TWI616333B - Resin sheet with support - Google Patents

Abstract

An object of the present invention is to provide a resin sheet with a support which has a dielectric positive connection and a low coefficient of thermal expansion, but which has excellent slag removal property and plating peel strength.

The solution is to use a resin sheet with a support having a support, a specific first layer formed on the support, and a specific second layer formed on the first layer. The present invention has been completed.

Description

Resin sheet with support

The present invention relates to a resin sheet with a support. Further, the present invention relates to a multilayer printed wiring board and a semiconductor device including the resin sheet with the support.

In recent years, with the miniaturization and high performance of electronic equipment, in the semiconductor package substrate, the build-up layer is multilayered, and wiring is required to be made finer and higher in density.

Various discussions have been made on this. For example, Patent Document 1 discloses a resin composition containing an epoxy resin and an active ester resin. It is described that the insulating layer formed by the composition can achieve both dielectric properties and heat resistance. However, its performance may not be met.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-235165

In the resin composition, it is preferred to blend a large amount of the active ester compound to obtain a cured product having excellent dielectric properties; and to reduce the thermal expansion rate, it is preferred to blend a large amount of the inorganic filler, but in this case, carbonic acid is used. In the formation of through-holes by gas lasers, it has been newly discovered that laser processing properties or slag removal properties are likely to deteriorate. On the other hand, as the amount of the active ester compound is reduced, the slag removal property is improved, but the dielectric positive connection is increased, and it is confirmed that the plating peeling strength after the desmear formation is likely to be lowered. problem.

The present invention has been made in view of the above-mentioned circumstances, and it is an object of the present invention to provide a resin sheet with a support which has a dielectric positive connection and a low coefficient of thermal expansion, but which has excellent slag removal property and plating peel strength.

As a result of intensive studies to solve the above problems, the present inventors have used a resin sheet with a support having a support, a specific first layer formed on the support, and a first layer formed thereon. The present invention has been completed by a specific second layer on the layer.

That is, the present invention includes the following.

[1] A resin sheet with a support comprising a support; a first layer comprising an epoxy resin, an active ester compound, and an inorganic filler formed on the support, wherein the first layer is not When the volatile component is 100% by mass, the active ester compound is 5% by mass or more; and the epoxy resin, the active ester compound, and the inorganic filler are formed on the first layer. In the second layer of the filler, when the nonvolatile component in the second layer is 100% by mass, the active ester compound is 5% by mass or less.

[2] The resin sheet according to the above [1], wherein the inorganic filler has an average particle diameter of 0.01 to 3 μm.

[3] The resin sheet with a support according to [1] or [2], wherein the content of the inorganic filler is 40 to 90% by mass.

[4] The resin sheet with a support according to any one of [1] to [3] wherein the inorganic filler is surface-treated with a surface treatment agent.

[5] The resin sheet with a support according to [4], wherein the inorganic filler has a carbon amount per unit surface area of 0.02 to 1 mg/m ² .

[6] The resin sheet with a support according to any one of [1] to [5] wherein the thickness of the second layer is 2 μm or more.

[7] The resin sheet with a support according to any one of [1] to [6] wherein the resin sheet is thermally cured to form an insulating layer having a linear thermal expansion coefficient of 25 ppm or less.

[8] The resin sheet with a support according to any one of [1], wherein the resin sheet is thermally cured to form an insulating layer, and the dielectric front of the insulating layer (measuring frequency: 5.8 GHz) is Below 0.0065.

[9] The resin sheet with a support according to any one of [1] to [8] wherein the resin sheet is thermally cured to form an insulating layer, and the arithmetic mean roughness after roughening the surface of the insulating layer (Ra) is 150 nm or less, and the root mean square roughness (Rq) is 220 nm or less.

[10] The resin sheet with a support according to any one of [1] to [9] wherein the resin sheet is thermally cured to form an insulating layer, and the insulating layer is formed. The peeling strength of the conductor layer and the insulating layer obtained by the surface roughening treatment and plating is 0.5 kgf/cm or more.

[11] The resin sheet with a support according to any one of [1] to [10], which is a resin sheet with a support for an insulating layer of a multilayer printed wiring board.

[12] The resin sheet with a support according to any one of [1] to [11], which is a resin sheet with a support for a build-up layer of a multilayer printed wiring board.

[13] A method of producing a multilayer printed wiring board, comprising: (A) laminating a resin sheet with a support according to any one of [1] to [12] on one or both sides of an inner layer circuit board; And (B) a step of thermally hardening the resin sheet with the support to form an insulating layer, (C) a step of drilling the insulating layer to form a through hole, and (D) a step of peeling the support, ( E) a method of manufacturing a multilayer printed wiring board by a step of roughening the surface of the insulating layer, and (F) a step of forming a conductor layer by plating the surface of the insulating layer after the roughening treatment, wherein the (C) pair of insulating layers In the step of performing the hole drilling to form the through hole, the top diameter (diameter) of the through hole of the insulating layer is 65 μm or less.

[14] A semiconductor device characterized by using a multilayer printed wiring board manufactured by the method according to [13].

By using a resin sheet with a support, which is characterized by having a support, a specific first layer formed on the support, and The specific second layer formed on the first layer can provide a resin sheet with a support which has a dielectric positive connection and a low coefficient of thermal expansion, but which has excellent slag removal property and plating peel strength.

[Resin sheet with support]

The resin sheet with a support according to the present invention is characterized by comprising a support, a first layer containing an epoxy resin, an active ester compound, and an inorganic filler formed on the support, and a first layer formed on the first layer. In the second layer containing the epoxy resin, the active ester compound, and the inorganic filler, when the nonvolatile content in the first layer is 100% by mass, the active ester compound is 5% by mass or more; and the second layer is not When the volatile component is 100% by mass, the active ester compound is 5% by mass or less. Further, a protective film may be provided on the exposed surface side of the second layer in order to prevent adhesion of waste or the like.

In the resin sheet with a support of the present invention, when the non-volatile content in the first layer is 100% by mass, the active ester compound is 5% by mass or more, the dielectric positive connection can be made low, and the plating peel strength can be made. good. In addition, when the nonvolatile content in the second layer is 100% by mass, the active ester compound is 5% by mass or less, the thermal expansion coefficient can be lowered, and the slag removal property in the carbonation laser processing is good. Therefore, the multilayer printed wiring board is excellent in interlayer communication and is suitable as a resin sheet for supporting the insulating layer of the multilayer printed wiring board. Further, it can be more suitably used as a resin thinner as a support for a build-up layer of a multilayer printed wiring board. A sheet or a resin sheet for supporting the support of the conductor layer by plating.

