and suppresses openings. From the viewpoint of generating resin residue during processing, it is preferably 5 μm or less, more preferably 3 μm or less, even more preferably 1 μm or less, more preferably 0.7 μm or less, more preferably 0.5 μm or less, particularly preferably 0.4 μm or less, and 0.3 It is particularly preferable to be less than μm. On the other hand, when the epoxy resin composition is used as a varnish, the lower limit of the average particle diameter of the inorganic filler is preferably 0.01 μm or more, and 0.03 μm or more from the viewpoint of preventing an increase in the viscosity of the varnish and a decrease in workability. For the better, 0.05 μm or more is better, and 0.07 μm or more is better. It is particularly preferred that it is 0.1 μm or more. The average particle diameter of the above-mentioned inorganic filling materials can be determined by laser diffraction based on the Mie scattering theory. Determination by scattering method. Specifically, the particle size distribution of the inorganic filler is made on a volume basis by a laser diffraction type particle size distribution measuring device, and the median diameter can be measured by the average particle size. The measurement sample is preferably one in which an inorganic filler is dispersed in water by ultrasonic waves. The laser diffraction type particle size distribution measuring device can be LA-500, 750, 950, etc. manufactured by Horiba.

(D) The content of the inorganic filler is not particularly limited, and from the viewpoint of preventing a reduction in flexibility when the resin composition is in the form of a film, when the non-volatile content in the resin composition is 100% by mass, it is preferably 85% by mass. % Or less, more preferably 80% by mass or less, and still more preferably 75% by mass or less. In addition, from the viewpoint of reducing the thermal expansion coefficient of the insulating layer, increasing the total surface area of the inorganic filler, suppressing the occurrence of resin residues during the hole-opening process, and easily removing the resin residues during the roughening process, the non-volatile components in the resin composition are 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 even more preferably 70% by mass or more.

(D) From the viewpoint of improving moisture resistance and dispersibility, the inorganic filler is preferably an amine-based silane-based coupling agent, a urea-based silane-based coupling agent, an epoxy-based silane-based coupling agent, a mercaptosilane-based coupling agent, or silane. Coupling Agent, Vinyl Silane Coupling Agent, Styryl Silane Coupling Agent, Acrylate Silane Coupling Agent, Isocyanate Silane Coupling Agent, Sulfide Silane Coupling Agent, Organic Silazane Compound, Titanate Surface treatment agents such as coupling agents are surface-treated. Organic inorganic nitrogen After the surface treatment of the alkane compound, the surface treatment with the silane coupling agent is performed to further improve the moisture resistance or dispersibility of the inorganic filler. These can be used singly or in combination of two or more kinds.

Specific examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, and N-phenyl-3- Aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-amine (Ethylethyl) -3-aminopropyldimethoxymethylsilane and other aminosilane-based coupling agents, 3-ureidopropyltriethoxysilane and other urea-based silane coupling agents, 3-shrink Glyceryloxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethoxydiethoxysilane, 3-glycidoxypropyl ( Dimethoxy) methylsilane, glycidylbutyltrimethoxysilane, 2- (3,4-ethoxycyclohexyl) ethyltrimethoxysilane, and other epoxysilane-based coupling agents, 3- Mercaptosilane coupling agents such as mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 11-mercaptoundecyltrimethoxysilane, etc. , Methyltrimethoxysilane, octadecyltrimethoxysilane , Silane-based coupling agents such as phenyltrimethoxysilane, methacryloxy, propyltrimethoxysilane, imidazole silane, triazine silane, tert-butyltrimethoxysilane, vinyl Trimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, vinyl silane-based coupling agents, p-styryltrimethoxysilane, styrene-based silane-based coupling agents, 3-propenyloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methylpropylene Acrylic silane-based coupling agents such as methoxypropyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-methacryloxypropyldiethoxysilane , Isocyanate silane coupling agents such as 3-isocyanatepropyltrimethoxysilane, thiosilanes such as bis (triethoxysilylpropyl) disulfide, bis (triethoxysilylpropyl) tetrasulfide, etc. Coupling agent, hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, hexaphenyldisilazane, trisilazane, cyclotris Silazane, 2,2,4,4,6,6-hexamethylcyclotrisilazane, octamethylcyclotetrasilazane, hexabutyldisilazane, hexaoctyldisilazane, 1,3-diethyltetramethyldisilazane, 1,3-di-n-octyltetramethyldisilazane, 1,3-diphenyltetramethyldisilazane, 1, 3-dimethyltetraphenyldisilazane, 1,3-diethyltetramethyldisilazane, 1,1,3,3-tetraphenyl-1,3-dimethyldisilazane Organosilicon nitrogen, 1,3-dipropyltetramethyldisilazane, hexamethylcyclotrisilazane, dimethylaminotrimethylsilazane, tetramethyldisilazane, etc. Alkanes, tetra-n-butane Butyl titanate dimer, i-propoxy titanium octanediol, tetra-n-butyl titanate, titanium octanediol, titanium diisopropoxy bis (triethanolvalerate), dihydroxy Titanium lactate, titanium dihydroxybis (ammonium lactate), bis (dioctyl pyrophosphate) ethylene titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, tri-n-butyl Oxymonostearate, tetra-n-butyl titanate, tetra (2-ethylhexyl) titanate, tetraisopropylbis (dioctyl phosphate) titanate, tetraoctylbis (di ( Tridecyl) phosphate) Titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (di (tridecyl)) phosphate titanate, isopropyl Trioctylfluorenyl titanate, isopropyltricumylphenyl titanate, isopropyltriisostearylfluorenyl titanate, isopropylisostearylfluorenyldipropenylfluorenyl titanate Ester, isopropyldimethylpropenyl isostearyl isopropyl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tri (dodecyl) benzenesulfonyl titanium Esters, isopropyl tris (dioctyl pyrophosphate) titanates, isopropyl tris (N-fluorenylaminoethyl.aminoethyl) titanates, and other titanate silicon coupling agents. Among these, an amine-based silane-based coupling agent is preferred because it is excellent in re-moisture resistance, dispersibility, and characteristics of hardened materials, and an organosilazane compound is excellent in improving the dispersibility of a resin varnish. Commercially available products of the surface treatment agent are, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., and "KBM803" (3-mercaptopropyl) manufactured by Shin-Etsu Chemical Industry Co., Ltd. (Trimethoxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., and "KBM573" (N-phenyl-3-amino) manufactured by Shin-Etsu Chemical Industry Co., Ltd. Propyltrimethoxysilane) and the like.

