JP2014015608A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which can prevent resin cracks regardless of a low linear thermal expansion coefficient of a hardened body of the resin composition.SOLUTION: A resin composition contains an inorganic filler, an epoxy resin and a hardener. If a nonvolatile component in the resin composition is 100 mass%, the inorganic filler is 60 mass% or more, and the folding endurance number of the hardened body of the resin composition is 10 times or more.

Description

  The present invention relates to a resin composition. Furthermore, it is related with the sheet-like laminated material, multilayer printed wiring board, and semiconductor device containing the said resin composition.

  In recent years, miniaturization and high performance of electronic devices have progressed, and in a semiconductor package substrate, a build-up layer has been formed into multiple layers, and miniaturization and high density of wiring have been demanded. Furthermore, with the widespread use of smartphones and tablet PCs, there is an increasing demand for thinning, and a thin package substrate such as a thin core material and a coreless structure is required. However, since a thin package substrate is likely to be warped, and problems are likely to occur in the mounting process, the build-up layer is required to have characteristics that reduce warpage such as a high elastic modulus and a low thermal expansion coefficient. Resin compositions containing fillers have been studied. For example, Patent Document 1 discusses the minimum melt viscosity.

JP 2012-36349 A

  However, in a resin composition containing a large amount of an inorganic filler, the cured body of the resin composition becomes brittle, and thus there is a problem that the cured body lacks resin from the end when the package substrate is handled. A new problem has occurred. Thus, as a result of intensive studies, the present inventors have found that the problem of lack of resin can be solved when the cured body after thermosetting has sufficient bending resistance.

  Therefore, the problem to be solved by the present invention is to provide a resin composition capable of preventing resin chipping even though the linear thermal expansion coefficient of the cured product of the resin composition is low.

  As a result of earnest research to solve the above problems, the present inventor is a resin composition containing an inorganic filler, an epoxy resin, and a curing agent, and the nonvolatile component in the resin composition is 100% by mass. In addition, the present invention has been completed in a resin composition in which the inorganic filler is 60% by mass or more and the number of folding resistances of the cured product of the resin composition is 10 times or more.

That is, the present invention includes the following contents.
[1] A resin composition containing an inorganic filler, an epoxy resin, and a curing agent, and when the nonvolatile component in the resin composition is 100% by mass, the inorganic filler is 60% by mass or more, A resin composition, wherein the cured product of the resin composition has a folding resistance of 10 times or more.
[2] The resin composition as described in [1] above, wherein a linear thermal expansion coefficient of the cured product of the resin composition is 25 ppm or less.
[3] The resin composition as described in [1] or [2] above, wherein the inorganic filler is 65% by mass or more.
[4] The above [1] to [3], wherein the mass ratio of the inorganic filler to the epoxy resin (inorganic filler: epoxy resin) is 1: 0.1 to 1: 0.3. The resin composition in any one of these.
[5] The resin composition as described in any one of [1] to [4] above, wherein the inorganic filler has an average particle size of 0.01 to 5 μm.
[6] The resin composition according to any one of [1] to [5], wherein the inorganic filler has an average particle size of 0.01 to 0.4 μm.
[7] The inorganic filler is an amino silane coupling agent, an epoxy silane coupling agent, a mercapto silane coupling agent, a styryl silane coupling agent, an acrylate silane coupling agent, an isocyanate silane coupling agent, [1] to [1], wherein the surface treatment is carried out with one or more surface treatment agents selected from sulfide silane coupling agents, silane coupling agents, organosilazane compounds and titanate coupling agents. 6]. The resin composition according to any one of [6].
[8] The resin composition according to any one of [1] to [7], wherein the inorganic filler has a carbon amount per unit surface area of 0.02 to 1 mg / m ² .
[9] The resin composition according to any one of [1] to [8], wherein the epoxy resin includes a liquid epoxy resin.
[10] The epoxy resin is bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, glycidyl ester type epoxy resin, anthracene type The resin composition as described in any one of [1] to [9] above, which is at least one selected from an epoxy resin and an epoxy resin having a butadiene structure.
[11] The above [1] to [10], wherein the curing agent is at least one selected from a phenolic curing agent, an active ester curing agent and a cyanate ester curing agent. Resin composition.
[12] Activity wherein the curing agent includes a biphenyl type curing agent, a naphthalene type curing agent, a phenol novolac type curing agent, a naphthylene ether type curing agent, a triazine skeleton-containing phenolic curing agent, a dicyclopentadienyl diphenol structure The resin composition as described in any one of [1] to [11] above, which is at least one selected from an ester-based curing agent and a bisphenol-type cyanate ester-based curing agent.
[13] The curing agent contains an active ester curing agent, and the resin composition has a thickness of 10 to 100 μm when thermally cured at 180 ° C. for 30 minutes, then at 150 ° C. for 30 minutes, and further at 190 ° C. for 60 minutes. When the sheet-like cured product is measured under the measurement conditions of a load of 2.5 N, a bending angle of 90 degrees, a bending radius of 1.0 mm, and a bending speed of 175 times / minute by an MIT test apparatus, the folding resistance is 100 times or more. The resin composition according to any one of [1] to [12].
[14] The amount of carbon per unit surface area of the inorganic filler is 0.2 to 1 mg / m ² , the curing agent includes an active ester curing agent, and the resin composition is heated at 180 ° C. for 30 minutes. Next, a sheet-like cured product having a thickness of 10 to 100 μm when thermally cured at 150 ° C. for 30 minutes and further at 190 ° C. for 60 minutes was subjected to a load of 2.5 N, a bending angle of 90 degrees, a bending radius of 1. The resin composition according to any one of [1] to [13], wherein the number of folding resistances is 100 times or more when measured under measurement conditions of 0 mm and a bending speed of 175 times / minute.
[15] The inorganic filler has an average particle size of 0.01 to 0.4 μm, the curing agent contains an active ester curing agent, and the resin composition is heated at 180 ° C. for 30 minutes, and then at 150 ° C. for 30 minutes. The sheet-like cured product having a thickness of 10 to 100 μm when thermally cured at 190 ° C. for 60 minutes for 1 minute, a load of 2.5 N, a bending angle of 90 degrees, a bending radius of 1.0 mm, and a bending speed of 175 by an MIT test apparatus. The resin composition according to any one of [1] to [14], wherein the folding endurance is 300 or more when measured under measurement conditions of times / minute.
[16] The resin composition as described in any one of [1] to [15] above, which is a resin composition for a buildup layer of a multilayer printed wiring board.
[17] A cured product obtained by thermosetting the resin composition according to any one of [1] to [16].
[18] The cured product according to the above [17], wherein the thickness is 10 to 100 μm.
[19] A sheet-like laminated material comprising the resin composition according to any one of [1] to [16].
[20] A multilayer printed wiring board in which a build-up layer is formed from the sheet-like laminated material according to [19].
[21] A semiconductor device using the multilayer printed wiring board according to [20].

  A resin composition containing an inorganic filler, an epoxy resin, and a curing agent, wherein the inorganic filler is 60% by mass or more when the nonvolatile component in the resin composition is 100% by mass, and the resin composition The resin composition in which the number of times of folding of the cured product is 10 times or more can prevent resin chipping even though the coefficient of linear thermal expansion is low.

<Resin composition>
The present invention is a resin composition containing an inorganic filler, an epoxy resin and a curing agent, and when the nonvolatile component in the resin composition is 100% by mass, the inorganic filler is 60% by mass or more, The resin composition has a folding number of 10 times or more of the cured body of the resin composition.

  The feature of the present invention is that the content of the inorganic filler when using a resin composition containing an inorganic filler, an epoxy resin, and a curing agent, and when the nonvolatile component in the resin composition is 100% by mass. In addition to setting it to 60 mass% or more, the number of folding times of the cured body of the resin composition is set to 10 times or more. By adopting this configuration, it is possible to exhibit the excellent performance of preventing the resin from being chipped without making the cured body brittle while reducing the linear thermal expansion coefficient of the cured body. By preventing the resin from being chipped, it is possible to improve the yield at the time of preparing the substrate and improve the handleability of the substrate. Therefore, the resin composition of the present invention is suitable as a resin composition for an insulating layer of a multilayer printed wiring board, and further suitable as a multilayer printed wiring board in which a build-up layer is formed by a cured body of the resin composition of the present invention. is there.