[Support]

The support of the present invention may be a plastic film or a metal foil. Specifically, as the plastic film, polyethylene terephthalate (hereinafter also referred to as "PET"), polyester such as polyethylene naphthalate, polycarbonate, and acrylic are preferable. Force, cyclic polyolefin, triacetyl cellulose, sulfurized polyether, polyether ketone, polyimine, and the like. Among them, a polyethylene terephthalate film or a polyethylene naphthalate film is preferable, and a polyethylene terephthalate film having an inexpensive price is particularly preferable. Examples of the metal foil include copper foil, aluminum foil, and the like. From the viewpoint of general use, it is preferably a plastic film. When a plastic film is used, in order to improve the peeling property, it is preferred to use a support which is subjected to mold release treatment in contact with the first layer. The release agent to be used for the release treatment is not particularly limited as long as the first layer can be peeled off from the support, and examples thereof include a oxime release agent, an alkyd resin release agent, a polyolefin resin, and a urethane resin. , fluororesin, etc. Further, a commercially available plastic film with a release layer may be used, and preferably, for example, SK-1, AL- of a PET film having a release layer containing an alkyd-based release agent as a main component. 5, AL-7 (Lintec (share) system) and so on. Further, the plastic film may be subjected to a matte treatment or a corona treatment, and a release layer may be formed on the treated surface. On the other hand, the metal foil can be used as a conductor layer by removing it with or without removing the etching solution. The thickness of the support is not particularly limited, and is preferably in the range of 10 to 150 μm, more preferably in the range of 25 to 50 μm.

In the case of a protective film, it can be used with the support Kind of plastic film. Further, the protective film may be subjected to a surface treatment such as matte treatment or corona treatment, or may be subjected to a release treatment similar to the above. The thickness of the protective film is preferably from 3 to 30 μm.

[Resin composition]

The first layer and the second layer of the present invention are resin sheets in which a resin composition is formed through a layer. The resin composition can be used without particular limitation as long as it contains an epoxy resin, an active ester compound, and an inorganic filler. Further, a thermoplastic resin, a curing accelerator, and other components may be further blended. Hereinafter, the blending component will be described.

(a) Epoxy resin

The epoxy resin used in the present invention is preferably an epoxy resin having two or more epoxy groups in one molecule, although it is not particularly limited. Specific examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, phenol novolak type epoxy resin, tert-butyl- Catechol epoxy resin, naphthol epoxy resin, naphthalene epoxy resin, naphthyl ether epoxy resin, epoxypropyl amine epoxy resin, epoxypropyl ester epoxy resin, Cresol novolak type epoxy resin, biphenyl type epoxy resin, bismuth type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic type Epoxy resin, epoxy resin containing spiro ring, 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, in view of improving heat resistance, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a naphthol type epoxy resin, a naphthalene type epoxy resin, and a biphenyl type epoxy resin are particularly preferable. The resin, the naphthyl ether type epoxy resin, the epoxy propyl ester type epoxy resin, the fluorene type epoxy resin, and the epoxy resin having a butadiene structure are preferable. Specific examples thereof include bisphenol A type epoxy resin ("Epikote 828EL" manufactured by Mitsubishi Chemical Corporation, "YL980"), and bisphenol F type epoxy resin ("JER806H" manufactured by Mitsubishi Chemical Corporation", "YL983U" "), a naphthalene type bifunctional epoxy resin ("HP4032", "HP4032D", "HP4032SS", "EXA4032SS") made of DIC), a naphthalene type 4-functional epoxy resin ("HP4700" made by DIC) "HP4710"), naphthol type epoxy resin ("ESN-475V" manufactured by Nippon Steel Chemical Co., Ltd.), and epoxy resin having a butadiene structure ("PB-3600" manufactured by Daicel Chemical Industry Co., Ltd.) Epoxy resin with a biphenyl structure ("NC3000H", "NC3000L", "NC3100", "YX4000", "YX4000H", "YX4000HK", "YL6121" made by Nippon Chemical Co., Ltd. ), 蒽-type epoxy resin ("YX8800" manufactured by Mitsubishi Chemical Corporation), and naphthyl ether epoxy resin (EXA-7310, "EXA-7311", "EXA-7311L" made by DIC) "EXA7311-G3"), epoxy acrylate type epoxy resin ("AV711" manufactured by Nagase ChemteX Co., Ltd., "EX721", "R540" manufactured by Printec).

The epoxy resin can improve the handleability of the resin sheet by containing a liquid epoxy resin. Further, it is preferred to use a liquid epoxy tree in combination Grease and solid epoxy resin. The liquid epoxy resin is preferably an aromatic epoxy resin having two or more epoxy groups in one molecule and being liquid at a temperature of 20 ° C, and preferably has a solid epoxy resin in one molecule. An aromatic 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 a liquid epoxy resin and a solid epoxy resin are used in combination as an epoxy resin, the blending ratio (liquid epoxy resin: solid epoxy) is obtained from the viewpoint of the balance of the cured physical properties of the resin composition. The resin is preferably in the range of 1:0.1 to 1:2, more preferably in the range of 1:0.3 to 1:1.8, and still more preferably in the range of 1:0.6 to 1:1.5.

The liquid epoxy resin is preferably a bisphenol A epoxy resin, a bisphenol F epoxy resin, a phenol novolak epoxy resin, a epoxy propyl ester epoxy resin, or a naphthalene epoxy resin; It is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a naphthalene type epoxy resin. These may be used alone or in combination of two or more. The solid epoxy resin is preferably a 4-functional naphthalene type epoxy resin, a cresol novolac type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol epoxy resin, a naphthol type epoxy resin, or a quinoid type. Epoxy resin, biphenyl type epoxy resin, and naphthyl ether type epoxy resin; more preferably naphthol type epoxy resin, biphenyl type epoxy resin. These may be used alone or in combination of two or more.

The content of the epoxy resin is preferably from 3 to 40% by mass, more preferably from 3 to 40% by mass, more preferably from 5 to 40% by mass in terms of the non-volatile content in the first layer, from the viewpoint of lowering the linear thermal expansion coefficient of the cured product of the resin sheet. ~30% by mass, More preferably, it is 7 to 20% by mass. The second layer is also preferably in the same range.

(b) Active ester compound

The active ester compound used in the present invention is a compound having one or more active ester groups in one molecule. The active ester compound can be reacted with an epoxy resin or the like, and is preferably a compound having two or more active ester groups in one molecule. In general, a compound having a phenol ester, a thiophenol ester, an N-hydroxylamine, or a heterocyclic hydroxy compound is preferably used, which has two or more ester groups having a high reactivity.

