JP6595336B2 - Resin composition - Google Patents

Description

  The present invention relates to a resin composition.

  As a manufacturing technique of a multilayer printed wiring board, a manufacturing method by a build-up method in which insulating layers and conductor layers are alternately stacked is known. In the manufacturing method by the build-up method, the insulating layer is generally formed by thermosetting a resin composition. For example, Patent Document 1 discloses a technique for forming an insulating layer by thermally curing a resin composition containing an epoxy resin, an active ester curing agent, a phenol curing agent, and silica.

  In recent years, electronic devices are becoming smaller and more functional, and the mounting density of semiconductor elements in a multilayer printed wiring board tends to increase. A technology for efficiently diffusing heat generated by a semiconductor element is demanded in combination with enhancement of functions of a semiconductor element to be mounted. For example, in Patent Document 2, as a technique for diffusing heat generated by a semiconductor element, the semiconductor element is mounted on a multilayer printed wiring board using a film-like adhesive containing a highly thermally conductive inorganic filler such as aluminum nitride. Technology is disclosed.

JP 2011-132507 A JP 2012-207222 A

  The present inventors paid attention to the thermal diffusivity of the insulating layer in order to more efficiently diffuse the heat generated by the semiconductor element. In order to improve the thermal diffusivity of the insulating layer, a resin composition containing a highly heat-conductive inorganic filler such as aluminum nitride, which exhibits a higher thermal conductivity than conventionally used silica, is thermally cured to provide the insulating layer. Attempted formation. As a result, as the content of the high thermal conductivity inorganic filler in the resin composition is increased, the thermal diffusibility of the resulting cured body (insulating layer) increases, but the thermal conductivity is sufficiently high to exhibit sufficient thermal diffusivity. When the content of the inorganic filler is increased, the surface roughness of the resulting cured body (particularly the surface roughness of the cured body after the roughening treatment) increases, and the conductor is formed with a fine wiring pattern on the surface of the cured body (insulating layer). The present inventors have found that there may be an obstacle in forming the layer. The present inventors further provide a cured product obtained by thermally curing a resin composition containing a high thermal conductive inorganic filler such as aluminum nitride in a high content, although the surface roughness is high. It was found that the adhesion strength (peeling strength) was extremely inferior.

  An object of the present invention is to provide a high level of characteristics required for an insulating layer of a multilayer printed wiring board that exhibits sufficient thermal diffusivity and has low surface roughness and good adhesion strength (peel strength) with a conductor layer. It is providing the resin composition which brings about the hardened | cured material satisfy | filled by.

  As a result of intensive studies on the above problems, the present inventors have used a filler obtained by treating at least one highly thermally conductive inorganic filler selected from the group consisting of aluminum nitride and silicon nitride with a silane compound. The present inventors have found that the above problems can be solved and have completed the present invention.

That is, the present invention includes the following contents.
[1] (A) at least one highly thermally conductive inorganic filler selected from the group consisting of aluminum nitride and silicon nitride;
(B) an epoxy resin, and (C) a resin composition containing a curing agent,
(A) The resin composition by which the component is processed with the silane compound.
[2] The resin composition according to [1], wherein the silane compound has a phenyl group.
[3] The resin composition according to [1] or [2], wherein a treatment amount of the silane compound is 0.05 parts by mass or more with respect to 100 parts by mass of the high thermal conductive inorganic filler.
[4] The component (C) includes a first curing agent and a second curing agent different from the first curing agent, and the first curing agent is an active ester curing agent. ] The resin composition in any one of [3].
[5] The resin composition according to [4], wherein the second curing agent is a triazine structure-containing curing agent.
[6] The resin composition according to [4] or [5], wherein the second curing agent is a triazine structure-containing phenol-based curing agent or a triazine structure-containing cyanate ester-based curing agent.
[7] Any of [4] to [6], wherein the mass ratio of the first curing agent to the second curing agent (first curing agent / second curing agent) is 0.3 to 2. The resin composition described in 1.
[8] A cured product obtained by thermosetting the resin composition according to any one of [1] to [7].
[9] The cured product according to [8], wherein the arithmetic average roughness (Ra) of the surface is 180 nm or less.
[10] The cured product according to [8] or [9], which has a thermal conductivity of 1 W / m · K or more.
[11] A roughened cured body obtained by roughening the cured body according to any one of [8] to [10].
[12] A laminate comprising the roughened cured body according to [11] and a conductor layer formed on the surface of the roughened cured body.
[13] The laminate according to [12], wherein the peel strength between the roughened cured body and the conductor layer is 0.25 kgf / cm or more.
[14] A multilayer printed wiring board comprising the cured product according to any one of [8] to [10] or the roughened cured product according to [11].
[15] A semiconductor device comprising the multilayer printed wiring board according to [14].

  According to the present invention, there is provided a resin composition that provides a cured product that exhibits sufficient thermal diffusivity and has low surface roughness and good adhesion strength (peel strength) with a conductor layer.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

[Resin composition]
The resin composition of the present invention comprises (A) at least one highly thermally conductive inorganic filler selected from the group consisting of aluminum nitride and silicon nitride, (B) an epoxy resin, and (C) a curing agent. The component A) is treated with a silane compound.

<(A) component>
Component (A) of the present invention is at least one highly thermally conductive inorganic filler selected from the group consisting of aluminum nitride and silicon nitride, and is characterized by being treated with a silane compound.

  The high thermal conductivity inorganic filler selected from the group consisting of aluminum nitride and silicon nitride is very high compared to silica conventionally used as an inorganic filler (thermal conductivity is 1.5 W / m · K at most). Has thermal conductivity. From the viewpoint of obtaining a cured product having sufficient thermal diffusivity, the thermal conductivity of the high thermal conductive inorganic filler used for the component (A) is preferably 25 W / m · K or more, more preferably 50 W / m ·. K or more, more preferably 75 W / m · K or more, even more preferably 100 W / m · K or more, particularly preferably 125 W / m · K or more, 150 W / m · K or more, 175 W / m · K or more, 200 W / m · K or more, or 225 W / m · K or more. The upper limit of the thermal conductivity of the high thermal conductive inorganic filler is not particularly limited, but is usually 400 W / m · K or less. The thermal conductivity of the high thermal conductive inorganic filler can be measured by a known method such as a heat flow meter method or a temperature wave analysis method.

  The shape of the highly thermally conductive inorganic filler used as the component (A) is not particularly limited, but a spherical shape is preferable. The average particle diameter of the high thermal conductive inorganic filler is preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 2 μm or less from the viewpoint of obtaining a cured product having sufficient thermal diffusibility and low surface roughness. Even more preferably, it is 1.5 μm or less. The lower limit of the average particle diameter of the highly heat-conductive inorganic filler is not particularly limited, but is usually 0.01 μm or more, preferably 0.05 μm or more. The average particle diameter of the highly heat-conductive inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the high thermal conductive filler can be prepared on a volume basis with a laser diffraction / scattering particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter. As the measurement sample, a high thermal conductive inorganic filler dispersed in a solvent by ultrasonic waves can be preferably used. As a laser diffraction scattering type particle size distribution measuring apparatus, LA-500 manufactured by Horiba, Ltd. can be used.

As a commercial item of aluminum nitride, for example, “Shape H” (average particle size 1.1 μm, specific surface area 2.6 m ² / g) manufactured by Tokuyama Corporation can be mentioned, and as a commercial item of silicon nitride, for example, “SN-9S” (average particle size 1.1 μm, specific surface area 7 m ² / g) manufactured by Denki Kagaku Kogyo K.K.

  In the present invention, by using a filler obtained by treating a high thermal conductivity inorganic filler selected from the group consisting of aluminum nitride and silicon nitride with a silane compound, sufficient thermal diffusibility is exhibited and surface roughness is increased. Realizes a resin composition that provides a cured product having a low adhesion strength (peeling strength) with a conductor layer. Here, the aluminum nitride and silicon nitride used for the component (A) have a very small amount of functional groups such as surface hydroxyl groups capable of reacting with the silane compound, unlike conventionally used silica. Therefore, it is not common to treat aluminum nitride and silicon nitride with a silane compound. Furthermore, when aluminum nitride and silicon nitride are treated with a silane compound, the surface roughness of the resulting cured product and adhesion to the conductor layer The knowledge found in the present invention that the properties such as strength (peel strength) change remarkably cannot be predicted from the conventional knowledge. Moreover, even if it sees thermal diffusivity, the hardening body containing the filler which processed aluminum nitride and silicon nitride with the silane compound is compared with the hardening body containing untreated aluminum nitride and silicon nitride in the same content, The present inventors have confirmed that a higher value is exhibited. In this regard, with respect to conventionally used silica, in addition to silane compounds, aluminum-based coupling agents, titanium-based coupling agents, and zirconium-based coupling agents are known as surface treatment agents. The present inventors have found that the effects of the present invention are not achieved with other surface treatment agents such as a ring agent, and that the effects of the present invention can be achieved specifically when a silane compound is used.

  Silane compounds used for the treatment of highly thermally conductive inorganic fillers contain at least one organic group in the molecule. The organic group has 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 10 carbon atoms) from the viewpoint of obtaining a cured product having low surface roughness and good adhesion strength (peel strength) to the conductor layer. 6, more preferably 1 to 4) alkyl groups, and aryl groups having 6 to 20 carbon atoms (preferably 6 to 14, more preferably 6 to 12 and even more preferably 6 to 10) are preferable. Is preferred.