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

The amount of carbon per unit weight of the inorganic filler increases from the root-mean-square roughness of the inorganic filler to improve the dispersibility of the inorganic filler or the roughening of the hardened material. A stable viewpoint is preferably 0.02% or more, more preferably 0.05% or more, and still more preferably 0.1% or more. In addition, from the viewpoint of preventing an increase in 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, and even more preferably 1% or less.

<(E) Hardening accelerator>

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

Examples of the imidazole-based hardening accelerator include 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-undecylimidazolium 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-phenylimidazolium Cyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl Methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrole [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride , 2-methylimidazoline, 2-phenylimidazoline and other imidazole compounds and adducts of imidazole compounds and epoxy resins. These can be used singly or in combination of two or more kinds.

Examples of the amine-based hardening accelerator include trialkylamines such as triethylamine, tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, and 2,4,6, -ginseng (dimethyl Amine compounds such as aminomethyl) phenol, 1,8-diazabicyclo (5,4,0) -undecene (hereinafter abbreviated as DBU), and the like. These can be used singly or in combination of two or more kinds.

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 (stock) trade name). These can be used singly or in combination of two or more kinds.

(E) The content of the hardening accelerator is preferably 0.01 to 3% by mass, and more preferably 100% by mass of the nonvolatile component in the resin composition, from the viewpoint of storage stability of the resin varnish or efficiency of hardening. 0.1 ~ 2 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, and the flexibility of the cured product can be improved. The thermoplastic resin is not particularly limited, and examples thereof include phenoxy resin, polyvinylacetal resin, polyimide resin, polyimide resin, polyimide resin, polyether resin, Polyfluorene resin, polybutadiene resin, ABS resin, etc. Among these, from the viewpoints of improving the flexibility of the cured product and contributing to adhesion, a phenoxy resin and a polyethylene acetal resin are preferred, and a phenoxy resin is more preferred. These can be used singly or in combination of two or more kinds. The thermoplastic resin is preferably one having 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 still more preferably in the range of 20,000 to 100,000. When it is within this range, the effect of film forming energy or mechanical strength can be fully exerted, and compatibility with 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, a measuring device using LC-9A / RID-6A manufactured by Shimadzu Corporation, and a column used Shodex K-800P / K-804L manufactured by Showa Denko Corporation / K-804L, the mobile phase was measured with chloroform, etc. at a column temperature of 40 ° C, 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, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a phenolic skeleton, a biphenyl skeleton, a fluorene skeleton, a dicyclopentadiene skeleton, and norbornene. One of one or more of a skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The phenoxy resin can be used as a mixture of two or more. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. Commercial products include, for example, Mitsubishi Chemical Corporation's 1256 and 4250 (phenoxy resin containing a bisphenol A skeleton), and Mitsubishi Chemical Corporation's YX8100 (phenoxy resin containing bisphenol S skeleton), YX6954 (phenoxy resin containing bisphenol acetophenone skeleton) manufactured by Mitsubishi Chemical Corporation. Commercial products include, for example, FX280, FX293 manufactured by Nippon Steel Chemical Co., Ltd., YL7553, YL6954, YL6794, YL7213, YL7290, YL7482, and the like manufactured by Mitsubishi Chemical Corporation.

Specific examples of the polyacetal acetal resin include, for example, those manufactured by the Electrochemical Industry Co., Ltd., electrochemical butyral 4000-2, 5000-A, 6000-C, 6000-EP, and 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, polyimide "RIKACOAT SN20" and "RIKACOAT PN20" made by Nippon Rika Co., Ltd. In addition, a linear polyimide obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid dianhydride (as described in Japanese Patent Application Laid-Open No. 2006-37083), containing polysilicon Modified polyimide of an oxane skeleton (described in Japanese Patent Application Laid-Open No. 2002-12667, Japanese Patent Application Laid-Open No. 2000-319386) and the like. Specific examples of the polyamidoimide resin include, for example, polyamidoimide "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Corporation. In addition, Hitachi Chemical Industries, Ltd. has modified polyamidoimines such as polyamidoimide "KS9100" and "KS9300" containing a polysiloxane skeleton. Specific examples of the polyether resin include, for example, polyether resin "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. and the like. Specific examples of the polymer resin include, for example, polymer "P1700" and "P3500" made of solve advanced polymers.