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. Further, it is more preferably an aromatic compound obtained by reacting a compound having at least two or more carboxylic acids in one molecule with an aromatic compound having a phenolic hydroxyl group, and having 2 in one molecule of the aromatic compound More than one active ester group aromatic compound. Further, it may be linear or multi-branched. In addition, when a compound having at least two or more carboxylic acids in one molecule is a compound containing an aliphatic chain, the compatibility with the resin composition can be increased, and if it is a compound having an aromatic ring, heat resistance can be increased. .

Specific examples of the carboxylic acid compound include benzoic acid and B. Acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like. Among them, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferred from the viewpoint of heat resistance; more preferably, isophthalic acid or terephthalic acid . Specific examples of the thiocarboxylic acid compound include thioacetic acid, thiobenzoic acid, and the like.

Specific examples of the phenol compound or the naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, and methylation. 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, phloroglucinol, benzenetriol, dicyclopentadienyl diphenol, phenol novolac Varnish, etc. Among them, in view of improving heat resistance and improving solubility, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, and children are especially used. Tea phenol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone , tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadienyl diphenol, phenol novolak lacquer; more preferably catechol, 1,5-dihydroxynaphthalene, 1,6 -dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadienyl Phenol, phenol novolac; more preferably 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxyl Benzophenone, dicyclopentadienyl diphenol, phenol novolac; Preferred is 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadienyl diphenol, phenol novolac; and more preferably 1,5-dihydroxy Naphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadienyl diphenol; particularly preferably dicyclopentadienyl diphenol. Specific examples of the thiol compound include benzenedithiol and triazinedithiol. The active ester compound may be used alone or in combination of two or more.

Specifically, it is preferably an active ester compound containing a dicyclopentadienyl diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetyl phenol aldehyde varnish, and a benzyl group containing a phenol novolak. The active ester compound of a mercapto compound is more preferably an active ester compound containing a naphthalene structure or an active ester compound containing a dicyclopentadienyl diphenol structure. Examples of the active ester compound containing a dicyclopentadienyl diphenol structure include EXB9451, EXB9460, EXB9460S, and HPC-8000-65T (manufactured by DIC); and an active ester compound containing a naphthalene structure can be cited as EXB9416. -70BK (manufactured by DIC Co., Ltd.); an active ester compound containing an acetohydrin of a phenol novolak; DC 808 (manufactured by Mitsubishi Chemical Corporation); and an active ester compound containing a benzyl sulfonate of a phenol novolak; YLH1026 (Mitsubishi Chemical Co., Ltd.) and so on.

From the viewpoint of reducing the dielectric positive connection and improving the plating peel strength, the non-volatile content in the first layer is 100 mass from the viewpoint of exhibiting sufficient peel strength even when thermally cured in the state of the support. In the case of %, the content of the active ester compound contained in the first layer is 5% by mass or more, preferably 5 to 30% by mass, more preferably 5 to 25% by mass, still more preferably 5 to 20% by mass. On the other hand, reduce the linear thermal expansion coefficient so that When the amount of the non-volatile component in the second layer is 100% by mass, the content of the active ester compound contained in the second layer is 5% by mass or less, and the amount of the non-volatile component in the second layer is preferably 5% by mass or less. It is preferably 0 to 5% by mass, more preferably 0.5 to 5% by mass, still more preferably 1 to 4% by mass.

Further, when the number of epoxy groups of the (a) epoxy resin is 1, the number of reactive groups of the (b) active ester compound is preferably 0.2 to 2, more preferably 0.3 to the viewpoint of improving the mechanical properties of the cured product. 1.5, and more preferably 0.4~1. Here, the "epoxy group number of epoxy resin" means a value obtained by dividing the solid content of each epoxy resin present in the resin composition by the value of the epoxy equivalent and then totaling the total epoxy resin. Further, the "reactive group" means a functional group reactive with an epoxy group, and the "number of reactive groups" means that the total mass of the solid component of the active ester compound present in the resin composition is divided by the value of the reactive group equivalent. The value.

(c) Inorganic filler

The inorganic filler used in the present invention may, for example, be cerium oxide, aluminum oxide, mica, mica, cerium sulphate, barium sulfate, magnesium hydroxide or titanium oxide, preferably cerium oxide or aluminum oxide. It is amorphous cerium oxide, molten cerium oxide, crystalline cerium oxide, synthetic cerium oxide, hollow cerium oxide, spherical cerium oxide, etc., especially spherical cerium oxide, molten cerium oxide. It is better. From the viewpoint of improving the filling property of the resin sheet, it is more preferable to be spherical molten cerium oxide. These may be used alone or in combination of two or more. As a commercially available spherical molten cerium oxide, "SOC2" and "SOC1" manufactured by Admatechs can be cited.

Although the average particle diameter of the inorganic filler is not particularly limited, it is preferable from the viewpoint of forming fine wiring on the insulating layer and increasing the total surface area of the inorganic filler to suppress generation of slag during the drilling process. It is 3 μm or less, more preferably 2 μm or less, still more preferably 1 μm or less, still more preferably 0.8 μm or less, and still more preferably 0.6 μm or less. On the other hand, when the resin composition is used as a varnish, it is preferably 0.01 μm or more, more preferably 0.03 μm or more, still more preferably 0.07 μm or more, from the viewpoint of increasing the viscosity of the varnish and preventing the workability from being lowered. More preferably, it is 0.1 μm or more. The average particle diameter of the above inorganic filler can be obtained by laser diffraction based on the Mie scattering theory. Determine by scattering method. Specifically, the particle size distribution of the inorganic filler can be determined on a volume basis by a laser diffraction scattering type particle size distribution measuring apparatus, and the median diameter is measured as an average particle diameter. As the measurement sample, those in which the inorganic filler is dispersed in water by ultrasonic waves can be preferably used. For the laser diffraction scattering type particle size distribution measuring apparatus, LA-950 or the like manufactured by Horiba, Ltd. can be used.

The content of the inorganic filler is not particularly limited, but when the non-volatile content in the first layer is 100% by mass, it is preferably 90% by mass or less, more preferably, from the viewpoint of preventing the flexibility of the sheet form from being lowered. It is 85 mass% or less, and more preferably 80 mass% or less. The second layer is also preferably in the same range. Further, from the viewpoint of lowering the thermal expansion coefficient of the insulating layer, increasing the total surface area of the inorganic filler, and suppressing generation of slag during the drilling process, it is easy to remove the slag during the roughening treatment, and the first layer is not When the volatile component 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 65% by mass. on. The second layer is also preferably in the same range.