  The silane compound used for the treatment of the high thermal conductive inorganic filler is not particularly limited as long as the above organic group can be introduced on the surface of the high thermal conductive inorganic filler, and can react with the component (B) described later. It may further have a reactive group (for example, an amino group, an epoxy group, a mercapto group, etc.) or may not have a reactive group. As the silane compound having a reactive group, for example, i) a silane compound in which a part of hydrogen atoms of an organic group bonded to a Si atom is substituted with a reactive group or a group containing a reactive group, ii) bonded to a Si atom And a silane compound in which a part of hydrogen atoms of the reactive group or the group containing the reactive group is substituted with an organic group.

  The molecular weight of the silane compound used for the treatment of the high thermal conductive inorganic filler is preferably 70 or more, more preferably 90 or more, still more preferably 110 or more, 130 or more, 150 or more, 170 or more, or 190 or more. The upper limit of the molecular weight of the silane compound is preferably 500 or less, more preferably 400 or less, still more preferably 350 or less, 300 or less, 280 or less, or 260 or less.

In one embodiment, the silane compound used for the treatment of the high thermal conductive inorganic filler is a compound represented by the following formula (1).
Si (R ¹ ) _n (R ² ) _4-n (1)
[Where:
R ^{1 is,} -R 11, represents a ^{-R 11 '-R 12,} or ^{-R 12' -R 11, wherein, R 11} represents an alkyl group or an aryl ^{group, R 12} is an amino group, an epoxy group or Represents a mercapto group or a monovalent group containing an amino group, an epoxy group or a mercapto group, and R ¹¹ ′ represents a divalent group obtained by removing one hydrogen atom from a monovalent group represented by R ^11. R ¹² ′ represents a divalent group obtained by removing one hydrogen atom from the monovalent group represented by R ¹² ;
R ² represents a hydrogen atom or an alkoxy group,
n represents an integer of 1 to 3. When a plurality of R ¹ are present, they may be the same or different, and when a plurality of R ² are present, they may be the same or different. ]

The number of carbon atoms of the alkyl group represented by R ¹¹ is preferably 1-20, more preferably 1-10, even more preferably 1-6, and even more preferably 1-4. The number of carbon atoms of the aryl group represented by R ¹¹ is preferably 6-20, more preferably 6-14, still more preferably 6-12, and even more preferably 6-10. R ¹¹ is preferably an aryl group, particularly preferably a phenyl group.

R ¹² is preferably an amino group, a mercapto group, a monovalent group containing an amino group, or a monovalent group containing an epoxy group. Examples of the monovalent group containing an amino group include an N- (amino C _1-10 alkyl) amino group, an amino C _1-10 alkoxy group, and an amino C _1-10 alkyl group, and N- (2 -Aminoethyl) amino group, N- (3-aminopropyl) amino group, aminoethoxy group, aminopropoxy group, aminoethyl group, aminopropyl group are preferred. Examples of the monovalent group containing an epoxy group include an epoxyalkyl group and an epoxyalkyloxy group, and the number of these carbon atoms is preferably 3 to 10, more preferably 3 to 6. Preferable specific examples include a glycidyl group, a glycidoxy group, and a 3,4-epoxycyclohexyl group.

R ¹¹ ′ represents a divalent group obtained by removing one hydrogen atom from the monovalent group represented by R ¹¹ , that is, an alkylene group or an arylene group. A suitable number of carbon atoms of the divalent group represented by R ¹¹ ′ may be the same as that described for R ¹¹ . R ¹¹ ′ is preferably an alkylene group.

R ¹² ′ represents a divalent group obtained by removing one hydrogen atom from the monovalent group represented by R ¹² , and a divalent group obtained by removing one hydrogen atom from a monovalent group containing an amino group. And a divalent group excluding one hydrogen atom bonded to the nitrogen atom of an amino C _1-10 alkyl group (preferably an aminoethyl group or aminopropyl group) is more preferable.

n represents an integer of 1 to 3, and is preferably 1 or 2. When a plurality of R ¹ are present, they may be the same or different. From the viewpoint of obtaining a cured product having low surface roughness and good adhesion strength (peel strength) to the conductor layer, at least one R ¹ in formula (1) is -R ¹¹ or -R ¹² '-R ^11. It is preferable that

The number of carbon atoms of the alkoxy group represented by R ² is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 or 2. R ² is preferably an alkoxy group.

  Specific examples of the silane compound include silane compounds such as methyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, aminopropylmethoxysilane, aminopropyltriethoxysilane, and N-phenyl-3-aminopropyl. Aminosilane compounds such as trimethoxysilane, N- (2-aminoethyl) aminopropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidoxy Epoxysilane compounds such as propylphenyldiethoxysilane, glycidylbutyltrimethoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, mercaptopropyltri Examples include mercaptosilane compounds such as methoxysilane, mercaptopropylphenyldimethoxysilane, and mercaptopropyltriethoxysilane. Examples of commercially available silane compounds include “KBM103” (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. and “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., manufactured by Shin-Etsu Chemical Co., Ltd. “KBM803” (3-mercaptopropyltrimethoxysilane) and the like. A silane compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  The treatment of the high thermal conductive inorganic filler with the silane compound may be carried out by any conventionally known dry method or wet method.

  From the viewpoint of obtaining a cured product having low surface roughness and good adhesion strength (peel strength) to the conductor layer, the amount of the silane compound is preferably 0.05 with respect to 100 parts by mass of the high thermal conductive inorganic filler. It is at least 0.1 part by mass, more preferably at least 0.1 part by mass, even more preferably at least 0.3 part by mass, even more preferably at least 0.5 part by mass. The upper limit of the treatment amount is not particularly limited, but is preferably 5 parts by mass or less. Here, the treatment amount of the silane compound is a value calculated based on the mass of the silane compound and the mass of the high thermal conductivity inorganic filler used for the treatment of the high thermal conductivity inorganic filler with the silane compound.

The degree of treatment with the silane compound can also be evaluated by the amount of carbon per unit surface area of the highly thermally conductive inorganic filler. The amount of carbon per unit surface area of the highly heat-conductive inorganic filler is preferably 0.05 mg / m ² or more from the viewpoint of obtaining a cured body having low surface roughness and good adhesion strength (peel strength) with the conductor layer, 0.10 mg / m ² or more is more preferable, and 0.15 mg / m ² or more is more preferable. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin varnish and the film form, 1.0 mg / m ² or less is preferable, 0.8 mg / m ² or less is more preferable, and 0.6 mg / m ² or less. Is more preferable.

  The amount of carbon per unit surface area of the high thermal conductive inorganic filler can be measured after the high thermal conductive inorganic filler after the treatment with the silane compound is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the high thermal conductive inorganic filler treated with the silane compound, and ultrasonic cleaning is performed at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid content, the carbon amount per unit surface area of the high thermal conductivity inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, “EMIA-320V” manufactured by HORIBA, Ltd. can be used.

  In addition, you may attach | subject the highly heat conductive inorganic filler used for (A) component to the hydrophobization process before the process by a silane compound. Examples of the hydrophobization treatment of the high thermal conductive inorganic filler include a heat treatment at a high temperature (eg, 200 ° C. or higher, preferably 300 ° C. or higher, more preferably 400 ° C. or higher).

From the viewpoint of obtaining a cured product having sufficient thermal diffusivity, the content of the highly thermally conductive inorganic filler in the resin composition is preferably 50% by mass or more, more preferably 55% by mass or more, and further preferably 60% by mass. % Or more.
In addition, in this invention, content of each component in a resin composition is a value when the sum total of the non-volatile component in a resin composition shall be 100 mass% unless there is separate description.

  In the present invention using a filler obtained by treating a highly thermally conductive inorganic filler selected from the group consisting of aluminum nitride and silicon nitride with a silane compound, without excessively increasing the surface roughness of the resulting cured product, and The content of the high thermal conductive inorganic filler can be further increased without lowering the adhesion strength (peel strength) with the conductor layer. For example, the content of the high thermal conductive inorganic filler in the resin composition is 62% by mass or more, 64% by mass or more, 66% by mass or more, 68% by mass or more, 70% by mass or more, 72% by mass or more, 74% by mass. % Or more, 76 mass% or more, 78 mass% or more, or 80 mass% or more.

  The upper limit of the content of the highly thermally conductive inorganic filler in the resin composition is preferably 95% by mass or less, more preferably 90% by mass or less, from the viewpoint of the mechanical strength of a cured product obtained by thermal curing of the resin composition. More preferably, it is 85% by mass or less.

<(B) component>
Component (B) contained in the resin composition of the present invention is an epoxy resin.

  Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, anthracene type epoxy Resin, fluorene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, trisphenol epoxy resin, phosphorus-containing epoxy resin, alicyclic epoxy resin, linear aliphatic epoxy resin, phenol novolac type epoxy resin, cresol novolac Type epoxy resin, bisphenol A novolac type epoxy resin, epoxy resin having butadiene structure, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexa Dimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, diglycidyl etherification product of bisphenols, diglycidyl etherification product of naphthalenediol, glycidyl etherification product of phenols, and diglycidyl etherification product of alcohols And alkyl-substituted products, halides and hydrogenated products of these epoxy resins. These epoxy resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile component of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Among them, it has two or more epoxy groups in one molecule and has a liquid epoxy resin (hereinafter referred to as “liquid epoxy resin”) at a temperature of 20 ° C. and three or more epoxy groups in one molecule. And a solid epoxy resin at a temperature of 20 ° C. (hereinafter referred to as “solid epoxy resin”). By using a liquid epoxy resin and a solid epoxy resin in combination as an epoxy resin, a resin composition having excellent flexibility can be obtained. Moreover, the breaking strength of the insulating layer formed by curing the resin composition is also improved.

  As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, or naphthalene type epoxy resin are preferable, and bisphenol A type epoxy resin, bisphenol F type epoxy resin, or naphthalene type epoxy resin are preferable. More preferred. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D”, “EXA4032SS”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC Corporation, and “jER828EL” (bisphenol A) manufactured by Mitsubishi Chemical Corporation. Type epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "ZX1059" (bisphenol A type epoxy resin and bisphenol F type epoxy) manufactured by Nippon Steel Chemical Co., Ltd. Resin mixture). These may be used individually by 1 type, or may use 2 or more types together.

  Solid epoxy resins include tetrafunctional naphthalene type epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol epoxy resins, naphthol novolac epoxy resins, biphenyl type epoxy resins, bixylenol type epoxy resins, and naphthylene. Ether type epoxy resins or fluorene type epoxy resins are preferable, and tetrafunctional naphthalene type epoxy resins, biphenyl type epoxy resins, bixylenol type epoxy resins, naphthylene ether type epoxy resins or fluorene type epoxy resins are more preferable. Specific examples of the solid epoxy resin include “HP-4700”, “HP-4710” (tetrafunctional naphthalene type epoxy resin), “N-690” (cresol novolac type epoxy resin) manufactured by DIC Corporation, “ N-695 ”(cresol novolac type epoxy resin),“ HP-7200 ”(dicyclopentadiene type epoxy resin),“ EXA7311 ”,“ EXA7311-G3 ”,“ HP6000 ”(naphthylene ether type epoxy resin), Nippon Kayaku “EPPN-502H” (trisphenol epoxy resin), “NC7000L” (naphthol novolac epoxy resin), “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type epoxy resin), manufactured by Yakuhin Co., Ltd. “ESN475” manufactured by Nippon Steel Chemical Co., Ltd. Toll novolac type epoxy resin), “ESN485” (naphthol novolak type epoxy resin), “YX4000H”, “YL6121” (biphenyl type epoxy resin), “YX4000HK” (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "YL7800" (fluorene type epoxy resin) etc. are mentioned.

  When the liquid epoxy resin and the solid epoxy resin are used in combination as the epoxy resin, the quantitative ratio thereof (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.1 to 1: 6 by mass ratio. preferable. By making the quantitative ratio of the liquid epoxy resin and the solid epoxy resin within such a range, i) suitable adhesiveness is obtained when used in the form of an adhesive film, ii) when used in the form of an adhesive film Sufficient flexibility and handleability are improved, and iii) an insulating layer having sufficient breaking strength can be obtained. From the viewpoint of the effects i) to iii) above, the quantitative ratio of liquid epoxy resin to solid epoxy resin (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.3 to 1: 5 by mass ratio. Is more preferable, the range of 1: 0.6 to 1: 4.5 is more preferable, and the range of 1: 0.8 to 1: 4 is particularly preferable.

  The content of the epoxy resin in the resin composition is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 45% by mass, still more preferably 5% by mass to 40% by mass, and 7% by mass to 35% by mass. % Is particularly preferred.

  The epoxy equivalent of the epoxy resin is preferably 50 to 4500, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000. By being in this range, the crosslink density of the cured product is sufficient and an insulating layer having a low surface roughness is obtained. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.

  The weight average molecular weight in terms of polystyrene of the epoxy resin is preferably in the range of 100 to 3000, more preferably in the range of 200 to 2500, and still more preferably in the range of 300 to 2000. The weight average molecular weight in terms of polystyrene of the epoxy resin is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-converted weight average molecular weight of the epoxy resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L manufactured by Showa Denko KK as a column. / K-804L is 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.

<(C) component>
(C) component contained in the resin composition of this invention is a hardening | curing agent.

  The curing agent is not particularly limited as long as it has a function of curing the epoxy resin (B), for example, an active ester curing agent, a phenol curing agent, a naphthol curing agent, a cyanate ester curing agent, a benzoxazine curing. Agents, acid anhydride curing agents, epoxy adducts, microencapsulated products, and the like. A hardening | curing agent may be used individually by 1 type, and may be used in combination of 2 or more type.

  Although there is no restriction | limiting in particular as an active ester type hardening | curing agent, Generally ester groups with high reaction activity, such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of heterocyclic hydroxy compound, are in 1 molecule. A compound having two or more in the above 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. Among these, 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 an aliphatic carboxylic acid having 1 to 20 carbon atoms (preferably 2 to 10 and more preferably 2 to 8) and an aromatic having 7 to 20 carbon atoms (preferably 7 to 10). Carboxylic acid is mentioned. Suitable aliphatic carboxylic acids include, for example, acetic acid, malonic acid, succinic acid, maleic acid, itaconic acid and the like. Suitable examples of the aromatic carboxylic acid include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like.

  Examples of the phenol compound include phenol compounds having 6 to 40 carbon atoms (preferably 6 to 30, more preferably 6 to 23, and further preferably 6 to 22). Specific examples include hydroquinone, Resorcin, bisphenol A, bisphenol F, bisphenol S, phenol phthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, dihydroxybenzophenone, tri Examples thereof include hydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene type diphenol and the like. A phenol novolac may also be used as the phenol compound. Examples of the naphthol compound include naphthol compounds having 10 to 40 carbon atoms (preferably 10 to 30, more preferably 10 to 20), and specific examples include α-naphthol, β-naphthol, , 5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and the like. A naphthol novolak may also be used as the naphthol compound.

  Preferable specific examples of the active ester curing agent include an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and a benzoylated product of phenol novolac. An active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene type diphenol structure are more preferable. In the present invention, the “dicyclopentadiene type diphenol structure” represents a divalent structural unit composed of phenylene-dicyclopentalene-phenylene.

  As a commercial product of an active ester type curing agent, as an active ester compound containing a dicyclopentadiene type diphenol structure, “EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000-65T” (manufactured by DIC Corporation) ), “EXB9416-70BK” (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, “DC808” (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated product of phenol novolac, and benzoyl of phenol novolac Examples of the active ester compound containing a compound include “YLH1026” (manufactured by Mitsubishi Chemical Corporation).

  As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. In addition, in the combination with the component (A), a triazine structure-containing phenol-based curing agent is more preferable from the viewpoint of obtaining a cured product having excellent adhesion strength (peel strength) to the conductor layer. Among these, a triazine structure-containing phenol novolac curing agent is preferable from the viewpoint of obtaining a cured product that satisfies the heat resistance, water resistance, and adhesion strength (peel strength) with the conductor layer in combination with the component (A).

  Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7785” manufactured by Meiwa Kasei Co., Ltd., and Nippon Kayaku Co., Ltd. “NHN”, “CBN”, “GPH”, “SN170”, “SN180”, “SN190”, “SN475”, “SN485”, “SN495”, “SN375”, “SN395” manufactured by Toto Kasei Co., Ltd. And “TD2090” manufactured by DIC Corporation. Specific examples of the triazine structure-containing phenolic curing agent include “LA3018” manufactured by DIC Corporation. Specific examples of the triazine structure-containing phenol novolak curing agent include “LA7052”, “LA7054”, “LA1356” and the like manufactured by DIC Corporation.

  Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate)), 4,4′-methylene bis (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- Bifunctional cyanate resins such as dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether; Phenol novolac and Polyfunctional cyanate resin derived from resol novolac, prepolymers of these cyanate resin is partially triazine of (hereinafter also referred to as "triazine structure-containing cyanate ester curing agents".) And the like. Among these, a triazine structure-containing cyanate ester-based curing agent is preferable from the viewpoint of obtaining a cured product having excellent adhesion strength (peel strength) to the conductor layer in combination with the component (A).

  Specific examples of the cyanate ester curing agent include “PT30” and “PT60” (both phenol novolak polyfunctional cyanate ester resins) and “BA230” (part or all of bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. Is a triazine structure-containing cyanate ester-based curing agent).

  Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Polymer Co., Ltd., “Pd” and “Fa” manufactured by Shikoku Kasei Kogyo Co., Ltd.

  Examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, hydrogenated methylnadic acid anhydride. , Trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride Acid, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonetetra Carboxylic dianhydride, 1,3,3a, 4,5,9b-hex Hydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C] furan-1,3-dione, ethylene glycol bis (anhydrotrimellitate), styrene and maleic acid Examples thereof include polymer-type acid anhydrides such as copolymerized styrene / maleic acid resins.

  From the viewpoint of further reducing the surface roughness of the resulting cured product (particularly the surface roughness of the cured product after the roughening treatment) in combination with the component (A), the component (C) contains an active ester curing agent. It is preferable to include.

