JP5864299B2 - Resin composition - Google Patents

Description

  The present invention relates to a resin composition. The present invention also relates to an insulating resin sheet such as an adhesive film and prepreg obtained from the resin composition, and a multilayer printed wiring board and a semiconductor device in which an insulating layer is formed from a cured product of the resin composition.

  In recent years, there has been a demand for downsizing electronic devices, increasing signal speed, and increasing wiring density. In order to satisfy this requirement, the build-up substrate is required to have a low dielectric constant, a low dielectric loss tangent, a low thermal expansion coefficient, and a multilayer structure. In order to satisfy these requirements, Patent Document 1 discusses a reduction in dielectric loss tangent and a reduction in thermal expansion coefficient by blending hollow particles with a low dielectric loss tangent resin. However, since the amount of hollow particles is small, it cannot be said that the dielectric loss tangent and the coefficient of thermal expansion of the resin composition are sufficiently small. In addition, there are problems that the hollow silica having a broad particle size distribution is purposely classified and the hollow structure of the hollow particles is easily damaged. Further, the cured product of the resin composition generally has a glass transition point between 150 ° C. and 250 ° C., and it is difficult to reduce the thermal expansion coefficient at 150 ° C. or higher.

JP 2008-31409 A

  The problem to be solved by the present invention is a resin composition having a sufficiently small dielectric constant, dielectric loss tangent, and thermal expansion coefficient, in particular, a dielectric constant and dielectric loss tangent that are sufficiently small and having a thermal expansion of 150 ° C. or higher. It is to provide a resin composition having a sufficiently low rate.

  The present inventors diligently studied to solve the above-mentioned problems. By using hollow silica and fused silica in combination, the resin composition is suppressed while suppressing an increase in the melt viscosity of the resin composition by blending the hollow silica. The present inventors have found that the dielectric constant, dielectric loss tangent and thermal expansion coefficient of the cured product can be made sufficiently small, and have further advanced research based on the knowledge, thereby completing the present invention.

That is, the present invention includes the following contents.
[1] A resin composition containing (A) an epoxy resin, (B) a curing agent, (C) hollow silica, and (D) fused silica, wherein the nonvolatile component in the resin composition is 100% by mass. In this case, the resin composition is characterized in that the content of (C) hollow silica is 5 to 22% by mass, and the total content of (C) hollow silica and (D) fused silica is 50 to 70% by mass. object.
[2] The above-mentioned [1], wherein the blending ratio of (C) hollow silica to (D) fused silica is “(C) hollow silica / (D) fused silica” in a mass ratio of 0.070 or more and 0.67 or less. The resin composition as described.
[3] The resin composition as described in [1] or [2] above, wherein (C) hollow silica is produced using a sol-gel method.
[4] Any of the above [1] to [3], wherein (C) the porosity (%) of the hollow silica is 15% or more and 90% or less, and the average particle diameter is 0.1 μm or more and 5 μm or less. The resin composition as described in any one.
[5] The resin composition according to any one of [1] to [4], wherein the coefficient of variation of the particle size of the hollow silica is 50% or less.
[6] The ratio of the average thickness of silica skeleton to the average particle diameter of hollow silica (average thickness of silica skeleton of hollow silica / average particle diameter of hollow silica) of 0.02 or more and 0.3 or less, [1 ] The resin composition as described in any one of [5].
[7] The resin composition according to any one of [1] to [6], wherein the hollow silica has a BET specific surface area of 0.5 m ² / g or more and 30 m ² / g or less.
[8] The dielectric loss tangent (measurement frequency 5.8 GHz) of the cured product of the resin composition is 0.0005 to 0.007, and the average thermal expansion coefficient from 150 ° C. to 250 ° C. is 1 ppm to 80 ppm. The resin composition according to any one of [1] to [7], which is characterized in that
[9] When the average thermal expansion coefficient from 25 ° C. to 150 ° C. of the cured product of the resin composition is α1, and the average thermal expansion coefficient from 150 ° C. to 250 ° C. is α2, the value of α2 / α1 The resin composition as described in any one of [1] to [8] above, wherein 1.0 is from 3.3 to 3.3.
[10] An adhesive film in which the resin composition according to any one of [1] to [9] is layered on a support.
[11] A prepreg in which the resin composition according to any one of [1] to [9] is impregnated in a sheet-like reinforcing base material.
[12] A multilayer printed wiring board in which an insulating layer is formed from a cured product of the resin composition according to any one of [1] to [9].
[13] A semiconductor device using the multilayer printed wiring board according to [12].

  A resin composition containing an epoxy resin, a curing agent, hollow silica, and fused silica can provide a resin composition having a sufficiently low dielectric constant and dielectric loss tangent and a sufficiently low thermal expansion coefficient of 150 ° C. or higher. Became.

  The present invention is a resin composition comprising (A) an epoxy resin, (B) a curing agent, (C) hollow silica, and (D) fused silica.

  In this specification, a dielectric constant, a dielectric loss tangent, and a thermal expansion coefficient mean the dielectric constant, dielectric loss tangent, and thermal expansion coefficient of the hardened | cured material of a resin composition, respectively.

<(A) Epoxy resin>
The (A) epoxy resin used in the present invention is not particularly limited. For example, 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, alkylphenol novolac type epoxy resin, biphenyl type epoxy resin, aralkyl type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, adamantane type epoxy resin Epoxidized products of condensates of phenols and aromatic aldehydes having phenolic hydroxyl groups, biphenyl aralkyl type epoxy resins, fluorene type epoxy resins Xanthene-type epoxy resins, and triglycidyl isocyanurate. These may be used alone or in combination of two or more.

  In particular, when the resin composition is used in the form of an adhesive film, a bisphenol A type epoxy resin and a butadiene structure are provided from the viewpoint that an adhesive film exhibiting sufficient flexibility and excellent handleability can be formed. An epoxy resin having bisphenol F, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin, a biphenyl type epoxy resin, and a naphthalene type epoxy resin are preferred. In addition, an epoxy equivalent (g / eq) is the gram number of resin containing 1 g equivalent epoxy group prescribed | regulated to JISK7236.

  Examples of commercially available epoxy resins include “jER828EL” (liquid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “HP4032”, “HP4032D”, and “HP4032SS” (naphthalene type bifunctional) manufactured by DIC Corporation. Epoxy resin), DIC Corporation "HP4700" (naphthalene type tetrafunctional epoxy resin), Toto Kasei Co., Ltd. "ESN-475V", "ESN-185V" (naphthol type epoxy resin), Daicel Chemical Industries, Ltd. ) "PB-3600" (epoxy resin having a butadiene structure), Nippon Kayaku Co., Ltd. "NC3000H", "NC3100", "NC3000L", "NC3000" (biphenyl type epoxy resin), Mitsubishi Chemical Corporation "YX4000" (biphenyl type epoxy resin) made by Toto Kasei Co., Ltd. 3207 "(biphenyl type epoxy resin), Mitsubishi Chemical Co., Ltd." YX8800 "(anthracene skeleton-containing epoxy resin) and the like.

  The content of the (A) epoxy resin in the resin composition is not particularly limited, but it is 5% by mass with respect to 100% by mass of the nonvolatile component in the resin composition from the viewpoint of reducing the coefficient of thermal expansion. The above is preferable, 8 mass% or more is more preferable, 11 mass% or more is further preferable, and 14 mass% or more is still more preferable. On the other hand, from the viewpoint of preventing the cured product from becoming brittle, it is preferably 50% by mass or less, more preferably 45% by mass or less, and further preferably 40% by mass or less, with respect to 100% by mass of the nonvolatile component in the resin composition. Preferably, 35 mass% or less is still more preferable.