In order to improve moisture resistance and to improve dispersibility, the inorganic filler is preferably a surface treatment agent. The surface treatment agent is preferably one selected from the group consisting of an epoxy decane coupling agent, an amino decane coupling agent, a mercapto decane coupling agent, a decane coupling agent, an organic decazane compound, and a titanate coupling agent. the above. Among these, an amine-based decane coupling agent is preferable because it is excellent in moisture resistance, dispersibility, and properties of a cured product. As a commercial product, "KBM403" (3-glycidoxypropyltrimethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM803" (3-mercaptopropyltrimethyl) manufactured by Shin-Etsu Chemical Co., Ltd. "Ketamine" (Ketamine) "KBE903" (3-aminopropyltriethoxydecane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyl) "Methyl methoxy decane", "KBM103" (phenyl trimethoxy decane) manufactured by Shin-Etsu Chemical Co., Ltd., and "SZ-31" (hexamethyldioxane) manufactured by Shin-Etsu Chemical Co., Ltd.

Further, the amount of carbon per unit surface area of the inorganic filler after washing with a solvent (for example, methyl ethyl ketone) can be measured by the inorganic filler surface-treated with the surface treatment agent. Specifically, a sufficient amount of MEK as a solvent was added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonically washed at 25 ° C for 5 minutes. After removing the supernatant and drying the solid component, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. For the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and still more preferably 0.2 mg/m from the viewpoint of improving the dispersibility of the inorganic filler. ² or more. On the other hand, from the viewpoint of preventing the melt viscosity of the resin varnish or the melt viscosity of the film form from increasing, it is preferably 1 mg/m ² or less, more preferably 0.8 mg/m ² or less, still more preferably 0.5 mg/ Below m ² .

(d) Thermoplastic resin

The thermoplastic resin may, for example, be a phenoxy resin, a polyvinyl acetal resin, a polyimide resin, a polyamidoximine resin, a polyether oxime resin, or a polyfluorene resin, and is preferably a phenoxy resin. Polyethylene acetal resin. The thermoplastic resin may be used alone or in combination of two or more.

The weight average molecular weight of the thermoplastic resin in terms of polystyrene is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, still more preferably in the range of 20,000 to 60,000. The weight average molecular weight in terms of polystyrene of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, in the polystyrene-equivalent weight average molecular weight of the thermoplastic resin, LC-9A/RID-6A manufactured by Shimadzu Corporation can be used as a measuring device, and Shodex K-800P/K manufactured by Showa Denko Co., Ltd. can be used. The -804L/K-804L was used as a mobile column as a mobile phase, and was measured at a column temperature of 40 ° C using a calibration curve of standard polystyrene.

The phenoxy resin preferably has a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolac skeleton, a biphenyl skeleton, an anthracene skeleton, a dicyclopentadiene skeleton, and a phenanthrene skeleton. Terpene skeleton, naphthalene bone A phenoxy resin having at least one selected from the group consisting of a framework, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resin may be used alone or in combination of two or more. Specific examples of the phenoxy resin include "1256" and "4250" (all are phenoxy resins containing a bisphenol A skeleton) and "YX8100" (a phenoxy group containing a bisphenol S skeleton) manufactured by Mitsubishi Chemical Corporation. "Base resin", "YX6954" (phenoxy resin containing bisphenol acetophenone skeleton), "YL7553" (phenoxy resin containing anthracene skeleton), "FX280" and "FX293" manufactured by Toho Chemical Co., Ltd. Mitsubishi Chemical Corporation's "YL6794", "YL7213", "YL7290" and "YL7482".

Specific examples of the polyvinyl acetal resin include an electrochemically charged Butyral 4000-2, 5000-A, 6000-C, 6000-EP, and S-LEC BH series manufactured by Sekisui Chemical Industry Co., Ltd. BX series, KS series, BL series, BM series, etc.

The content of the thermoplastic resin is preferably from 0.5 to 15% by mass based on 100% by mass of the nonvolatile component in the first layer. The second layer is also preferably in the same range.

(e) hardening accelerator

Examples of the hardening accelerator include an organic phosphine compound, an imidazole compound, an amine adduct compound, and a tertiary amine compound. When the total amount of the non-volatile components of the epoxy resin and the active ester compound is 100% by mass, the content of the curing accelerator is preferably in the range of 0.01 to 3% by mass. Hardening accelerator These may be used alone or in combination of two or more.

In the resin composition of the invention of the present invention, a curing agent such as a phenol resin, a cyanate resin or a benzoxazine resin; a flame retardant such as a phosphorus compound or a metal hydroxide; Organic fillers such as rayon powder, fluorine powder, and rubber particles; organic solvents, additives, and the like.

The resin composition of the present invention may be suitably mixed with the above components, or may be stirred by a three-roller, a ball mill, a bead mill, a sand mixer or the like, or a super mixer or a planetary mixer as needed. Means to mix or mix to make a resin varnish.

[Layer 1]

The first layer of the invention of the present invention can be produced as a resin composition layer on which a resin composition is formed on a support. The resin composition layer can be formed by, for example, preparing a resin composition containing an organic solvent, coating the resin composition on a support, and drying and heating to form a resin composition layer. The drying and heating conditions can be appropriately set in the range of 80 to 170 ° C and 1 to 60 minutes, preferably 80 to 130 ° C and 1 to 30 minutes.

In order to lower the dielectric continuity of the resin sheet and to improve the plating peel strength, the thickness of the first layer is preferably 2 μm or more, more preferably 2 to 50 μm, still more preferably 4 to 35 μm.

[Layer 2]

The second layer of the invention of the present invention can be used as a layer forming resin composition in the first It is produced by the resin composition layer on the layer. Drying conditions and the like can be appropriately set in the same manner as in the first layer.

In order to lower the thermal expansion coefficient of the resin sheet and improve the slag removal property, the thickness of the second layer is preferably 2 μm or more, more preferably 2 to 50 μm, still more preferably 4 to 35 μm.

[Manufacturing method of resin sheet with support]

Various methods can be used for the method of producing the resin sheet with the support. For example, a resin composition layer of the first layer may be formed on a support, and a resin composition may be applied thereon and dried to form a resin composition layer of the second layer. Further, in the case where the resin composition layer of the first layer is formed on the support, and the resin composition layer of the second layer is formed on the other support, the resin composition layer is borrowed. A method of bonding by lamination. The conditions for lamination by lamination are preferably a lamination temperature of 70 to 110 ° C, a lamination time of 5 to 30 seconds, and a lamination pressure of 1 to 10 kgf/cm ² . Further, the resin composition may be applied to the support, and another resin composition may be applied thereon, and then dried to form the first layer and the second layer simultaneously.

The ratio of the thickness of the first layer to the second layer can be appropriately set according to the necessary performance, and is preferably 1:9 to 9:1 and more preferably 3:7 to 7:3.

[Multilayer printed wiring board using a resin sheet with a support]

Hereinafter, the details of the resin sheet using the support of the present invention will be described in detail. An example of a method of manufacturing a layer printed wiring board.