  In a preferred embodiment, the component (C) includes a first curing agent and a second curing agent that is different from the first curing agent, and the first curing agent is an active ester curing agent. . In such an embodiment, as the second curing agent, the above-mentioned phenol-based curing agent, naphthol-based curing agent, benzoxazine-based curing agent, cyanate ester-based curing agent, acid anhydride-based curing agent, and these epoxy adducts Or one or more curing agents selected from the group consisting of microencapsulated materials may be used, but in combination with the component (A), a viewpoint of obtaining a cured product having excellent adhesion strength (peeling strength) with the conductor layer Among these curing agents, a curing agent containing a triazine structure (hereinafter also referred to as “triazine structure-containing curing agent”) is preferable, and a triazine structure-containing phenol-based curing agent or a triazine structure-containing cyanate ester-based curing agent is more preferable. . By using such a combination of specific curing agents as the component (C), the surface roughness of the resulting cured body (particularly the surface roughness of the cured body after the roughening treatment) is further reduced, and the conductor layer A cured product having excellent adhesion strength (peeling strength) can be obtained. Further, when the content of the high thermal conductive inorganic filler in the resin composition is increased by using such a combination of specific curing agents (for example, 70% by mass or more), the surface roughness is low. A cured body having excellent adhesion strength with the conductor layer can be realized.

  When the combination of the first curing agent and the second curing agent is used as the component (C), the mass ratio of the first curing agent to the second curing agent (first curing agent / second curing The agent is preferably from 0.3 to 2, more preferably from 0.4 to 1.8, and even more preferably from the viewpoint of obtaining a cured product having low surface roughness and excellent adhesion strength (peel strength) to the conductor layer. 0.5 to 1.6. Further, [number of reactive groups of first curing agent] / [number of reactive groups of second curing agent] provides a cured body having a low surface roughness and excellent adhesion strength (peeling strength) with the conductor layer. From the viewpoint, it is preferably 0.1 to 2, more preferably 0.2 to 1.8, still more preferably 0.3 to 1.6, still more preferably 0.4 to 1.4, particularly preferably 0. 5 to 1.2. Here, the reactive group of the first curing agent is an active ester group. The reactive group of the second curing agent is an active hydroxyl group or the like and varies depending on the type of the curing agent. The number of reactive groups in the first curing agent is a value obtained by dividing the solid content mass of the active ester curing agent used for the component (C) by the reactive group equivalent. The number of reactive groups in the second curing agent is a value obtained by totaling the values obtained by dividing the solid content mass of the curing agent other than the active ester curing agent used for the component (C) by the reactive group equivalent for all curing agents. It is.

  The quantity ratio of the component (B) and the component (C) in the resin composition is a ratio of [(B) the total number of epoxy groups of the epoxy resin]: [(C) the total number of reactive groups of the curing agent]. The range of 1: 0.2 to 1: 2 is preferable, 1: 0.3 to 1: 1.5 is more preferable, and 1: 0.4 to 1: 1 is more preferable. Here, (B) the total number of epoxy groups in the epoxy resin is a value obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and (C) reaction of the curing agent. The total number of groups is a value obtained by adding the values obtained by dividing the solid mass of each curing agent by the reactive group equivalent for all curing agents.

<Other ingredients>
The resin composition of the present invention comprises (D) an inorganic filler other than aluminum nitride and silicon nitride (hereinafter simply referred to as “inorganic filler”), (E) a thermoplastic resin, and (F) curing as required. Additives such as accelerators, (G) flame retardants, and (H) rubber particles may be included.

(D) Inorganic filler Examples of the inorganic filler include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, Aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, manganese nitride, aluminum borate, barium titanate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, Examples thereof include titanium oxide, zirconium oxide, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

  The average particle size of the inorganic filler is preferably 3 μm or less, more preferably 1.5 μm or less. Although the minimum of the average particle diameter of an inorganic filler is not specifically limited, Usually, it is 0.01 micrometer or more, Preferably it is 0.05 micrometer or more. The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory, similarly to the high thermal conductive inorganic filler.

  The inorganic filler is treated with a surface treatment agent such as an aminosilane compound, an epoxysilane compound, a mercaptosilane compound, a silane compound, an organosilazane compound, an aluminum coupling agent, a titanium coupling agent, or a zirconium coupling agent. Also good.

  When the inorganic filler is used, the total content of the high thermal conductivity inorganic filler and the inorganic filler in the resin composition is preferably in the range of 50% by mass to 95% by mass, more preferably 60% by mass to 95%. What is necessary is just to use so that it may become the range of the mass%.

(E) Thermoplastic resin Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyethersulfone resin, polyphenylene ether resin, and polysulfone resin. . A thermoplastic resin may be used individually by 1 type, and may be used in combination of 2 or more type.

  The weight average molecular weight in terms of polystyrene of the thermoplastic resin is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, still more preferably in the range of 15,000 to 60,000, and 20 More preferably, the range is from 6,000 to 60,000. The weight average molecular weight in terms of polystyrene of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-reduced weight average molecular weight of the thermoplastic resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K- manufactured by Showa Denko KK as a column. 804L / K-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, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene Examples thereof include phenoxy resins having a skeleton and one or more skeletons selected from the group consisting of a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. A phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. Specific examples of the phenoxy resin include “1256” and “4250” (both bisphenol A skeleton-containing phenoxy resin), “YX8100” (bisphenol S skeleton-containing phenoxy resin), and “YX6954” (manufactured by Mitsubishi Chemical Corporation). In addition, “FX280” and “FX293” manufactured by Toto Kasei Co., Ltd., “YL7553”, “YL6794”, “YL7213” manufactured by Mitsubishi Chemical Corporation, YL7290 "," YL7482 ", etc. are mentioned.

  Specific examples of the polyvinyl acetal resin include: Electric Butyral 4000-2, 5000-A, 6000-C, 6000-EP manufactured by Denki Kagaku Kogyo Co., Ltd., S-Lec BH Series, BX Series manufactured by Sekisui Chemical Co., Ltd. KS series, BL series, BM series, etc. are mentioned.

  Specific examples of the polyimide resin include “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd. Specific examples of the polyimide resin include linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (described in JP-A-2006-37083), a polysiloxane skeleton. Examples thereof include modified polyimides such as containing polyimide (described in JP-A No. 2002-12667 and JP-A No. 2000-319386).

  Specific examples of the polyamide-imide resin include “Bilomax HR11NN” and “Bilomax HR16NN” manufactured by Toyobo Co., Ltd. Specific examples of the polyamideimide resin also include modified polyamideimides such as polysiloxane skeleton-containing polyamideimides “KS9100” and “KS9300” manufactured by Hitachi Chemical Co., Ltd.

  Specific examples of the polyethersulfone resin include “PES5003P” manufactured by Sumitomo Chemical Co., Ltd.

  Specific examples of the polysulfone resin include polysulfone “P1700” and “P3500” manufactured by Solvay Advanced Polymers Co., Ltd.

  The content of the thermoplastic resin in the resin composition is preferably 0.1% by mass to 60% by mass, more preferably 0.1% by mass to 50% by mass, and further preferably 0.5% by mass to 30% by mass. Still more preferably, it is 0.5 mass%-10 mass%. By setting the content of the thermoplastic resin in such a range, the viscosity of the resin composition becomes appropriate, and a uniform resin composition having a thickness and a bulk property can be formed.

(F) Curing accelerator Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and the like. A curing accelerator and an imidazole curing accelerator are preferable, and an amine curing accelerator and an imidazole curing accelerator are more preferable. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of phosphorus curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate. , Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like.

  Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo. (5, 4, 0) -undecene and the like.

  Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2 Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino- 6- [2′-Methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl- 4-methyl-5-hydroxymethylimidazole, 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.

  Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, 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 biguanide, 1- ( - tolyl) biguanide, and the like.

  The content of the curing accelerator in the resin composition is preferably 0.01% by mass to 3% by mass, more preferably 0.01% by mass to 2% by mass, and still more preferably 0.01% by mass to 1% by mass. It is.

  As the curing accelerator, a metal-based curing accelerator may be used. 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, for example. 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. Specific examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

  When using a metal curing accelerator, the content of the metal curing accelerator in the resin composition is preferably in the range of 25 ppm to 500 ppm, more preferably 40 ppm to 200 ppm, based on the metal curing accelerator. Set to be in the range.

(G) Flame retardant 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 and may be used in combination of 2 or more type. The content of the flame retardant in the resin composition layer is not particularly limited, but is preferably 0.5% by mass to 10% by mass, more preferably 1% by mass to 9% by mass, and 1.5% by mass to 8% by mass. Is more preferable.

(H) Rubber Particles As the rubber particles, for example, those that do not dissolve in the 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 and may be used in combination of 2 or more type.

  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. The content of the rubber particles in the resin composition is preferably 1% by mass to 10% by mass, and more preferably 2% by mass to 5% by mass.

  The resin composition of the present invention may contain other additives as necessary. Examples of such other additives include organic fillers, thickeners, antifoaming agents, leveling agents, and adhesion. Examples thereof include resin additives such as a property-imparting agent and a colorant.