<(B) Curing agent>
The (B) curing agent used in the present invention is not particularly limited. For example, a cyanate ester curing agent, an active ester curing agent, a phenol curing agent, a benzoxazine curing agent, and an acid anhydride curing. An agent etc. can be mentioned. These can use 1 type (s) or 2 or more types. Among these, a cyanate ester curing agent and an active ester curing agent are preferable from the viewpoint of improving dielectric properties.

  The cyanate ester curing agent is not particularly limited, but is a novolak type (phenol novolac type, alkylphenol novolak type, etc.) cyanate ester type curing agent, bisphenol type (bisphenol A type, bisphenol F type, bisphenol S type, etc.) cyanate ester. Examples thereof include a system curing agent, a dicyclopentadiene-type cyanate ester-based curing agent, and a prepolymer in which a part thereof is triazine. Specifically, the phenol novolac type polyfunctional cyanate ester curing agent represented by the following formula (1) (Lonza Japan Co., Ltd., “PT30”, “PT60”), represented by the following formula (2): Prepolymer in which a part or all of bisphenol A dicyanate is triazine-modified into a trimer (Lonza Japan Co., Ltd., “BA230”), dicyclopentadiene type cyanate ester-based curing represented by the following formula (3) Agents (Lonza Japan Co., Ltd., “DT-4000”, “DT-7000”) and the like. The cyanate ester curing agent may be used alone or in combination of two or more.

(In the formula, n represents an arbitrary number (preferably 0 to 20) as an average value.)

(In formula, n represents the number of 0-5 as an average value.)

  As the active ester curing agent, a compound 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 compound esters is preferable. . 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 heat resistance and the like, those obtained from a carboxylic acid compound and a hydroxy compound are more preferred, and those obtained from a carboxylic acid compound and a phenol compound or a naphthol compound are more preferred. 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.

  Especially, the active ester type hardening | curing agent containing a dicyclopentadienyl diphenol structure is still more preferable, and the thing of the following Formula (4) is mentioned more specifically.

(In the formula, R is a phenyl group or a naphthyl group, k represents 0 or 1, and n is 0.05 to 2.5 on the average of repeating units.)

  From the viewpoint of reducing the dielectric loss tangent of the resin composition and improving the heat resistance, R is preferably a naphthyl group. Further, from the same viewpoint, k is preferably 0, and n is preferably 0.25 to 1.5.

  The production method of the active ester curing agent is not particularly limited and can be produced by a known method. Among them, as a condensation reaction between a carboxylic acid compound and a hydroxy compound, (a) a carboxylic acid compound or a halide thereof, (b ) Hydroxy compound, (c) aromatic monohydroxy compound, (b) phenolic hydroxyl group of 0.05 to 0.75 mol per mol of carboxyl group or acid halide group, (c) Is preferably obtained by reacting at a ratio of 0.25 to 0.95 mol. Moreover, the active ester type hardening | curing agent currently disclosed by Unexamined-Japanese-Patent No. 2004-277460 may be used, and a commercially available active ester type hardening | curing agent can also be used. Commercially available active ester curing agents include, for example, EXB-9451, EXB-9460, HP-8000 (manufactured by DIC Corporation), and acetyl of phenol novolac as those containing a dicyclopentadienyl diphenol structure. Examples of the compound include DC808 (manufactured by Mitsubishi Chemical Corporation), and examples of the benzoylated phenol novolac include YLH1026 (manufactured by Mitsubishi Chemical Corporation). The active ester curing agent may be used alone or in combination of two or more.

  The phenolic curing agent is not particularly limited, and examples thereof include a phenol novolak resin, a triazine skeleton-containing phenol novolak resin, a naphthol novolak resin, a naphthol aralkyl type resin, a triazine skeleton-containing naphthol resin, and a biphenyl aralkyl type phenol resin. For example, “MEH-7700”, “MEH-7810”, “MEH-7785” (manufactured by Meiwa Kasei Co., Ltd.), “NHN”, “CBN”, “GPH” (Nippon Kayaku) As a naphthol aralkyl type resin, “SN170”, “SN180”, “SN190”, “SN475”, “SN485”, “SN495”, “SN375”, “SN395” (manufactured by Tohto Kasei Co., Ltd.) ), “TD2090” (manufactured by DIC Corporation) as a phenol novolac resin, and “LA3018”, “LA7052”, “LA7054”, “LA1356” (manufactured by DIC Corporation) as triazine skeleton-containing phenol novolac resins. . A phenol type hardening | curing agent may use together 1 type (s) or 2 or more types.

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

  The content of the curing agent (B) in the resin composition is not particularly limited, but from the viewpoint of reducing the dielectric loss tangent of the resin composition, with respect to 100% by mass of the nonvolatile component in the resin composition, 5 mass% or more is preferable, 8 mass% or more is more preferable, 11 mass% or more is further more preferable, and 14 mass% or more is still more preferable. On the other hand, from the viewpoint of preventing the cured product from becoming brittle, it is preferably 50% by mass or less, more preferably 45% by mass or less, and further preferably 40% by mass or less, with respect to 100% by mass of the nonvolatile component in the resin composition. Preferably, 35 mass% or less is still more preferable.

  When (A) the number of epoxy groups of the epoxy resin is 1, (B) the number of reactive groups of the curing agent is preferably 0.2 to 2, more preferably 0.3 to 1.5, and still more preferably 0.4 to 1. preferable. When the ratio of the number of reactive groups of the curing agent to the number of epoxy groups of the epoxy resin is outside the above range, the mechanical properties of the resin composition tend to be inferior. Here, “the number of epoxy groups of the epoxy resin” is a value obtained by totaling the values obtained by dividing the solid mass of each epoxy resin present in the resin composition by the epoxy equivalent for all epoxy resins. In addition, “reactive group” means a functional group capable of reacting with an epoxy group, and “the number of reactive groups of the curing agent” refers to the reaction of the solid content mass of each curing agent present in the resin composition. The value obtained by dividing the value by the group equivalent is the sum of all the curing agents.

<(C) Hollow silica>
The hollow silica (C) in the present invention is not particularly limited, and various hollow silicas can be used. The hollow silica is preferably produced by a sol-gel method from the viewpoint of obtaining a product having a uniform particle size distribution. The sol-gel method refers to a method of obtaining ceramic particles by using metal alkoxide or metal halide as a raw material and performing hydrolysis and polycondensation in a solution. For example, according to the following steps (a) to (d), the sol-gel method is efficiently hollow Silica is obtained.
Step (a): Step of preparing an aqueous solution containing a substance capable of forming a hollow part and a basic compound Step (b): Add alkoxysilane to the aqueous solution and stir at 0 ° C. to 100 ° C. to obtain silica particles. Step of precipitation Step (c): Step of removing a substance capable of forming a hollow part from the silica particles obtained in step (b) to obtain a hollow silica precursor Step (d): Obtained by step (c) Step of calcining the hollow silica precursor at a temperature exceeding 900 ° C. to obtain hollow silica Hereinafter, details of each step will be described.

Step (a)
Examples of the substance capable of forming the hollow part include fine particles such as metals, metal oxides, metal salts and polymers insoluble in the aqueous solution, and oil droplets of hydrophobic organic compounds. From the viewpoint of avoiding contamination by metal impurities, polymer fine particles and hydrophobic organic compound oil droplets are preferred. Specifically, examples of the polymer fine particles include a cationic acrylic polymer, and examples of the hydrophobic organic compound include hexane. In addition to acting as an alkali catalyst in step (b), the basic compound acts to prevent aggregation of the produced hollow silica particles. Examples of basic compounds include alkali metal hydroxides, amines, ammonia, quaternary ammonium compounds, and the like. From the viewpoint of avoiding contamination with metal impurities, amines, ammonia and quaternary ammonium compounds are preferable, and from the viewpoint of obtaining uniform particles, ammonia and quaternary ammonium are more preferable. Specific examples include tetramethylammonium hydroxide.
The solvent of the aqueous solution may be an aqueous medium such as distilled water, ion-exchanged water, or ultrapure water alone, but is water-soluble organic such as alcohol such as methanol, ethanol, ethylene glycol, propylene glycol, and glycerin, and ketone such as acetone and methyl ethyl ketone. You may mix with a solvent.