The method for producing a multilayer printed wiring board according to the present invention may comprise (A) a step of laminating a resin sheet with a support on one side or both sides of the inner layer circuit substrate, and (B) heating the resin sheet with the support. a step of hardening to form an insulating layer, (C) a step of performing an opening process on the insulating layer to form a through hole, (D) a step of peeling off the support, and (E) a step of roughening the surface of the insulating layer, ( F) a step of forming a conductor layer by plating the surface of the insulating layer after the roughening treatment.

(A) a step of laminating a resin sheet with a support on one or both sides of the inner layer circuit board (step (A)), and using the second layer of the resin sheet with the support as the inner layer circuit substrate side, Laminated on one or both sides of the inner circuit board. The inner layer circuit substrate as used herein refers to a pattern on one or both sides of a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, or a thermosetting polyphenylene ether substrate. The processed (formed circuit) conductor layer further forms an intermediate product of the insulating layer and the conductor layer when manufacturing the multilayer printed wiring board. Further, from the viewpoint of improving the adhesion between the insulating layer and the inner layer circuit board, the surface of the conductor layer is preferably subjected to a roughening treatment in advance by a blackening treatment or the like.

In the step (A), when the resin sheet with the support has a protective film, the protective film is removed, and the resin sheet and the inner layer circuit substrate with the support are preheated as needed, and the resin sheet with the support is attached. Pressurized and heated while being pressed against the inner circuit board. The resin sheet with a support of the present invention is preferably a method in which a circuit board is laminated under reduced pressure by a vacuum lamination method. The conditions of the lamination are not particularly limited. For example, the lamination temperature (stacking temperature) is preferably 70 to 140 ° C, and the lamination 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 (stacking time) is preferably 5 to 180 seconds, and it is preferably laminated under a reduced pressure of 20 mmHg (26.7 hPa) or less. Further, the lamination method may be a batch type or a continuous type by a roll. The vacuum lamination can be carried out using a commercially available vacuum laminator. The commercially available vacuum laminating machine may, for example, be a vacuum applicator manufactured by Nichigo-Morton Co., Ltd., a vacuum pressurizing laminator manufactured by Nihon Seiki Co., Ltd., or a roll dryer made by Hitachi Industries. An applicator, a vacuum laminator made of Hitachi AIC (share), and the like.

(B) a step of thermally curing a resin sheet with a support to form an insulating layer (step (B)), which can be thermally cured by laminating a resin sheet with a support to the inner layer circuit substrate An insulating layer (hardened material) is formed on the inner layer circuit substrate. The conditions of the heat curing may be appropriately selected depending on the type and content of the resin component in the resin composition, and are preferably from 150 ° C to 220 ° C, from 20 minutes to 180 minutes, more preferably from 160 ° C to 210 ° C, 30. ~120 points range selection. Further, by thermally peeling without peeling off the support, it is possible to prevent foreign matter such as waste or dust from adhering during heat hardening.

The resin sheet is thermally cured to form an insulating layer, and the linear thermal expansion coefficient of the insulating layer is preferably 25 ppm or less, more preferably 20 ppm or less. The lower limit is not particularly limited and is generally 4 ppm. Thereby, deformation of the buildup layer and the wiring can be prevented, and a multilayer printed wiring board having high reliability can be obtained.

Resin the resin sheet to form an insulating layer, the insulating layer The dielectric positive connection (measured cycle number 5.8 GHz) is preferably 0.0065 or less, more preferably 0.006 or less. The lower limit is not particularly limited and is generally 0.001. Thereby, a multilayer printed wiring board having less electrical signal loss can be obtained.

(C) In the step of performing the hole processing on the insulating layer to form the through hole (step (C)), the insulating layer is subjected to a hole drilling process to form a through hole. The drilling process can be carried out by a known method such as a drill, a laser, a plasma, or the like, and the methods are combined as needed, and it is preferably a laser drilling process such as a carbon dioxide laser or a YAG laser. More preferably, it is a carbon dioxide laser from the viewpoint of generality.

When a through hole is formed by a carbon dioxide laser, the number of shots varies depending on the depth and aperture of the through hole to be formed, and is usually selected between 1 and 5 shots. In order to improve the processing speed of the through hole and improve the productivity of the multilayer printed wiring board, it is preferable that the number of shots is small, and the number of shots is preferably from 1 to 3. Furthermore, when processing with a plurality of emissions, it may be a burst mode of continuous emission or a cyclic mode of complex emission with temporal intervals.

The pulse width of the carbon dioxide laser is not particularly limited and can be selected from a wide range of short pulses of a moderate range of 28 μsec to 4 μsec. From the viewpoint of efficiency, it is more preferably from 10 μsec to 26 μsec.

In the resin sheet with a support of the present invention, it is preferable to adjust the laser energy to 0.1 to 3 W, preferably from the viewpoint of good mold removal property. The system is adjusted to 0.3~2W.

In the resin sheet with a support of the present invention, the slag removal property is improved, so that even if the multilayer printed wiring board is thinned, even if it is insulated The top diameter (diameter) of the through hole of the layer is small, and good hole drilling can also be performed. Specifically, in the step (C), the top diameter (diameter) of the through hole of the insulating layer is preferably 65 μm or less, more preferably 60 μm or less, still more preferably 55 μm or less. On the other hand, in order to prevent the roughening treatment in the through hole from being difficult, the top diameter (diameter) of the through hole is preferably 15 μm or more.

(D) In the step of peeling off the support (step (D)), the support is peeled off. When the substrate is a plastic film, the peeling of the substrate can be performed by mechanical removal by a manual or automatic peeling device. Further, when the substrate is a metal foil, the metal foil can be dissolved and removed by an etching solution or the like to remove the metal foil. Further, the step (D) may be carried out before the step (C) or after the step (C), and it is preferably carried out before the step (D) from the viewpoint of improving the mold removal property. step.

(E) In the step of roughening the surface of the insulating layer (step (E)), after the support is peeled off, the surface of the insulating layer is roughened. In the dry roughening treatment, a plasma treatment or the like may be mentioned, and in the wet roughening treatment, a method of sequentially performing a swelling treatment of a swelling liquid, a roughening treatment of an oxidizing agent, and a neutralization treatment of a neutralizing liquid may be mentioned. It is preferable to use a wet roughening treatment from the viewpoint of forming a concave and convex anchor groove on the surface of the insulating layer while removing the dross in the through hole.

The swelling treatment of the swelling liquid is carried out by immersing the insulating layer 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 solution may, for example, be an alkali solution or a surfactant solution, and is preferably an alkali solution, and examples of the alkali solution include a sodium hydroxide solution and a potassium hydroxide solution. Commercially available swelling liquids include, for example, Atotech Japan Swelling Dip Securiganth P, Swelling Dip Securiganth SBU, etc.