In the resin composition of the present invention, since the number of folding times of the cured body is 10 times or more, the cured body does not become brittle and can prevent resin chipping. Here, the number of folding resistances is a measurement condition for a sheet-like cured body having a thickness of 10 to 100 μm, with a load of 2.5 N, a bending angle of 90 degrees, a bending radius of 1.0 mm, and a bending speed of 175 times / min. It is the number of times when measured at.
The folding endurance can be adjusted by appropriately adopting various conditions that affect the folding endurance as described later. For example, using an active ester curing agent as the curing agent, using an inorganic filler having a small average particle size (for example, an average particle size of 0.01 to 0.4 μm), per unit surface area of the inorganic filler Folding resistance tends to be improved by using an inorganic filler whose affinity with the resin is improved by appropriate surface treatment such as setting the carbon amount of 0.02 to 1 mg / m ² .
In order to further prevent resin chipping, the folding endurance of the cured body is preferably 20 times or more, more preferably 30 times or more, further preferably 50 times or more, still more preferably 80 times or more, and even more preferably 100 times or more. 200 times or more is particularly preferable, and 300 times or more, 400 times or more, and 500 times or more are even more preferable. The number of folding times is preferably as many as possible, and there is no particular limitation. However, it is usually sufficient if it is 100,000 times or less, but it is 50,000 times or less, 10,000 times or less, 5000 times or less, 3000 times or less, 1500 times or less. Also good.

  Hereinafter, the details of the above-described resin composition will be described.

(A) Inorganic filler The resin composition of this invention can reduce the linear thermal expansion coefficient of a hardening body by containing an inorganic filler. Examples of the inorganic filler include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, Examples include strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Of these, silica is preferable. Further, amorphous silica, pulverized silica, fused silica, crystalline silica, synthetic silica, hollow silica, spherical silica and the like are preferred, fused silica and spherical silica are more preferred, and spherical fused silica is even more preferred. These may be used alone or in combination of two or more. Examples of commercially available spherical fused silica include “SOC2” and “SOC1” manufactured by Admatechs Co., Ltd.

  The content of the inorganic filler is at least 60% by mass or more when the nonvolatile component in the resin composition is 100% by mass. Thereby, the linear thermal expansion coefficient of the hardening body of a resin composition can be made low enough. From the viewpoint of lowering the linear thermal expansion coefficient of the cured body, when the nonvolatile component in the resin composition is 100% by mass, it is preferably 65% by mass or more, more preferably 70% by mass or more, and 72% by mass or more. More preferably, 74 mass% or more is still more preferable. On the other hand, from the viewpoint of preventing a decrease in the folding endurance of the cured product, when the nonvolatile component in the resin composition is 100% by mass, it is preferably 95% by mass or less, more preferably 90% by mass or less, 85 It is more preferably no greater than mass%, even more preferably no greater than 80 mass%, and even more preferably no greater than 77 mass%.

  Since the resin composition of the present invention contains 60% by mass or more of an inorganic filler, it is excellent in reducing the linear thermal expansion coefficient of the cured body, and the linear thermal expansion coefficient of the cured body can be 25 ppm / ° C. or less. It becomes. Here, the linear thermal expansion coefficient means an average linear thermal expansion coefficient from 25 ° C. to 150 ° C. From the viewpoint of reducing the warpage of the substrate, it is more preferably 23 ppm / ° C. or less. The lower the linear thermal expansion coefficient, the better. There is no particular lower limit, but it is generally preferably 4 ppm / ° C. or higher in terms of preventing the cured product from becoming brittle.

  In order to improve the folding resistance of the cured body and obtain the effects of the present invention, the average particle size of the inorganic filler can be adjusted. The average particle size of the inorganic filler is preferably 5 μm or less, more preferably 3 μm or less, still more preferably 1 μm or less, still more preferably 0.7 μm or less, and particularly preferably 0.4 μm or less. On the other hand, when the resin composition is a resin varnish, it is preferably 0.01 μm or more, more preferably 0.03 μm or more, from the viewpoint of preventing the viscosity of the varnish from increasing and handling properties from decreasing. 05 μm or more is more preferable, 0.07 μm or more is particularly preferable, and 0.1 μm or more is particularly preferable. The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction / scattering type particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction / scattering type particle size distribution measuring apparatus, LA-750 manufactured by Horiba Ltd. can be used.

  Inorganic fillers include amino silane coupling agents, epoxy silane coupling agents, mercapto silane coupling agents, styryl silane coupling agents, acrylate silane coupling agents, isocyanate silane coupling agents, and sulfide silane cups. Surface treatment is preferably performed with one or more surface treatment agents selected from a ring agent, a silane coupling agent, an organosilazane compound, and a titanate coupling agent. Thereby, even if the inorganic filler is contained in the resin composition in an amount of 60% by mass or more, it is possible to improve the folding resistance of the cured body and prevent resin chipping.

  Specifically, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane Aminosilane coupling agents such as N-2 (-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane, 3-glycidyloxypropyltrimethoxysilane , 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, glycidylbutyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) Epoxysilane coupling agents such as ethyltrimethoxysilane, mercaptosilanes such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 11-mercaptoundecyltrimethoxysilane Coupling agents, styrylsilane coupling agents such as p-styryltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyldimethoxysilane, 3-methacryloxypropyl Acrylate silane coupling agents such as triethoxysilane and 3-methacryloxypropyldiethoxysilane, and isocyanates such as 3-isocyanatopropyltrimethoxysilane Silane coupling agents, sulfide silane coupling agents such as bis (triethoxysilylpropyl) disulfide, bis (triethoxysilylpropyl) tetrasulfide, methyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, methacloxy Silane coupling agents such as propyltrimethoxysilane, imidazolesilane, triazinesilane, t-butyltrimethoxysilane, hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, hexa Phenyldisilazane, trisilazane, cyclotrisilazane, 2,2,4,4,6,6-hexamethylcyclotrisilazane, octamethylcyclotetrasilazane, hexabutyldisilazane, hexaoctyldisilazane, , 3-diethyltetramethyldisilazane, 1,3-di-n-octyltetramethyldisilazane, 1,3-diphenyltetramethyldisilazane, 1,3-dimethyltetraphenyldisilazane, 1,3-diethyltetramethyl Such as disilazane, 1,1,3,3-tetraphenyl-1,3-dimethyldisilazane, 1,3-dipropyltetramethyldisilazane, hexamethylcyclotrisilazane, dimethylaminotrimethylsilazane, tetramethyldisilazane, etc. Organosilazane compound, tetra-n-butyl titanate dimer, titanium-i-propoxyoctylene glycolate, tetra-n-butyl titanate, titanium octylene glycolate, diisopropoxy titanium bis (triethanolamate), dihydroxy titanium bis lactate, Jihi Roxybis (ammonium lactate) titanium, bis (dioctyl pyrophosphate) ethylene titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, tri-n-butoxy titanium monostearate, tetra-n-butyl titanate, tetra (2-ethylhexyl) titanate Tetraisopropylbis (dioctylphosphite) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, isopropyltrioctanoyl titanate, Isopropyl tricumyl phenyl titanate, isopropyl triisostearoyl titanate, isopropyl isostearoyl diacryl titanate , Titanate coupling agents such as isopropyldimethacrylisostearoyl titanate, isopropyltri (dioctylphosphate) titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropyltris (dioctylpyrophosphate) titanate, isopropyltri (N-amidoethylaminoethyl) titanate Etc. Among these, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, and organosilazane compounds are superior in terms of improving the folding resistance of the cured product and preventing resin chipping. Aminosilane coupling agents, epoxysilane coupling agents and organosilazane compounds are more preferred. Commercially available products include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ" manufactured by Shin-Etsu Chemical Co., Ltd. -31 "(hexamethyldisilazane) and the like.

  Moreover, the inorganic filler surface-treated with the surface treatment agent can measure the amount of carbon per unit surface area of the inorganic filler after being washed with a solvent (for example, methyl ethyl ketone). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent and ultrasonically cleaned at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid, the carbon amount per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, “EMIA-320V” manufactured by HORIBA, Ltd. can be used.