Step (b)
The alkoxysilane is hydrolyzed by the catalytic action of the basic compound and forms a silica component of the silica powder through a sol state. Any alkoxysilane may be used as long as it can generate a silanol compound by hydrolysis, and examples thereof include compounds represented by the following general formulas (5) to (9).

SiY ₄ (5)
R ³ SiY ₃ (6)
R ³ ₂ SiY ₂ (7)
R ³ ₃ SiY (8)
Y ₃ Si—R ⁴ —SiY ₃ (9)

(In the formula, each R ³ independently represents an organic group in which a carbon atom is directly bonded to a silicon atom, R ⁴ represents a hydrocarbon group or a phenylene group having 1 to 4 carbon atoms, and Y represents Each independently represents a monovalent hydrolyzable group that becomes a hydroxy group by hydrolysis.)
From the viewpoint of obtaining uniform silica particles, the alkoxysilane is preferably represented by the general formula (5), and among them, tetraethoxysilane and tetramethoxysilane, in which Y is a methoxy group or an ethoxy group, are particularly preferable.

Step (c)
Examples of the method for removing the substance capable of forming the hollow part used in the step (a) include an extraction treatment with an acid such as hydrochloric acid, an organic solvent such as toluene, or a decomposition treatment such as heating and UV irradiation. From the viewpoint of completely removing a substance capable of forming the hollow portion, a decomposition treatment by heating at a temperature equal to or higher than the decomposition temperature of the substance is preferable. As heating temperature, 500-700 degreeC is preferable.

Step (d)
By firing at a temperature exceeding 900 ° C., the silica skeleton is densified, and a hollow silica having a BET specific surface area of 30 m ² / g or less can be obtained. The firing temperature is preferably 900 ° C. or higher, more preferably 930 ° C. or higher, and still more preferably 960 ° C. or higher. When performing the decomposition process by heating in the step (c), the decomposition may be performed continuously without being distinguished from the step (d).

  As an example of the hollow silica obtained by the sol-gel method, for example, hollow silica obtained by Production Example 1 described in JP-A No. 2011-21068 can be mentioned.

  In the present invention, the average particle diameter of hollow silica refers to an average particle diameter based on volume. (C) The average particle diameter of the hollow silica is not particularly limited, but is preferably 5 μm or less, more preferably 4 μm or less, still more preferably 3 μm or less, and further preferably 2 μm or less from the viewpoint of reducing the dielectric loss tangent and dielectric constant. Is more preferably 1.5 μm or less, particularly preferably 1 μm or less. On the other hand, from the viewpoint of improving dispersibility in the resin composition, 0.1 μm or more is preferable, 0.2 μm or more is more preferable, 0.3 μm or more is further preferable, 0.4 μm or more is even more preferable, and 0 More preferably, it is 5 μm or more. The variation coefficient of the particle diameter of the hollow silica particles is preferably 50% or less, more preferably 45% or less, still more preferably 40% or less, and particularly preferably 35% or less, from the viewpoint of preventing damage to the hollow structure. It is desirable that the particles are composed of particles having very uniform particle diameters.

The average particle diameter and the coefficient of variation of the particle diameter of the hollow silica can be measured by directly measuring a particle image taken with a scanning electron microscope. Specifically, observation with a scanning electron microscope is performed at a magnification including about 50 to 500 particles, and the diameter is measured and the volume is calculated for all particles in the field of view, assuming that the hollow silica particles are spheres. This operation is performed in a plurality of fields of view, and the variation coefficient of the average particle diameter and the particle diameter can be calculated by the following formula.
Mean particle size _{(nm) = Σ (φ n} × v n ÷ Σ (v n))
Coefficient of variation of particle diameter (%) = (Σ (φ _n −average particle diameter (nm)) ² ÷ (v _n ÷ Σ (v _n ))) ^0.5 ÷ average particle diameter (nm) × 100
Where phi _n's each particle diameter (nm), _{v n} denotes the volume (nm ³⁾ of each particle.
As a scanning electron microscope, S-4000 manufactured by Hitachi, Ltd. can be used.

  In the present invention, the silica skeleton of the hollow silica refers to a silica shell part of the outer shell excluding the hollow part of the hollow silica particles. The ratio of the average thickness of the silica skeleton to the average particle diameter of the hollow silica is preferably 0.02 or more, more preferably 0.04 or more, from the viewpoint of preventing breakage of the particles. On the other hand, from the viewpoint of expression of low dielectric constant and low dielectric loss tangent, 0.3 or less is preferable, and 0.2 or less is more preferable. The average thickness of the silica skeleton of the hollow silica can be measured by directly measuring the thickness of the silica skeleton of a particle image taken with a transmission electron microscope. Specifically, the average thickness of the silica skeleton of the hollow silica can be measured by photographing multiple fields of view, measuring the outer shell thickness of about 50 hollow silica particles, and determining the average value. The ratio of the average thickness of the silica skeleton to the average particle diameter of the hollow silica can be calculated by dividing the measured average thickness of the silica skeleton of the hollow silica by the average particle diameter of the hollow silica. As a transmission electron microscope, JEM-2100 manufactured by JEOL Ltd. can be used.

BET specific surface area of the hollow silica is dispersed in the resin composition, low dielectric constant, in view of the expression, such as a low dielectric loss tangent, preferably ^{30 m} 2 / g or less, more preferably ^{20m 2} / g, 15m 2 / G or less is more preferable. On the other hand, from the viewpoint of handling properties of the resin composition, BET specific surface area of the hollow silica is preferably not less than 0.5 m ² / g, more preferably at least ^{1 m} 2 / g, more preferably more than 1.5 m ² / g. For measurement of the BET specific surface area, Flowsorb III manufactured by Shimadzu Corporation can be used.

From the viewpoint of the strength of the hollow silica particles, the porosity (%), which is the volume ratio of the hollow part to the hollow silica of the present invention, is preferably 90% or less, and more preferably 80% or less. On the other hand, 15% or more is preferable and 25% or more is more preferable from the viewpoint of the expression of a low dielectric constant and a low dielectric loss tangent. Specifically, the porosity (%) can be calculated according to the following equation using the density measured using a true density measuring apparatus with nitrogen as the measurement gas. As the true density measuring device, ULTRAPYCNOMETER 1000 manufactured by QUANTACHROME can be used. The material density of silica is 2.2 (g / cm ³ ).
Porosity (%) = (Measured density (g / cm ³ ) / Material density of silica (g / cm ³ )) × 100

  (C) Hollow silica is surface-treated with a surface treatment agent such as an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an organosilazane compound, or a titanate coupling agent. And what improved the moisture resistance is preferable. You may use these 1 type or in combination of 2 or more types. Specifically, aminosilanes such as aminopropylmethoxysilane, aminopropyltriethoxysilane, ureidopropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, and N-2 (aminoethyl) aminopropyltrimethoxysilane are used as the surface treatment agent. Coupling agents, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidylbutyltrimethoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. Epoxysilane coupling agents, mercaptosilane coupling agents such as mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, methyltrimethoxysilane, octadecylto Silane coupling agents such as Limethoxysilane, Phenyltrimethoxysilane, Methacryloxypropyltrimethoxysilane, Imidazolesilane, Triazinesilane, Hexamethyldisilazane, Hexaphenyldisilazane, Trisilazane, Cyclotrisilazane, 1,1,3 Organosilazane compounds such as 1,3,5,5-hexamethylcyclotrisilazane, butyl titanate dimer, titanium octylene glycolate, diisopropoxy titanium bis (triethanolaminate), dihydroxy titanium bis lactate, dihydroxy bis (ammonium lactate) titanium Bis (dioctylpyrophosphate) ethylene titanate, bis (dioctylpyrophosphate) oxyacetate titanate, tri-n-butoxytitanium monos Allate, tetra-n-butyl titanate, tetra (2-ethylhexyl) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1- Butyl) bis (ditridecyl) phosphite titanate, isopropyl trioctanoyl titanate, isopropyl tricumyl phenyl titanate, isopropyl triisostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl tri (dioctyl phosphate) titanate, Isopropyltridodecylbenzenesulfonyl titanate, isopropyltris (dioctylpyro Sufeto) titanate, isopropyl tri (N- amidoethyl-aminoethyl) titanate coupling agents such as titanates.