The roughening treatment of the oxidizing agent is carried out by immersing the insulating layer in an 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 may, for example, be 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, nitric acid or the like. Further, in the alkaline permanganic acid solution, the concentration of the permanganate is preferably 5 to 10% by weight. The commercially available oxidizing agent may, for example, be an alkaline permanganic acid solution such as Concentrate Compact CP or Dosing Solution P manufactured by Atotech Japan Co., Ltd.

The neutralization treatment of the neutralization solution is carried out by immersing in the neutralization solution at 30 to 50 ° C for 3 to 10 minutes (preferably 35 to 45 ° C, 3 to 8 minutes). The neutralizing liquid is preferably an acidic aqueous solution, and a commercially available product is a Reduction Solution Securiganth P manufactured by Atotech Japan Co., Ltd.

The resin sheet is thermally cured to form an insulating layer, and the surface roughness of the surface of the insulating layer after roughening treatment is preferably 150 nm or less, and more preferably 100 nm or less in order to promote formation of fine wiring. The lower limit of the arithmetic mean roughness (Ra) is not limited, and is generally 10 nm or more. The root mean square roughness (Rq) is preferably 220 nm or less, more preferably 200 nm or less, still more preferably 150 nm or less, still more preferably 100 nm or less. The lower limit of the root mean square roughness (Rq) is not limited, and is generally 20 nm or more. Further, the root mean square roughness (Rq) reflects the state of the surface of the insulating layer. Therefore, by grasping Rq, it was confirmed that a denser and smoother insulating layer surface was formed.

(F) In the step of forming a conductor layer by plating the surface of the insulating layer after the roughening treatment ((F step)), a conductor layer may be formed on the surface of the insulating layer. The method of forming the plating includes forming a conductor layer on the insulating layer by dry plating or wet plating. Dry plating can be carried out by a known method such as vapor deposition, sputtering, or ion plating. The wet plating may be a method of forming a conductor layer by combining electroless plating and electrolytic plating after the roughening treatment; forming a plating resist having a pattern opposite to that of the conductor layer, and forming the conductor layer only by electroless plating. Method and so on. As a method of forming the pattern later, for example, a subtractive method, a semi-additive method, or the like which is well known to those skilled in the art can be used.

The resin sheet is thermally cured to form an insulating layer, and the surface of the insulating layer is subjected to a roughening treatment, and then the peeling strength of the conductor layer and the insulating layer obtained by plating is preferably 0.5 kgf/cm or more. The upper limit is not particularly limited and is generally 1.2 kgf/cm.

By repeating the above-described series of steps plural times, it becomes a multilayer printed wiring board in which a plurality of layers are laminated. In the present invention, since the dielectric positive connection and the linear thermal expansion coefficient are low, the slag removal property and the plating peeling strength are excellent, and therefore it can be suitably used as a resin sheet for a build-up support for a build-up of a multilayer printed wiring board.

<semiconductor device>

A semiconductor device can be manufactured by using a multilayer printed wiring board manufactured by the method of the present invention. A semiconductor device can be manufactured by mounting a semiconductor wafer on a conductive portion of the multilayer printed wiring board of the present invention. "Connecting Department "Bit" means "the part where the electrical signal is transmitted in the multilayer printed wiring board", and the location may be either a surface or a buried portion. Further, the semiconductor wafer is not particularly limited as long as it is an electrical 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 function effectively, and specifically, a wire bonding method, a flip chip mounting method, and a bump-free layering ( BBUL) mounting method, mounting method of anisotropic conductive film (ACF), mounting method of non-conductive film (NCF), and the like.

[Examples]

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

First, the determination method of physical property evaluation in this specification is explained. evaluation method.

<Arithmetic mean roughness (Ra value), root mean square thickness (Rq value), and preparation of sample for measurement of peel strength> (1) Base processing of the inner layer circuit substrate

The glass cloth substrate epoxy resin double-sided copper-clad laminate (the thickness of the copper foil is 18 μm, the substrate thickness is 0.3 mm, and the R5715ES made by Matsushita Electric Co., Ltd.) having the inner layer circuit is etched by the CZ8100 manufactured by MEC (stock). 1um, roughening of the copper surface.

(2) Lamination of resin sheets with support

The resin sheet with the support prepared in the examples and the comparative examples was laminated on both sides of the inner layer circuit board using a batch vacuum press laminator MVLP-500 (trade name, manufactured by a famous machine). The lamination was performed under reduced pressure for 30 seconds to be 13 hPa or less, and then press-bonded at 30 seconds, 100 ° C, and pressure of 0.74 MPa.

(3) Hardening of resin composition

The laminated film was laminated at 80 ° C for 30 minutes, and then the resin composition was cured at 170 ° C for 30 minutes to form an insulating layer.

(4) Through hole formation

Using a CO ₂ laser processing machine (LC-2E21B/1C) manufactured by Hitachi Via Mechanics Co., Ltd., with a mask diameter of 1.60 mm, a focus offset value of 0.050, a pulse width of 25 μs, a power of 0.66 W, a diameter of 13, and a number of shots of 2. In the condition of the burst mode, the insulating layer is opened to form a via hole having a top diameter (diameter) of 50 μm in the surface of the insulating layer. Thereafter, the PET film was peeled off.

(5) roughening treatment

An inner layer circuit board having an insulating layer formed thereon, which is immersed in a swelling liquid of Atotech Japan (sand) containing diethylene glycol monobutyl ether at 60 ° C Swelling Dip Securiganth P (glycol ether, aqueous solution of sodium hydroxide) for 10 minutes, followed by Concentrate CompactP (KMnO4: 60 g/L, NaOH: 40 g/L of Atotech Japan) as a roughening solution at 80 °C The aqueous solution was immersed for 20 minutes, and finally immersed in Atotech Japan's Reduction Solution Securiganth P (aqueous solution of sulfuric acid) as a neutralizing solution at 40 ° C for 5 minutes, and then dried at 80 ° C for 30 minutes. This substrate was used as the evaluation substrate A.

(6) Plating with semi-additive method

The evaluation substrate A was immersed in a solution for electroless plating containing PdCl ₂ at 40 ° C for 5 minutes, and then immersed in an electroless copper plating solution at 25 ° C for 20 minutes. After annealing at 150 ° C for 30 minutes and annealing treatment, a resist was formed, and after etching to form a pattern, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 30 μm. Next, annealing treatment was performed at 200 ° C for 60 minutes. This substrate was used as the evaluation substrate B.