In order to improve the number of folding times of the cured body and obtain the effects of the present invention, the amount of carbon per unit surface area of the inorganic filler can be adjusted. Carbon content per unit surface area of the inorganic filler is preferably from 0.02 mg / ^{m 2} or more, 0.05 mg / ^{m 2} or more preferably, 0.1 mg / ^{m 2} or more is more preferred, 0.2 mg / ^{m 2} As described above, 0.3 mg / m ² or more is particularly preferable. On the other hand, the amount of carbon per unit surface area of the inorganic filler is preferably 1 mg / m ² or less in terms of preventing the melt viscosity of the resin varnish and the melt viscosity in the form of an adhesive film, and 0.8 mg / m ^2. The following is more preferable, and 0.6 mg / m ² or less is still more preferable.

(B) Epoxy resin Although it does not specifically limit as an epoxy resin used for this invention, It is preferable to contain the epoxy resin which has a 2 or more epoxy group in 1 molecule. Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthol type epoxy resin, naphthalene Type epoxy resin, naphthylene ether type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, anthracene type epoxy resin, linear aliphatic epoxy resin, butadiene structure Epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy resin, halo Emissions epoxy resins. These may be used alone or in combination of two or more.

  Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin from the viewpoints of improving heat resistance, decreasing linear thermal expansion coefficient, and improving folding resistance. It is preferable to use one or more selected from naphthylene ether type epoxy resins, glycidyl ester type epoxy resins, anthracene type epoxy resins and epoxy resins having a butadiene structure. Specifically, for example, bisphenol A type epoxy resin (“Epicoat 828EL”, “YL980” manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resin (“jER806H”, “YL983U” manufactured by Mitsubishi Chemical Corporation), Naphthalene type bifunctional epoxy resin (“HP4032”, “HP4032D”, “HP4032SS”, “EXA4032SS” manufactured by DIC Corporation), naphthalene type tetrafunctional epoxy resin (“HP4700”, “HP4710” manufactured by DIC Corporation), Naphthol type epoxy resin (“ESN-475V” manufactured by Nippon Steel Chemical Co., Ltd.), epoxy resin having butadiene structure (“PB-3600” manufactured by Daicel Chemical Industries, Ltd.), epoxy resin having biphenyl structure (Nipponization) “NC3000H”, “NC3000L”, “NC31” manufactured by Yakuhin Co., Ltd. "00", "YX4000", "YX4000H", "YX4000HK", "YL6121") manufactured by Mitsubishi Chemical Corporation, anthracene type epoxy resin ("YX8800" manufactured by Mitsubishi Chemical Corporation), naphthylene ether type epoxy resin (DIC) “EXA-7310”, “EXA-7311”, “EXA-7311L”, “EXA7311-G3”), glycidyl ester type epoxy resin (“EX711”, “EX721” manufactured by Nagase ChemteX Corp.) ("R540" manufactured by Printec Co., Ltd.). In particular, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, and biphenyl type epoxy resin are more preferable.

  Moreover, the epoxy resin contains a liquid epoxy resin, so that the number of folding times can be further improved, and resin chipping can be prevented. Furthermore, it is preferable to use a liquid epoxy resin and a solid epoxy resin in combination. The liquid epoxy resin is preferably an aromatic epoxy resin having two or more epoxy groups in one molecule and a liquid at a temperature of 20 ° C. The solid epoxy resin has three or more epoxy groups in one molecule. And an aromatic epoxy resin that is solid at a temperature of 20 ° C. is preferable. In addition, the aromatic epoxy resin as used in the field of this invention means the epoxy resin which has an aromatic ring structure in the molecule | numerator. 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) from the viewpoint of having a balance of a decrease in the linear thermal expansion coefficient of the resin composition and an improvement in the folding resistance. The epoxy resin) is preferably in the range of 1: 0.1 to 1: 2 by mass ratio, more preferably in the range of 1: 0.3 to 1: 1.8, and 1: 0.6 to 1: 1.5. The range of is more preferable.

  As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, glycidyl ester type epoxy resin, or naphthalene type epoxy resin are preferable, bisphenol A type epoxy resin, bisphenol F type epoxy resin, Or a naphthalene type epoxy resin is more preferable. You may use these 1 type or in combination of 2 or more types. As the solid epoxy resin, tetrafunctional naphthalene type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, or naphthylene. An ether type epoxy resin is preferable, and a naphthol type epoxy resin or a biphenyl type epoxy resin is more preferable. You may use these 1 type or in combination of 2 or more types.

In the resin composition of the present invention, from the viewpoint of improving the mechanical strength and water resistance of the cured product of the resin composition, when the nonvolatile component in the resin composition is 100% by mass, the content of the epoxy resin is 3 to 3. It is preferably 40% by mass, more preferably 5 to 35% by mass, and still more preferably 8 to 30% by mass.
The epoxy equivalent of the epoxy resin is preferably 100 to 500, more preferably 150 to 400, and further preferably 200 to 350. When the epoxy equivalent is in such a range, the crosslink density of the cured product becomes sufficient, and the linear thermal expansion coefficient can be lowered. The epoxy equivalent can be measured according to JIS K7236 (2001).

  In the resin composition of the present invention, the mass ratio of the inorganic filler to the epoxy resin (inorganic filler: epoxy resin) is 1: 0.1 to 1: 0.3 from the viewpoint of improving the folding resistance. It is preferable that the ratio is 1: 0.1 to 1: 0.2.

(C) Curing Agent The curing agent used in the present invention is not particularly limited, and examples thereof include phenolic curing agents, active ester curing agents, cyanate ester curing agents, benzoxazine curing agents, and linear thermal expansion. It is preferable to use one or more selected from a phenolic curing agent, an active ester curing agent and a cyanate ester curing agent, particularly from the point of providing a balance of reduction in coefficient and prevention of resin chipping. It is more preferable to use an active ester curing agent from the viewpoint that the number of times can be improved. These may be used alone or in combination of two or more.
In order to reduce the crosslink density of the cured product and improve the folding resistance, the reactive group equivalent of the curing agent is preferably 150 to 500, more preferably 200 to 400. Moreover, in order to lower the crosslinking density of the cured product and improve the folding resistance, the weight average molecular weight of the curing agent is preferably 1500 to 5000, more preferably 2000 to 4500, and further preferably 2000 to 3000. Here, the “reactive group” means a functional group capable of reacting with an epoxy group, and the reactive group equivalent means the mass of the resin containing 1 equivalent of the reactive group. Accordingly, a curing agent having a reactive group equivalent of 150 to 500 and a weight average molecular weight of 1500 to 5000 is more preferable.

  Although it does not restrict | limit especially as a phenol type hardening | curing agent, A biphenyl type hardening | curing agent, a naphthalene type hardening | curing agent, a phenol novolak type hardening | curing agent, a naphthylene ether type hardening | curing agent, and a triazine skeleton containing phenol type hardening | curing agent are preferable. Specifically, biphenyl type curing agents MEH-7700, MEH-7810, MEH-7785 (Maywa Kasei Co., Ltd.), naphthalene type curing agents NHN, CBN, GPH (Nippon Kayaku Co., Ltd.), SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (manufactured by Nippon Steel Chemical Co., Ltd.), EXB9500 (manufactured by DIC Corporation), phenol novolac type curing agent TD2090 (manufactured by DIC Corporation), Examples include naphthylene ether type curing agent EXB-6000 (manufactured by DIC Corporation). Specific examples of the triazine skeleton-containing phenolic curing agent include LA3018, LA7052, LA7054, LA1356 (manufactured by DIC Corporation) and the like. In particular, a biphenyl type curing agent, a naphthalene type curing agent, and a naphthylene ether type curing agent are more preferable from the viewpoint of improving the folding resistance.