  The surface treatment of the hollow silica with the coupling agent can be performed, for example, by adding and spraying the silane coupling agent and stirring for 5 to 15 minutes while stirring and dispersing untreated hollow silica at room temperature with a mixer. it can. In addition, after this stirring, you may heat about 60-80 degreeC as needed. As a mixer, a well-known mixer can be used, For example, blenders, such as V blender, a ribbon blender, and a bubble cone blender, mixers, such as a Henschel mixer and a concrete mixer, a ball mill, a cutter mill, etc. are mentioned. A method of adding a coupling agent to the slurry while stirring a slurry obtained by adding silica to a solvent generally referred to as a wet method to the above dry method, followed by filtration, washing, and drying. The treatment amount of the coupling agent varies depending on the type of the coupling agent and the like, but is preferably 0.1 to 200% by mass, more preferably 0.2 to 150% by mass, and 0.3 to 100% by mass with respect to the hollow silica. % Is more preferable.

  (C) The content of the hollow silica in the resin composition is 5% by mass or more when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of reducing the dielectric loss tangent of the resin composition. 6 mass% or more, more preferably 7 mass% or more, still more preferably 8 mass% or more, still more preferably 9 mass% or more, particularly preferably 10 mass% or more, and particularly preferably 11 mass% or more. On the other hand, when the nonvolatile component in the resin composition is defined as 100% by mass from the viewpoint of preventing the handling property from being lowered due to an increase in the viscosity of the resin composition and improving the formability of the adhesive film, the content is 22% by mass or less. Yes, 20 mass% or less is more preferable. In addition, when using the hollow silica surface-treated with the silane coupling agent, “the content of the hollow silica” means “the content of the hollow silica surface-treated with the silane coupling agent”.

<(D) Fused silica>
The (D) fused silica in the present invention is not particularly limited, and various fused silicas can be used. Of these, spherical fused silica is preferable. Here, (D) fused silica refers to non-porous silica obtained by melting a silica raw material at a high temperature. (D) By using fused silica, the thermal expansion coefficient of the resin composition can be lowered without greatly increasing the viscosity of the resin composition. (D) As a specific example (brand) of fused silica, SC-2050 (manufactured by Admatechs) can be cited.

  (D) The average particle size of the fused silica is not particularly limited, but is preferably 5 μm or less, more preferably 4 μm or less, further preferably 3 μm or less, and more preferably 2 μm or less from the viewpoint of improving the insulation of the circuit board. Is more preferably 1.5 μm or less, particularly preferably 1 μm or less. On the other hand, from the viewpoint of improving the dispersibility in the resin composition, it is preferably 0.1 μm or more, more preferably 0.2 μm or more, still more preferably 0.3 μm or more, still more preferably 0.4 μm or more, and 5 μm or more is particularly preferable. (D) The average particle diameter of fused silica can be measured in the same manner as described above. In addition, (D) fused silica is preferably treated with a silane coupling agent in the same manner as hollow silica to improve its moisture resistance. The treatment amount of the coupling agent varies depending on the type of the coupling agent and the like, but is preferably 0.1 to 5% by mass, more preferably 0.2 to 4% by mass, and 0.3 to 3% by mass with respect to the fused silica. % Is more preferable. The types of silane coupling agents and the treatment method are the same as those for hollow silica.

  The total content of (C) hollow silica and (D) fused silica in the resin composition is 100% by mass of the non-volatile component in the resin composition from the viewpoint of reducing the thermal expansion coefficient of the resin composition. In this case, it is 50% by mass or more, more preferably 52% by mass or more, further preferably 54% by mass or more, still more preferably 56% by mass or more, particularly preferably 58% by mass or more, and particularly preferably 60% by mass or more. . On the other hand, from the viewpoint of improving the handleability of the resin composition and from the viewpoint of improving the formability of the adhesive film, when the nonvolatile component in the resin composition is 100% by mass, it is 70% by mass or less and 68% by mass or less. Is more preferable. In addition, when using the fused silica surface-treated with the silane coupling agent, “the content of the fused silica” means “the content of the fused silica surface-treated with the silane coupling agent”.

  The ratio of the content of (C) hollow silica to the content of (D) fused silica in the resin composition, that is, the blending ratio of (C) hollow silica to (D) fused silica in the resin composition “(C) “Hollow silica / (D) fused silica” (mass ratio) is preferably 0.070 or more, more preferably 0.080 or more, and more preferably 0.090 or more from the viewpoint of reducing the dielectric loss tangent of the cured product of the resin composition. More preferably, 0.10 or higher is even more preferable, 0.11 or higher is particularly preferable, 0.12 or higher is particularly preferable, and 0.13 or higher is particularly preferable. On the other hand, from the viewpoint of improving the handleability of the resin composition, from the viewpoint of reducing the thermal expansion coefficient of the cured product of the resin composition, and from the viewpoint of improving the formability of the adhesive film, 0.67 or less is preferable. The following is more preferable, 0.61 or less is further preferable, 0.58 or less is further more preferable, 0.55 or less is particularly preferable, 0.52 or less is particularly preferable, and 0.49 or less is particularly preferable.

  In the present invention, the dielectric constant can be grasped by the measurement method described in <Measurement of Dielectric Constant (εr)> described later. The upper limit of the dielectric constant of the cured product of the resin composition of the present invention is preferably 3.3 or less, and preferably 3.2 or less, from the viewpoint of preventing an increase in the capacitance of the insulating layer when the film is thinned. Is more preferably 3.1 or less, and even more preferably 3.0 or less. The lower limit of the dielectric constant of the cured product of the resin composition of the present invention is preferably 2.5 or more, more preferably 2.0 or more, still more preferably 1.5 or more, and even more preferably 1.0 or more.

  In the present invention, the dielectric loss tangent can be grasped by the measurement method described in <Measurement and evaluation of dielectric loss tangent> described later. The upper limit value of the dielectric loss tangent of the cured product of the resin composition of the present invention is preferably 0.007 or less, more preferably 0.0069 or less, from the viewpoint of prevention of heat generation at high frequencies, signal delay and signal noise reduction. Is more preferably 0.0065 or less, still more preferably 0.0065 or less, particularly preferably 0.0063 or less, particularly preferably 0.0061 or less, particularly preferably 0.0058 or less, and still more preferably 0.0054 or less. The lower limit of the dielectric loss tangent of the cured product of the resin composition of the present invention is preferably 0.0005 or more, more preferably 0.001 or more, still more preferably 0.002 or more, still more preferably 0.003 or more, 0 .0035 or more is particularly preferable, 0.004 or more is particularly preferable, and 0.005 or more is particularly preferable.