The content of the thermoplastic resin is not particularly limited. From the viewpoint of adjusting the melt viscosity of the laminar laminated material or adjusting the viscosity of the resin varnish, it is preferably 0.5 to 30 masses with respect to 100% by mass of the nonvolatile component in the resin composition. %, More preferably 1 to 20% by mass.

<(G) Hardener>

The resin composition of the present invention may further contain (G) a hardener. This improves the insulation reliability, peel strength, and mechanical properties of the hardened material of the resin composition. (G) The hardener is not particularly limited, and examples thereof include a phenol-based hardener, a cyanate-based hardener, a Benzoxazine-based hardener, and an acid anhydride-based hardener. These can be used singly or in combination of two or more kinds. Among these, from the viewpoints of improving the removal of resin residues and improving the dielectric properties, phenol-based hardeners and cyanate-based hardeners are preferred.

The phenol-based hardener is not particularly limited, and examples thereof include a phenol resin, a phenol resin containing a triazine skeleton, a naphthol resin, a naphthol aralkyl resin, a naphthol resin containing a triazine skeleton, and a biphenylaralkyl resin. Phenol resin and so on. Examples of biphenylaralkyl phenol resins are "MEH-7700", "MEH-7810", "MEH-7851" (made by Meiwa Chemical Co., Ltd.), NHN "," CBN "," GPH "(Japanese version) (Made by Pharmaceutical Co., Ltd.) and naphthol aralkyl resins include, for example, "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN375", "SN395" (Product), phenol resins such as "TD2090" (manufactured by DIC), and phenol resins containing a triazine skeleton, such as "LA3018", "LA7052", "LA7054", "LA1356" (DIC (shares) system), etc. A phenolic hardener can be used individually by 1 type or in combination of 2 or more types.

The cyanate-based hardener is not particularly limited, and examples thereof include phenol-based (phenol-based phenol-based, alkylphenol-based, etc.) cyanate-based hardener, dicyclopentadiene-based cyanate-based hardener, and bisphenol-based (Bisphenol A type, bisphenol F type, bisphenol S type, etc.) cyanate ester hardeners, and some of these prepolymers are triazinated. The weight average molecular weight of the cyanate ester-based hardener is not particularly limited, but is preferably 500 to 4500, and more preferably 600 to 3000. Specific examples of the cyanate-based curing agent include, for example, bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4 ' -Methylenebis (2,6-dimethylphenylcyanate), 4,4'-ethylenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2- Bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, 1, 3-bis (4-cyanatephenyl-1- (methylethylene)) benzene, bis (4-cyanatephenyl) sulfide, bis (4-cyanatephenyl) ether, etc. Polyfunctional cyanate resins derived from 2-functional cyanate resins, phenols, cresol novolacs, phenol resins containing a dicyclopentadiene structure, etc., part of these cyanate resins are prepolymerized with triazination These can be used alone or in combination of two or more. Commercially available cyanate resins include, for example, Phenol Novolac type polyfunctional cyanate resin (Lonza Japan Co., Ltd., PT30, cyanic acid). Ester equivalent 124), part or all of the bisphenol A dicyanate was triazinated to become a terpolymer prepolymer (manufactured by Lonza Japan Co., Ltd., BA230, cyanate equivalent 232), containing two Cyclopentane Alkenyl cyanate resin structures (Lonza Japan (shares) system, DT- 4000, DT-7000), etc.

The benzoxazine-based hardener is not particularly limited, and specific examples include F-a, P-d (manufactured by Shikoku Kasei Co., Ltd.), HFB2006M (manufactured by Showa Polymer Co., Ltd.), and the like.

The content of the (G) hardener in the resin composition is not particularly limited. From the viewpoint of preventing the hardened material of the resin composition from becoming brittle, it is preferably 0.5 to 10 mass% with respect to 100% by mass of the non-volatile content 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 propenyl nadiimide compound, a vinyl benzyl resin, ethylene, and the like, as long as the effect of the present invention is not hindered. Thermosetting ingredients such as benzyl ether resin, organic fillers such as silicon powder, durable powder, fluorine powder, tackifiers such as Orben, Benton, polysiloxane-based, fluorine-based, and polymer-based defoamers or Adhesion imparting agents such as leveling agents, imidazole-based, thiazole-based, triazole-based, and silane-based coupling agents; flame-retardants such as phosphorus-based compounds; and metal hydroxides.

The resin composition of the present invention appropriately mixes the above-mentioned ingredients, and if necessary, it can be carried out by a kneading means such as a three-roller, a ball mill, a bead mill, a sand mill, or the agitating means such as a super mixer, a planetary mixer, or the like. Knead or mix to make resin varnish. The hardened product of the resin composition of the present invention can achieve a low dielectric loss tangent, and can suppress the resin residue in the via hole after the hardened product is subjected to a hole-opening process and a roughening process.