  Active ester-based curing agents generally include compounds having two or more ester groups with high reaction activity in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxy compounds. Is preferably used. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol , Dicyclopentadienyl diphenol, phenol novolac and the like. 1 type (s) or 2 or more types can be used for an active ester type hardening | curing agent. As the active ester curing agent, an active ester compound disclosed in JP-A-2004-277460 may be used, or a commercially available one may be used. Commercially available active ester hardeners include active ester hardeners containing dicyclopentadienyl diphenol structures, active ester hardeners containing naphthalene structures, and active ester hardeners that are acetylated phenol novolacs. An active ester type curing agent that is a benzoylated product of phenol novolac is preferable, and an active ester type curing agent containing a dicyclopentadienyl diphenol structure is more preferable in that it is excellent in improving the folding resistance. Although the weight average molecular weight of an active ester type hardening | curing agent is not specifically limited, 1000-5000 are preferable and 1500-4000 are more preferable. Specifically, EXB9451, EXB9460, EXB9460S-65T, HPC8000-65T (produced by DIC Corporation, active group equivalent of about 223), an activity that is an acetylated product of phenol novolak as containing a dicyclopentadienyl diphenol structure DC808 (produced by Mitsubishi Chemical Corporation, active group equivalent of about 149) as an ester-based curing agent, YLH1026 (produced by Mitsubishi Chemical Corporation, active group equivalent of about 200) as an active ester-based curing agent that is a benzoylated phenol novolak, YLH1030 (Mitsubishi Chemical Corporation, active group equivalent of about 201), YLH1048 (Mitsubishi Chemical Corporation, active group equivalent of about 245) and the like can be mentioned. When using an active ester type curing agent, when the curing agent is 100 parts by mass, the active ester type curing agent is preferably contained in an amount of 60 parts by mass or more, more preferably 80 parts by mass or more.

  Although there is no restriction | limiting in particular as cyanate ester type hardening | curing agent, Novolac type (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester type hardening agent, dicyclopentadiene type cyanate ester type hardening agent, bisphenol type (bisphenol A type, bisphenol) Fate, bisphenol S type, etc.) cyanate ester curing agents, and prepolymers in which these are partially triazines. In particular, a bisphenol-type cyanate ester curing agent is preferable from the viewpoint of preventing resin application. Although the weight average molecular weight of a cyanate ester hardening | curing agent is not specifically limited, 500-4500 are preferable and 600-3000 are more preferable. Specific examples of the cyanate ester-based curing agent include, for example, bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate)), and 4,4′-methylenebis (2,6-dimethylphenyl cyanate). 4,4′-ethylidenediphenyl dicyanate, 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- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, bis (4-cyanatephenyl) ether, etc. Resin, phenol novolac Cresol novolac, a polyfunctional cyanate resins derived from dicyclopentadiene structure-containing phenol resin, these cyanate resins and partially triazine of prepolymer. These may be used alone or in combination of two or more. Commercially available cyanate ester resins include phenol novolac polyfunctional cyanate ester resins (Lonza Japan Co., Ltd., PT30, cyanate equivalent 124), and some or all of bisphenol A dicyanate is triazine to form trimers. And prepolymers (Lonza Japan Co., Ltd., BA230, cyanate equivalent 232), dicyclopentadiene structure-containing cyanate ester resins (Lonza Japan Co., Ltd., DT-4000, DT-7000) and the like.

  Although there is no restriction | limiting in particular as a benzoxazine type hardening | curing agent, As a specific example, Fa, Pd (made by Shikoku Kasei Co., Ltd.), HFB2006M (made by Showa Polymer Co., Ltd.), etc. are mentioned.

  The mixing ratio of the epoxy resin and the curing agent is preferably a ratio in which the number of reactive groups of the curing agent is in the range of 0.4 to 2.0 when the number of epoxy groups of the epoxy resin is 1, preferably 0.5 to 1.5. The ratio which becomes a range is more preferable, and the ratio which becomes the range of 0.6-1.0 is still more preferable. In addition, the number of epoxy groups of the epoxy resin present in the resin composition is a total value of all epoxy resins obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent, and the number of reactive groups of the curing agent is: The value obtained by dividing the solid mass of each curing agent by the reactive group equivalent is the total value for all curing agents.

  In the resin composition of the present invention, from the viewpoint of improving the folding resistance of the cured product of the resin composition, when the nonvolatile component in the resin composition is 100 mass%, the content of the curing agent is 5 to 30 mass. %, More preferably 8 to 25% by mass, and still more preferably 10 to 20% by mass.

(D) Thermoplastic resin The resin composition of this invention can improve the handleability of the hardening body of the said resin composition by containing a thermoplastic resin. The thermoplastic resin is not particularly limited, and examples thereof include phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamideimide resin, polyamide resin, polyethersulfone resin, polysulfone resin, polybutadiene resin, and ABS resin. Of these, phenoxy resin and polyvinyl acetal resin are preferable. These may be used alone or in combination of two or more. The thermoplastic resin preferably has a glass transition temperature of 80 ° C. or higher.

  The weight average molecular weight of the thermoplastic resin is preferably in the range of 5,000 to 200,000, more preferably in the range of 10,000 to 100,000, from the viewpoint of improving compatibility with the resin composition and improving handleability. Is more preferably in the range of 25000 to 60000. In addition, the weight average molecular weight in this invention is measured by the gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the weight average molecular weight by the GPC method is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L / K manufactured by Showa Denko KK as a column. -804L can be measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.

  Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, Examples thereof include those having one or more skeletons selected from a trimethylcyclohexane skeleton. In particular, a fluorene skeleton-containing phenoxy resin is preferable. Two or more phenoxy resins may be mixed and used. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. Examples of commercially available products include YL7553 (biscresol fluorenone skeleton) manufactured by Mitsubishi Chemical Corporation as a fluorene skeleton-containing phenoxy resin.

  Specific examples of the polyvinyl acetal resin include those manufactured by Denki Kagaku Kogyo Co., Ltd., electrified butyral 4000-2, 5000-A, 6000-C, 6000-EP, and Sekisui Chemical Co., Ltd., ESREC BH series, BX series, and KS. Series, BL series, BM series and the like.

  Although content of a thermoplastic resin is not specifically limited, From the point of adjustment of the melt viscosity of a sheet-like laminated material, it is 0.1-20 mass% with respect to 100 mass% of non-volatile components in a resin composition. Is preferable, and 0.1-10 mass% or less is more preferable.

(E) Hardening accelerator The resin composition of this invention can harden an epoxy resin and a hardening | curing agent efficiently by containing a hardening accelerator. Although it does not specifically limit as a hardening accelerator, An amine hardening accelerator, a guanidine hardening accelerator, an imidazole hardening accelerator, a phosphonium hardening accelerator, a metal hardening accelerator, etc. are mentioned. These may be used alone or in combination of two or more.

  The amine curing accelerator is not particularly limited, but trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl). And amine compounds such as phenol and 1,8-diazabicyclo (5,4,0) -undecene (hereinafter abbreviated as DBU). You may use these 1 type or in combination of 2 or more types.

  Although it does not specifically limit as a guanidine type hardening accelerator, Dicyandiamide, 1-methyl guanidine, 1-ethyl guanidine, 1-cyclohexyl guanidine, 1-phenyl guanidine, 1- (o-tolyl) guanidine, dimethyl guanidine , Diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl Rubiguanido, 1-(o-tolyl) biguanide, and the like. You may use these 1 type or in combination of 2 or more types.

  The imidazole curing accelerator is not particularly limited, but 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 tri Meritate 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2 '-Undecylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethyl Imidazole, 2-phenyl-4-methyl-5hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1 Dodecyl-2-methyl-3-benzyl-imidazolium chloride, 2-methyl-imidazoline, adduct of 2-phenyl-imidazo imidazole compounds such as phosphorus and imidazole compound and an epoxy resin. You may use these 1 type or in combination of 2 or more types.

  Although it does not specifically limit as a phosphonium type hardening accelerator, Triphenylphosphine, a phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4- Methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like. You may use these 1 type or in combination of 2 or more types.

  In the resin composition of the present invention, the content of the curing accelerator (excluding the metal curing accelerator) is in the range of 0.005 to 1% by mass when the nonvolatile component in the resin composition is 100% by mass. Preferably, the range of 0.01-0.5 mass% is more preferable.