  In the present invention, the average coefficient of thermal expansion from 25 ° C. to 150 ° C. can be grasped by the evaluation method described in <Measurement and evaluation of coefficient of thermal expansion> described later. The “thermal expansion coefficient” in the present invention means “linear thermal expansion coefficient”. The upper limit of the average thermal expansion coefficient from 25 ° C. to 150 ° C. of the cured product of the resin composition is preferably 32 ppm or less, more preferably 30 ppm or less, still more preferably 28 ppm or less, even more preferably 26 ppm or less, and even more preferably 24 ppm or less. Is more preferably 22 ppm or less, particularly preferably 20 ppm or less, and even more preferably 18 ppm or less. The lower limit of the average thermal expansion coefficient from 25 ° C. to 150 ° C. of the cured product of the resin composition is preferably 1 ppm or more, more preferably 3 ppm or more, further preferably 5 ppm or more, still more preferably 7 ppm or more, and 9 ppm or more. Is more preferable, and 11 ppm or more is particularly preferable.

  In the present invention, the average thermal expansion coefficient at 150 ° C. or higher can be grasped by the evaluation method described in <Measurement and Evaluation of Thermal Expansion Coefficient> described later. The reason why the average thermal expansion coefficient of the cured product of the resin composition at 150 ° C. or higher is measured is that the thermal expansion of the cured product during reflow affects the warpage of the substrate. For the average coefficient of thermal expansion at 150 ° C. or higher, the average coefficient of thermal expansion from 150 ° C. to 250 ° C. is adopted as a representative value. From the viewpoint of preventing warpage of the substrate, the upper limit value of the average thermal expansion coefficient of the cured product of the resin composition is preferably 80 ppm or less, more preferably 70 ppm or less, still more preferably 60 ppm or less, and 50 ppm or less. Even more preferred is 45 ppm or less, particularly preferred is 42 ppm or less, particularly preferred is 39 ppm or less, and even more preferred is 36 ppm or less. From the viewpoint of preventing warping of the substrate, the lower limit value of the average thermal expansion coefficient of the cured product of the resin composition is preferably 1 ppm or more, more preferably 3 ppm or more, further preferably 5 ppm or more, and more preferably 10 ppm or more. Even more preferred is 15 ppm or more, particularly preferred is 20 ppm or more.

  In the present invention, when the average thermal expansion coefficient from 25 ° C. to 150 ° C. of the cured product of the resin composition is α1, and the average thermal expansion coefficient from 150 ° C. to 250 ° C. is α2, “α2 / α1” Is specified as the rate of increase in the thermal expansion coefficient. The rate of increase of the thermal expansion coefficient can be grasped by the evaluation method described in <Measurement and evaluation of thermal expansion coefficient> described later. The upper limit of the rate of increase in the coefficient of thermal expansion of the cured product of the resin composition of the present invention is preferably 3.3 or less, more preferably 3.0 or less, still more preferably 2.7 or less, and further preferably 2.4 or less. More preferred is 2.1 or less, particularly preferred is 1.8 or less, and particularly preferred is 1.5 or less. Moreover, 1.1 or less is preferable and, as for a lower limit, 1.0 or less is more preferable.

<(E) Curing accelerator>
The epoxy resin and the curing agent can be efficiently cured by further containing (E) a curing accelerator in the resin composition of the present invention. Examples of such (E) curing accelerators include metal-based curing accelerators, imidazole-based curing accelerators, and amine-based curing accelerators. You may use these 1 type or in combination of 2 or more types.

  The metal-based curing accelerator is not particularly limited, and examples thereof include an organometallic complex or an organometallic salt of a metal such as cobalt, copper, zinc, iron, nickel, manganese, and tin. 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. As metal-based curing accelerators, from the viewpoint of curability and solvent solubility, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, zinc (II) acetylacetonate, zinc naphthenate, iron (III) Acetylacetonate is preferable, and cobalt (III) acetylacetonate and zinc naphthenate are particularly preferable. You may use a metal type hardening accelerator 1 type or in combination of 2 or more types.

  The content of the metal-based curing accelerator in the resin composition is a metal-based curing accelerator with respect to 100% by mass of the nonvolatile component in the resin composition from the viewpoint of preventing the storage stability of the resin composition from decreasing. The amount of the metal based on the content is preferably 500 ppm or less, and more preferably 200 ppm or less. On the other hand, from the viewpoint of accelerating curing, the amount of the metal based on the metal-based curing accelerator is preferably 20 ppm or more with respect to 100% by mass of the non-volatile component in the resin composition, and more preferably 30 ppm or more. preferable.

  The imidazole curing accelerator is not particularly limited, but 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl Imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1- Cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4 -Diamino 6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2 , 4-Diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1') ] -Ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5hydroxymethylimidazole, 2,3- Dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazole Phosphorus, adduct of 2-phenyl-imidazo imidazole compounds such as phosphorus and imidazole compound and an epoxy resin. The imidazole curing accelerators 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) phenol, 1 , 8-diazabicyclo (5,4,0) -undecene (hereinafter abbreviated as DBU) and the like. You may use an amine hardening accelerator 1 type or in combination of 2 or more types.

  The content of the imidazole curing accelerator and the amine curing accelerator is not particularly limited, but is preferably in the range of 0.001 to 1% by mass with respect to 100% by mass of the nonvolatile component in the resin composition, 0.005 The range of -0.5 mass% is more preferable. When the amount is less than 0.001% by mass, the effect of the curing accelerator tends not to be sufficiently exhibited. When the amount exceeds 1% by mass, the storage stability of the resin composition tends to decrease.

<(F) Thermoplastic resin>
The resin composition of the present invention can further improve the flexibility of the cured product by further containing (F) a thermoplastic resin, and further improve the film forming ability when used in the form of an adhesive film. You can also. Examples of the thermoplastic resin (F) include phenoxy resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, and polyester resin. Etc. These may be used alone or in combination of two or more. The weight average molecular weight of the thermoplastic resin is preferably in the range of 5,000 to 200,000. If it is smaller than this range, the effect of improving the film-forming ability tends not to be sufficiently exhibited. If it is larger than this range, the compatibility with the resin composition tends to be lowered. 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.

  When (F) a thermoplastic resin is blended with the resin composition of the present invention, the content of the thermoplastic resin in the resin composition is not particularly limited, but the non-volatile component in the resin composition is 100 masses. % To 0.1% by mass is preferable, and 0.5% to 5% by mass is more preferable. When the content of the thermoplastic resin is too small, the effect of improving the film forming ability tends not to be exhibited. When the content is too large, the handleability tends to decrease due to the increase in the viscosity of the resin composition.

<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 thermosetting resins such as vinyl benzyl compounds, acrylic compounds, maleimide compounds, organic fillers such as silicon powder, nylon powder, fluorine powder, rubber particles, alumina, barium sulfate, talc, clay, etc. Inorganic fillers, organic phosphorus compounds, nitrogen compounds, silicone compounds, flame retardants such as metal hydroxides, thickeners such as olben and benton, silicone-based, fluorine-based, polymer-based antifoaming agents or leveling agents, Examples thereof include adhesion imparting agents such as imidazole, thiazole, triazole, and silane coupling agents, and coloring agents such as phthalocyanine / blue, phthalocyanine / green, iodin / green, disazo yellow, and carbon black.

  The method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method in which the components are mixed using a rotary mixer or the like, if necessary, by adding a solvent or the like.

  The use of the resin composition of the present invention is not particularly limited, but a sheet-like laminated material such as an adhesive film or prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor sealing material, a hole-filling resin, a component-filling resin, It can be used in a wide range of applications where a resin composition is required, such as circuit boards (laminated boards, multilayer printed wiring boards, etc.), semiconductor devices and the like. Especially, in manufacture of a multilayer printed wiring board, it can use suitably as a resin composition for forming an insulating layer, and can use it more suitably as a resin composition for forming plating. The resin composition of the present invention can be applied to a circuit board in a varnish state to form an insulating layer, but in general, it is preferably used in the form of a sheet-like laminated material such as an adhesive film or a prepreg. . The softening point of the resin composition is preferably 40 to 150 ° C. from the viewpoint of the laminate property of the sheet-like 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 (hereinafter abbreviated as “MEK”), cyclohexanone, and acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate. Carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. You may use an organic solvent combining 1 type (s) or 2 or more types.