  The resin composition of the present invention can be used for various applications because the cured product exhibits sufficient thermal diffusibility. For example, the resin composition of the present invention includes an insulating resin sheet such as an adhesive film or prepreg, a circuit board (for laminated board use, multilayer printed wiring board use, etc.), solder resist, underfill material, die bonding material, semiconductor sealing material. It can be used for a wide range of applications that can enjoy the benefits of thermal diffusivity, such as resin for filling holes and resin for filling parts. Among them, a resin composition for forming an insulating layer of a metal-clad laminate (resin composition for an insulating layer of a metal-clad laminate), a resin composition for forming an insulating layer of a multilayer printed wiring board (multilayer printed wiring) Resin composition for forming an insulating layer in manufacturing a multilayer printed wiring board by a build-up method (build-up insulating layer for a multilayer printed wiring board). As a resin composition for forming a conductor layer by plating (resin composition for build-up insulating layers of multilayer printed wiring boards in which a conductor layer is formed by plating). Furthermore, it can be used suitably.

  The resin composition of the present invention can be applied in a varnish state and used for various purposes, but industrially, it is generally preferable to use it in the form of a sheet-like laminated material such as an adhesive film or a prepreg described later. is there.

  In one embodiment, the adhesive film includes a support and a resin composition layer (adhesive layer) bonded to the support, and the resin composition layer (adhesive layer) is the resin composition of the present invention. Formed from.

  The thickness of the resin composition layer varies depending on the use, but when used as an insulating layer of a multilayer printed wiring board, it is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 60 μm or less, and even more preferably 50 μm or less. It is. Although the minimum of the thickness of a resin composition layer changes with uses, when using as an insulating layer of a multilayer printed wiring board, it is 10 micrometers or more normally.

  A film made of a plastic material is preferably used as the support. Examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) and polyethylene naphthalate (hereinafter sometimes abbreviated as “PEN”), polycarbonate (hereinafter referred to as “PET”). PC ”), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide and the like. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable. In a preferred embodiment, the support is a polyethylene terephthalate film.

  The support may be subjected to a mat treatment or a corona treatment on the surface to be joined to the resin composition layer. Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used.

  Although the thickness of a support body is not specifically limited, The range of 5 micrometers-75 micrometers is preferable, and the range of 10 micrometers-60 micrometers is more preferable. In addition, when a support body is a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

  The adhesive film is prepared, for example, by preparing a resin varnish in which a resin composition is dissolved in an organic solvent, and applying the resin varnish onto a support using a die coater or the like, and further heating or blowing hot air to the organic solvent. It can manufacture by drying and forming a 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. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

  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 boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of the organic solvent, the resin composition is dried at 50 ° C. to 150 ° C. for 3 to 10 minutes. A layer can be formed.

  In the adhesive film, a protective film according to the support can be further laminated on the surface of the resin composition layer that is not joined to the support (that is, the surface opposite to the support). Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer-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 be stored in a roll. When an adhesive film has a protective film, it can be used by peeling off the protective film.

  In one embodiment, the prepreg is formed by impregnating the sheet-like fiber base material with the resin composition of the present invention.

  The sheet-like fiber base material used for a prepreg is not specifically limited, What is used normally as base materials for prepregs, such as a glass cloth, an aramid nonwoven fabric, a liquid crystal polymer nonwoven fabric, can be used. When used for forming an insulating layer of a multilayer printed wiring board, a thin sheet-like fiber substrate having a thickness of 50 μm or less is preferably used, and particularly a sheet-like fiber substrate having a thickness of 10 μm to 40 μm is preferable. A sheet-like fiber substrate of 10 μm to 30 μm is more preferable, and a sheet-like fiber substrate of 10 to 20 μm is more preferable.

  The prepreg can be produced by a known method such as a hot melt method or a solvent method.

  The thickness of the prepreg can be in the same range as the resin composition layer in the adhesive film described above.

[Hardened body]
The cured product of the present invention is obtained by thermally curing the resin composition of the present invention.

  The thermosetting conditions for the resin composition are not particularly limited, and for example, the conditions normally employed when forming the insulating layer of the multilayer printed wiring board may be used.

  For example, although the thermosetting conditions of the resin composition vary depending on the composition of the resin composition, the curing temperature is in the range of 120 ° C to 240 ° C (preferably in the range of 150 ° C to 210 ° C, more preferably in the range of 170 ° C to 190 ° C. C.) and the curing time can be in the range of 5 minutes to 90 minutes (preferably 10 minutes to 75 minutes, more preferably 15 minutes to 60 minutes).

  Before the resin composition is thermally cured, the resin composition may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition, the resin composition is kept at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 110 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower) for 5 minutes. Preheating may be performed as described above (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

  The cured body of the present invention can exhibit sufficient thermal diffusivity. For example, the cured product of the present invention is preferably 1 W / m · K or more, more preferably 1.2 W / m · K or more, although it varies depending on the content of the high thermal conductive inorganic filler in the resin composition to be used. More preferably, 1.4 W / m · K or more, still more preferably 1.5 W / m · K or more, particularly preferably 1.6 W / m · K or more, 1.7 W / m · K or more, 1.8 W / M · K or more, 1.9 W / m · K or more, 2.0 W / m · K or more, 2.1 W / m · K or more, 2.2 W / m · K or more, 2.3 W / m · K or more Thermal conductivity of 2.4 W / m · K or higher, 2.5 W / m · K or higher, 2.6 W / m · K or higher, 2.7 W / m · K or higher, or 2.8 W / m · K or higher. It can be expressed. The upper limit of the thermal conductivity of the cured product of the present invention is not particularly limited, but is usually 30 W / m · K or less. The thermal conductivity of the cured product of the present invention can be measured by known methods such as a heat flow meter method and a temperature wave analysis method. Although it varies depending on the application, when the thickness of the cured product of the present invention is thin (for example, 100 μm or less), the thermal conductivity can be measured using a cured product having the same thickness as the actual use state. It is preferable to measure by a wave analysis method. As a specific example of the thermal conductivity measuring device by the temperature wave analysis method, “ai-Phase Mobile 1u” manufactured by ai-Phase can be cited.

  The cured product of the present invention is characterized by exhibiting sufficient thermal diffusivity as described above and having a low surface roughness. Regarding the cured product of the present invention, the arithmetic average roughness (Ra value) of the surface is preferably 300 nm or less, more preferably 260 nm or less, still more preferably 220 nm or less, even more preferably 180 nm or less, particularly preferably 160 nm or less, 150 nm. Hereinafter, they are 140 nm or less, 130 nm or less, 120 nm or less, 110 nm or less, 100 nm or less, 90 nm or less, or 80 nm or less. The lower limit of the Ra value is not particularly limited, but can usually be 10 nm or more. The arithmetic average roughness (Ra value) of the cured body surface can be measured using a non-contact type surface roughness meter. As a specific example of the non-contact type surface roughness meter, “WYKO NT3300” manufactured by Bee Coins Instruments can be cited.

  The cured body of the present invention is characterized by exhibiting sufficient thermal diffusibility and low surface roughness. This is thought to be due to the extremely good dispersion of the high thermal conductive inorganic filler selected from the group consisting of aluminum nitride and silicon nitride in the cured body of the present invention.

  The thickness of the cured product of the present invention varies depending on the application, but when used as an insulating layer of a multilayer printed wiring board, it is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 60 μm or less, and even more preferably 50 μm. It is as follows. Although the minimum of the thickness of a hardening body changes with uses, when using as an insulating layer of a multilayer printed wiring board, it is 10 micrometers or more normally.

[Roughened hardened body]
The roughened cured body of the present invention is obtained by roughening the cured body of the present invention.

  The procedure and conditions for the roughening treatment are not particularly limited, and known procedures and conditions that are usually used when forming the insulating layer of the multilayer printed wiring board can be adopted. For example, the surface of the cured body can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. Although it does not specifically limit as a swelling liquid, An alkaline solution, surfactant solution, etc. are mentioned, Preferably it is an alkaline solution, As this alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include Swelling Dip Securigans P and Swelling Dip Securigans SBU manufactured by Atotech Japan. Although the swelling process by a swelling liquid is not specifically limited, For example, it can carry out by immersing a hardening body for 1 minute-20 minutes in 30-90 degreeC swelling liquid. From the viewpoint of suppressing the swelling of the resin of the cured body to an appropriate level, it is preferable to immerse the cured body in a swelling liquid at 40 to 80 ° C. for 5 seconds to 15 minutes. Although it does not specifically limit as an oxidizing agent, For example, the alkaline permanganate solution which melt | dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the cured product in an oxidizing agent solution heated to 60 ° C. to 80 ° C. for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. 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. Moreover, as a neutralization liquid, acidic aqueous solution is preferable, As a commercial item, the reduction solution securigant P by Atotech Japan Co., Ltd. is mentioned, for example. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidant solution in the neutralizing solution at 30 to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing an object subjected to roughening treatment with an oxidant solution in a neutralizing solution at 40 to 70 ° C. for 5 to 20 minutes is preferable.

  The present inventors have found that the surface roughness of a cured body containing a highly thermally conductive inorganic filler selected from the group consisting of aluminum nitride and silicon nitride may increase rapidly due to the roughening treatment. It was. The increase in surface roughness due to such roughening treatment tended to become more prominent when aluminum nitride was used as the high thermal conductive inorganic filler. On the other hand, in the present invention using a filler obtained by treating a highly thermally conductive inorganic filler with a silane compound, an increase in surface roughness due to the roughening treatment can be suppressed, and sufficient thermal diffusivity is expressed. It is possible to realize a roughened cured body having a low surface roughness. It is known that aluminum nitride and silicon nitride are easily decomposed by water and alkali, respectively. In the present invention, it is considered that a surface exhibiting excellent resistance to water and alkali is formed by treating aluminum nitride and silicon nitride with a silane compound.