  Although it does not specifically limit as a metal type hardening accelerator, The organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, tin, is mentioned. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. These may be used alone or in combination of two or more.

  In the resin composition of the present invention, the addition amount of the metal-based curing accelerator is such that the metal content based on the metal-based curing accelerator is 25 to 500 ppm when the nonvolatile component in the resin composition is 100% by mass. Is preferable, and the range of 40 to 200 ppm is more preferable.

  Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. A flame retardant may be used individually by 1 type, or may use 2 or more types together. The content of the flame retardant in the resin composition layer is not particularly limited, but is preferably 0.3% by mass to 10% by mass, and more preferably 0.5% by mass to 4% by mass.

  As the rubber particles, for example, those that do not dissolve in an organic solvent described later and are incompatible with the above-described epoxy resin, curing agent, thermoplastic resin, and the like are used. Such rubber particles are generally prepared by increasing the molecular weight of the rubber component to a level at which it does not dissolve in an organic solvent or resin and making it into particles.

  Examples of the rubber particles include core-shell type rubber particles, cross-linked acrylonitrile butadiene rubber particles, cross-linked styrene butadiene rubber particles, and acrylic rubber particles. The core-shell type rubber particles are rubber particles having a core layer and a shell layer. For example, a two-layer structure in which an outer shell layer is made of a glassy polymer and an inner core layer is made of a rubbery polymer, or Examples include a three-layer structure in which the outer shell layer is made of a glassy polymer, the intermediate layer is made of a rubbery polymer, and the core layer is made of a glassy polymer. The glassy polymer layer is made of, for example, methyl methacrylate polymer, and the rubbery polymer layer is made of, for example, butyl acrylate polymer (butyl rubber). A rubber particle may be used individually by 1 type, or may use 2 or more types together.

  The average particle size of the rubber particles is preferably in the range of 0.005 μm to 1 μm, more preferably in the range of 0.2 μm to 0.6 μm. The average particle diameter of the rubber particles can be measured using a dynamic light scattering method. For example, rubber particles are uniformly dispersed in an appropriate organic solvent by ultrasonic waves, etc., and a particle size distribution of rubber particles is created on a mass basis using a concentrated particle size analyzer (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.). And it can measure by making the median diameter into an average particle diameter. Content of the rubber particle in a thermosetting resin composition becomes like this. Preferably it is 0.3 mass%-10 mass%, More preferably, it is 0.5 mass%-3 mass%.

(Other ingredients)
In the resin composition of the present invention, other components can be blended as necessary within a range not inhibiting the effects of the present invention. Other components include vinyl benzyl compounds, acrylic compounds, maleimide compounds, thermosetting resins such as blocked isocyanate compounds, organic fillers such as silicon powder, nylon powder and fluorine powder, thickeners such as Orben and Benton, Silicone-based, fluorine-based, polymer-based antifoaming or leveling agents, imidazole-based, thiazole-based, triazole-based, silane-based coupling agents, etc., phthalocyanine blue, phthalocyanine green, iodin green, Examples thereof include colorants such as disazo yellow and carbon black.

  The resin composition of the present invention is appropriately mixed with the above components and, if necessary, kneaded or mixed by a kneading means such as a three-roll, ball mill, bead mill, or sand mill, or a stirring means such as a super mixer or a planetary mixer. Can be prepared. Further, it can be prepared as a resin varnish by further adding an organic solvent.

  The resin composition of the present invention is suitable as a resin composition for an insulating layer of a multilayer printed wiring board because it can form a cured body that prevents resin chipping despite its low coefficient of linear thermal expansion. However, in the production of multilayer printed wiring boards, resin compositions for buildup layers (resin compositions for buildup layers of multilayer printed wiring boards) and resin compositions for forming conductor layers by plating (plating) Can be more suitably used as a resin composition for a multilayer printed wiring board for forming a conductor layer.

  The resin composition of the present invention can be applied to a circuit board in a resin varnish to form a cured body, but industrially, it is generally used in the form of a sheet-like laminated material such as an adhesive film or a prepreg. preferable. The softening point of the sheet-like laminated material is preferably 40 to 150 ° C. from the viewpoint of laminating properties.

<Sheet laminated material>
(Adhesive film)
The adhesive film of the present invention is prepared by a method known to those skilled in the art, for example, by preparing a resin varnish in which a resin composition is dissolved in an organic solvent, and applying the resin varnish to a support using a die coater or the like. It can be produced by drying the organic solvent by heating or blowing hot air to form the resin composition layer.

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, and carbitols such as cellosolve and butyl carbitol. And aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Two or more organic solvents may be used in combination.

  The drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Depending on the amount of organic solvent in the varnish and the boiling point of the organic solvent, for example, a resin composition layer is formed by drying a varnish containing 30 to 60% by mass of an organic solvent at 50 to 150 ° C. for about 3 to 10 minutes. can do.

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

  Examples of the support include polyolefin films such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester films such as polyethylene naphthalate, polycarbonate films, and polyimide films. Various plastic films are listed. Moreover, you may use release foil, metal foil, such as copper foil and aluminum foil. Among these, 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 treatment such as mud treatment or corona treatment. The release treatment may be performed with a release agent such as a silicone resin release agent, an alkyd resin release agent, or a fluororesin release agent.

  Although the thickness of a support body is not specifically limited, 10-150 micrometers is preferable and 25-50 micrometers is more preferable.

  A protective film according to the support can be further laminated on the surface of the resin composition layer on which the support is not in close contact. Although the thickness of a protective film is not specifically limited, For example, it is 1-40 micrometers. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The adhesive film can also be stored in a roll.

(Prepreg)
The prepreg of the present invention can be produced by impregnating the resin composition of the present invention into a sheet-like reinforcing base material by a hot melt method or a solvent method, and heating and semi-curing it. That is, it can be set as the prepreg which will be in the state which the resin composition of this invention impregnated the sheet-like reinforcement base material. As a sheet-like reinforcement base material, what consists of a fiber currently used as prepreg fibers, such as glass cloth and an aramid fiber, can be used, for example. And what formed the prepreg on the support body is suitable.

  In the hot melt method, the resin composition is once coated on a support without being dissolved in an organic solvent, and then laminated on a sheet-like reinforcing substrate, or directly applied to a sheet-like reinforcing substrate by a die coater. This is a method for manufacturing a prepreg. In the solvent method, a resin varnish is prepared by dissolving a resin in an organic solvent in the same manner as the adhesive film, and a sheet-like reinforcing base material is immersed in the varnish, and then the resin-like varnish is impregnated into the sheet-like reinforcing base material. It is a method of drying. Alternatively, the adhesive film can be prepared by continuously laminating the adhesive film from both sides of the sheet-like reinforcing substrate under heating and pressure conditions. A support, a protective film, and the like can be used in the same manner as the adhesive film.

<Multilayer printed wiring board using sheet-like laminated material>
Next, an example of a method for producing a multilayer printed wiring board using the sheet-like laminated material produced as described above will be described.

  First, a sheet-like laminated material is laminated (laminated) on one side or both sides of a circuit board using a vacuum laminator. Examples of the substrate used for the circuit substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, a circuit board means here that the conductor layer (circuit) patterned was formed in the one or both surfaces of the above boards. Also, in a multilayer printed wiring board in which conductor layers and insulating layers are alternately laminated, one of the outermost layers of the multilayer printed wiring board is a conductor layer (circuit) in which one or both sides are patterned. It is included in the circuit board. The surface of the conductor layer may be previously roughened by blackening, copper etching, or the like.

In the above laminate, when the sheet-like laminate material has a protective film, after removing the protective film, the sheet-like laminate material and the circuit board are preheated as necessary, and the sheet-like laminate material is pressurized and Laminate to circuit board while heating. In the sheet-like laminated material of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is suitably used. Lamination conditions are not particularly limited. For example, the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., and the pressure bonding pressure (laminating pressure) is preferably 1 to 11 kgf / cm ² (9.8 × 10 ^{4 to} 107.9 × 10 ⁴ N / m ² ), the pressure bonding time (laminating time) is preferably 5 to 180 seconds, and the lamination is preferably performed under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less. The laminating method may be a batch method or a continuous method using a roll. The vacuum lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum applicator manufactured by Nichigo-Morton, a vacuum pressurizing laminator manufactured by Meiki Seisakusho, a roll dry coater manufactured by Hitachi Industries, Ltd., and Hitachi IC Corporation. Examples thereof include a vacuum laminator.