  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. Although it depends 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 3 to 10 minutes. be able to.

  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.

  Supports include polyolefin films such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter abbreviated as “PET”), polyester films such as polyethylene naphthalate, various plastic films such as polycarbonate films and polyimide films. Is mentioned. Moreover, you may use release foil, metal foil, such as copper foil and aluminum foil. 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.

<Laminated board and multilayer printed wiring board using adhesive film>
Next, an example of a method for producing a laminated board and a multilayer printed wiring board using the adhesive film produced as described above will be described.

  A laminated board can be produced by facing and laminating and curing the resin composition layer of the adhesive film. A multilayer printed wiring board can be produced by laminating an adhesive film on one 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 adhesive film has a protective film, after removing the protective film, the adhesive film and the circuit board are preheated as necessary, and the adhesive film is pressed and heated to the circuit board. Crimp. In the adhesive film of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is preferably 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 is preferably 1 to 11 kgf / cm ² (9.8 × 10 ^{4 to} 107). 9.9 × 10 ⁴ N / m ² ), and 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. Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nichigo-Morton Co., Ltd., a vacuum pressurizing laminator manufactured by Meiki Seisakusho Co., Ltd., a roll dry coater manufactured by Hitachi Industries, Ltd., and Hitachi AIC Co., Ltd. ) Made vacuum laminator and the like.

Moreover, the lamination process which heats and pressurizes under reduced pressure can also 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 stage, it is preferable to carry out the conditions separately in two or more stages from the viewpoint of controlling the oozing of the resin. For example, the first stage press has a temperature of 70 to 150 ° C. and the pressure is in a range of 1 to 15 kgf / cm ² , and the second stage press has a temperature of 150 to 200 ° C. and a pressure of 1 to 40 kgf / cm ² It is preferable to carry out within a range. The time for each stage is preferably 30 to 120 minutes. 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.

  After laminating the adhesive film on the circuit board, it is cooled to around room temperature, and when the support is peeled off, the insulating film can be formed on the circuit board by peeling and thermosetting. The thermosetting conditions may be appropriately selected according to the type and content of the resin component in the resin composition, but preferably 150 ° C. to 220 ° C. for 20 minutes to 180 minutes, more preferably 160 ° C. to 200 ° C. It is selected in the range of 30 minutes to 120 minutes at ° C.

  If the support is not peeled off after the insulating layer is formed, it is peeled off here. Next, if necessary, holes are formed in the insulating layer formed on the circuit board to form via holes and through holes. Drilling can be performed, for example, by a known method such as drilling, laser, or plasma, or by combining these methods as necessary. However, drilling by a laser such as a carbon dioxide gas laser or a YAG laser is the most common method. is there.

  Next, a conductor layer is formed on the insulating layer by dry plating or wet plating. As the dry plating, a known method such as vapor deposition, sputtering, or ion plating can be used. In the case of wet plating, first, the surface of the cured resin composition layer (insulating layer) is coated with permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / Roughening treatment is performed with an oxidizing agent such as sulfuric acid or nitric acid to form an uneven anchor. As the oxidizing agent, an aqueous sodium hydroxide solution (alkaline permanganate aqueous solution) such as potassium permanganate and sodium permanganate is particularly preferably used. Next, a conductor layer is formed by a method combining electroless plating and electrolytic plating. Alternatively, a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating. As a subsequent pattern formation method, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used.

<Prepreg>
The prepreg of the present invention can be produced by impregnating the resin composition of the present invention into a sheet-like fiber base material by a hot melt method or a solvent method, followed by heating and semi-curing. 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 fiber base material. As the sheet-like fiber base material, for example, fibers that are commonly used as prepreg fibers such as glass cloth and aramid fibers can be used.

  In the hot melt method, the resin is once coated on a coated paper having good releasability from the resin without being dissolved in the organic solvent, and then laminated on the sheet-like fiber base material, or the resin is used in the organic solvent. This is a method for producing a prepreg by directly coating a sheet-like fiber substrate with a die coater without dissolving it. 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 the sheet-like fiber substrate is immersed in the varnish, and then the resin-varnish is impregnated into the sheet-like fiber substrate. It is a method of drying.

<Laminated board and multilayer printed wiring board using prepreg>
Next, an example of a method for producing a multilayer printed wiring board using the prepreg produced as described above will be described.

A laminated board can be produced by stacking and curing one prepreg or several sheets as necessary, sandwiching them with a metal plate via a release film. A multilayer printed wiring board is manufactured by stacking one or several prepregs of the present invention on a circuit board, sandwiching them with a metal plate through a release film, and vacuum-pressing them under pressure and heating conditions. can do. The pressurizing / heating conditions are preferably a pressure of 5 to 40 kgf / cm ² (49 × 10 ^{4 to} 392 × 10 ⁴ N / m ² ) and a temperature of 120 to 200 ° C. for 20 to 100 minutes. Similarly to the adhesive film, the prepreg can be laminated on a circuit board by a vacuum laminating method and then cured by heating. Thereafter, in the same manner as described above, the surface of the cured prepreg is roughened, and then a conductor layer is formed by plating to produce a multilayer printed wiring board.

<Semiconductor device>
Furthermore, the semiconductor device of the present invention can be manufactured by using the multilayer printed wiring board of the present invention. A semiconductor device is manufactured by bonding a semiconductor element to the connection electrode portion on the multilayer printed wiring board. The mounting method of the semiconductor element is not particularly limited, and examples thereof include wire bonding mounting, flip chip mounting, mounting with an anisotropic conductive film (ACF), mounting with a non-conductive film (NCF), and the like.

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

<Measurement of dielectric constant (εr)>
A dielectric constant measurement sample was cut into a length of 80 mm and a width of 2 mm to obtain an evaluation sample. The dielectric constant of this evaluation sample was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. by a cavity resonance perturbation method using an HP 8362B apparatus manufactured by Agilent Technologies. When the dielectric constant is 2.9 or less, “◎◎”, 3.0 is “◎ ○”, 3.1 is “◎”, 3.2 is “○”, The case of 3.3 or more was designated as “Δ”. Those that could not be measured were displayed as “−”.

<Measurement and evaluation of dielectric loss tangent>
In Examples and Comparative Examples, each of the Examples and Comparative Examples was the same except that PET (Mitsubishi Resin “Fluoroge RL50KSE”) treated with a fluororesin-based release agent (ETFE) was used as the support. An adhesive film having the same resin composition layer was obtained. The obtained adhesive film was thermally cured by heating at 190 ° C. for 90 minutes, and the support was peeled off to obtain a sheet-like cured product. The cured product was cut into a length of 80 mm and a width of 2 mm and used as an evaluation sample. The dielectric loss tangent of this evaluation sample was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. by a cavity resonance perturbation method using an HP 8362B apparatus manufactured by Agilent Technologies. Two test pieces were measured, and the average value was calculated. A case where the dielectric loss tangent is less than 0.0055 is designated as “◎”, a case where the dielectric loss tangent is 0.0055 or more and less than 0.0059 is designated as “◎”, and a case where the dielectric loss tangent is 0.0059 or more and less than 0.0063 is designated as “◎”. The case where it was .0063 or more and less than 0.0067 was set as “◯”, the case where it was 0.0067 or more and less than 0.0071 was set as “Δ”, and the case where it was 0.0071 or more was set as “x”. Those that could not be measured were displayed as “−”.