The dielectric loss tangent of the hardened material of the resin composition of the present invention can be measured by the method described in <Measurement of Dielectric Loss Tangent> 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 heating, signal delay, and reduction of signal noise, 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. 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 hardened | cured material of the resin composition of this invention can be measured by the measuring method as described in "Measurement of root-mean-square roughness (Rq)" mentioned later. From the viewpoint of reducing the loss of electrical signals, the surface of the insulating layer after the roughening treatment is preferably fine unevenness. Examples of the tightness of the unevenness on the surface of the insulating layer include, for example, the root-mean-square roughness Rq. From this index, it can be seen that not only the average value of the unevenness on the surface of the insulating layer, but also that the surface of the insulating layer has a dense uneven shape. Specifically, the resin composition is hardened to form an insulating layer, and the root-mean-square roughness Rq of the surface of the insulating layer after roughening the surface of the insulating layer is preferably 500 nm or less, more preferably 400 nm or less, and more It is preferably below 300 nm, more preferably below 200 nm, and particularly preferably below 100 nm. 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 measured by a measuring method described in "Measurement of Pulling Strength (Peeling Strength) of Plating Conductive Layer" described later. Specifically, the resin composition is hardened to form Insulating layer, on the surface of the insulating layer after the roughening treatment, the peel strength of the conductive layer and the insulating layer obtained by plating is preferably 0.3 kgf / cm or more, more preferably 0.5 kgf / cm or more, and more preferably It is 0.6 kgf / cm or more. The upper limit value 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 as a sheet-like laminated material for bonding a film, a prepreg, or the like, a circuit board (such as a laminated board, a multilayer printed circuit board, etc.), or a solder resist. , Underfill material, wafer bonding material, semiconductor sealing material, buried-hole resin, parts-embedded resin, etc., a wide range of uses for resin compositions are required. Among them, the resin composition of the present invention can suppress the resin residue in the via hole after roughening the hardened material, and thus can improve the plating adhesion in the via hole and prevent the occurrence of pores in the via hole. It can ensure the conductivity between the insulating layers of the multilayer printed circuit board formed in multiple stages. In other words, when manufacturing a multilayer printed circuit board, it can be suitably used as a resin composition for forming an insulating layer (resin composition for an insulating layer of a multilayer printed circuit board), and can be more suitable as a resin for forming a conductor layer by plating. A 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 varnished state. However, it is generally preferably used in the form of a sheet-like laminated material such as a film, a prepreg, or the like in the industry. 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 laminated material.

<Laminar laminate material> (Adhesive film)

In an embodiment, the sheet-like laminated material of the present invention is an adhesive film. This adhesive film forms a resin composition layer on a support. 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. The resin varnish is applied to a support using a die coater, and then heated or blown. It is produced by drying an organic solvent with hot air or the like to form a resin composition layer.

Examples of organic solvents include ketones such as acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate. Acetates, cellosolves, carbitols such as butyl carbitol, aromatic hydrocarbons such as toluene, xylene, dimethylformamide, dimethylacetamide, N-methyl Amidamine-based solvents such as pyrrolidone. 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 for drying. The amount of the organic solvent in the varnish varies depending on the boiling point of the organic solvent. For example, the varnish containing 30 to 60% by mass of the organic solvent is dried at 50 to 150 ° C. for about 3 to 10 minutes to form a resin composition layer.

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

Examples of the support include films of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, and polyethylene terephthalate (hereinafter sometimes referred to simply as "PET"), polyester films such as polyethylene naphthalate, polycarbonate films, and polyimide films. It is also possible to use release paper, metal foils such as copper foil and aluminum foil. Among them, from the viewpoint of versatility, a plastic film is preferable, and a polyethylene terephthalate film is more preferable. The support and a protective film described later may be subjected to surface treatments such as an electron impact (mad) treatment and a corona treatment. In addition, a release treatment such as a silicone resin-based release agent, an alkyd resin-based release agent, or a fluororesin-based release agent may be applied.

There is no particular limitation on the thickness of the support body. When the hole is processed from the support body, even if the energy of laser irradiation is large, the resin residue is not easy to remain, and the viewpoint of suppressing the occurrence of the resin residue is preferably 10 μm or more. It is more preferably 20 μm or more, and even more preferably 30 μm or more. In addition, from the viewpoint of improving cost performance or effective hole formation from the support, it is preferably 150 μm or less, more preferably 100 μm or less, and still more preferably 50 μm or less.

On the opposite side of the support surface of the resin composition layer, the support film according to the support body may be further laminated. At this time, the adhesive film 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 being attached to the surface of the resin composition layer or to cause scratches. The film can then be rolled into a roll and stored.

(Prepreg)

In an embodiment, the sheet-like laminated material of the present invention is a prepreg. The prepreg can be produced by impregnating the resin composition of the present invention in a sheet-like reinforcing substrate by a hot-melt method or a solvent method, and heating to produce a semi-hardened material. In other words, it is possible to form a prepreg in a state where the resin composition of the present invention is impregnated into a sheet-like reinforcing substrate. The sheet-like reinforcing substrate may be, for example, glass cloth, aromatic polyamide fiber, or the like, and is often composed of fibers for prepreg. In addition, a prepreg is preferably formed on the support.

The hot-melt method does not need to dissolve the resin composition in an organic solvent, but once it is coated on a support, and then laminated to a sheet-shaped reinforcing substrate, or directly coated on a sheet-shaped reinforcement by a die coater. A method of manufacturing a prepreg, such as a substrate. In addition, the solvent method is a method of dissolving a resin in an organic solvent to prepare a resin varnish in the same manner as an adhesive film, immersing the sheet-shaped reinforcing substrate in the varnish, impregnating the sheet-shaped reinforcing substrate with the resin varnish, and then drying the resin varnish. In addition, an adhesive film can be produced by continuous thermal lamination of both sides of the sheet-like reinforcing base material under heating and pressure conditions. A support, a protective film, etc. can also be used similarly to an adhesive film.

<Multilayer printed circuit board using sheet-like laminated material>

Next, a method for manufacturing a multilayer printed wiring board using the sheet-like laminated material manufactured as described above will be described.