  In a preferred embodiment, the roughened cured body of the present invention has a surface arithmetic average roughness (Ra value) of preferably 500 nm or less, more preferably 400 nm or less, still more preferably 300 nm or less, and even more preferably 280 nm or less. Particularly preferably, it is 260 nm or less, 240 nm or less, 220 nm or less, or 200 nm or less. The lower limit of the Ra value is not particularly limited, but can usually be 10 nm or more. Further, the cured product of the present invention has a surface root mean square roughness (Rq value) of preferably 650 nm or less, more preferably 600 nm or less, further preferably 550 nm or less, particularly preferably 500 nm or less, 550 nm or less, 500 nm or less. 450 nm or less, 400 nm or less, 350 nm or less, or 300 nm or less. The lower limit of the Rq value is not particularly limited, but is usually 10 nm or more, 30 nm or more, 50 nm or more, or the like. The arithmetic average roughness (Ra value) and root mean square roughness (Rq value) of the surface of the roughened cured body can be measured using a non-contact type surface roughness meter. As a specific example of the non-contact type surface roughness meter, “WYKO NT3300” manufactured by Bee Coins Instruments can be cited.

[Laminate]
The laminated body of this invention is equipped with the roughening hardening body of this invention, and the conductor layer formed in the surface of this roughening hardening body.

  The metal used for the conductor layer is not particularly limited, but in a preferred embodiment, the conductor layer is made of gold, platinum, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. One or more metals selected from the group consisting of: The conductor layer may be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper- A layer formed from a nickel alloy and a copper / titanium alloy). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of removal by etching, etc., single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, silver or copper, or nickel-chromium alloy, copper Nickel alloy, copper / titanium alloy alloy layer is preferable, chromium, nickel, titanium, aluminum, zinc, gold, silver or copper single metal layer, or nickel / chromium alloy alloy layer is more preferable, copper single metal layer Is more preferable.

  The conductor layer may have a single layer structure or a multilayer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor layer has a multilayer structure, the layer in contact with the roughened cured body is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel / chromium alloy.

  The thickness of the conductor layer is preferably 40 μm or less, more preferably 1 to 35 μm, and even more preferably 3 to 30 μm, from the viewpoint of fine wiring of the multilayer printed wiring board. Even when the conductor layer has a multilayer structure, the thickness of the entire conductor layer is preferably within the above range.

  The conductor layer can be formed on the surface of the roughened cured body by dry plating or wet plating. Examples of the dry plating include known methods such as vapor deposition, sputtering, and ion plating. In the case of wet plating, for example, the conductive layer is formed by 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 method for forming the wiring pattern, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used.

  When forming a conductor layer by a semi-additive method, you may form in the following procedures. First, a plating seed layer is formed on the surface of the roughened cured body by electroless plating. Next, a mask pattern that exposes a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. A metal layer is formed by electrolytic plating on the exposed plating seed layer, and then the mask pattern is removed. Thereafter, an unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

  The roughened cured body (insulating layer) and the conductor layer are required to exhibit sufficient adhesion strength (peeling strength), and in general, such adhesion is obtained by the anchor effect caused by the unevenness of the surface of the roughened cured body. Yes. However, if the roughness of the surface of the roughened cured body is large, when removing an unnecessary plating seed layer by etching when forming a wiring pattern, it is difficult to remove the seed layer of the uneven portion, and the plating seed layer of the uneven portion is sufficiently removed. When etching is performed under conditions that can be removed, the dissolution of the wiring pattern becomes noticeable, which hinders fine wiring. In this regard, as for the cured body containing the high thermal conductive inorganic filler selected from the group consisting of aluminum nitride and silicon nitride, as described above, not only the surface roughness increases rapidly but also the surface. The present inventors have found that, although the roughness is high, it may result in a roughened cured body that is remarkably inferior in adhesion strength (peel strength) to the conductor layer. On the other hand, in the present invention using a filler obtained by treating a highly thermally conductive inorganic filler with a silane compound, a roughened cured body having a low surface roughness and good adhesion strength (peeling strength) with a conductor layer is advantageous. (The surface roughness of the roughened cured body is as described above). Combined with the effect of realizing sufficient thermal diffusivity, the laminate of the present invention contributes significantly to both the thermal diffusibility and the miniaturization of the multilayer printed wiring board.

  In the laminate of the present invention, the peel strength between the roughened cured body and the conductor layer is preferably 0.25 kgf / cm or more, more preferably 0.30 kgf / cm or more, further preferably 0.35 kgf / cm or more, particularly Preferably it is 0.40 kgf / cm or more or 0.45 kgf / cm or more. The upper limit of the peel strength is not particularly limited, but is usually 1.0 kgf / cm or less, 0.9 kgf / cm or less, or the like. The peel strength between the roughened cured body and the conductor layer refers to the peel strength (90 degree peel strength) when the conductor layer is peeled in the direction perpendicular to the roughened cured body (90-degree direction). The peel strength when the conductor layer is peeled in the direction perpendicular to the roughened cured body (90-degree direction) can be determined by measuring with a tensile tester. Examples of the tensile tester include “AC-50C-SL” manufactured by TSE Corporation.

[Multilayer printed wiring board]
The multilayer printed wiring board of this invention contains the hardening body or roughening hardening body of this invention.

  In one embodiment, the multilayer printed wiring board of the present invention includes the roughened cured body of the present invention as an insulating layer. In another embodiment, the multilayer printed wiring board of the present invention includes the cured body of the present invention as a solder resist. In the multilayer printed wiring board of the present invention, the cured product or roughened cured product of the present invention is included as an appropriate member depending on the specific application.

  Hereinafter, an embodiment of a multilayer printed wiring board including the cured body or roughened cured body of the present invention as an insulating layer will be described.

  In one embodiment, the multilayer printed wiring board of the present invention can be manufactured using the adhesive film described above. In such an embodiment, after laminating so that the resin composition layer of the adhesive film is bonded to the circuit board, the above-described “preheating” and “thermosetting” are performed, and the cured body of the present invention is replaced with the circuit board. Can be formed on top. In addition, when an adhesive film has a protective film, it can use for manufacture after removing a protective film.

The conditions for the lamination treatment are not particularly limited, and known conditions used for forming an insulating layer of a multilayer printed wiring board using an adhesive film can be employed. For example, it can be carried out by pressing a heated metal plate such as a SUS mirror plate from the support side of the adhesive film. In this case, it is preferable not to press the metal plate directly, but to press through an elastic material such as heat-resistant rubber so that the adhesive film sufficiently follows the circuit irregularities of the circuit board. The pressing temperature is preferably in the range of 70 ° C. to 140 ° C., the pressing pressure is preferably in the range of 1 kgf / cm ^{2 to} 11 kgf / cm ² (0.098 MPa to 1.079 MPa), and the pressing time is preferably The range is from 5 seconds to 3 minutes. The laminating process is preferably performed under a reduced pressure of 20 mmHg (26.7 hPa) or less. Lamination treatment can be performed using a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressure laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nichigo Morton, and the like.

  In the present invention, the “circuit board” is mainly patterned on one or both sides of a substrate such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. This means that a conductor layer (circuit) is formed. Further, when manufacturing a multilayer printed wiring board, an inner layer circuit board of an intermediate product on which an insulating layer and / or a conductor layer is to be further formed is also included in the “circuit board” in the present invention.

  In other embodiment, the printed wiring board of this invention can be manufactured using the above-mentioned resin varnish. In such an embodiment, after the resin varnish is uniformly applied on the circuit board by a die coater or the like, and the resin composition layer is formed on the circuit board by heating and drying, the above-mentioned “preheating” and “ The cured product of the present invention can be formed on a circuit board by performing “thermosetting”. The organic solvent used for the resin varnish and the heating and drying conditions may be the same as those described for the production of the adhesive film.

  Next, after the above-described “roughening treatment” is performed on the cured body formed on the circuit board to form a roughened cured body, a conductor layer is formed on the surface of the roughened cured body. In the production of the multilayer printed wiring board, a drilling step for drilling the insulating layer may be further included. These steps can be performed according to various methods known to those skilled in the art and used in the production of multilayer printed wiring boards.

[Semiconductor device]
A semiconductor device can be manufactured using the multilayer printed wiring board.

  Examples of such semiconductor devices include various semiconductor devices used for electrical products (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircrafts). .

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following description, “parts” and “%” mean “parts by mass” and “% by mass”, respectively, unless otherwise specified.

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

[Preparation of measurement and evaluation substrate]
(1) Ground treatment of inner layer circuit board Glass cloth base epoxy resin double-sided copper clad laminate with inner layer circuit formed on both sides (copper foil thickness 18 μm, substrate thickness 0.3 mm, manufactured by Matsushita Electric Works, Ltd. R5715ES ”) was dipped in“ CZ8100 ”manufactured by Mec Co., Ltd., and the copper surface was roughened (copper etching amount 1 μm).