<Measurement and evaluation of thermal expansion coefficient>
In Examples and Comparative Examples, adhesion having the same resin composition layer as in each of Examples and Comparative Examples was carried out in the same manner except that ETFE-treated PET ("Fluoroge RL50KSE" manufactured by Mitsubishi Plastics, Inc.) was used as the support. A film was obtained. The obtained adhesive film was thermally cured by heating at 190 ° C. for 90 minutes, and the support was peeled off to obtain a sheet-like cured product. The cured product was cut into a test piece having a width of about 5 mm and a length of about 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. In the second measurement, an average coefficient of thermal expansion (referred to as α1) (ppm) from 25 ° C. to 150 ° C. and an average coefficient of thermal expansion (referred to as α2) (ppm) from 150 ° C. to 250 ° C. were calculated. α2 was a coefficient of thermal expansion of 150 ° C. or higher. Further, “α2 / α1” was calculated as the rate of increase in the coefficient of thermal expansion. The average coefficient of thermal expansion from 25 ° C. to 150 ° C. was “◯” when 25 ppm or more, “、” when 20 ppm or more and less than 25 ppm, and “◎” when less than 20 ppm. The thermal expansion coefficient at 150 ° C. or higher is less than 30 ppm as “◎◎”, 30 ppm to less than 40 ppm as “「 ”, 40 ppm to less than 50 ppm as“ ◎ ”, 50 ppm to less than 60 ppm as“ ◯ ”, 60 ppm More than 82 ppm is defined as “Δ”, and 82 ppm or more is defined as “x”. The rate of increase in the coefficient of thermal expansion is less than 1.6 as “◎”, from 1.6 to less than 1.9 as “「 ”, and from 1.9 to less than 2.2 as“ ◎ ”, 2.2 or more and less than 2.5 were set as “◯”, 2.5 or more and less than 3.4 were set as “Δ”, and 3.4 or more were set as “X”. Those that could not be measured were displayed as “−”.

<Production Example 1 (Production of hollow silica particles)>
In a 20 L reactor, 4 kg of methanol, 33 g of a 25% solid content tetramethylammonium hydroxide aqueous solution, 68 g of dodecyltrimethylammonium chloride, and 40 g of hexane were stirred and dissolved. 12 kg of ion-exchanged water was added to the methanol solution to precipitate hexane emulsified droplets. Thereafter, 85 g of tetramethoxysilane was slowly added, stirred at room temperature (25 ° C.) for 5 hours, and then aged for 12 hours. Next, the obtained white precipitate was filtered with Advantech filter paper (5C), washed with 10 L of water, and dried at a temperature of 100 ° C. for 5 hours to obtain a dry powder of silica particles. The obtained dry powder was heated up to 600 ° C. at a rate of 1 ° C./min with air flow (3 L / min) using a high-speed heating furnace (trade name: SK-2535E, manufactured by Motoyama Co., Ltd.). The organic component was removed by heating and baking at 600 ° C. for 2 hours to obtain hollow silica precursor particles. The hollow silica precursor particles (50 g) were transferred to an alumina crucible and fired at 1000 ° C. for 72 hours in the air using the electric furnace to obtain hollow silica (average particle size 0.96 μm, variation coefficient 22%, average particle size The ratio of the average thickness of the silica skeleton with respect to 0.13, the BET specific surface area 6.5 m ² / g, and the porosity 38%). In a 1 L glass container, 150 g of toluene, 50 g of hollow silica, and 5 g of N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. “KBM573”) were added and reacted at 110 ° C. for 12 hours with stirring. The solution after the reaction was filtered through an Advantech membrane filter (PTFE, pore size 0.2 μm), and then washed with ethanol. The obtained powder was dried at 100 ° C. for 12 hours to obtain a surface-treated hollow silica.

<Production Example 2 (Production of hollow silica particles)>
In a 20 L reactor, 16 kg of water, 66 g of 25% tetramethylammonium hydroxide aqueous solution, 68 g of dodecyltrimethylammonium chloride, and 144 g of cationic acrylic polymer particles (average particle size of 0.75 μm, manufactured by Nippon Paint) are stirred. Then, 136 g of tetramethoxysilane was slowly added to the aqueous solution, stirred for 5 hours at room temperature (25 ° C.), and then aged for 12 hours. Next, the obtained white precipitate was filtered through a membrane filter having a pore size of 0.2 μm, washed with 10 L of water, dried at 100 ° C. for 5 hours, polymer particles as a core, and silica particles as a shell. A dry powder of core-shell type silica particles was obtained. The obtained dry powder was heated up to 600 ° C. at a rate of 1 ° C./min with air flow (3 L / min) using a high-speed heating furnace (trade name: SK-2535E, manufactured by Motoyama Co., Ltd.). The organic component was removed by heating and baking at 600 ° C. for 2 hours to obtain hollow silica precursor particles. The hollow silica precursor particles (50 g) were transferred to an alumina crucible and fired at 1000 ° C. for 72 hours in air using the electric furnace to obtain hollow silica (average particle size 0.65 μm, coefficient of variation 7%, average particle size The ratio of the average thickness of the silica skeleton to 0.075, the BET specific surface area of 15 m ² / g, and the porosity of 62% were obtained. In a 1 L glass container, 150 g of toluene, 50 g of hollow silica, and 50 g of N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. “KBM573”) were added and reacted at 110 ° C. for 12 hours with stirring. The solution after the reaction was filtered through an Advantech membrane filter (PTFE, pore size 0.2 μm), and then washed with ethanol. The obtained powder was dried at 100 ° C. for 12 hours to obtain a surface-treated hollow silica.

<Example 1>
12 parts by mass of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “jER828EL” manufactured by Mitsubishi Chemical Corporation) and 13 parts by mass of biphenyl type epoxy resin (epoxy equivalent 225, “NC3100” manufactured by Nippon Kayaku Co., Ltd.) 5 parts by mass of a phenoxy resin (1: 1 solution of MEK and cyclohexanone having a weight average molecular weight of 38000, “YL6954BH30” nonvolatile component of 30% by mass, manufactured by Mitsubishi Chemical Corporation) is 10 parts by mass of MEK, 5 parts by mass of cyclohexanone, and 10 parts by mass of solvent naphtha. The mixture was heated and dissolved with stirring. After cooling to room temperature, there are 16 parts by weight of a prepolymer of bisphenol A dicyanate (Lonza Japan Co., Ltd. “BA230S”, cyanate equivalent 232, non-volatile component 75% by mass MEK solution), phenol novolac type polyfunctional cyanate ester system Stir and mix with 6 parts by weight of a curing agent ("PT30" manufactured by Lonza Japan Co., Ltd., MEK solution with cyanate equivalent 124, non-volatile component 80% by mass), and an active ester curing agent ("HP8000-65T manufactured by DIC Corporation"). ”, 12 parts by mass of an active group equivalent 223, 65% by mass of a non-volatile component in toluene), 2 parts by mass of a 1% by mass MEK solution of 4-dimethylaminopyridine (DMAP) as a curing accelerator, cobalt (III) acetylacetonate 1 quality (manufactured by Tokyo Chemical Industry Co., Ltd., cobalt content 16.5% by mass) % MEK solution (4.5 parts by mass), fused silica (manufactured by Admatechs Co., Ltd., “SC2050-SXF”, average particle size 0.5 μm), 88 parts by mass, and hollow silica (surface treatment produced in Production Example 1) 8 parts by mass of hollow silica having an average particle size of 0.96 μm were mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish. Next, such a resin varnish is uniformly applied on a PET film (thickness 38 μm) by a die coater so that the thickness of the resin composition layer after drying is 40 μm, and 80 to 110 ° C. (average 95 ° C.). ) For 6 minutes (residual solvent amount in the resin composition layer: 1.5% by mass). Subsequently, it wound up in roll shape, bonding a 15-micrometer-thick polypropylene film on the surface of a resin composition layer. The roll-like adhesive film was slit to a width of 507 mm to obtain a sheet-like adhesive film having a size of 507 × 336 mm.