First, a sheet lamination material is laminated on one or both sides of a circuit board using a vacuum laminator. Examples of the substrate for the circuit substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. Circuit board means One or both sides of the substrate are formed with a patterned conductive layer (circuit). In addition, in a multilayer printed circuit board in which a conductor layer and an insulating layer are laminated on each other, one or both sides of the outermost layer of the multilayer printed circuit board becomes a conductor layer (circuit) after pattern processing, and is also included in In this circuit board. In addition, the surface of the conductor layer may be previously roughened by blackening treatment, copper etching, or the like.

When the sheet-like laminated material has a protective film, after removing the protective film, the sheet-like laminated material and the circuit board may be preheated if necessary, and the sheet-like laminated material may be laminated on the circuit board while being pressurized and heated. In a preferred embodiment, the sheet-like laminated material of the present invention is laminated on a circuit board by a vacuum layer under reduced pressure. The conditions for lamination are not particularly limited. For example, the pressing pressure (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 pressing time (lamination time) is preferably 5 to 180 seconds, and lamination is preferably performed under a reduced pressure of an air pressure of 20 mmHg (26.7 hPa) or less. The lamination method may be a batch method or a continuous method using a roll. Vacuum lamination can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, vacuum laminators made by Nichigo-Morton, vacuum pressure laminators made by Meiki Seisakusho, roll drying coaters made by Hitachi Industries, and Hitachi. AIC (stock) vacuum laminator.

After laminating the sheet-like laminated material on the circuit board, it is cooled to around room temperature. After the support is peeled off, the resin composition is thermally cured to form an insulating layer. Thereby, an insulating layer can be formed on the circuit substrate. The conditions for heat curing are suitable for the type and content of the resin components in the resin composition. When selected, it is preferably selected at 150 ° C to 220 ° C for 20 to 180 minutes, and more preferably at 160 ° C to 210 ° C for 30 to 120 minutes. After forming the insulating layer, if the support is not peeled before curing, it can be peeled at this time if necessary.

Furthermore, the sheet-shaped laminated material was laminated on one side or both sides of the circuit board using a vacuum hot press. The lamination step of heating and pressing under reduced pressure can be performed using a general vacuum hot press. For example, a metal plate such as a heated SUS plate is pressed from the support layer side. The pressure condition is such that the degree of pressure reduction is usually 1 × 10 ^-2 MPa or less, and 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 resin bleeding. For example, the pressurization in the first stage is performed at a temperature of 70 to 150 ° C and a pressure of 1 to 15 kgf / cm ² , and the pressurization in the second stage is at a temperature of 150 to 200 ° C and a pressure of 1 to 40 kgf / cm A range of ² is preferred. The duration of each stage is preferably 30 to 120 minutes. By thermally curing the resin composition layer in this manner, an insulating layer can be formed on the circuit board. Commercially available vacuum hot-pressing machines include, for example, MNPC-V-750-5-200 (manufactured by Seiki Co., Ltd.), VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.), and the like.

Next, a hole processing is performed on the insulating layer formed on the circuit substrate to form via holes and via holes. The drilling process is performed by a known method such as drilling, laser, plasma, and the like, and a combination of these methods may be used to perform the drilling process. Among them, carbon dioxide gas laser, YAG laser, and other laser drilling are the most common methods. Furthermore, the sheet-like laminated material of the present invention is laminated on a circuit board, and the resin composition layer is heated. The insulating layer is hardened to form the insulating layer formed on the circuit substrate. The through hole can be formed on the support to form a through hole to make a multilayer printed circuit board. After the hole is processed, the support is preferably peeled off. In this way, the via hole is formed by performing a hole-forming process on the support, and the occurrence of resin residue can be suppressed. In addition, in order to support the thinning of the multilayer printed circuit board, the diameter of the via hole is preferably 15 to 70 μm, more preferably 20 to 65 μm, and even more preferably 25 to 60 μm.

Secondly, the surface of the insulating layer is roughened. Dry roughening treatment includes, for example, plasma treatment, and wet roughening treatment includes, for example, swelling treatment with a swelling solution, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing solution. method. Either dry or wet roughening can be used, but wet roughening can form convex and concave anchors on the surface of the insulating layer and remove resin residues in the vias. The insulation layer is immersed in a swelling liquid at 50 to 80 ° C for 5 to 20 minutes (preferably 55 to 70 ° C, 8 to 15 minutes) by a swelling treatment using a swelling liquid. Examples of the swelling liquid include an alkaline solution and a surfactant solution, and preferably an alkaline solution. Examples of the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution. Commercially available swelling liquids include, for example, Swelling Dip Securiganth P and Swelling Dip Securiganth SBU manufactured by Atotech Japan. The roughening treatment of the oxidant is to immerse the insulating layer in the oxidant solution at 60 to 80 ° C for 10 to 30 minutes (preferably 70 to 80 ° C and 15 to 25 minutes). Examples of the oxidizing agent include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous sodium hydroxide solution, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid, and the like. In addition, the concentration of permanganate in the alkaline permanganate solution is preferably It is 5 to 10% by weight. Commercially available oxidants include, for example, Concentrate made by Atotech Japan. Compact CP, Dosing Solution Securiganth P and other alkaline permanganic acid solutions. In a neutralizing solution, the insulating layer is immersed in a neutralizing solution at 30 to 50 ° C for 3 to 10 minutes (preferably 35 to 45 ° C and 3 to 8 minutes). The neutralizing solution is preferably an acidic aqueous solution, and a commercially available product is, for example, a Reduction solution made by Atotech Japan. Securiganth P.