  After laminating the sheet-like laminated material on the circuit board, after cooling to near room temperature, if the support is peeled off, it is peeled off, and the resin composition is thermally cured to form a cured body. An insulating layer can be formed. The thermosetting conditions may be appropriately selected according to the type and content of the resin component in the resin composition. However, by sufficiently curing the resin composition, the linear thermal expansion coefficient of the cured product is lowered. However, in order to improve the folding endurance, it is preferable to give a heat history of 150 to 220 ° C. for 20 to 180 minutes, and a heat history of 160 to 210 ° C. for 30 to 120 minutes. More preferably. After forming the cured body, if the support is not peeled before curing, the support can be peeled off as necessary. The thickness of the cured body is preferably 10 to 100 μm, more preferably 15 to 80 μm, and still more preferably 20 to 60 μm from the viewpoint of thinning and improving folding resistance.

Moreover, a sheet-like laminated material can also be laminated | stacked on the single side | surface or both surfaces of a circuit board using a vacuum press machine. The lamination process for heating and pressurizing under reduced pressure can be performed using a general vacuum hot press machine. For example, it can be performed by pressing a metal plate such as a heated SUS plate from the support layer side. The pressing condition is that the degree of vacuum is usually 1 × 10 ⁻² MPa or less, preferably 1 × 10 ⁻³ MPa or less. Although heating and pressurization can be carried out in one step, it is preferable to carry out two or more steps, that is, a plurality of times under different conditions from the viewpoint of controlling the oozing of the resin. For example, the first stage press is performed at a temperature of 70 to 150 ° C. and the pressure is in the range of 1 to 15 kgf / cm ² , and the second stage press is performed at a temperature of 150 to 200 ° C. and the pressure is 1 to 40 kgf. / Cm ² is preferable. The time required for each stage is preferably 30 minutes to 120 minutes. Thus, a hardening body can be formed on a circuit board by thermosetting the resin composition layer. Examples of commercially available vacuum hot press machines include MNPC-V-750-5-200 (manufactured by Meiki Seisakusho Co., Ltd.), VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.), and the like.

  Next, drilling is performed on the cured body formed on the circuit board to form via holes and through holes. For example, the drilling can be performed by a known method such as drilling, laser, or plasma, or a combination of these methods if necessary, but drilling by a laser such as a carbon dioxide gas laser or a YAG laser is the most common. Is the method. If the support is not peeled before drilling, the support is peeled off here.

  Next, a roughening treatment is performed on the surface of the cured body. In the case of dry-type roughening treatment, plasma treatment and the like can be mentioned, and in the case of wet-type roughening treatment, a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid are performed in this order. It is done. The wet roughening treatment is preferable in that smear in the via hole can be removed while forming an uneven anchor on the surface of the cured body. The swelling treatment with the swelling liquid is performed by immersing the cured body in the swelling liquid at 50 to 80 ° C. for 5 to 20 minutes (preferably at 55 to 70 ° C. for 8 to 15 minutes). Examples of the swelling liquid include an alkaline solution and a surfactant solution, and an alkaline solution is preferable. Examples of the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution. Examples of commercially available swelling liquids include Swelling Dip Securiganth P (Swelling Dip Securiganth S) and Swelling Dip Securiganth SBU (ABUTEC Japan). be able to. The roughening treatment with an oxidizing agent is performed by immersing the cured body in an oxidizing agent solution at 60 to 80 ° C. for 10 to 30 minutes (preferably at 70 to 80 ° C. for 15 to 25 minutes). Examples of the oxidizing agent include alkaline permanganate solution in which potassium permanganate and sodium permanganate are dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid and the like. it can. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10% by weight. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as Concentrate Compact CP and Dosing Solution Securigans P manufactured by Atotech Japan. The neutralization treatment with the neutralizing solution is performed by immersing in a neutralizing solution at 30 to 50 ° C. for 3 to 10 minutes (preferably at 35 to 45 ° C. for 3 to 8 minutes). As the neutralizing solution, an acidic aqueous solution is preferable, and as a commercially available product, Reduction Solution / Secligant P manufactured by Atotech Japan Co., Ltd. may be mentioned.

  Next, a conductor layer is formed on the cured body by dry plating or wet plating. As the dry plating, a known method such as vapor deposition, sputtering, or ion plating can be used. Examples of wet plating include a method in which a conductive layer is formed by combining electroless plating and electrolytic plating, a method in which a plating resist having a pattern opposite to that of the conductive layer is formed, and a conductive layer is formed only by electroless plating. It is done. As a pattern formation method thereafter, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used, and the above-described series of steps is repeated a plurality of times to build with the sheet-like laminated material of the present invention. A multilayer printed wiring board having an up layer is formed. In the cured product of the resin composition of the present invention, it is possible to prevent resin chipping even though the coefficient of linear thermal expansion is low, so that it can be suitably used as a resin composition for buildup layers of multilayer printed wiring boards. .

<Semiconductor device>
A semiconductor device can be manufactured by using the multilayer printed wiring board of the present invention. A semiconductor device can be manufactured by mounting a semiconductor chip in a conductive portion of the multilayer printed wiring board of the present invention. The “conduction location” is a “location where an electrical signal is transmitted in a multilayer printed wiring board”, and the location may be a surface or an embedded location. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

  The semiconductor chip mounting method for manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps. Examples include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF).

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

<Measurement method / Evaluation method>
First, various measurement methods and evaluation methods will be described.

<Rubbing test evaluation>
(1) Underlayer treatment of inner layer circuit board Both sides of a glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, Matsushita Electric Works R5715ES) on which an inner layer circuit is formed The copper surface was roughened by dipping in CZ8100 manufactured by MEC.

(2) Lamination of adhesive film Adhesive films prepared in Examples and Comparative Examples were applied to both sides of the inner layer circuit board using a batch type vacuum pressure laminator MVLP-500 (trade name, manufactured by Meiki Seisakusho Co., Ltd.). Laminated. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

(3) Curing of resin composition The PET film was peeled from the laminated adhesive film, the resin composition was cured under curing conditions at 180 ° C for 30 minutes, and an inner layer circuit board (evaluation board A) on which a cured body was formed was obtained. Created.

(4) Roughening treatment The evaluation substrate A is immersed in a swelling dip securigant P containing diethylene glycol monobutyl ether of Atotech Japan Co., Ltd., which is a swelling liquid, at 60 ° C. for 10 minutes. Immersion in Japan's Concentrate Compact P (KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) at 80 ° C. for 20 minutes, and finally use Atotech Japan Co., Ltd. as a neutralization solution. It was immersed in thin securigant P at 40 ° C. for 5 minutes.

(5) Copper plating In order to form a conductor layer on the surface of the cured body, electroless copper plating was performed (copper thickness: about 1 μm). After heat drying at 150 ° C. for 30 minutes, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of about 25 μm. Next, annealing treatment was performed at 190 ° C. for 60 minutes.

(6) Evaluation The conductor layer on the evaluation board A is completely removed with a copper chloride etching solution, dried with a hot air knife, then made into small pieces using a router with a 40 mm square size, and rubber gloves on the four edges of the board. The finger was rubbed up and down three times, and the resin chipping of the cured body portion was evaluated.
No resin chipping: ○
Resin missing: ×

<Drop test evaluation>
(1) The above-mentioned evaluation substrate A was made into a small piece using a router in a 40 mm square size. And it dropped 3 times on the SUS301 board of thickness 1m to 1mm thickness, and the resin chip of the hardening body part was evaluated.
No resin chipping: ◎
Only the corners are slightly missing, so there is no problem in use: ○
Resin missing: ×

<Measurement of linear thermal expansion coefficient>
The adhesive films prepared in Examples and Comparative Examples were thermally cured at 180 ° C. for 30 minutes. Thereafter, it was thermally cured at 150 ° C. for 30 minutes and further at 190 ° C. for 60 minutes, and the support was peeled off to obtain a sheet-like cured body. The cured body was cut into test pieces having a width of 5 mm and a length of 15 mm, and thermomechanical analysis was performed by a tensile load method using a thermomechanical analyzer Thermo Plus TMA8310 (manufactured by Rigaku Corporation). After mounting the test piece on the apparatus, the test piece was measured twice continuously under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./min. The average linear thermal expansion coefficient (ppm / ° C.) from 25 ° C. to 150 ° C. in the second measurement was calculated.