(2) Laminating treatment of adhesive film The adhesive film produced in the examples and comparative examples was obtained by using a batch type vacuum pressure laminator (“MVLP-500” manufactured by Meiki Co., Ltd.) and the resin composition layer was an inner layer circuit. Lamination was performed on both sides of the inner circuit board so as to be bonded to the board. The laminating process was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less and then pressing at 120 ° C. and a pressure of 0.74 MPa for 30 seconds.

(3) Thermosetting of resin composition layer After laminating the resin composition layer, the PET film as a support was peeled off. Next, the inner layer circuit board on which the resin composition layer was laminated was preheated at 100 ° C. for 30 minutes, and then heated at 180 ° C. for 30 minutes, and the resin composition layer was thermally cured to form a cured body.

(4) Roughening treatment An inner layer circuit board having a cured body formed on both sides is placed in a swelling liquid (“Swelling Dip Securigant P” manufactured by Atotech Japan Co., Ltd., sodium hydroxide aqueous solution containing diethylene glycol monobutyl ether) at 60 ° C. And then immersed in an oxidizing agent (“Concentrate Compact CP” manufactured by Atotech Japan KK, an aqueous solution having a potassium permanganate concentration of about 6 mass% and a sodium hydroxide concentration of about 4 mass%) at 80 ° C. for 20 minutes. It was immersed for 5 minutes, and finally immersed in a neutralizing solution (“Reduction Solution Securigant P” manufactured by Atotech Japan Co., Ltd., hydroxylamine sulfate aqueous solution) at 40 ° C. for 5 minutes. Then, it dried for 30 minutes at 80 degreeC, and formed the roughening hardening body on both surfaces of the inner-layer circuit board.

(5) Formation of conductor layer According to a semi-additive method, a conductor layer was formed on the surface of the roughened cured body.
That is, an inner layer circuit board having a roughened cured body formed on both sides is immersed in an electroless plating solution containing PdCl ₂ at 40 ° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25 ° C. for 20 minutes. Then, a plating seed layer was formed on the surface of the roughened cured body. After annealing at 150 ° C. for 30 minutes, an etching resist was provided on the plating seed layer, and the plating seed layer was patterned by etching. Subsequently, copper sulfate electrolytic plating was performed to form a conductor layer having a thickness of 30 μm, and then annealed at 190 ° C. for 60 minutes to form a conductor layer on the surface of the roughened cured body.

[Measurement of arithmetic average roughness (Ra value), root mean square roughness (Rq value)]
The arithmetic average roughness (Ra value) of the surface of the cured body, the arithmetic average roughness (Ra value) of the surface of the roughened cured body, and the root mean square roughness (Rq value) were measured using a non-contact type surface roughness meter (Beeco). Using “WYKO NT3300” manufactured by Instruments Co., Ltd.), a VSI contact mode and a 50 × lens were used to obtain a numerical value obtained with a measurement range of 121 μm × 92 μm. For each cured body and roughened cured body, an average value of 10 points randomly selected was obtained.

[Measurement of peel strength (peel strength) of conductor layer]
The conductor layer of the evaluation board is cut into a 10 mm wide and 100 mm long part, and one end is peeled off to grasp the grip (Autocom type tester “AC-50C-SL” manufactured by TS E Co., Ltd.) The peel strength was determined by measuring the load (kgf / cm) when 35 mm was peeled off in the vertical direction at a speed of 50 mm / min at room temperature.

[Measurement and evaluation of thermal diffusivity of cured product]
The thermal diffusivity of the cured product was evaluated by measuring the thermal conductivity of the cured product according to the following procedure. That is, the adhesive films prepared in Examples and Comparative Examples were heated at 190 ° C. for 90 minutes to heat cure the resin composition layer. After thermosetting the resin composition layer, the PET film as the support was peeled off to obtain a sheet-like cured body. About the obtained hardening body, the heat conductivity of the thickness direction of this hardening body was measured by the temperature wave analysis method using "ai-Phase Mobile 1u" made from ai-Phase. The same test piece was measured three times, and the average value was calculated. When the average value is 1.5 W / m · K or more, “◯”, when the average value is 1 W / m · K or more and less than 1.5 W / m · K, “Δ”, and the average value is 1 W / m. -The case of less than K was evaluated as "x".

<Example 1>
12 parts of naphthalene type epoxy resin (DIC Corporation "HP4032SS", epoxy equivalent of about 144), naphthylene ether type epoxy resin (DIC Corporation "HP6000", epoxy equivalent of about 250), 6 parts of xylenol type epoxy Resin (Mitsubishi Chemical Corporation "YX4000HK", epoxy equivalent of about 185) 4 parts, and phenoxy resin (Mitsubishi Chemical Corporation "YL7553BH30", solid content of 30% by weight methyl ethyl ketone (MEK) and cyclohexanone 1: 1. 6 parts of the solution was dissolved in 30 parts of solvent naphtha with stirring. After cooling to room temperature, 9 parts of triazine structure-containing cresol novolac resin (“LA-3018-50P” manufactured by DIC Corporation, 2-methoxypropanol solution having a hydroxyl equivalent of 151 and a solid content of 50%), active ester -Based curing agent (DIC Corporation "HPC8000-65T", active group equivalent of about 223, non-volatile component 65% by weight toluene solution) 10 parts, curing accelerator (4-dimethylaminopyridine, "DMAP", solid content 5 Aluminum nitride surface-treated with 2 parts by mass of MEK solution (mass%) and 0.7 part of an aminosilane compound (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd., N-phenyl-3-aminopropyltrimethoxysilane) Tokuyama "Shapal H", average particle diameter 1.1 .mu.m, specific surface area 2.6 m ² / g, a specific gravity of 3.3g ^/ cm 3) 120 parts of mixture And uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish.
Next, the resin varnish is uniformly applied to the release layer side of the PET film with a release layer ("PET501010" manufactured by Lintec Co., Ltd., thickness 50 μm) so that the thickness of the resin composition layer after drying is 30 μm. It apply | coated and dried at 80-120 degreeC (average 100 degreeC) for 4 minutes, and produced the adhesive film.

<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 of about 169), 6 parts, biphenyl type epoxy resin (Nippon Kayaku Co., Ltd.) "NC3000H", epoxy equivalent of about 288) 9 parts, xylenol type epoxy resin (Mitsubishi Chemical Corporation "YX4000HK", epoxy equivalent of about 185) 12 parts, fluorene type epoxy resin (Mitsubishi Chemical Corporation "YL7800BH40") 6 parts of a methyl ethyl ketone (MEK) and cyclohexanone 1: 1 solution having a solid content of 40% by mass and an epoxy equivalent of about 4100 were dissolved in 40 parts of solvent naphtha with stirring. After cooling to room temperature, 10 parts of a 60% solid MEK solution of a triazine structure-containing phenol novolac resin (“LA-1356” manufactured by DIC Corporation, hydroxyl equivalent 146), an active ester type curing agent (DIC) "HPC8000-65T" manufactured by Co., Ltd., 10 parts of a non-volatile component 65 mass% toluene solution having an active group equivalent of about 223), 2 parts of a curing accelerator (4-dimethylaminopyridine, MEK solution having a solid content of 5 mass%), 1. Aluminum nitride surface-treated with 1 part of silane compound (“KBM103” manufactured by Shin-Etsu Chemical Co., Ltd., phenyltrimethoxysilane) (“Shapal H” manufactured by Tokuyama Co., Ltd.), average particle size 1.1 μm, specific surface area 170 parts of 6 m < ² > / g, specific gravity 3.3 g / cm < ³ >) were mixed, and it disperse | distributed uniformly with the high-speed rotary mixer, and prepared the resin varnish. Next, an adhesive film was produced in the same manner as in Example 1.

<Example 3>
4 parts of naphthalene type epoxy resin (DIC Corporation “HP4032SS”, epoxy equivalent of about 144), biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. “NC3000H”, epoxy equivalent of about 288), 12 parts of bixylenol type epoxy Resin (Mitsubishi Chemical Corporation "YX4000HK", epoxy equivalent of about 185) 6 parts, Phenoxy resin (Mitsubishi Chemical Corporation "YL7553BH30", solid content of 30% by weight methyl ethyl ketone (MEK) and cyclohexanone 1: 1 solution ) 9 parts were heated and dissolved in 30 parts of solvent naphtha with stirring. After cooling to room temperature, 12 parts of a triazine structure-containing cyanate ester resin ("BA230S75" manufactured by Lonza Japan Co., Ltd., MEK solution with a cyanate equivalent of about 232 and a non-volatile component of 75% by mass), a phenol novolac-type cyanate ester resin (Lonza Japan Co., Ltd. “PT30S”, cyanate equivalent of about 133, MEK solution having a nonvolatile content of 85% by mass), 3 parts, active ester curing agent (DIC Corporation “HPC8000-65T”, active group equivalent of about 223 12 parts of a toluene solution having a nonvolatile content of 65% by weight, 0.4 part of a hardening accelerator (4-dimethylaminopyridine, MEK solution having a solid content of 5% by weight), a hardening accelerator (manufactured by Tokyo Chemical Industry Co., Ltd., cobalt ( III) 3 parts of acetylacetonate, MEK solution with a solid content of 1% by mass, flame retardant (“HCA-HQ” manufactured by Sanko Co., Ltd.) 10 parts of 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle size 2 μm, aminosilane compound (manufactured by Shin-Etsu Chemical Co., Ltd.) “KBM573”, aluminum nitride surface-treated with 0.6 part of N-phenyl-3-aminopropyltrimethoxysilane (“Shapal H” manufactured by Tokuyama Corporation), average particle size 1.1 μm, specific surface area 2.6 m ² / g, specific gravity 3.3 g / cm ³ ) 110 parts were mixed and uniformly dispersed 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.