Next, a conductive layer is formed on the insulating layer by dry plating or wet plating. For the dry plating, conventional methods such as vapor deposition, sputtering, and ion plating can be used. Wet plating is a method of forming a conductive layer by combining electroless plating and electrolytic plating, forming a plating resist having a pattern opposite to that of a conductive layer, and forming a conductive layer only by electroless plating. For the subsequent pattern formation method, for example, a subtractive process, an additive process and the like known to those skilled in the art can be used. Repeating the above series of steps multiple times can produce a multi-stage build-up multilayer printed circuit board. The present invention can suppress the occurrence of resin residues, and thus can ensure the communication reliability between layers. Therefore, the sheet-like laminated material of the present invention is suitable for forming a build-up layer of a multilayer printed circuit board.

<Semiconductor device>

A semiconductor device can be manufactured using the multilayer printed circuit board of the present invention. At the conducting point of the multilayer printed circuit board of the present invention, a semiconductor device can be manufactured by mounting a semiconductor wafer. The so-called "conduction point" refers to "a point where an electrical signal is transmitted in a multilayer printed circuit board", and the point may be on the surface or a buried point. The semiconductor wafer is not particularly limited as long as it is an electronic circuit element using a semiconductor as a material.

The method for mounting a semiconductor wafer when manufacturing 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 no bump increase. Installation method of BBUL, installation method using anisotropic conductive film (ACF), installation method using non-conductive film (NCF), etc.

[Example]

Hereinafter, the present invention will be described in detail using examples and comparative examples, but the present invention is not limited to these examples. In the following description, "part" means "mass part".

<Measurement method. Evaluation method>

First, various measurement methods are explained. Evaluation method.

<Resin residue evaluation>

About the adhesive films obtained by each Example and each comparative example, resin smear was evaluated based on the following.

(1) Fabrication of circuit board

Laminate a copper-clad laminated board (thickness of copper foil of 18 μm, substrate thickness of 0.8 mm, and Matsushita Electric Works Co., Ltd. R5715ES) on the glass cloth substrate epoxy resin surface to form a circuit pattern by etching. Micro-etchants are used. (CZ8100 manufactured by MEC Co., Ltd.) was roughened to prepare a circuit board.

(2) Laminating the film

The adhesive films produced in the examples and comparative examples were laminated on both sides of the circuit board produced in the above-mentioned (1) using a batch-type vacuum pressure laminator MVLP-500 (trade name, manufactured by Meiki Co., Ltd.). . The lamination was performed by depressurizing for 30 seconds, the air pressure was 13 hPa or less, and then performing pressure bonding at 100 ° C, 30 seconds, and a 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 from the adhesive film after lamination, and the resin composition layer was hardened at 170 ° C for 30 minutes to form an insulating layer. Example 9 was a non-peeling PET film, and the resin composition layer was cured under a curing condition of 170 ° C. for 30 minutes to form an insulating layer.

(4) Via formation

Using a CO ₂ laser processing machine (YB-HCS03T04) made by Panasonic Welding System, the insulation layer was opened at a frequency of 1000 Hz, a punch width of 13 μs, and an impact number of 3. The via hole has a via hole diameter of 60 μm. In Example 9, the PET film was peeled thereafter.

(5) Roughening

The circuit board was immersed in a swelling liquid, that is, Swelling Dip Securiganth P of Atotech Japan (stock) at 60 ° C for 10 minutes. Then at 80 ° C, the crude solution (oxidant), that is, the Concentrate of Atotech Japan (stock). Compact P (KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) was immersed for 20 minutes. Finally, the solution was neutralized at 40 ° C, which is the Reduction Solution of Atotech Japan. Immerse in Securiganth P for 5 minutes.

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

The periphery of the bottom of the via hole was observed with a scanning electron microscope (SEM), and the maximum resin residue length from the wall surface of the bottom of the via hole was measured from the obtained image. ◎ indicates the maximum resin residue length is less than 2 μm, ◎ indicates the maximum resin residue length is 2 μm or more and less than 3.5 μm, ○ indicates 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 plated conductor layer, measurement of root mean square roughness (Rq), and evaluation of insulation reliability> (1) Bottom treatment of laminated board

A glass cloth substrate with an internal circuit formed with an epoxy-acrylic surface and a copper-clad layer Both sides of the plywood (copper foil thickness: 18 μm, copper residual rate: 60%, substrate thickness: 0.3 mm, Matsushita Electric Works Co., Ltd. R5715ES) were immersed in CZ8100 manufactured by MEC Co., Ltd. to roughen the copper surface.

(2) Laminating the film

The adhesive films produced in each of the Examples and Comparative Examples were laminated on both sides of a laminated board using a batch-type vacuum pressure laminator MVLP-500 (manufactured by Meiki Co., Ltd., trade name). The lamination was performed by depressurizing for 30 seconds, the air pressure was 13 hPa or less, and then performing pressure bonding at 100 ° C and a pressure of 0.74 MPa for 30 seconds.

(3) Hardening of the resin composition layer

From the laminated film, the PET film was peeled off, and the resin composition was cured under the curing conditions of 170 ° C. and 30 minutes.

(4) Roughening

The laminate was immersed in a swelling liquid, that is, Swelling Dip Securiganth P containing diethylene glycol monobutyl ether at 60 ° C. for 10 minutes, and then at 80 ° C. in a roughening solution, namely Atotech Concentrate of Japan (shares). Compact P (KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) was immersed for 20 minutes. Finally, the solution was neutralized at 40 ° C, which is the Reduction Solution of Atotech Japan. Immerse in Securiganth P for 5 minutes. The roughened laminate was used as Sample A.