<Example 1>
(Preparation of resin varnish)
Bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel Chemical Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169), biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd.) “NC3000H”, 10 parts of epoxy equivalent 265), 5 parts of phenoxy resin (“YL7553BH30” manufactured by Mitsubishi Chemical Corporation, MEK solution having a weight average molecular weight of 36000, solid content of 30% by mass), 2 parts of MEK, 2 parts of cyclohexanone and solvent The mixture was dissolved in 20 parts of naphtha by heating with stirring. After cooling to room temperature, a triazine skeleton-containing phenol novolak resin (hydroxyl equivalent 125, “LA7054” manufactured by DIC Corporation, weight average molecular weight 1800, nitrogen content about 12 mass%, solid content 60 mass% MEK solution ) 12 parts, naphthol type curing agent (hydroxyl equivalent 215, “SN485” manufactured by Nippon Steel Chemical Co., Ltd., MEK solution having a weight average molecular weight of 490, solid content of 60% by mass), curing accelerator (4-dimethylamino) Spherical silica (average particle size 0.25 μm, Co., Ltd.) surface-treated with 3 parts of pyridine, MEK solution having a solid content of 2% by mass, and an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) Adsorbex “SOC1” and 130 parts of carbon per unit area 0.36 mg / m ² ) are mixed and dispersed uniformly with a high-speed rotating mixer. A resin varnish was prepared.

(Preparation of adhesive film)
Next, the above resin varnish is applied on the mold release surface of ETFE-treated mold release PET (Mitsubishi Resin “Fluoroge RL50KSE”) so that the thickness of the resin composition layer after drying is 40 μm. The film was uniformly applied with a tar and dried at 80 to 110 ° C. (average 95 ° C.) for 6 minutes to prepare an adhesive film.

(Measure folding times)
The adhesive film was thermally cured at 180 ° C. for 30 minutes, further cured at 150 ° C. for 30 minutes and 190 ° C. for 60 minutes, and the support was peeled off to obtain a sheet-like cured body (thickness 40 μm). The cured body was cut into a test piece having a width of 15 mm and a length of 110 mm, and a load of 2. using a MIT test apparatus (manufactured by Toyo Seiki Seisakusho, MIT Folding Fatigue Tester “MIT-DA”). The number of folds to break of the cured body was measured under 5N, a bending angle of 90 degrees, a bending radius of 1.0 mm, and a bending speed of 175 times / min. The result was 77 times. The measurement was performed on 5 samples, and the average value of the top 3 points was calculated.

<Example 2>
5 parts of liquid naphthalene type epoxy resin (epoxy equivalent 144, DIC Corporation "HP4032SS", epoxy equivalent 144), crystalline bifunctional epoxy resin (Mitsubishi Chemical Corporation "YX4000HK", epoxy equivalent about 185) 5 parts , 10 parts of biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. “NC3000H”, epoxy equivalent 265), phenoxy resin (Mitsubishi Chemical Co., Ltd. “YL7553BH30”, MEK solution having a weight average molecular weight of 36000 and a solid content of 30% by mass ) 5 parts were heated and dissolved in 40 parts of solvent naphtha with stirring. After cooling to room temperature, 30 parts of a prepolymer of bisphenol A dicyanate ("BA230S75" manufactured by Lonza Japan Co., Ltd., a cyanate equivalent of about 232, a weight average molecular weight of less than 1000 and a non-volatile content of 75% by mass of MEK solution), 30 parts Accelerator (4-dimethylaminopyridine, MEK solution with a solid content of 2% by mass), curing accelerator (manufactured by Tokyo Chemical Industry Co., Ltd., cobalt (III) acetylacetonate, MEK solution with a solid content of 1% by mass) 3 Part, rubber particles (manufactured by Ganz Kasei Co., Ltd., Staphyloid AC3816N), flame retardant (“HCA-HQ” manufactured by Sanko Co., Ltd.), 10- (2,5-dihydroxyphenyl) -10-hydro-9- 2 parts of oxa-10-phosphaphenanthrene-10-oxide, average particle size 2 μm), surface with aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) Management by spherical silica (average particle diameter 0.25 [mu] m, (Ltd.) Admatechs Ltd. "SOC1", carbon content 0.36 mg ^/ m 2 per unit area) 160 parts, were mixed, uniformly dispersed in a high-speed rotary mixer Thus, a resin varnish was produced. Next, an adhesive film was produced in the same manner as in Example 1, and the number of folding times was measured.

<Example 3>
Bisphenol-type epoxy resin (“ZX1059” manufactured by Nippon Steel Chemical Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169), 5 parts, crystalline bifunctional epoxy resin (Mitsubishi Chemical Corporation) "YX4000HK" manufactured by Epoxy equivalent of about 185), 10 parts biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of 265), phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Corporation), weight 10 parts of MEK solution having an average molecular weight of 36000 and a solid content of 30% by mass was dissolved in 30 parts of solvent naphtha with stirring. After cooling to room temperature, 40 parts of an active ester curing agent (“HPC8000-65T” manufactured by DIC Corporation, a toluene solution having a weight average molecular weight of about 2700 and an active group equivalent of about 223 with a nonvolatile content of 65% by mass), curing Accelerator (4-dimethylaminopyridine, MEK solution having a solid content of 2% by mass), flame retardant (“HCA-HQ” manufactured by Sanko Co., Ltd., 10- (2,5-dihydroxyphenyl) -10-hydro- Spherical silica surface-treated with 2 parts of 9-oxa-10-phosphaphenanthrene-10-oxide (average particle size 2 μm) and aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) An average particle diameter of 0.25 μm, “SOC1” manufactured by Admatex Co., Ltd., 150 parts of carbon per unit area 0.35 mg / m ² ) are mixed and dispersed uniformly with a high-speed rotating mixer to obtain a resin varnish. Production It was. Next, an adhesive film was produced in the same manner as in Example 1, and the number of folding times was measured. As a result, it was 1001 times.

<Example 4>
Bisphenol-type epoxy resin (“ZX1059” manufactured by Nippon Steel Chemical Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169), 5 parts, crystalline bifunctional epoxy resin (Mitsubishi Chemical Corporation) "YX4000HK" manufactured by Epoxy equivalent of about 185), 10 parts biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of 265), phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Corporation), weight 5 parts of MEK solution having an average molecular weight of 36000 and a solid content of 30% by mass was dissolved in 30 parts of solvent naphtha with stirring. After cooling to room temperature, 40 parts of an active ester curing agent (“HPC8000-65T” manufactured by DIC Corporation, a toluene solution having a weight average molecular weight of about 2700 and an active group equivalent of about 223 with a nonvolatile content of 65% by mass), curing Accelerator (4-dimethylaminopyridine, MEK solution having a solid content of 2% by mass), flame retardant (“HCA-HQ” manufactured by Sanko Co., Ltd., 10- (2,5-dihydroxyphenyl) -10-hydro- Spherical silica surface-treated with 9 parts of 9-oxa-10-phosphaphenanthrene-10-oxide (average particle size 2 μm) and hexamethyldisilazane (“SZ-31” manufactured by Shin-Etsu Chemical Co., Ltd.) 200 parts (average particle size 0.5 μm, “SOC2” manufactured by Admatechs Co., Ltd., carbon amount 0.12 mg / m ² per unit area) are mixed and dispersed uniformly with a high-speed rotary mixer, and resin varnish Was prepared. Next, an adhesive film was produced in the same manner as in Example 1, and the number of folding times was measured.