<Example 4>
Instead of 10 parts of an active ester type curing agent (“HPC8000-65T” manufactured by DIC Corporation, active group equivalent of about 223, 65% by mass of a non-volatile component in toluene), a naphthol type curing agent (Nippon Steel Chemical Co., Ltd.) A resin varnish was prepared in the same manner as in Example 2 except that 10 parts of “SN-485” (MEK solution having a hydroxyl equivalent weight of 215 and a solid content of 60%) was used to prepare an adhesive film.

<Example 5>
The point that 10 parts of MEK solution having a solid content of 60% of triazine structure-containing phenol novolak resin (“LA-1356” hydroxyl equivalent 146 manufactured by DIC Corporation) was not added, and active ester curing agent (DIC Corporation) A resin varnish was prepared in the same manner as in Example 2 except that the blending amount of “HPC8000-65T”, an active group equivalent of about 223, and a toluene solution containing 65% by mass of non-volatile components) was increased from 10 parts to 24 parts. An adhesive film was prepared.

<Example 6>
Aluminum nitride surface-treated with 0.7 part of aminosilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd., N-phenyl-3-aminopropyltrimethoxysilane) ("Shapal H" manufactured by Tokuyama Corporation), average grain Instead of 120 parts in diameter 1.1 μm, specific surface area 2.6 m ² / g, specific gravity 3.3 g / cm ³ ), an aminosilane compound (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), N-phenyl-3-aminopropyl Silicon nitride surface-treated with 0.7 parts of trimethoxysilane (“SN-9S” manufactured by Denki Kagaku Kogyo Co., Ltd.), average particle size 1.1 μm, specific surface area 7 m ² / g, specific gravity 3.4 g / cm ³ A resin varnish was prepared in the same manner as in Example 1 except that the adhesive film was prepared.

<Comparative Example 1>
4 parts of naphthalene type epoxy resin (DIC Corporation “HP4032SS”, epoxy equivalent of about 144), biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. “NC3000H”, epoxy equivalent of about 288), 12 parts of bixylenol type epoxy Resin (Mitsubishi Chemical Corporation "YX4000HK", epoxy equivalent of about 185) 6 parts, Phenoxy resin (Mitsubishi Chemical Corporation "YL7553BH30", solid content of 30% by weight methyl ethyl ketone (MEK) and cyclohexanone 1: 1 solution ) 9 parts were heated and dissolved in 30 parts of solvent naphtha with stirring. After cooling to room temperature, there are 24 parts of a triazine structure-containing cyanate ester resin ("BA230S75" manufactured by Lonza Japan Co., Ltd., an MEK solution having a cyanate equivalent of about 232 and a non-volatile component of 75% by mass), a phenol novolac-type cyanate ester resin. 3 parts of "PT30S" manufactured by Lonza Japan Co., Ltd., MEK solution with cyanate equivalent of about 133 and non-volatile content of 85% by mass, curing accelerator (4-dimethylaminopyridine, MEK solution with a solid content of 5% by mass) 0.4 Part, curing accelerator (manufactured by Tokyo Chemical Industry Co., Ltd., cobalt (III) acetylacetonate, MEK solution having a solid content of 1% by mass), flame retardant (“HCA-HQ” manufactured by Sanko Co., Ltd., 10- ( 2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle size [mu] m) 3 parts, aluminum nitride without surface treatment (Tokuyama Corporation Ltd. "Shapal H", average particle diameter 1.1 .mu.m, specific surface area 2.6 m ² / g, specific gravity 3.3 g ^/ cm 3) 100 parts of And uniformly dispersed 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.

<Comparative example 2>
1. Aluminum nitride surface-treated with 1 part of silane compound (“KBM103” manufactured by Shin-Etsu Chemical Co., Ltd., phenyltrimethoxysilane) (“Shapal H” manufactured by Tokuyama Co., Ltd.), average particle size 1.1 μm, specific surface area Instead of 170 parts of 6 m ² / g, specific gravity 3.3 g / cm ³ ), aluminum nitride not subjected to surface treatment (“Shapal H” manufactured by Tokuyama Co., Ltd., average particle size 1.1 μm, specific surface area 2.6 m) ² / g, specific gravity 3.3 g / cm ³ ) A resin varnish was prepared in the same manner as in Example 5 except that 170 parts were used, and an adhesive film was produced.

<Comparative Example 3>
Aluminum nitride surface-treated with 0.7 part of aminosilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd., N-phenyl-3-aminopropyltrimethoxysilane) ("Shapal H" manufactured by Tokuyama Corporation), average grain Instead of 120 parts in diameter 1.1 μm, specific surface area 2.6 m ² / g, specific gravity 3.3 g / cm ³ ), an aluminum coupling agent (“Plenact AL-M” manufactured by Ajinomoto Fine Techno Co., Ltd., acetoalkoxyaluminum diisopropyl Rate) 120 parts of aluminum nitride surface-treated with 0.7 parts (“Shapal H” manufactured by Tokuyama Corporation, average particle size 1.1 μm, specific surface area 2.6 m ² / g, specific gravity 3.3 g / cm ³ ) A resin varnish was prepared in the same manner as in Example 1 except that the adhesive film was prepared.

  The results are shown in Table 1.

  In Examples 1 to 6 using a resin composition containing a filler obtained by treating a high thermal conductivity inorganic filler selected from the group consisting of aluminum nitride and silicon nitride with a silane compound, sufficient thermal diffusivity (thermal conductivity) Ratio) and a cured body and a roughened cured body having low surface roughness and good adhesion strength (peeling strength) with the conductor layer. Among them, in Examples 1 to 3 and 6 in which the active ester curing agent and the triazine structure-containing curing agent are used in combination, sufficient thermal diffusibility (thermal conductivity) is exhibited, and particularly, the surface roughness is low. A cured body and a roughened cured body having excellent adhesion strength (peeling strength) to the conductor layer were obtained. On the other hand, in Comparative Examples 1 and 2 using a resin composition containing an untreated high thermal conductive inorganic filler, increasing the content of the high thermal conductive inorganic filler increases the thermal diffusivity (heat of the cured body). Although the conductivity was increased (in comparison with Comparative Example 1 and Comparative Example 2), it resulted in a cured body and a roughened cured body having a high surface roughness and extremely poor adhesion strength (peeling strength) with the conductor layer. Moreover, also in Comparative Example 3 using a resin composition containing a filler obtained by treating a highly thermally conductive inorganic filler with an aluminum coupling agent, the surface roughness is high and the adhesion strength (peel strength) with the conductor layer is remarkably high. It resulted in an inferior cured body and a roughened cured body. Note that a cured product containing a filler obtained by treating a highly heat-conductive inorganic filler with a silane compound has a higher thermal diffusion than a cured product containing an untreated high-heat-conductive inorganic filler in almost the same content. (Contrast between Example 3 and Comparative Example 1 or between Example 5 and Comparative Example 2) is confirmed.

Claims (15)

(A) at least one highly thermally conductive inorganic filler selected from the group consisting of aluminum nitride and silicon nitride,
(B) an epoxy resin, and (C) a resin composition containing a curing agent,
(A) component is processed with the silane compound,
(A) The average particle diameter of a component is 3 micrometers or less,
(C) The resin composition whose component contains the 1st hardening | curing agent and the 2nd hardening | curing agent different from this 1st hardening | curing agent, and a 1st hardening | curing agent is an active ester type hardening | curing agent.   The resin composition according to claim 1, wherein the silane compound has a phenyl group.   The resin composition of Claim 1 or 2 whose processing amount of a silane compound is 0.05 mass part or more with respect to 100 mass parts of highly heat conductive inorganic fillers.   The resin composition of any one of Claims 1-3 whose content of (A) component is 70 mass% or more when the sum total of the non-volatile component in a resin composition is 100 mass%.   The resin composition according to any one of claims 1 to 4, wherein the second curing agent is a triazine structure-containing curing agent.   The resin composition according to any one of claims 1 to 5, wherein the second curing agent is a triazine structure-containing phenol-based curing agent or a triazine structure-containing cyanate ester-based curing agent.   The mass ratio of the first curing agent to the second curing agent (first curing agent / second curing agent) is 0.3 to 2, according to any one of claims 1 to 6. Resin composition.   The hardening body obtained by thermosetting the resin composition of any one of Claims 1-7.   The hardened | cured material of Claim 8 whose arithmetic mean roughness (Ra) of a surface is 180 nm or less.   The cured body according to claim 8 or 9, wherein the thermal conductivity is 1 W / m · K or more.   The roughening hardening body obtained by roughening the hardening body of any one of Claims 8-10.   A laminate comprising the roughened cured body according to claim 11 and a conductor layer formed on a surface of the roughened cured body.   The laminate according to claim 12, wherein the peel strength between the roughened cured body and the conductor layer is 0.25 kgf / cm or more.   The multilayer printed wiring board containing the hardening body of any one of Claims 8-10, or the roughening hardening body of Claim 11.   A semiconductor device comprising the multilayer printed wiring board according to claim 14.