(5) Formed by plating in a semi-additive process

In order to form a circuit on the surface of the insulating layer, the laminate is immersed in an electroless plating solution 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 was performed at 180 ° C for 60 minutes. This laminate was used as Sample B.

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

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

(7) Determination of Peel strength of plated conductor layer

A score of 10 mm in width and 100 mm in length was applied to the conductor layer of Sample B, and this end was peeled off and held by a holder (T.S.E, Auto com type testing machine AC-50C-SL). The load (kgf / cm) when pulling and peeling 35 mm in the vertical direction at a speed of 50 mm / minute was measured at room temperature.

(8) Evaluation of insulation reliability

A circular photoresist tape (ELIP MASKING N380, manufactured by Nitto Denko Corporation, Ltd.) was affixed to the conductive layer of Sample B, and immersed in an aqueous solution of ferrous chloride for 30 minutes. The conductive layer of the portion where the photoresist tape was not applied was removed, and an evaluation substrate having a circular conductive layer formed on the insulating layer was prepared. Then, a part of the insulating layer was removed to expose the copper foil at the bottom. The exposed copper foil is connected to a circular conductor layer by wiring (metal wire). The wiring of the evaluation substrate was connected to a DC power supply (TP018-3D, manufactured by Takasago Manufacturing Co., Ltd.), and a voltage of 3.3 V was supplied under conditions of 130 ° C and 85% RH for 200 hours. The resistance value was measured after 200 hours. When the resistance value was 1.0 × 10 ⁸ Ω or more, it was evaluated as “○”, and when the resistance value was 1.0 × 10 ⁷ Ω or more and less than 1.0 × 10 ⁸ Ω, it was evaluated as “△” and less than 1.0 × 10 ⁷ Ω was evaluated as “×”.

<Measurement of Dielectric Loss Tangent>

The adhesive films obtained in each example and each comparative example were thermally cured at 190 ° C for 90 minutes, and the PET film was peeled to obtain a sheet-like cured product. This hardened product was cut into a test piece having a width of 2 mm and a length of 80 mm. The cavity resonator perturbation permittivity measurement device CP521 manufactured by Kanto Electronics Application Development Co., Ltd. and Network Analyzer E8362B manufactured by Agilent Technologies Co., Ltd. were used for cavity resonance. The 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)

10 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, "828US" manufactured by Mitsubishi Chemical Corporation), biphenyl type epoxy resin (epoxy equivalent 291, manufactured by Nippon Kayaku Corporation) "NC3000H '') 20 parts in methyl ethyl 15 parts of ketone (hereinafter referred to as "MEK") and 15 parts of cyclohexanone were dissolved while heating while stirring. Then, 28 parts of an active ester compound ("HPC8000-65T" manufactured by DIC (stock), 223 equivalent of active ester, and 65% toluene solution in solid content), and a cresol resin containing triazine ("LA3018-50P" manufactured by DIC) '', Phenol equivalent 151, 2-methoxypropanol solution with 50% solid content) 7 parts, hardening accelerator (made by Guangrong Chemical Industry Co., Ltd., `` 4-dimethylaminopyridine '') 0.1 part, 140 parts of spherical silica (average particle size: 0.5 μm, amine-treated "SO-C2", manufactured by admatechs, carbon content per unit weight: 0.18%), phenoxy resin (YL7553BH30, solid content: 30 mass) 1: 1 solution of MEK and cyclohexanone, weight average molecular weight 40000), 7 parts of blue pigment (manufactured by Daiichi Seika Co., Ltd., cyanine blue4920), 0.04 parts of yellow pigment (manufactured by BASF (stock), Paliotol Yellow K1841) 0.07 part, 0.08 part of red pigment (Clariant Japan Co., Ltd., PV Fast Pink E01), uniformly dispersed with a high-speed rotary mixer to produce a resin varnish. Next, this resin varnish was applied to a polyethylene terephthalate film (thickness: 38 μm, hereinafter referred to as “PET film”), and a die coater was applied so that the thickness of the dried resin was 40 μm at 80 to 120 ° C. Drying (average 100 ° C.) for 6 minutes to obtain a sheet-like adhesive film.

(Example 2)

Except that 0.04 parts of blue pigments, 0.07 parts of yellow pigments, and 0.08 parts of red pigments of Example 1 were changed to 0.4 parts of blue pigments, 0.66 parts of yellow pigments, and 0.84 parts of red pigments, they were produced in the same manner as in Example 1. Resin varnish. Next, an adhesive film was obtained in the same manner as in Example 1.

(Example 3)

Except that 0.04 parts of blue pigments, 0.07 parts of yellow pigments, and 0.08 parts of red pigments of Example 1 were changed to 0.9 parts of blue pigments, 1.4 parts of yellow pigments, and 1.6 parts of red pigments, resin varnishes were completely produced in the same manner as in Example 1. Next, an adhesive film was obtained in the same manner as in Example 1.

(Example 4)

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

(Example 5)

Except that 0.04 parts of blue pigments, 0.07 parts of yellow pigments, and 0.08 parts of red pigments of Example 1 were changed to 3.5 parts of rubber particles ("AC3816N" manufactured by Gantsu Kasei Co., Ltd.), a resin varnish was prepared in the same manner as in Example 1. Next, an adhesive film was obtained in the same manner as in Example 1.