<Comparative Example 1>
5 parts of liquid naphthalene type epoxy resin (epoxy equivalent 144, “HP4032SS” manufactured by DIC Corporation), 5 parts of crystalline bifunctional epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), biphenyl type epoxy 10 parts of resin (“NC3000H” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 265), 5 parts of phenoxy resin (“YL7553BH30” manufactured by Mitsubishi Chemical Co., Ltd., MEK solution having a weight average molecular weight of 36000 and a solid content of 30% by mass) The solution was dissolved in 40 parts of solvent naphtha with stirring. After cooling to room temperature, a phenol novolac type polyfunctional cyanate ester resin ("PT60S" manufactured by Lonza Japan Co., Ltd., weight average molecular weight 2300, cyanate equivalent of about 135, MEK solution having a nonvolatile content of 75 mass%) 17.5 Parts, curing accelerator (4-dimethylaminopyridine, MEK solution having a solid content of 2% by mass), curing accelerator (manufactured by Tokyo Chemical Industry Co., Ltd., cobalt (III) acetylacetonate, MEK having a solid content of 1% by mass) Solution) 3 parts, rubber particles (manufactured by Ganz Kasei Co., Ltd., Staphyloid AC3816N), flame retardant (“HCA-HQ” manufactured by Sanko Co., Ltd.), 10- (2,5-dihydroxyphenyl) -10-hydro -9-Oxa-10-phosphaphenanthrene-10-oxide, average particle size 2 μm, 2 parts, represented by aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) Treated spherical silica (average particle diameter 0.25 [mu] m, (Ltd.) Admatechs Ltd. "SOC1") 120 parts, were mixed, and uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish. Next, an adhesive film was prepared in the same manner as in Example 1, and the number of folding times was measured.

<Comparative example 2>
Bisphenol-type epoxy resin (“ZX1059” manufactured by Nippon Steel Chemical Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169), 5 parts, crystalline bifunctional epoxy resin (Mitsubishi Chemical Corporation) "YX4000HK" manufactured by Epoxy equivalent of about 185), 10 parts biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of 265), phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Corporation), weight 5 parts of MEK solution having an average molecular weight of 36000 and a solid content of 30% by mass was dissolved in 30 parts of solvent naphtha with stirring. After cooling to room temperature, 12 parts of an active ester curing agent (“HPC8000-65T” manufactured by DIC Corporation, toluene solution with a nonvolatile content of 65% by mass having an active group equivalent of about 223), a triazine skeleton-containing phenol novolac resin ( Hydroxyl equivalent 125, “LA7054” manufactured by DIC Corporation, 12 parts of MEK solution having a nitrogen content of about 12% by mass and a solid content of 60% by mass, a curing accelerator (4-dimethylaminopyridine, MEK having a solid content of 2% by mass) Solution) 3 parts, flame retardant (“HCA-HQ” manufactured by Sanko Co., Ltd., 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, Spherical silica (average particle size 0.5 μm, manufactured by Admatechs Co., Ltd.) “SOC2” surface-treated with 2 parts of hexamethyldisilazane (manufactured by Shin-Etsu Chemical Co., Ltd., “SZ-31”) " 160 parts) was mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish. Next, an adhesive film was produced in the same manner as in Example 1, and the number of folding times was measured.

  The results are shown in Table 1.

  From the results of Table 1, it can be seen that in the examples, resin chipping can be prevented even though the coefficient of linear thermal expansion is low. On the other hand, in the comparative example, since the number of folding times was small, resin chipping occurred.

  In the present invention, it has become possible to provide a resin composition that can prevent resin chipping even though the linear thermal expansion coefficient of the cured product of the resin composition is low. Furthermore, sheet-like laminated materials, multilayer printed wiring boards, and semiconductor devices using the same can be provided. Furthermore, electric products such as computers, mobile phones, digital cameras, and televisions, and vehicles such as motorcycles, automobiles, trains, ships, and airplanes equipped with these can be provided.

Claims (21)

A resin composition containing an inorganic filler, an epoxy resin and a curing agent,
When the nonvolatile component in the resin composition is 100% by mass, the inorganic filler is 60% by mass or more, and the number of folding times of the cured product of the resin composition is 10 times or more. Composition.   The resin composition according to claim 1, wherein the cured product of the resin composition has a linear thermal expansion coefficient of 25 ppm / ° C. or less.   The resin composition according to claim 1 or 2, wherein the inorganic filler is 65 mass% or more.   The mass ratio (inorganic filler: epoxy resin) between the inorganic filler and the epoxy resin is 1: 0.1 to 1: 0.3. Resin composition.   5. The resin composition according to claim 1, wherein the inorganic filler has an average particle size of 0.01 to 5 μm.   6. The resin composition according to claim 1, wherein the inorganic filler has an average particle size of 0.01 to 0.4 μm.   The inorganic filler is an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a styrylsilane coupling agent, an acrylatesilane coupling agent, an isocyanatesilane coupling agent, or a sulfidesilane. The surface treatment is carried out with at least one surface treatment agent selected from a coupling agent, a silane coupling agent, an organosilazane compound and a titanate coupling agent. The resin composition according to Item. The carbon amount per unit surface area of the inorganic filler, the resin composition of any one of claims 1-7, characterized in that a 0.02~1mg / m ^2.   The resin composition according to claim 1, wherein the epoxy resin contains a liquid epoxy resin.   The epoxy resin is bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, glycidyl ester type epoxy resin, anthracene type epoxy resin, and It is 1 or more types selected from the epoxy resin which has a butadiene structure, The resin composition of any one of Claims 1-9 characterized by the above-mentioned.   The resin composition according to any one of claims 1 to 10, wherein the curing agent is at least one selected from a phenolic curing agent, an active ester curing agent, and a cyanate ester curing agent. .   The curing agent is a biphenyl type curing agent, a naphthalene type curing agent, a phenol novolac type curing agent, a naphthylene ether type curing agent, a triazine skeleton-containing phenol type curing agent, or an active ester type curing containing a dicyclopentadienyl diphenol structure. The resin composition according to claim 1, wherein the resin composition is at least one selected from an agent and a bisphenol-type cyanate ester-based curing agent. The curing agent includes an active ester curing agent,
1. A sheet-like cured body having a thickness of 10 to 100 μm when the resin composition is thermally cured at 180 ° C. for 30 minutes, then at 150 ° C. for 30 minutes, and further at 190 ° C. for 60 minutes, is loaded with an MIT test apparatus. The resin according to any one of claims 1 to 12, which has a folding resistance of 100 times or more when measured under 5N, a bending angle of 90 degrees, a bending radius of 1.0 mm, and a bending speed of 175 times / minute. Composition. The amount of carbon per unit surface area of the inorganic filler is 0.2-1 mg / m ² ,
The curing agent includes an active ester curing agent,
1. A sheet-like cured body having a thickness of 10 to 100 μm when the resin composition is thermally cured at 180 ° C. for 30 minutes, then at 150 ° C. for 30 minutes, and further at 190 ° C. for 60 minutes, is loaded with an MIT test apparatus. The resin according to any one of claims 1 to 13, which has a folding resistance of 100 times or more when measured under 5N, a bending angle of 90 degrees, a bending radius of 1.0 mm, and a bending speed of 175 times / minute. Composition. The inorganic filler has an average particle size of 0.01 to 0.4 μm,
The curing agent includes an active ester curing agent,
1. A sheet-like cured body having a thickness of 10 to 100 μm when the resin composition is thermally cured at 180 ° C. for 30 minutes, then at 150 ° C. for 30 minutes, and further at 190 ° C. for 60 minutes, is loaded with an MIT test apparatus. The resin according to any one of claims 1 to 14, which has a folding resistance of 300 times or more when measured under 5N, a bending angle of 90 degrees, a bending radius of 1.0 mm, and a bending speed of 175 times / minute. Composition.   The resin composition according to claim 1, which is a resin composition for a buildup layer of a multilayer printed wiring board.   A cured product obtained by thermosetting the resin composition according to claim 1.   The cured body according to claim 17, wherein the thickness is 10 to 100 μm.   A sheet-like laminated material comprising the resin composition according to any one of claims 1 to 16.   A multilayer printed wiring board having a build-up layer formed of the sheet-like laminated material according to claim 19.   21. A semiconductor device using the multilayer printed wiring board according to claim 20.