<Arithmetic mean roughness (Ra value), root mean square thickness (Rq value) measurement and evaluation>

The substrate A was evaluated, and a Ra value was obtained by using a non-contact surface roughness meter (WYKO NT3300, manufactured by Veeco Instruments Co., Ltd.) in a VSI contact mode and a 50-fold lens with a measurement range of 121 μm × 92 μm. Rq value. The average value of 10 points was randomly selected and determined. The evaluation system is as follows.

○: Ra value is 150 nm or less

×: Ra value is larger than 150 nm

○: Rq value is 220 nm or less

×: Rq value is larger than 220 nm

<Measurement and evaluation of tear strength (peel strength) of the plated conductor layer>

A slit having a width of 10 mm and a length of 100 mm was cut out from the conductor layer of the evaluation substrate B, and one end thereof was peeled off, and clamped by a jig (TSE Co., Ltd., Auto Com type tester AC-50C-SL), and measured at room temperature. The load (kgf/cm) when peeling 35 mm in the vertical direction at a speed of 50 mm/min. The evaluation system is as follows.

○: Peel strength is 0.5 kgf/cm or more

×: peeling strength is less than 0.5 kgf/cm

<Evaluation of the removal of the slag at the bottom of the through hole>

The periphery of the bottom of the through hole was observed by a scanning electron microscope (SEM), and the maximum slag length of the wall surface at the bottom of the through hole was measured from the obtained image. The evaluation system is as follows.

○: The maximum slag length is less than 3μm

×: The maximum slag length is 3 μm or more

<Measurement and evaluation of linear thermal expansion coefficient>

The resin sheets of the support obtained in the examples and the comparative examples were heated at 200 ° C for 90 minutes to be thermally cured, and a sheet-like cured product was obtained by peeling off the PET film. The cured product is cut into a width of about 5 mm and a length of about A 15 mm test piece was subjected to thermomechanical analysis by a tensile weighting method using a thermomechanical analysis device Thermo Plus TMA8310 (manufactured by Rigaku Co., Ltd.). After the test piece was placed in the above apparatus, the test piece was continuously measured twice under the measurement conditions of a load of 1 g and a temperature increase rate of 5 ° C /min. The average linear thermal expansion coefficient (ppm) from 25 ° C to 150 ° C in the second measurement was calculated. The evaluation system is as follows.

○: The average linear thermal expansion coefficient is less than 20 ppm

△: The average linear thermal expansion coefficient is 20 ppm or more and 25 ppm or less.

×: The average linear thermal expansion coefficient is larger than 25 ppm.

<Measurement and evaluation of dielectric positive connection>

The resin sheets of the support obtained in the examples and the comparative examples were thermally cured at 200 ° C for 90 minutes, and the support was peeled off to obtain a flaky cured product. The cured product was cut out to have a length of 80 mm and a width of 2 mm as an evaluation sample. For this evaluation sample, the dielectric positive connection was measured by a cavity resonance perturbation method using a cavity resonance perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. Two test pieces were measured, and the average value was calculated. The evaluation system is as follows.

○: The dielectric connection is below 0.0065

×: The dielectric connection is larger than 0.0065

<Modulation of Resin Varnish 1>

Bisphenol type epoxy resin (ZX1059 made by Nippon Steel Chemical Co., Ltd., 1:1 mixture of bisphenol A type and bisphenol F type), 5 parts of crystalline 2-functional epoxy resin (Mitsubishi Chemical ( 10 parts of "YX4000HK", epoxy equivalent: 185), 10 parts of biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd.), and phenoxy resin ("LM7553BH30" manufactured by Mitsubishi Chemical Corporation) 10 parts of a MEK solution having a solid content of 30% by mass, stirred in 30 parts of a solvent petroleum brain and dissolved by heating. After cooling to room temperature, 40 parts of an active ester compound ("HPC8000-65T" manufactured by DIC Co., Ltd., a toluene solution having a non-volatile content of about 223 as a non-volatile component of 223), and a hardening accelerator (4-two) were mixed. 7 parts of methylaminopyridine, a solid content of 2% by mass of MEK solution), a flame retardant ("HCA-HQ" manufactured by Sanguang Co., Ltd., 10-(2,5-dihydroxyphenyl)-10-hydrogen- 9-oxa-10-phosphaphenanthrene-10-oxide, average particle size 2 μm) 2 parts, phenylamino decane-based coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573") 160 parts of cerium oxide (average particle diameter: 0.5 μm, "SOC2" manufactured by Admatechs, and carbon content per unit area of 0.39 mg/m ² ) were uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish 1. The active ester compound was 12% by mass.

<Modulation of Resin Varnish 2>

Bisphenol type epoxy resin (ZX1059 made by Nippon Steel Chemical Co., Ltd., 1:1 mixture of bisphenol A type and bisphenol F type), 5 parts of crystalline 2-functional epoxy resin (Mitsubishi Chemical ( 10 parts of "YX4000HK", epoxy equivalent: 185), 10 parts of biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd.), and phenoxy resin ("LM7553BH30" manufactured by Mitsubishi Chemical Corporation) 10 parts of a MEK solution having a solid content of 30% by mass, stirred in 30 parts of a solvent petroleum brain and dissolved by heating. After cooling to room temperature, 20 parts of an active ester compound ("HPC 8000-65T" manufactured by DIC Co., Ltd., a toluene solution having a non-volatile content of about 223 as a non-volatile component of 223), and a naphthol-based curing agent (hydroxyl group) were mixed. 12 parts of MEK solution with 60% solid content of solid 215, SN-485, and a hardening accelerator (4-dimethylaminopyridine, 2% by mass of MEK solution) 4 parts, flame retardant ("HCO-HQ", 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide 2 parts of an average particle diameter of 2 μm, and a spherical cerium oxide surface-treated with a phenylamino decane-based coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573") (average particle diameter: 0.5 μm, manufactured by Admatechs) "SOC2" and 150 parts of carbon per unit area of 0.39 mg/m ² ) were uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish 2 . The active ester compound was 6.5% by mass.