(Example 6)

Except that 0.04 parts of blue pigments, 0.07 parts of yellow pigments, and 0.08 parts of red pigments of Example 1 were changed to 3.5 parts of an antioxidant ("IRGANOX 1010" manufactured by BASF), a resin varnish was prepared in the same manner as in Example 1. Next, an adhesive film was obtained in the same manner as in Example 1.

(Example 7)

Except that 0.04 parts of blue pigments, 0.07 parts of yellow pigments, and 0.08 parts of red pigments of Example 1 were changed to 3.5 parts of an infrared absorber ("IR-14" manufactured by Japan Catalyst Co., Ltd.), they were completely the same as those of Example 1. Make resin varnish. Next, an adhesive film was obtained in the same manner as in Example 1.

(Example 8)

Except changing 140 parts of the spherical silica (the average particle size is 0.5 μm, treated with amine silane “SO-C2”, manufactured by admatechs, and the carbon content per unit weight is 0.18%) into spherical silica ( A resin varnish was prepared in the same manner as in Example 2 except that the average particle diameter was 0.25 μm, and 100 parts of "SO-C1" (manufactured by Admatechs, 0.8% carbon content per unit weight) were treated with amine silane. Next, an adhesive 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)

Except that 0.04 parts of blue pigments, 0.07 parts of yellow pigments, and 0.08 parts of red pigments of Example 1 were not added, a resin varnish was completely produced in the same manner as in Example 1. Next, an adhesive film was obtained in the same manner as in Example 1.

The results are shown in Table 1.

It is known from Table 1 that the examples are of low dielectric loss tangent and excellent resin residue suppression in via holes. In addition, Examples 1 to 3 and 5 to 9 are particularly excellent in insulation reliability, and the results of Examples 3, 8, and 9 are further suppressed. On the other hand, although Comparative Example 1 had a low dielectric loss tangent, the resin residue remained.

[Industrial availability]

The present invention can provide a resin composition and lamellar laminate that can achieve a low dielectric loss tangent of a hardened material of a resin composition, and can suppress the resin residue in the via hole after the hardened material is roughened by opening processing. Materials, multilayer printed circuit boards, semiconductor devices. In addition, we can provide electrical products such as computers, mobile phones, digital cameras, and televisions, or vehicles such as motorcycles, automobiles, trams, ships, and airplanes.

Claims (17)

A resin composition comprising (A) an epoxy resin, (B) an active ester compound, (C) a residue-inhibiting component, and (D) an inorganic filler, and (C) a residue-inhibiting component selected from the group consisting of Pigments, dyes, antioxidants, and infrared absorbers in one or more groups. When the non-volatile content of the resin composition is 100% by mass, the content of the (C) residue suppression component is 0.001 to 10% by mass. The resin composition When the non-volatile content of the material is 100% by mass, the content of (D) the inorganic filler is 40% by mass or more, in which (B) the active ester compound is an active ester-based hardener containing a naphthalene structure or containing Active ester compound with phenol structure. For example, when the resin composition of the first scope of the patent application, wherein the non-volatile content in the resin composition is 100% by mass, the content of the (B) active ester compound is 1 to 30% by mass. For example, the resin composition of the first scope of the patent application, wherein the residue suppression component is one or more selected from the group consisting of a pigment, an antioxidant, and an infrared absorber. For example, the resin composition of the first patent application range, wherein the pigment is at least one selected from the group consisting of a blue pigment, a yellow pigment, a red pigment, and a green pigment. For example, the resin composition of the first patent application range, wherein the pigment is a mixed pigment obtained by mixing a blue pigment, a yellow pigment, and a red pigment. For example, the resin composition of the scope of patent application, wherein the antioxidant The agent is a hindered phenolic antioxidant. For example, the resin composition of the first patent application range, wherein the infrared absorber is a compound selected from a phthalocyanine compound, an anthraquinone compound, and a nickel complex. For example, the resin composition of item 1 of the patent application range, wherein the average particle diameter of the (D) inorganic filler is 0.01 to 5 μm. For example, if the resin composition of the first patent application range is 100% by mass of the nonvolatile component in the resin composition, the content of the (D) inorganic filler is 40 to 85% by mass. For example, the resin composition of the scope of application for patent No. 1 wherein the carbon content per unit weight of the (D) inorganic filler is 0.02 to 3%. For example, the resin composition of the first patent application range, wherein (D) the inorganic filler is silicon dioxide. For example, the resin composition of the scope of application for patent No. 1 is that the resin composition is hardened to form an insulating layer, and the surface of the insulating layer is subjected to a roughening treatment, and the root mean square (Rot Mean Square) roughness of the insulating layer is Rq The thickness is 500 nm or less, the peel strength of the conductive layer obtained by plating 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 hardened product of the resin composition is 0.05 or less. For example, the resin composition of the first patent application scope is a resin composition for an insulating layer of a multilayer printed circuit board. A sheet-like laminated material, which is characterized by containing a resin composition according to any one of claims 1 to 13 of the scope of patent application. A multilayer printed circuit board characterized by The hardened product of the resin composition according to any one of the items 1 to 13 to form an insulating layer. A semiconductor device characterized by using a multilayer printed circuit board such as the item 15 of the patent application scope. A method for manufacturing a multilayer printed circuit board, which is characterized in that a sheet-like laminated material such as the item No. 14 of the application for a patent is laminated on a circuit substrate, and the resin composition is thermally hardened to form an insulating layer. The insulating layer is formed with a through hole on the support to form a through hole.