<Example 2>
A resin varnish was prepared in the same manner as in Example 1, except that the hollow silica was changed to 15 parts by mass and the fused silica was changed to 81 parts by mass. Next, an adhesive film was obtained in the same manner as in Example 1.

<Example 3>
A resin varnish was prepared in the same manner as in Example 1 except that the hollow silica was changed to 22 parts by mass and the fused silica was changed to 74 parts by mass. Next, an adhesive film was obtained in the same manner as in Example 1.

<Example 4>
A resin varnish was prepared in the same manner as in Example 1 except that the hollow silica was changed to 30 parts by mass and the fused silica was changed to 66 parts by mass. Next, an adhesive film was obtained in the same manner as in Example 1.

<Example 5>
A resin varnish was prepared in the same manner as in Example 1 except that the hollow silica was changed to 9 parts by mass and the fused silica was changed to 110 parts by mass. Next, an adhesive film was obtained in the same manner as in Example 1.

<Example 6>
A resin varnish was prepared in the same manner as in Example 1 except that the hollow silica was changed to 34 parts by mass and the fused silica was changed to 85 parts by mass. Next, an adhesive film was obtained in the same manner as in Example 1.

<Example 7>
A resin varnish was prepared in the same manner as in Example 1 except that the hollow silica was changed to 5 parts by mass and the fused silica was changed to 47 parts by mass. Next, an adhesive film was obtained in the same manner as in Example 1.

<Example 8>
A resin varnish was prepared in the same manner as in Example 1 except that the hollow silica of Example 1 was changed to 20 parts by mass and the fused silica was changed to 31 parts by mass. Next, an adhesive film was obtained in the same manner as in Example 1.

<Example 9>
In place of the hollow silica produced in Production Example 1 used in Example 1, it was changed to 8 parts by mass of the hollow silica produced in Production Example 2 (average particle size 0.65 μm). A resin varnish was prepared. Next, an adhesive film was obtained in the same manner as in Example 1.

<Example 10>
Liquid bisphenol A type epoxy resin (epoxy equivalent 180, 15 parts by mass of “jER828EL” manufactured by Mitsubishi Chemical Corporation, and 15 parts by mass of biphenyl type epoxy resin (epoxy equivalent 225, “NC3100” manufactured by Nippon Kayaku Co., Ltd.), phenoxy 7 parts by mass of a resin (a 1: 1 solution of MEK and cyclohexanone having a weight average molecular weight of 38000, “YL6954BH30” nonvolatile component 30% by mass, manufactured by Mitsubishi Chemical Corporation) 10 parts by mass of MEK, 5 parts by mass of cyclohexanone, and 10 parts by mass of solvent naphtha After cooling to room temperature, an active ester curing agent (“HP8000-65T” manufactured by DIC Corporation, active group equivalent 223, toluene solution with 65% by mass of non-volatile components) was added thereto. Part by mass and triazine-containing cresol novolac resin (“L” manufactured by DIC Corporation) -7054 ", MEK solution of 60% by mass of nonvolatile components, 10 parts by mass of phenol equivalent 125), and 82 parts by mass of fused silica (" SC2050-SXF "manufactured by Admatechs Co., Ltd., average particle size 0.5 µm), hollow A resin varnish was prepared by mixing 12 parts by mass of silica (surface-treated hollow silica produced in Production Example 1, average particle size 0.96 μm) and uniformly dispersing with a high-speed rotary mixer. An adhesive film was obtained in the same manner as in Example 1.

<Comparative Example 1>
A resin varnish was prepared in the same manner as in Example 1 except that the fused silica in Example 1 was changed to 96 parts by mass and no hollow silica was blended. Next, an adhesive film was prepared in the same manner as in Example 1.

<Comparative Example 2>
A resin varnish was prepared in the same manner as in Example 1 except that the fused silica of Example 1 was changed to 93 parts by mass and the hollow silica was changed to 3 parts by mass. Next, an adhesive film was prepared in the same manner as in Example 1.

<Comparative Example 3>
A resin varnish was prepared in the same manner as in Example 1 except that the fused silica of Example 1 was changed to 60 parts by mass and the hollow silica was changed to 37 parts by mass, but the viscosity of the resin varnish increased and the handleability decreased, An adhesive film could not be created.

<Comparative Example 4>
The resin varnish was prepared in the same manner as in Example 1 except that the fused silica of Example 1 was changed to 140 parts by mass and the hollow silica was changed to 10 parts by mass, but because the viscosity of the resin varnish increased and the handleability decreased, An adhesive film could not be created.

  The results are shown in Table 1.

  From the results in Table 1, it can be seen that in the examples, the dielectric loss tangent is low and the thermal expansion coefficient at 150 ° C. or higher is also low. On the other hand, in Comparative Examples 1 and 2, since the amount of hollow silica is small, it can be seen that the dielectric loss tangent is high and the thermal expansion coefficient at 150 ° C. or higher is also high. In Comparative Example 3, since the amount of hollow silica was increased, the viscosity of the resin varnish increased and various measurements could not be performed. In Comparative Example 4, since the total amount of hollow silica and fused silica was large, the viscosity of the resin varnish increased and various measurements could not be performed.

  In the present invention, a resin composition having a sufficiently small dielectric constant, dielectric loss tangent, and thermal expansion coefficient, in particular, a dielectric constant and low dielectric loss tangent are sufficiently small, and a thermal expansion coefficient of 150 ° C. or higher is sufficiently low. Resin compositions, as well as adhesive films, prepregs, laminates, multilayer printed wiring boards, and semiconductor devices 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 (9)

A resin composition containing (A) an epoxy resin, (B) a curing agent, (C) hollow silica, and (D) fused silica,
(C) The average particle diameter of hollow silica is 0.1 μm or more and 5 μm or less, and the ratio of the average thickness of silica skeleton to the average particle diameter of hollow silica (average thickness of silica skeleton of hollow silica / average of hollow silica) Particle size) is 0.02 or more and 0.3 or less,
(D) The fused silica is a spherical fused silica having an average particle size of 5 μm or less,
When the nonvolatile component in the resin composition is 100% by mass, the content of (C) hollow silica is 5 to 22% by mass, and the total content of (C) hollow silica and (D) fused silica is 50%. Ri 70% by mass, (D) mixing ratio of (C) the hollow silica to fused silica "(C) hollow silica / (D) fused silica" is 0.070 or more at a mass ratio be 0.67 or less ,
Is the dielectric loss tangent of a cured product of the resin composition (measurement frequency 5.8 GHz) is from 0.0005 to 0.007, the average thermal expansion coefficient of from 0.99 ° C. to 250 ° C. and the said 1ppm~80ppm der Rukoto Resin composition. (C) The porosity of the hollow silica (%) 15% or more, Ru der 90% or less, according to claim 1 Symbol placement of the resin composition. The resin composition of Claim 1 or 2 whose coefficient of variation of the particle diameter of a hollow silica is 50% or less. The resin composition according to any one of claims 1 to 3 , wherein the hollow silica has a BET specific surface area of 0.5 m ² / g or more and 30 m ² / g or less. When the average thermal expansion coefficient from 25 ° C. to 150 ° C. of the cured product of the resin composition is α1, and the average thermal expansion coefficient from 150 ° C. to 250 ° C. is α2, the value of α2 / α1 is 1. characterized in that it is a 0 to 3.3, the resin composition according to any one of claims 1-4. The adhesive film by which the resin composition of any one of Claims 1-5 was layer-formed on the support body. A prepreg in which the resin composition according to any one of claims 1 to 5 is impregnated in a sheet-like reinforcing base material. The multilayer printed wiring board by which the insulating layer was formed with the hardened | cured material of the resin composition of any one of Claims 1-5 . A semiconductor device using the multilayer printed wiring board according to claim 8 .