<Modulation of Resin Varnish 3>

Bisphenol type epoxy resin (ZX1059 made by Nippon Steel Chemical Co., Ltd., 1:1 mixture of bisphenol A type and bisphenol F type), 5 parts of crystalline 2-functional epoxy resin (Mitsubishi Chemical ( 10 parts of "YX4000HK", epoxy equivalent: 185), 10 parts of biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd.), and phenoxy resin ("LM7553BH30" manufactured by Mitsubishi Chemical Corporation) 10 parts of a MEK solution having a solid content of 30% by mass, stirred in 30 parts of a solvent petroleum brain and dissolved by heating. After cooling to room temperature, 10 parts of an active ester compound ("HPC8000-65T" manufactured by DIC Co., Ltd., a toluene solution having a non-volatile content of about 223 as a non-volatile component of 223), and a phenol-based hardening containing triazine were mixed. 10 parts of a MEK solution containing 60% solid content of a hydroxyl group equivalent of 146, DIC ("LA-1356"), and a hardening accelerator (4-dimethylaminopyridine, a solid content of 2% by mass of MEK solution) 3 parts, flame retardant (Sanka (HQ-HQ), 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide 2 parts of an average particle diameter of 2 μm, and a spherical cerium oxide surface-treated with a phenylamino decane-based coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573") (average particle diameter: 0.5 μm, manufactured by Admatechs) "SOC2", a carbon content of 0.39 mg/m ² per unit area, 140 parts, was uniformly dispersed by a high-speed rotary mixer to prepare a resin varnish 3. The active ester compound was 3.6% by mass.

<Example 1> (Production of Resin Sheet 1 with Support)

The resin varnish 1 was applied to a release surface of a release PET (Fluoroju RL50KSE, manufactured by Mitsubishi Resin Co., Ltd., thickness: 50 μm) which was subjected to ETFE treatment, and the thickness of the resin composition layer after drying was 15 μm. , dried at 100 ° C for 1 minute. Further, the resin varnish 3 was applied onto the resin composition layer by a die coater, and the total thickness of the dried resin composition layer was 30 μm, and dried at 80 to 120 ° C (average 100 ° C) for 4 minutes on the resin surface. The smooth surface side of a polypropylene-coated film ("ALPHANE MA-411" manufactured by Oji Paper Co., Ltd.) having a thickness of 15 μm is attached. A resin sheet with a support formed by releasing the PET/resin composition layer 1 / the resin composition layer 3 / the coating film.

<Example 2> (Production of Resin Sheet 2 with Support)

In the same manner as in the first embodiment, a resin sheet with a support of the release PET/resin composition layer 2/resin composition layer 3/coated film was obtained.

<Comparative Example 1> (Production of Resin Sheet 3 with Support)

In addition to the release of PET, the resin varnish 1 was applied by a die coater to a thickness of 30 μm after drying the resin composition layer, and dried at 80 to 120 ° C (average 100 ° C) for 5 minutes. In the same manner, a resin sheet with a support of a release PET/resin composition layer 1 / a coating film was obtained.

<Comparative Example 2> (Production of Resin Sheet 4 with Support)

The resin varnish 2 was applied to a release-coated PET by a die coater, and the thickness of the resin composition layer after drying was 30 μm, and dried at 80 to 120 ° C (average 100 ° C) for 5 minutes. In the same manner, a resin sheet with a support of the release PET/resin composition layer 2/coated film was obtained.

<Comparative Example 3> (Production of Resin Sheet 5 with Support)

The resin varnish 3 was applied to the release-coated PET by a die coater, and the thickness of the resin composition layer after drying was 30 μm, and dried at 80 to 120 ° C (average 100 ° C) for 5 minutes. In the same manner, a resin sheet with a support of the release PET/resin composition layer 3/coated film was obtained.

The evaluation results are shown in Table 1.

As is apparent from the results of Table 1, the resin sheets of the support of Examples 1 to 2 exhibited excellent characteristics. On the other hand, in Comparative Examples 1 and 2, the slag removal property was poor. In Comparative Example 3, the surface roughness was large, the peel strength was also low, and the dielectric positive connection was also increased.

[Industrial availability]

In the present invention, a resin sheet with a dielectric support and a linear thermal expansion coefficient which is low in binder removal property and excellent in plating peel strength can be provided. Further, a multilayer printed wiring board or a semiconductor device using the same can be provided. Further, electronic products such as computers, mobile phones, digital cameras, televisions, and the like, or vehicles such as locomotives, automobiles, electric cars, ships, and aircraft may be provided.

Claims (14)

A resin sheet with a support comprising: a support; a first layer comprising an epoxy resin, an active ester compound, and an inorganic filler formed on the support, wherein the non-volatile component in the first layer When the amount is 100% by mass, the active ester compound is 5% by mass or more; and the second layer containing the epoxy resin, the active ester compound, and the inorganic filler formed on the first layer, wherein the second layer is non-volatile When the component is 100% by mass, the active ester compound is 5% by mass or less. The resin sheet of the support of claim 1, wherein the inorganic filler has an average particle diameter of 0.01 to 3 μm. The resin sheet of the support of claim 1, wherein the content of the inorganic filler is 40 to 90% by mass. A resin sheet according to claim 1, wherein the inorganic filler is surface-treated with a surface treatment agent. The resin sheet of the support of claim 4, wherein the amount of carbon per unit surface area of the inorganic filler is 0.02 to 1 mg/m ² . The resin sheet of the support of claim 1, wherein the thickness of the second layer is 2 μm or more. The resin sheet of the support of claim 1, wherein the resin sheet is thermally cured to form an insulating layer having a linear thermal expansion coefficient of 25 ppm or less. The resin sheet according to claim 1, wherein the resin sheet is thermally cured to form an insulating layer, and the dielectric layer of the insulating layer (measuring frequency: 5.8 GHz) is 0.0065 or less. The resin sheet of the support of claim 1, wherein the resin sheet is thermally cured to form an insulating layer, and the arithmetic mean roughness (Ra) after the surface of the insulating layer is roughened is 150 nm or less, and the root mean square is coarse. The degree (Rq) is 220 nm or less. The resin sheet of the support of claim 1, wherein the resin sheet is thermally cured to form an insulating layer, and the surface of the insulating layer is roughened and plated to obtain a peeling strength of the conductor layer and the insulating layer of 0.5. Kgf/cm or more. The resin sheet of the support according to any one of claims 1 to 10, which is a resin sheet with a support for the insulating layer of the multilayer printed wiring board. The resin sheet with a support according to any one of claims 1 to 10, which is a resin sheet with a support for a build-up layer of a multilayer printed wiring board. A method of manufacturing a multilayer printed wiring board, comprising: (A) a step of laminating a resin sheet of the support according to any one of claims 1 to 10 on one or both sides of an inner layer circuit substrate, ( B) a step of thermally hardening the resin sheet with the support to form an insulating layer, (C) a step of drilling the insulating layer to form a through hole, (D) a step of peeling the support, and (E) insulating a method of producing a multilayer printed wiring board by the step of roughening the surface of the layer, and (F) the step of forming a conductor layer by plating the surface of the insulating layer after the roughening treatment, wherein the (C) is performed on the insulating layer In the step of performing the hole forming to form the through hole, the top diameter (diameter) of the through hole of the insulating layer is 65 μm or less. A semiconductor device characterized by using a multilayer printed wiring board manufactured by the method of claim 13.